piperazinediium bis(µ -phthalato)zincate(ii) monohydrate: a new …11)1402-1408... · 2015. 11....

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Electronic Supplementary Data

Piperazinediium bis(micro2-phthalato)zincate(II) monohydrate A new ladder coordination polymer with a unique supramolecular architecture

Rita N Jyai amp Bikshandarkoil R Srinivasan Department of Chemistry Goa University Goa 403206 India

Email sriniunigoaacin

No Contents Pg No

1 Scheme S1- Different binding modes of phthalate anion in zinc(II) phthalates 2

2 Synthetic details of preparation of 1 and 2 2

3 Table S1 ndash List of reported zinc phthalates 4

4 Table S2 ndash Bond lengths [Aring] and angles [o] for the pipH2 cation and the pt ligands in (pipH2)[Zn(pt)2]middotH2O 1

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5 Table S3 ndash Structure details of zinc(II) phthalate compounds 6

6 Table S4 ndash H-bonding characteristics of piperazinediium compounds 7

7 Fig S1 ndash IR spectra of (A) ptH2 (B) [Zn(ptH)2(H2O)2] (C) 1 and (D) 2 8

8 Fig S2 ndash IR and Raman spectra of [Zn(ptH)2(H2O)2] 8

9 Fig S3 ndash IR and Raman spectra of (pipH)2[Zn(pt)2]middotH2O 1 9

10 Fig S4 ndash IR and Raman spectra of [(enH)2Zn(pt)2(H2O)] 2 9

11 Fig S5 ndash UV-Visible spectra of (A) ptH2 and (B) [Zn(ptH)2(H2O)2] in H2O 10

12 Fig S6 ndash UV-DRS spectra of 1and 2 10

13 Fig S7 ndash IR spectra of [Zn(ptH)2(H2O)2] 1 and 2 after heating at 500degC 11

14 Fig S8 ndash X-ray powder pattern of 1 11

15 Fig S9 ndash TG-DTA curves of 1 12

16 Fig S10 ndash X-ray powder pattern of 1 after heating at 500degC 12

17 Fig S11 ndash The micro2-bidentate bridging binding modes shown by two unique phthalates 13

18 Fig S12 ndash The H-bonding surroundings of the two unique (pipH2)2+ cations in 1 13

19 Fig S13 ndash Disposition of the unique cations in the crystal structure of 1 14

20 Fig S14 ndash A portion of the 1-D Zn(II) chain in [13-pnH2][Zn(pt)2] 14

21 CheckCIF PLATON report for 1 15

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Free phthalate micro2-bidentate micro2-tridentate micro3-tridentate

micro3-tetradentate micro3-tetradentate micro3-pentadentate micro4-pentadentate

SCHEME S1 ndash Different binding modes of phthalate anion in zinc(II) phthalates

Synthetic details of preparation of (pipH2)[Zn(pt)2]middotH2O (1) and [(enH2)Zn(pt)2H2O] (2)

Method I - [Zn(ptH)2(H2O)2] prepared by reacting zinc acetate dihydrate with ptH2 (04317 g 1

mmol) and piperazine (00861 g 1 mmol) was taken in distilled water (~15 mL) The volume of the

reaction mixture was reduced to ~10 mL by heating it on a water bath and the clear solution thus

obtained (pH 7) was then kept undisturbed for crystallization at room temperature The needle shaped

transparent crystals obtained in 4 days were washed with ice cold water followed by methanol and

dried in air to yield 04098 g (82 ) of compound 1 Use of ethylenediamine (007 mL 1 mmol) in

the above reaction instead of piperazine resulted in the formation of compound 2

Anal () (for 1) Found (calcd) for ZnC20O9N2H22 (49983) C 4812 (4806) H 441 (445) N 559 (561) ptH2 664 (6647) ZnO 1638 (1628) IR (cm-1) 3660 (s) 3427 (s) 3030-2220 (b) 1552 (s) 1400 (s) 1371(s) 1083 (s) 962 (w) 833 (w) 761(s) 706 (w) 650 (w) 613 (w) 586 (w) 459 (w) Raman (cm-1) 1591 (s) 1564 (w) 1406 1373 (w) 1149 (s) 1041 (s) 839 (s) 653 (w) 482 (w) UV-DRS (in nm) 246 274 DTA (in degC) 155 (endo) 347 (exo) 472 (exo) Anal () (for 2) Found (calcd) for ZnC18O9N2H20 (47379) C 4571 (4563) H 432 (426) N 589 (591) ZnO 172 (1718) IR (cm-1) 3630 (s) 3300-2538 (b) 1632 (s) 1564 (s) 1366 (b) 1138 (w) 1085 (w) 856 (w) 773 (b) 717 (s) 453 (w) Raman (cm-1) 3057 (w) 1587 (s) 1397 (s) 1363 (w) 1150 (w) 1041 (s) 829 (s) UV-DRS (in nm) 230 283 Method II - Zinc acetate dihydrate (02195 g 1 mmol) piperazine (00861 g 1 mmol) and phthalic

acid (03323 g 2 mmol) were taken in ~40 mL distilled water to get a clear solution The reaction

mixture was heated on a water bath to reduce the volume to ~25 ml The solution thus obtained was

