polymorphism tnb text&suppl · table 1. crystal data and structure refinement for tnb form i ....

Supporting Information

for

Angew. Chem. Int. Ed. Z52253

© Wiley-VCH 200369451 Weinheim, Germany

Polymorphism of 1,3,5-trinitrobenzene induced by trisindane additive**

Praveen K. Thallapally, Ram K. R. Jetti, Amy K. Katz, H. L. Carrell, Kuldeep Singh,

Kakali Lahiri, Sambasivarao Kotha, Roland Boese,* Gautam R. Desiraju*

[*] Prof. G. R. Desiraju, Dr. P. K. Thallapally

School of Chemistry, University of Hyderabad, Hyderabad 500 046, India

Fax: (+91) 40-2301-0567

E-mail: [email protected]

Prof. Dr. R. Boese, Dr. R. K. R. Jetti

Institut für Anorganische Chemie, Universität Duisburg-Essen, Standort Essen,

Universitätstrasse 5-7, D-45177 Essen, Germany

Fax: (+49) 201-183-2535

E-mail: [email protected]

Dr. H. L. Carrell, A. K. Katz

The Institute for Cancer Research, Fox Chase Cancer Center, 7701 Burholme Avenue,

Philadelphia, PA 19111, USA

Prof. S. Kotha, K. Singh, Dr. K. Lahiri

Department of Chemistry, Indian Institute of Technology, Powai, Mumbai, 400 076,

India

1

Form I

Form II

Form III

TI

2

Table 1. Crystal data and structure refinement for TNB Form I .

Identification code TNB Form I

Empirical formula C6 H3 N3 O6

Formula weight 213.11 Da

Density (calculated) 1.729 g cm-3

F(000) 1728

Temperature 183(2) K

Crystal size 0.43 x 0.21 x 0.07 mm

Crystal color colorless

Crystal description plate

Wavelength 0.71073 Å

Crystal system orthorhombic

Space group Pbca

Unit cell dimensions a = 12.587(11) Å α = 90°

b = 9.684(9) Å β = 90°

c = 26.86(2) Å γ = 90°

Volume 3274(5) Å3

Z 16

Cell measurement reflections used 1658

Cell measurement theta min/max 2.76° to 18.16°

Diffractometer control software Bruker AXS SMART Vers. 5.054 1997/98

Diffractometer measurement device Siemens SMART CCD area detector system

Diffractometer measurement method Full sphere data collection

in omega at 0.3° scan width

two runs with 720 frames, phi = 0°, 270°

and two runs with 436 frames, phi = 88°, 180°

Theta range for data collection 2.22° to 28.75°

Completeness to theta = 28.75° 98.5 %

Index ranges -16<=h<=16, -12<=k<=13, -35<=l<=35

Computing data reduction Bruker AXS SAINT program Vers. 6.02A

Absorption coefficient 0.159 mm-1

Computing absorption correction Bruker AXS SADABS program multiscan V2.03

Absorption correction details R.H. Blessing, Acta Cryst. (1995) A51 33-38

Max. / min. transmission 0.989/ 0.933

R(merg) before/after correction 0.1313 / 0.0545

Computing structure solution Bruker AXS SHELXTL Vers.6.10, DOS/WIN95/NT/2000

3

Computing structure refinement Bruker AXS SHELXTL Vers.6.10, DOS/WIN95/NT/2000

Refinement method Full-matrix least-squares on F2

Reflections collected 36564

Independent reflections 4188 [R(int) = 0.1760]

Data / restraints / parameters 1396 / 0 / 271

Goodness-of-fit on F2 0.831

Weighting details w = 1/[σ2 (Fo2)+ (0.0635*P)2]

where P = (Fo2+2Fc2)/3

Final R indices [I>2sigma(I)] R1 = 0.0450, wR2 = 0.0985

R indices (all data) R1 = 0.1883, wR2 = 0.1422

Largest diff. peak and hole 0.188 and -0.191 eÅ-3

Treatment of hydrogen atoms Riding model on idealized geometries

with the 1.2 fold isotropic displacement

parameters of the equivalent Uij of the

corresponding carbon atom

4

Table 1. Crystal data and structure refinement for TNB Form II

Identification code Form II


Formula weight 213.11



Crystal system Orthorhombic

Space group Pca21

Unit cell dimensions a = 9.2970(19) Å, α = 90°

b = 18.730(4) Å, β = 90°

c = 9.6330(19) Å, γ = 90°

Volume 1677.4(6) A3

Z, Calculated density 8, 1.688 Mg/m3


F(000) 864


Theta range for data collection 2.45 to 27.88°

Limiting indices 0<=h<=12, -24<=k<=0, 0<=l<=12

Reflections collected / unique 2117 / 2117 [R(int) = 0.0000]

Completeness to theta 27.88 99.3 %






Absolute structure parameter 0.3(12)

Largest diff. peak and hole 0.240 and -0.317 e.A-3

Table 2.Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (A2 x 103) for TNB Form II.

