Supporting information

Synthesis and structural elucidation of 1-D silver(I) aliphatic carboxylate coordination polymers with 1,3,5-triaza-7-phosphaadamantane/N-methyl-1,3,5-

triaza-7-phosphaadamantane

SIZWE J. ZAMISA and BERNARD OMONDI*

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 380.056.3

58

60

62

64

66

68

70

72

74

76

78

80

82

84

86

88

90

92

94

96

97.6

cm-1

%T

Ag(PTA)(O2CCH3)

3248.60

2926.421692.25

1534.121399.28

1340.55

1298.71

1280.02

1242.62

1108.12

1041.75

1015.67

975.00959.42

950.29

920.53

796.20

753.78

729.86

656.89606.93

583.93565.07

448.16

397.23

Figure S1: IR spectrum of 1

1

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 380.042.0

45

50

55

60

65

70

75

80

85

90

95

98.9

cm-1

%T

Ag(PTA)(O2CCF3)

2950.15

1654.15

1448.99

1419.32

1300.28

1285.22

1243.64

1181.20

1140.511107.76

1040.53

1015.46

992.57

973.32

951.64

898.61

835.85

809.75

793.33751.54

721.26

653.76

604.34

578.51565.46

519.61

451.33

413.53

398.61

Figure S2: IR spectrum of 2

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 380.020.0

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

99.0

cm-1

%T

Ag(PTAme)(O2CCF3)

2987.79

2942.22

1675.47

1463.041421.70

1374.04

1332.491314.82

1299.19

1255.08

1187.90

1127.49

1116.731094.68

1044.471022.091009.70

978.89

933.24

900.84

875.26

856.65

811.97774.03753.17719.10

655.88

564.88

517.67

448.05

440.84

393.25

Figure S3: IR spectrum of 3

2

Figure S4: 1H NMR spectrum of 1 in D2O

Figure S5: 31P NMR spectrum of 1 in D2O

3

Figure S6: 13C NMR spectrum of 1 in D2O

Figure S7: 1H NMR spectrum of 2 in D2O

4

Figure S8: 31P NMR spectrum of 2 in D2O

Figure S9: 19F NMR spectrum of 2 in D2O

5

Figure S10: 1H NMR spectrum of 3 in d6-DMSO

Figure S11: 31P NMR spectrum of 3 in d6-DMSO

6

Figure S12: 19F NMR spectrum of 3 in d6-DMSO

Figure S13: 13C NMR spectrum of 3 in d6-DMSO

7

Ag(PTA)(O2CCH3) 12

m/z300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650 1700 1750

%

0

100MS_Direct_140423_103 10 (0.142) AM2 (Ar,18000.0,0.00,0.00); Cm (7:20-1:3) 1: TOF MS ES+

3.38e3871.2136

797.1910

330.2931

610.2047

429.2578368.2487

371.1134548.3805

430.2592547.3828

487.3666

503.3546

575.1222

723.1687

702.2393

684.2268

776.2612

724.1708

725.1663

798.1906

850.2805

799.1874

800.1859

945.2328

872.2147

873.2111

926.3031

925.2999

874.2128

897.7615

946.2365

1019.2570947.2311

998.3243

948.2345

949.2267

1021.2535

1095.2767

1093.2769

1022.2523

1073.3453

1023.2515

1072.3445

1169.2977

1168.2938

1167.2976

1148.3678

1097.2815

1243.3174

1170.2979

1242.3192

1221.3792

1220.3820

1317.34051244.3140

1245.3188

1296.4186

1295.4149

1390.3712

1319.3364

1389.3535

1320.3413

1391.3584

1465.37921392.3661

1393.3481

1446.4470

1539.3811

1466.3795

1467.3666

1541.3810

1614.42331688.4086

Figure S14: Mass spectrum of 1

Ag (PTA)(O2CCF3) 10

m/z300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650 1700

%

0

100MS_Direct_140423_101 10 (0.142) AM2 (Ar,18000.0,0.00,0.00); Cm (8:20-1:3) 1: TOF MS ES+

7.62e3437.9471

429.2532

342.8714

371.1135421.1165

392.8274

610.2059

494.8243

575.1269

496.8258

548.3804503.3531

684.2254

611.2037

649.1457

797.1896

723.1672

776.2592

871.2135

850.2802

798.1923

799.1874

800.1902

945.2319

872.2120

873.2089

874.2104

947.23541019.2551

999.3241

998.3242

948.2330

949.2269

1094.27201021.2551

1093.2756

1022.2574

1023.2475

1024.2534

1095.2747

1168.30151167.3003

1147.3705

1096.2758

1243.31461169.3029

1241.3201 1317.33741244.3180 1318.3394

1392.3627

1393.3640

Figure S15: Mass spectrum of 2

8

Supramolecular architectures in 1 – 3

All three compounds contain a variety of hydrogen bonding interactions which

transform the 1D coordination polymers into multi-dimensional, hydrogen bonded

supramolecular architectures. The hydrogen bonding interactions and the crystal

packing diagrams of 1 - 3 are depicted in Figures S16 – S19 whilst the hydrogen

bonding parameters are given in Table S1.