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cooled and left undisturbed for crystallization at room temperature The needle shaped transparent

crystals isolated by filtration after 5 days were washed with ice cold water followed by methanol and

dried in air to yield 03998 g (80 ) of compound 1 Use of ethylenediamine (007 mL 1 mmol) in the

above reaction instead of piperazine resulted in the formation of 2

Method III (for synthesis of 1) - Piperazinediium bis(hydrogenphthalate) (pipH2)(ptH)2middot2H2O (04545

g 1 mmol) and zinc acetate dihydrate (02195 g 1 mmol) were mixed together in distilled water (~20

mL) to get a clear solution The reaction mixture was heated to reduce the volume to ~15 ml and kept

for crystallization at room temperature The crystals obtained in 2 days were isolated as before to yield

03749 g (75 ) of compound 1 The IR spectrum of the compound obtained was found identical to

compound 1 obtained from methods I and II

Method III (for synthesis of 2) ndash To a mixture of phthalic acid (03323 g 2 mmol) and NaHCO3

(03360 g 4 mmol) in water (~20 mL) ethylenediamine dihydrochloride (01330 g 1 mmol) and

ZnCl2 (01363 g 1 mmol) was added to obtain a clear solution The clear reaction mixture was left

undisturbed for crystallization Transparent crystals obtained after 2 days were filtered washed with

methanol and dried in air The IR spectrum of the compound obtained was found identical to


The reactions described above are summarised in the following reaction Scheme

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Table S1 List of reported zinc phthalates Compound Dimens

ionality Ref Compound Dimens

ionality Ref

Neutral complexes whose Znpt = 11

[Zn(pt)(Im)(H2O)]2 0-D 2 [Zn(pt)(44rsquo-bipy) (H2O)2]middot2H2O 2-D 24 [Zn(pt)(metu)2]2middot4H2O 0-D 3 [Zn(pt)] 2-D 25 [Zn(pt)(1-MeIm)2] 1-D 1 [Zn(pt)(biim-6)] 2-D 21 [Zn(pt)(Pyridine)2] 1-D 4 [Zn(pt)(bmb)05(H2O)]middot05(bmb)middotH2O 2-D 26 [Zn(pt)(β-Pic)2] 1-D 4 [Zn(pt)(thim)]middot2H2O 2-D 34 [Zn(pt)(γ-Pic)2] 1-D 4 [Zn(pt)(mib)]middot3H2O 2-D 35 [Zn(pt)(γ-Pic)] 1-D 4 [Zn(pt)(mib)05] 3-D 35 [Zn(pt)(Im)2] 1-D 2 [Zn(pt)(imp)(H2O)] 3-D 30 [Zn(pt)(2-MeIm)2] 1-D 2 [Zn(pt)(ib)] 3-D 36 [Zn(pt)(fimp)] 1-D 8 [Zn(pt)(tppa)]middot2H2O 3-D 37 [Zn(pt)(1-VnIm)] 1-D 9 [Zn(pt)(bimb)] 3-D 38 [Zn(pt)(Phen)(H2O)] 1-D 10 [Zn2(pt)2(Dpq)2(H2O)4]middot2H2O 0-D 39 [Zn(pt)(22rsquo-bpy)(H2O)] 1-D 11 [Zn2(pt)2(Dpds)2]middot2H2O 0-D 39 [Zn(pt)(cyclam)]middot2(CH3OH) 1-D 12 [Zn2(pt)2(tpt)2] 0-D 40 [Zn(pt)(Phen)(H2O)] 1-D 13 [Zn2(pt)2(22rsquo-bpy)2(H2O)2] 0-D 41 [Zn(pt)(dpz)] 1-D 14 [Zn2(pt)2(bpp)] 1-D 5 [Zn(pt)(micro-44rsquo-bpp)]middotH2O 1-D 19 [Zn2(pt)2(34rsquo-bpt)] 1-D 7 [Zn(pt)(bbip)]middotH2O 1-D 20 [Zn2(pt)2(bpp)2]middotH2O 1-D 15 [Zn(pt)(dmetu)2] 1-D 3 [Zn2(pt)2(22rsquo-bpy)2(H2O)]middotH2O 1-D 42 [Zn(pt)(tu)2] 1-D 18 [Zn2(pt)2(pmmi)2]middot6H2O 1-D 43 [Zn(pt)(pyrazole)2] 1-D 31 [Zn2(pt)2(ttmt)2]middotH2O 1-D 44 [Zn(pt)(23rsquo-tmbpt)(H2O)] 1-D 32 [Zn2(pt)2(4-dpaa)(H2O)2]middot2H2O 1-D 33 [Zn(pt)(33rsquo-tmbpt)]middotH2O 1-D 32 [Zn2(pt)2(Dpq)2]middotH2O 2-D 21 [Zn(pt)(3-dpaa)] 1-D 33 [Zn2(pt)2(bte)2]middot4H2O 2-D 28 [Zn(pt)(1-allylimidazole)2] 1-D 46 [Zn2(pt)2(bib)] 2-D 23 [Zn(pt)(bdmb)] 1-D 47 [Zn2(pt)2(imb)]middot2H2O 3-D 29 [Zn(pt)(44rsquo-bpt)] 2-D 7 [Zn2(pt)2(imm)]middot35H2O 3-D 45 [Zn(pt)(biim-5)] 2-D 22 [Zn4(pt)4(tib)2]middot2H2O 2-D 27