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

5

Table 1. Crystal data and structure refinement for TNB Form III .

Identification code TNB Form III




F(000) 432



Crystal color yellow

Crystal description plate


Crystal system monoclinic

Space group P 21/c


b = 5.723(2) Å β = 98.190(8)°

c = 11.287(5) Å γ = 90°

Volume 824.5(6) Å3

Z 4


Cell measurement theta min/max 3.19° to 27.32°









Index ranges -17<=h<=15, -7<=k<=6, -13<=l<=15





Max. / min. transmission 0.977 / 0.884


6

Computing structure solution Bruker AXS SHELXTL Vers.6.10, DOS/WIN95/NT/2000

Computing structure refinement Bruker AXS SHELXTL Vers.6.10, DOS/WIN95/NT/2000






Weighting details w = 1/[σ2 (Fo2)+ (0.1095*P)2]









7

Table 1. Crystal data and structure refinement for TI.

Identification code TI

Empirical formula C15 H18



F(000) 432



Crystal color colorless

Crystal description block


Crystal system monoclinic

Space group P21/c


b = 6.0733(13) Å β = 110.670(4)°

c = 16.584(4) Å γ = 90°

Volume 1123.4(4) Å3

Z 4


Cell measurement two theta min/max 5.196° to 47.370°









Index ranges -15<=h<=15, -7<=k<=7, -21<=l<=21





Max. / min. transmission 0.986 / 0.971


Computing structure solution Bruker AXS SHELXTL Vers. 6.10 DOS/WIN95/NT/2000

8

Computing structure refinement Bruker AXS SHELXTL Vers. 6.10 DOS/WIN95/NT/2000






Weighting details w = 1/[σ2 (Fo2)+ (0.0589P)2+0.5439P]









9

Crystal structure of TI

view along b-axis

view along a-axis

10

Powder X-ray Diffraction

Powder diffraction data were collected on a Siemens D5000 Powder X-ray Diffractometer with 7° OED. The sample was obtained by grinding the crystals grown from methanol solution of Form I and micro crystals of pure TNB. The powder diffractogram recorded is shown below. The powder patterns for Form I, II and III are simulated using the program, Platon.[1] There were no discrepancies noted between the experimental and simulation in terms of 2θ values for Form I and Pure TNB; the experimental pattern was found to be consistent in several samples. This shows there is no phase transition in the pure sample and is same as Form I. In contrast, the simulated powder patterns of form II and III shows that indeed they are different from Form I and are formed due to the additive, TI.

[1] Platon–version 1.05, 2002: A. L. Spek, Acta Crystallogr. 1990, A46, C34.

12

DSC Diffrential scanning thermograms for Form I and pure TNB were recorded on

NETZSCH, Phoenix DSC 2004. The thermograms are shown below. There were no

additional peaks in the thermograms indicating phase transition.

13

Melting Point Melting point of crystals of Form I and Form III were recorded on Olympus BX40 hot

stage microscope connected with Wagner & Munz Poly Therm A heater. The melting

point pictures are shown below. The Melting Point (MP) analysis shows that the Form I

crystals melts at lower temperature (mp: 121.8 °C) than Form III crystals (mp: 122.7 °C)

which suggests that Form I is kinetic and From III is thermodynamic.

Form I crystals

Form I crystal at room temperature

Melting of Form I crystal at 122.7 °C

14

Form III crystals

Form III crystal at room temperature

Melting of Form III crystal at 122.7 °C

15

Morphology of Form I

Crystal faces have been calculated using BDFH method in Morphology module in

Cerius2 program. Atom-atom potentials were estimated using Dreiding 2.21 force field

and atomic charges were estimated using the charge equilibration method. Cerius2,

Accelrys, Cambridge (UK). See www.accelrys.com

Morphology of Form I Form I : Pbca (two molecules in the asymmetric unit) ------------------

specified minimum slice thickness gave rise to too many faces. Minimum slice thickness actually used is 3.000 Angstroms. The total surface area is 2308.7288 units Area of face ( 4 0 2) is 0.0000 units List Areas by form Form { 1 0 2} accounts for 27.27 percent of the total area.