Figure S116: Hydrogen bonding patterns (shown as dashed green bonds) in 1 (a)

forming a ring via O—H…O and (b) forming a 2D supramolecular architecture via O—

H…N and O—H…O interactions in 1

Figure S117: Representation of hydrogen bonding patterns (dashed green lines) present

in the crystal packing of 1 shown along the crystallographic b axis. All methylene

hydrogen atoms have been omitted for clarity

9

(b

)

(a)

Both water molecules and the [Ag(PTA)(µ2-O2CCH3)] molecules are involved in

intermolecular hydrogen bonding. The water molecule with O2S interacts with

bridging acetate anions through O—H…O hydrogen bonds forming chains along the

crystallographic b axis (Figure S116a). In doing so, a 12-membered ring described by a

R44 (12) graph-set notation is formed. The second water molecule with O1S interacts

with the PTA molecule through O—H…N and C—H…O intermolecular interactions in

one direction and through a O—H…O hydrogen bond to the other water molecule

(Figure S116b). All hydrogen bonds result in two dimensional hydrogen bonded sheets

along the bc face as depicted Figure S117.

Figure S118: (a) Representation of hydrogen bonding patterns (dashed green lines)

present in the crystal packing of 2 shown along the crystallographic a-axis and (b)

hydrogen bonding network (shown as dashed green bonds) observed in 2. R1 and R2

represent graph-set descriptions R22(10) and S1

1(8), respectively

The crystal lattice in 2 is predominantly stabilized by three of non-classical

hydrogen bonds, C-H…O. Trifluoroacetate anions are linked to PTA moieties through

two C—H…N and C—H…O hydrogen bonds to give a 3D supramolecular architecture

10

(a) (b

)

as seen in Figure S18a. The C-H…O and C-H…N hydrogen bonds results in hydrogen

bonding networks that give a 10-membered ring, R1, described by the graph-set

notation R22(10) shown in Figure S118b. Charge assisted C-H…F intramolecular

interactions are also observed between the hydrogen atom of PTA groups and the

fluorine atom of the trifluoroacetate group forming a ring described by the graph-set

notation S11(8) as shown in Figure S118b (R2).

Figure S119: (a) C-H…O hydrogen bonding network observed in 3. R1 and R2

represent graph-set descriptions S11(9) and R2

2(8), respectively and (b) representation of

hydrogen bonding patterns forming a three dimensional supramolecular structure of 3

shown along the crystallographic c-axis. Ag atoms are displayed in the space-filling

model.

The crystal structure of 3 features mainly C—H…O intermolecular interactions.

One of the methylene hydrogen atoms of the PTAMe moiety in 3 links up with an

oxygen atom of the trifluoroacetate moiety through intramolecular C-H…O hydrogen

bonds. This forms a nine membered ring that can be described by the graph-set notation

S11(9) as shown in Figure S119a as R1. The hydrogen atoms of the PTAMe moieties

also link up with oxygen atoms of two separate trifluoroacetate moieties of a

11

(a) (b

neighbouring coil-like coordination polymer through intermolecular C-H…O hydrogen

bonds. In linking the molecules in this manner, an eight membered ring is formed and

can be described by the graph-set notation R22(8) depicted in Figure S119a as R2. The

PTAMe molecules not only take part in intramolecular hydrogen bonding but they are

also involved in intermolecular hydrogen bonding. The latter sews the neighbouring 1D

coil-like molecules together to form a 3D supramolecular structure as shown in Figure

S119b.

Table S1: Selected hydrogen bonding parameters in 1, 2 and 3D-H…A d(D-H) d(H…A) d(D…A) <(DHA)

Compound 1

O(1S)-H(1S)…N(3)i 0.82(3) 2.09(3) 2.892(2) 165

O(1S)-H(2S)…O(2S)ii 0.80(3) 2.03(3) 2.823(2) 174

O(2S)-H(3S)…O(1)iii 0.81(3) 1.98(3) 2.7890(18) 175

O(2S)-H(4S)…O(2)iv 0.86(3) 2.02(3) 2.8700(18) 168

Compound 2

C(1)-H(1A)…N(3)i 0.99 2.41 3.382(7) 165

C(4)-H(4A)…F(1)ii 0.99 2.51 3.444(8) 158

C(5A)-H(5A)…O(2)iii 0.99 2.47 3.391(7) 155

Compound 3

C(3)-H(3A)...O(5)i 0.99 2.30 3.192(2) 149

C(4)-H(4A)...O(2)ii 0.99 2.29 3.249(2) 164

C(4)-H(4B)...O(1)iii 0.99 2.46 3.395(2) 157

Symmetry codes: 1 (i) ½ - x, ½ - y, 1 - z; (ii) x - ½ , 1½ - y, z - ½; (iii) 1 - x, 1 - y, 1 - z; (iv) x, 1 + y, z. 2 (i) x, 1 + y ,z; (ii) x - ½ ,1½ y, -z; (iii) x - 1, y, z. 3 (i) = x, 1 + y, z; (ii) = x - ½ , 1½- y, -z; (iii) = x -

1, y, z; #4 = x + 1, y + 1, z

12