[Zn2(pt)(ppa)(H2O)]middot2H2O 1-D 16 [Zn2(pt)(tib)Cl2] 3-D 27 [Zn2(pt)(pp)2(H2O)] 1-D 6

Cationic complexes whose Znpt = 21

[Zn2(pt)(tib)](NO3)2 3-D 27 [Zn2(pt)(tib)2]I2 3-D 27

Anionic complexes whose Znpt = 12

(13-pnH2)[Zn(pt)2] 1-D 17 (pipH2)[Zn(pt)2]middotH2O 1-D This [Zn(ptH)2(H2O)2] 0-D 48 [(enH2)Zn(pt)2H2O] Work

Abbreviations Im= imidazole metu=N-methyl thiourea 1-MeIm= 1-methyl imidazole β-Pic=3-methyl pyridine γ-Pic=4-methyl pyridine 2-MeIm= 2-methyl imidazole fimp=2-(2-furyl)-1H-imidazo[45-f](110-phenanthroline) 1-VnIm =1-vinylimidazole Phen=110-phenanthroline 22rsquo-bpy= 22rsquo-bipyridine dpz=dipyrido[32-a2rsquo3rsquo-c]phenazine micro-44rsquo-bpp= 22rsquo-bis(4-pyridylmethyleneoxy)-110 -biphenylene bbip=11rsquo-(14-butanediyl)bis(imidazole-2-phenyl) dmetu=NNrsquo-dimethyl thiourea tu= thiourea 23rsquo-tmbpt= 1-((1H-124-trizol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-124-trazole 33rsquo-tmbpt= 1-((1H-124-trizol-1-yl)methyl)-35-bis(3-pyridyl)-124-trazole 3-dpaa= NNrsquo-di(3-pyridyl)adipoamide bdmb= 11rsquo-(Biphenyl-44rsquo-diyl)bis(methylene)bis(1H-benzimidazole) 44rsquo-bpt=1H-35-bis(4-pyridyl)-124-triazole biim-5=11rsquo-(15-pentanedidyl)bis(imidazole) 44rsquo-bpy= 44rsquo-bipyridine biim-6=11rsquo-(16-hexane-didyl)bis(imidazole) bmb=14-bis(2-methyl benzimidazol-1-ylmethyl) thim= 25-bis(imidazol-1-yl)thiophene mib= 14-bis(2-methylimidazole-3-ium-1-yl)biphenyl imp=35-Bis(imidazole-1-yl)pyridine ib= 14-bis(imidazol-1-yl)benzene tppa= tri(4-pyridylphenyl)amine bimb= 14-bis(imidazol-1-yl-methyl)benzene Dpq=dipyrido[32-d2rsquo3rsquo-f]quinoxaline Dpds= 44rsquo-Dipyridyldisulfide tpt= 4rsquo-4(124-triazol-1-yl)phenyl-22rsquo6rsquo2rdquo-terpyridine bpp=13-bis(4-pyridyl)propane 34rsquo-bpt=1H-3-(3-pyridyl)-5-(4-pyridyl)-12-4-triazole pmmi= bis(11rsquo-((2356-tetramethyl-14-phenylene)bis(methylene))bis(2-methyl-1H-imidazole)) ttmt= 135-tris(1H-124-triazol-1-ylmethyl)-246-trimethylbenzene 4-dpaa= NNrsquo-di(4-pyridyl)adipoamide bte=bis(124-triazole-1-yl)ethane bib=44rsquo-bis(2-methylimidazol-1-ylmethyl)biphenyl imb=14-di(1H-imidazol-4-yl)benzene imm= tetrakis(imidazol-1-ylmethyl)methane tib=135-tris(1-imidazolyl)benzene ppa=2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate pp=3-(2-pyridyl)pyrazole ptH = hydrogen phthalate

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Table S2 ndash Bond lengths [Aring] and angles [o] for (pipH2)[Zn(pt)2]middotH2O 1 O(2)-C(7) 1229(4) O(11)-C(17) 1266(4) O(13)-C(18) 1265(4) O(3)-C(8) 1275(3) N(1)-C(22) 1481(4) N(1)-C(21) 1483(4) O(1)-C(7) 1271(4) O(4)-C(8) 1240(3) C(7)-C(1) 1499(4) C(1)-C(6) 1388(4) C(1)-C(2) 1393(4) C(8)-C(2)1 1508(4) C(2)-C(3) 1387(4) C(2)-C(8)1 1508(4) C(3)-C(4) 1383(5) C(4)-C(5) 1372(5) C(21)-C(22)2 1496(5)