16

Form { 1 1 1} accounts for 39.42 percent of the total area. Form { 0 0 2} accounts for 33.31 percent of the total area.

Calculate Angle between 4 0 2 and -4 0 2 is Angle between normals to ( 4 0 2) and ( -4 0 2) is 153.4763 degrees Internal angle between ( 4 0 2) ) and ( -4 0 2) is 26.5237 degrees. Aspect ratio is : 2.3754 List of First Two Faces -------------------------------------------------------------- H K L Distance Color D-spacing Area Corners ( 0 0 2) 7.5182 PINK 13.3011 384.5252 6 ( 0 0 -2) 7.5182 PINK 13.3011 384.5252 6 ( 1 0 2) 10.9599 PINK 9.1241 157.3730 4 ( -1 0 2) 10.9599 PINK 9.1241 157.3730 4 ( -1 0 -2) 10.9599 PINK 9.1241 157.3730 4 ( 1 0 -2) 10.9599 PINK 9.1241 157.3730 4

17

Table 3. Dihedral angles of TNB polymorphs

Form I Form II Form II I

τ1 5.5 1.6 3.5

τ2 4.1 13.5 6.7

τ3 31.9 4.2 8.7

τ4 6.6 4.3

τ5 9.9 3.9

τ6 10.4 2.5

Table 4. Geometrical parameters of hydrogen bonds

Interaction d (Å)a D (Å) θ (º)

Form I C–H···O 2.98 3.84 137.1

C–H···O 2.21 3.29 173.0

C–H···O 2.25 3.26 155.0

C–H···O 2.87 3.90 160.4

C–H···O 2.90 3.93 159.0

N–O···O 3.04 157.0

N–O···O 2.97 151.0

N–O···N 2.86 152.0

N–O···N 2.97 142.2

Form II C–H···O 2.35 3.41 165.5

C–H···O 2.45 3.48 158.7

C–H···O 2.41 3.48 170.1

C–H···O 2.63 3.48 134.9

C–H···O 2.27 3.31 159.2

C–H···N 3.08 4.13 164.0

C–H···N 2.69 3.70 154.1

18

C–H···N 2.81 3.84 158.1

N–O···O 3.00 153.0

N–O···O 3.14 156.6

N–O···O 2.97 139.3

N–O···N 2.84 143.0

N–O···N 2.97 146.0

N–O···N 2.78 159.0

Form III C–H···O 2.69 3.73 161.1

C–H···O 2.46 3.21 125.3

C–H···O 2.43 3.40 147.6

C–H···O 2.34 3.40 166.0

C–H···O 2.85 3.78 144.1

N–O···O 2.94 144.6

N–O···N 2.99 124.2

N–O···N 2.989 124.0

N–O···N 2.99 150.2

N–O···N 3.01 140.0

19

Cambridge Structural Database (CSD)

The N-O···N interactions were searched in aromatic nitro compounds in the CSD. The search was performed using CSD 5.23 April 2002 version. The following screens were used: R-factor < or = 7.5, no disorder, no ions, only organics, 3D coordinates present.

Scatter plot of N···O interactions in CSD

The N···O distances in the Forms I, II and III are shown with colour in the figure. Blue

circle (Form I), Red square (Form II), Pink triangle (Form III). The N···O interaction in

Form II is one of the shortest such interactions in CSD.

20

Supramolecular Synthons

H

O2N

O2N

N

O

O N

O

O

N

O

O

NO

OH

N

OO H

NOO

HN O

O

H

O2N

H

NO O

H

NO

O

H

N

O

O

NO2

NO2

N

O

O

N OO

HO2N

I (Form I) II (Form II)

III (Form II) IV (Form III)

Hits = 2 Hits = 342

Hits = 0 Hits = 6

The occurrences of the above supramolecular synthons in Forms I, II and III was

searched for aromatic nitro compounds in the Cambridge Structural Database (CSD). The

search was performed using CSD 5.23 April 2002 version. There are only 2 hits for

synthon I (Form I), 0 hits for synthon III (Form II) and 6 hits for synthon IV (Form III).

However, synthon II in Form II (hits 342) is very commonly observed in the CSD. The

N-O···N distance in synthon II which is observed in Form II is one of the shortest in

CSD.

polymorphism tnb text&suppl · table 1. crystal data and structure refinement for tnb form i ....

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