C(5)-C(6) 1386(5) C(22)-C(21)2 1496(5) O(14)-C(18) 1246(4) O(12)-C(17) 1222(4 C(18)-C(12) 1501(4) N(2)-C(32)3 1478(4) N(2)-C(31) 1482(4) C(17)-C(11)4 1497(4) C(12)-C(13) 1395(4) C(12)-C(11) 1406(4) C(32)-N(2)3 1478(4) C(32)-C(31) 1504(4) C(11)-C(16) 1390(4) C(11)-C(17)5 1497(4) C(13)-C(14) 1371(4) C(16)-C(15) 1385(4) C(15)-C(14) 1382(4)

O(11)-Zn-O(1) 10870(10) O(11)-Zn-O(3) 12222(9) O(1)-Zn-O(3) 10417(9) O(11)-Zn-O(13) 9907(10) O(1)-Zn-O(13) 11013(9) O(3)-Zn-O(13) 11238(9) C(17)-O(11)-Zn 1196(2) C(18)-O(13)-Zn 1236(2) C(8)-O(3)-Zn 11786(18) C(22)-N(1)-C(21) 1117(2) C(7)-O(1)-Zn 1284(2) O(2)-C(7)-O(1) 1262(3) O(2)-C(7)-C(1) 1179(3) O(1)-C(7)-C(1) 1157(3) C(6)-C(1)-C(2) 1195(3) C(6)-C(1)-C(7) 1172(3) C(2)-C(1)-C(7) 1232(3) O(4)-C(8)-O(3) 1234(3) O(4)-C(8)-C(2)1 1192(3) O(3)-C(8)-C(2)1 1174(2) C(3)-C(2)-C(1) 1187(3) C(3)-C(2)-C(8)1 1172(3) C(1)-C(2)-C(8)1 1239(3) C(4)-C(3)-C(2) 1217(3)

C(5)-C(4)-C(3) 1193(3) N(1)-C(21)-C(22)2 1113(3) C(4)-C(5)-C(6) 1200(3) C(5)-C(6)-C(1) 1208(3) N(1)-C(22)-C(21)2 1101(3) O(14)-C(18)-O(13) 1233(3) O(14)-C(18)-C(12) 1194(3) O(13)-C(18)-C(12) 1172(3) C(32)3-N(2)-C(31) 1120(3) O(12)-C(17)-O(11) 1226(3) O(12)-C(17)-C(11)4 1213(3) O(11)-C(17)-C(11)4 1161(3) C(13)-C(12)-C(11) 1185(3) C(13)-C(12)-C(18) 1145(3) C(11)-C(12)-C(18) 1266(3) N(2)3-C(32)-C(31) 1097(3) N(2)-C(31)-C(32) 1095(3) C(16)-C(11)-C(12) 1187(3) C(16)-C(11)-C(17)5 1183(3) C(12)-C(11)-C(17)5 1230(3) C(14)-C(13)-C(12) 1222(3) C(15)-C(16)-C(11) 1215(3) C(14)-C(15)-C(16) 1199(3) C(13)-C(14)-C(15) 1191(3)

Symmetry transformations used to generate equivalent atoms 1 -x+1 -y+1 -z+2 2 -x+2 -y+1 -z 3 -x -y+1 -z+1 4 x-1 y z 5 x+1 y z

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Table S3 ndash Structural details of known zinc(II) phthalate compounds No Compound Coordination

Sphere (CN) Phthalate binding mode

Space group

Ref

1 [Zn(pt)(Im)(H2O)]2 NO3 (4) micro2-bidentate P21c 2 2 [Zn(pt)(metu)2]2middot4H2O S2O2 (4) micro2-bidentate P21c 3 3 [Zn(pt)(β-Pic)2] N2O2 (4) micro2-bidentate P21c 4 4 [Zn(pt)(1-VnIm)] N2O2 (4) micro2-bidentate P21c 9 5 [Zn(pt)(pyrazole)2] N2O2 (4) micro2-bidentate P21c 31 6 [Zn(pt)(bdmb)] N2O2 (4) micro2-bidentate P21c 47 7 [Zn(pt)] O4 (4) micro4-tetradentate P21c 25 8 [Zn(pt)(mib)]middot3H2O N2O2 (4) micro2-bidentate P21c 35 9 [Zn(pt)(mib)05] NO3 (4) micro3-tridentate P21c 35 10 (pipH2)[Zn(pt)2]middotH2O O4 (4) micro2-bidentate P21c This

work 11 [Zn2(pt)2(imb)]middot2H2O NO3 (4) micro2-tridentate P21c 29 12 [Zn(pt)(ib)] N2O2 (4) micro2-bidentate P21c 36 13 [Zn2(pt)2(34rsquo-bpt)] NO3 NO3 (44) micro3-tridentate P21c 7 14 [Zn2(pt)2(pmmi)2]middot6H2O N2O2 N2O2 (44) micro2-bidentate P21c 43 15 [Zn(pt)(thim)]middot2H2O N2O2 (4) micro2-bidentate P21n 34 16 [Zn2(pt)(tib)Cl2] N2O2 NOCl2 (44) micro2-bidentate P21n 27 17 [Zn2(pt)2(22rsquo-bpy)2(H2O)]middotH2O N2O2 N2O3 (45) micro2-bidentate P21n 42 18 [Zn(pt)(micro-44rsquo-bpp)]middotH2O N2O2 (4) micro2-bidentate Pī 19 19 [Zn(pt)(bbip)]middotH2O N2O2 (4) micro2-bidentate Pī 20 20 [Zn(pt)(3-dpaa)] N2O2 (4) micro2-bidentate Pī 33 21 [Zn(pt)(biim-6)] N2O2 (4) micro2-bidentate Pī 21 22 [Zn2(pt)2(ttmt)2]middotH2O N2O2 (4) micro2-bidentate Pī 44 23 [Zn2(pt)2(4-dpaa)(H2O)2]middot2H2O NO3 (4) micro2-bidentate Pī 33 24 [Zn2(pt)(tib)](NO3)2 N3O (4) micro2-bidentate C2c 27 25 [Zn2(pt)(tib)2]I2 N3O (4) micro2-bidentate C2c 27 26 [Zn2(pt)2(Dpds)2]middot2H2O N2O2 N2O2 (44) micro2-bidentate C2c 39 27 [Zn2(pt)2(imm)]middot35H2O N2O2 N2O3 (45) micro2-tridentate micro2-

bidentate C2c 45

28 [Zn(pt)(Pyridine)2] N2O2 (4) micro2-bidentate Pbca 4 29 [Zn(pt)(biim-5)] N2O2 (4) micro2-bidentate Pbca 22 30 [13-pnH2][Zn(pt)2] O4 (4) micro2-bidentate Pbca 17 31 [Zn(pt)(1-MeIm)2] N2O2 (4) micro2-bidentate Pccn 1 32 [Zn(pt)(bimb)] N2O2 (4) micro2-bidentate Cc 38 33 [Zn(pt)(γ-Pic)] NO3NO5 (46) micro3-tetradentate Cc 4 34 [Zn2(pt)2(bpp)] NO3 NO5 (46) micro3-tetradentate Cc 5 35 [Zn2(pt)2(bpp)2]middotH2O N2O2 (4) micro2-bidentate P21 15 36 [Zn(pt)(γ-Pic)2] N2O2 N2O3 (45) micro2-bidentate P21 4 37 [Zn(pt)(Im)2] N2O2 (4) micro2-bidentate Pn 2 38 [Zn(pt)(tu)2] S2O2 (4) micro2-bidentate P212121 18 39 [Zn(pt)(imp)(H2O)] N2O2 (4) micro2-bidentate P212121 30 40 [Zn(pt)(2-MeIm)2] NO3 (4) micro2-tridentate Pnc2 2 41 [Zn(pt)(dmetu)2] S2O2 (4) micro2-bidentate Pna21 3 42 [Zn2(pt)2(bte)2]middot4H2O N2O2 (4) micro2-bidentate Pna21 28 43 [Zn(pt)(1-allylimidazole)2] N2O2 (4) micro2-bidentate Pca21 46 44 [Zn4(pt)4(tib)2]middot2H2O N2O2 NO4 NO4

N2O3 (4555) micro2-bidentate Pca21 27

45 [Zn(pt)(44rsquo-bpt)] N2O3 (5) micro2-tridentate P21c 7 46 [Zn2(pt)2(Dpq)2]middotH2O N2O3 (5) micro3-tridentate P21c 21 47 [Zn(pt)(dpz)] N2O3 (5) micro2-bidentate Pī 14 48 [Zn(pt)(23rsquo-tmbpt)(H2O)] N2O3 (5) micro2-bidentate Pī 32 49 [Zn(pt)(33rsquo-tmbpt)]middotH2O N2O3 (5) micro2-bidentate Pī 32 50 [Zn(pt)(bmb)05(H2O)]middot05(bmb)middotH2O NO4 (5) micro2-bidentate Pī 26 51 [Zn2(pt)2(bib)] NO4 (5) micro3-tetradentate Pī 23 52 [Zn2(pt)2(22rsquo-bpy)2(H2O)2] N2O3 N2O3 (55) micro2-bidentate Pī 41 53 [Zn2(pt)(ppa)(H2O)]middot2H2O N2O3 N2O4 (56) micro2-bidentate Pī 16 54 [Zn(pt)(fimp)] N2O3 (5) micro2-tridentate C2c 8 55 [Zn2(pt)2(tpt)2] N3O2 N3O2 (55) micro2-bidentate Pbca 40 56 [Zn2(pt)(pp)2(H2O)] N4O2 N2O4 (66) micro4-pentadentate P21c 6

7

57 [Zn(pt)(Phen)(H2O)] N2O4 (6) micro2-tridentate P21n 10 58 [Zn(pt)(Phen)(H2O)] N2O4 (6) micro2-bidentate P21n 13 59 [Zn(pt)(cyclam)]middot2(CH3OH) N4O2 (6) micro2-bidentate Pī 12 60 [Zn(pt)(44rsquo-bipy)(H2O)2]middot2H2O N2O4 (6) micro2-bidentate P2n 24 61 [Zn2(pt)2(Dpq)2(H2O)4]middot2H2O N2O4 (6) micro2-bidentate C2c 39 62 [Zn(pt)(tppa)]middot2H2O N2O4 (6) micro2-tetradentate Pbcn 37 63 [Zn(pt)(22rsquo-bpy)(H2O)] N2O4 (6) micro2-tridentate Pna21 11 Abbreviations CN = Coordination number Im= imidazole metu=N-methyl thiourea 1-MeIm= 1-methyl imidazole β-Pic=3-methyl pyridine γ-Pic=4-methyl pyridine 2-MeIm= 2-methyl imidazole fimp=2-(2-furyl)-1H-imidazo[45-f](110-phenanthroline) 1-VnIm =1-vinylimidazole Phen=110-phenanthroline 22rsquo-bpy= 22rsquo-bipyridine dpz=dipyrido[32-a2rsquo3rsquo-c]phenazine micro-44rsquo-bpp= 22rsquo-bis(4-pyridylmethyleneoxy)-110 -biphenylene bbip=11rsquo-(14-butanediyl)bis(imidazole-2-phenyl) dmetu=NNrsquo-dimethyl thiourea tu= thiourea 23rsquo-tmbpt= 1-((1H-124-trizol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-124-trazole 33rsquo-tmbpt= 1-((1H-124-trizol-1-yl)methyl)-35-bis(3-pyridyl)-124-trazole 3-dpaa= NNrsquo-di(3-pyridyl)adipoamide bdmb= 11rsquo-(Biphenyl-44rsquo-diyl)bis(methylene)bis(1H-benzimidazole) 44rsquo-bpt=1H-35-bis(4-pyridyl)-124-triazole biim-5=11rsquo-(15-pentanedidyl)bis(imidazole) 44rsquo-bpy= 44rsquo-bipyridine biim-6=11rsquo-(16-hexane-didyl)bis(imidazole) bmb=14-bis(2-methyl benzimidazol-1-ylmethyl) thim= 25-bis(imidazol-1-yl)thiophene mib= 14-bis(2-methylimidazole-3-ium-1-yl)biphenyl imp=35-Bis(imidazole-1-yl)pyridine ib= 14-bis(imidazol-1-yl)benzene tppa= tri(4-pyridylphenyl)amine bimb= 14-bis(imidazol-1-yl-methyl)benzene Dpq=dipyrido[32-d2rsquo3rsquo-f]quinoxaline Dpds= 44rsquo-Dipyridyldisulfide tpt= 4rsquo-4(124-triazol-1-yl)phenyl-22rsquo6rsquo2rdquo-terpyridine bpp=13-bis(4-pyridyl)propane 34rsquo-bpt=1H-3-(3-pyridyl)-5-(4-pyridyl)-12-4-triazole pmmi= bis(11rsquo-((2356-tetramethyl-14-phenylene)bis(methylene))bis(2-methyl-1H-imidazole)) ttmt= 135-tris(1H-124-triazol-1-ylmethyl)-246-trimethylbenzene 4-dpaa= NNrsquo-di(4-pyridyl)adipoamide bte=bis(124-triazole-1-yl)ethane bib=44rsquo-bis(2-methylimidazol-1-ylmethyl)biphenyl imb=14-di(1H-imidazol-4-yl)benzene imm= tetrakis(imidazol-1-ylmethyl)methane tib=135-tris(1-imidazolyl)benzene ppa=2-[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate pp=3-(2-pyridyl)pyrazole Note Compounds synthesised under ambient conditions and remaining compounds synthesised under HydroSolvothermal conditions Table S4 ndashH-bonding characteristics of piperazinediium compounds

SNo Compound Space group Secondary interactions Ref

1 (pipH2)[MoS4] P21c NndashHmiddotmiddotmiddotS CndashHmiddotmiddotmiddotS 52 2 (pipH2)[WS4] P21c NndashHmiddotmiddotmiddotS CndashHmiddotmiddotmiddotS 53 3 (pipH2)[CrO4] P21n NndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotO 54 4 (pipH2)[Cr2O7] P21c NndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotO 55 5 (pipH2)[CdBr4]middotH2O P21c NndashHmiddotmiddotmiddotO NndashHmiddotmiddotmiddotBr OndashHmiddotmiddotmiddotBr 56 6 (pipH2)[CoCl4]middotH2O P21a NndashHmiddotmiddotmiddotCl OndashHmiddotmiddotmiddotCl CndashHmiddotmiddotmiddotCl 57 7 (pipH2)[SeO4]middotH2O P21n NndashHmiddotmiddotmiddotO OndashHmiddotmiddotmiddotO 57 8 (pipH2)[SO4]middotH2O P21n NndashHmiddotmiddotmiddotO OndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotO 58 9 (pipH2)[S2O3]middotH2O P21c NndashHmiddotmiddotmiddotO NndashHmiddotmiddotmiddotS OndashHmiddotmiddotmiddotO

OndashHmiddotmiddotmiddotS CndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotS 59

10 (pipH2)(ptH)2middot2H2O P21c NndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotO OndashHmiddotmiddotmiddotO 49 11 (pipH2)[Zn(pt)2]middotH2O P21c NndashHmiddotmiddotmiddotO CndashHmiddotmiddotmiddotO OndashHmiddotmiddotmiddotO This work 12 (pipH2)[ZnBr4] P212121 NndashHmiddotmiddotmiddotBr 60 13 (pipH2)[ZnI4] P212121 NndashHmiddotmiddotmiddotI 60 14 (pipH2)[HgBr4] P212121 NndashHmiddotmiddotmiddotBr 60 15 (pipH2)[HgI4] P212121 NndashHmiddotmiddotmiddotI 60 16 (pipH2)[CdI4] P212121 NndashHmiddotmiddotmiddotI 61

8

Fig S1 ndash IR spectra of (A) phthalic acid (ptH2) (B) [Zn(ptH)2(H2O)2] and (C) (pipH)2[Zn(pt)2]middotH2O 1

Fig S2 ndash IR and Raman spectra of [Zn(ptH)2(H2O)2]

9

Fig S3 ndash IR and Raman spectra of (pipH)2[Zn(pt)2]middotH2O 1

Fig S4 ndash IR and Raman spectra of [(enH)2Zn(pt)2(H2O)]

10

Fig S5 ndash UV-Visible spectra of (A) ptH2 and (B) [Zn(ptH)2(H2O)2] in H2O

Fig S6 ndashDiffused reflectance spectra of 1 and 2

11

Fig S7 ndash IR spectra of residues obtained after heating at 500degC (A) [Zn(ptH)2(H2O)2] (B) 1 and (C) 2

Fig S8 ndash (A) Experimental and (B) theoretical X-ray powder pattern of 1

12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m

Fig S9 ndash TG-DTA curves of 1 in air atmosphere at heating rate of 10K min

Fig S10 ndash X-ray powder pattern of 1 after heating at 500degC

13

Fig S11 ndash micro2-bidentate bridging binding modes shown by two unique phthalate ligands in 1 First unique phthalate ligand linking to two Zn(II) ions via O13 and O11 (Left) and second unique phthalate ligand linking to two Zn(II) ions via O3 and O1 (Right) with two carboxylate groups displaying monodentate coordination in both Zn-O bonds are shown in blue

Fig S12 ndash The H-bonding surroundings of the unique cations showing N-HmiddotmiddotmiddotO and C-HmiddotmiddotmiddotO interactions (shown in broken lines) Symmetry code i) x y z-1 ii) x+1 y z-1 iii) x y z-1 iv) ndashx+1 -y+1 -z+1 v) x y z

14

Fig S13 ndash The disposition of the unique piperazinediium (N1 and N2) in the crystal structure of 1

Fig S14 ndash A portion of the 1-D Zn(II) chain in [13-pnH2][Zn(pt)2] with ZnZn separations of 5453 Aring This compound also contains two [(O1 O7) amp (O5 O3)] unique micro2-bridging bidentate phthalate ligands which take alternate positions on either side of the infinite chain Figure is drawn using the CIF file from Ref 17

15

checkCIFPLATON report You have not supplied any structure factors As a result the full set of tests cannot be run THIS REPORT IS FOR GUIDANCE ONLY IF USED AS PART OF A REVIEW PROCEDURE FOR PUBLICATION IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED CRYSTALLOGRAPHIC REFEREE No syntax errors found CIF dictionary Interpreting this report

Datablock skd1189m

Bond precision C-C = 00044 A Wavelength=071073

Cell a=8142(3) b=21537(8) c=11782(5)

alpha=90 beta=99441(7) gamma=90

Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)

Space group P 21c P2(1)c

Hall group -P 2ybc -P 2ybc

Moiety formula C16 H8 O8 Zn C4 H12 N2 C16 H8 O8 Zn C4 H12 N2

H2 O H2 O

Sum formula C20 H22 N2 O9 Zn C20 H22 N2 O9 Zn

Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817

Correction method= Reported T Limits Tmin=0817 Tmax=0859

AbsCorr = MULTI SCAN Data completeness= 0995 Theta(max)= 26500 R(reflections)= 00412(3058) wR2(reflections)= 01107(4201) S = 0981 Npar= 286

16

The following ALERTS were generated Each ALERT has the

format test-name_ALERT_alert-type_alert-level Click on the hyperlinks for more details of the test Alert level B

PLAT420_ALERT_2_B D-H Without Acceptor Ow - H1W Please Check Alert level C

PLAT165_ALERT_3_C Nr of Status R Flagged Non-Hydrogen Atoms 1 PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for C17 Check Alert level G

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 3 Note PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension 1 Info PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms 6 Report PLAT066_ALERT_1_G Predicted and Reported TminampTmax Range Identical Check PLAT093_ALERT_1_G No sus on H-positions refinement reported as mixed PLAT199_ALERT_1_G Reported _cell_measurement_temperature (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature (K) 293 Check PLAT720_ALERT_4_G Number of UnusualNon-Standard Labels 1 Note PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (RepExpd) 112 Ratio PLAT860_ALERT_3_G Number of Least-Squares Restraints 3 Note PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note

0 ALERT level A = Most likely a serious problem - resolve or explain 1

ALERT level B = A potentially serious problem consider carefully 2 ALERT level C = Check Ensure it is not caused by an omission or oversight 12

ALERT level G = General informationcheck it is not something unexpected

4 ALERT type 1 CIF constructionsyntax error inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be Low 3 ALERT type 4 Improvement methodology query or suggestion 3 ALERT type 5 Informative message check

It is advisable to attempt to resolve as many as possible of the alerts in all categories Often the minor alerts point to easily fixed oversights errors and omissions in your CIF or refinement strategy so attention to these fine details can be worthwhile In order to resolve some of the more serious problems it may be necessary to carry out additional measurements or structure refinements However the purpose of your study may justify the reported deviations and the more serious of these should normally be commented upon in the discussion or experimental section of a paper or in the special_details fields of the CIF checkCIF was carefully designed to identify outliers and unusual parameters but every test has its limitations and alerts that are not important in a particular case may appear Conversely the absence of alerts does not guarantee there are no aspects of the results needing attention It is up to the individual to critically assess their own results and if necessary seek expert advice

Publication of your CIF in IUCr journals

A basic structural check has been run on your CIF These basic checks will be run on all CIFs submitted for publication in IUCr journals ( Acta Crystallographica Journal of Applied Crystallography Journal of Synchrotron Radiation) however if you intend to submit to Acta

Crystallographica Section C or E you should make sure that full publication checks are run on the

final version of your CIF prior to submission Publication of your CIF in other journals

Please refer to the Notes for Authors of the relevant journal for any special instructions relating to

17

CIF submission PLATON version of 29012015 checkdef file version of 29012015 Datablock skd1189m - ellipsoid plot

2

Free phthalate micro2-bidentate micro2-tridentate micro3-tridentate

micro3-tetradentate micro3-tetradentate micro3-pentadentate micro4-pentadentate

SCHEME S1 ndash Different binding modes of phthalate anion in zinc(II) phthalates

Synthetic details of preparation of (pipH2)[Zn(pt)2]middotH2O (1) and [(enH2)Zn(pt)2H2O] (2)

Method I - [Zn(ptH)2(H2O)2] prepared by reacting zinc acetate dihydrate with ptH2 (04317 g 1

mmol) and piperazine (00861 g 1 mmol) was taken in distilled water (~15 mL) The volume of the

reaction mixture was reduced to ~10 mL by heating it on a water bath and the clear solution thus

obtained (pH 7) was then kept undisturbed for crystallization at room temperature The needle shaped

transparent crystals obtained in 4 days were washed with ice cold water followed by methanol and

dried in air to yield 04098 g (82 ) of compound 1 Use of ethylenediamine (007 mL 1 mmol) in

the above reaction instead of piperazine resulted in the formation of compound 2

Anal () (for 1) Found (calcd) for ZnC20O9N2H22 (49983) C 4812 (4806) H 441 (445) N 559 (561) ptH2 664 (6647) ZnO 1638 (1628) IR (cm-1) 3660 (s) 3427 (s) 3030-2220 (b) 1552 (s) 1400 (s) 1371(s) 1083 (s) 962 (w) 833 (w) 761(s) 706 (w) 650 (w) 613 (w) 586 (w) 459 (w) Raman (cm-1) 1591 (s) 1564 (w) 1406 1373 (w) 1149 (s) 1041 (s) 839 (s) 653 (w) 482 (w) UV-DRS (in nm) 246 274 DTA (in degC) 155 (endo) 347 (exo) 472 (exo) Anal () (for 2) Found (calcd) for ZnC18O9N2H20 (47379) C 4571 (4563) H 432 (426) N 589 (591) ZnO 172 (1718) IR (cm-1) 3630 (s) 3300-2538 (b) 1632 (s) 1564 (s) 1366 (b) 1138 (w) 1085 (w) 856 (w) 773 (b) 717 (s) 453 (w) Raman (cm-1) 3057 (w) 1587 (s) 1397 (s) 1363 (w) 1150 (w) 1041 (s) 829 (s) UV-DRS (in nm) 230 283 Method II - Zinc acetate dihydrate (02195 g 1 mmol) piperazine (00861 g 1 mmol) and phthalic

acid (03323 g 2 mmol) were taken in ~40 mL distilled water to get a clear solution The reaction

mixture was heated on a water bath to reduce the volume to ~25 ml The solution thus obtained was

3


















4



ionality Ref










5






6



Space group

Ref



bidentate C2c 45




7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


3


















4



ionality Ref










5






6



Space group

Ref



bidentate C2c 45




7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


4



ionality Ref










5






6



Space group

Ref



bidentate C2c 45




7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


5






6



Space group

Ref



bidentate C2c 45




7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


6



Space group

Ref



bidentate C2c 45




7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


7






8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


8



9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


9



10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


10



11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


11



12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


12

200 400

0

20

40

60

80

100

-5

0

5

10

Temperature oC

TG

DTA

exo

∆T

∆m



13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


13



14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


14



15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


15


Datablock skd1189m


Cell a=8142(3) b=21537(8) c=11782(5)


Temperature 293 K

Calculated Reported

Volume 20380(14) 20381(14)




H2 O H2 O


Mr 49979 49977

Dxg cm-3 1629 1629

Z 4 4

Mu (mm-1) 1263 1263

F000 10320 10320

F000 103366

hklmax 102714 102614

Nref 4221 4201

TminTmax 08170859 08170859

Tmin 0817



16
















17


16
















17


17


piperazinediium bis(µ -phthalato)zincate(ii) monohydrate: a new …11)1402-1408... · 2015. 11....

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