4-Methyl-3,5-di­nitrobenzoic acid–dimethyl sulfoxide (1/1)

Trask, A.V.; Abthorpe, M.; Jones, W.

doi:10.1107/S1600536805008779

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o1100-o1102

https://doi.org/10.1107/S1600536805008779

4-Methyl-3,5-dinitrobenzoic acid–dimethyl sulfoxide (1/1)

A. V. Trask,^a ^* M. Abthorpe ^b and W. Jones ^a

^aPfizer Institute for Pharmaceutical Materials Science, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England, and ^bDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
^*Correspondence e-mail: avt21@cam.ac.uk

(Received 15 March 2005; accepted 18 March 2005; online 25 March 2005)

The title complex, C₈H₆N₂O₆·C₂H₆OS, was predicted to illustrate an intermolecular hydrogen-bond motif between the carboxylic acid and the sulfoxide funtionalities, based upon a previously published structure of an analogous complex. The predicted hydrogen-bond motif was observed, thereby indicating a certain robustness of this intermolecular interaction for crystal engineering purposes.

Comment

The asymmetric unit of the title crystal structure, (I), consists of one molecule each of 4-methyl-3,5-dinitrobenzoic acid and dimethyl sulfoxide (DMSO) (Fig. 1).

The crystallization was performed to evaluate the robustness of an intermolecular hydrogen bond involving an O—H⋯O=S contact between a carboxylic acid and a sulfoxide. This interaction was recently observed in the crystal structure of an analogous complex involving 3,5-dinitrobenzoic acid and DMSO (Abthorpe et al., 2005 ). This interaction also is found in 29 of a possible 37 instances in the Cambridge Structural Database (CSD Version 5.25 Update 3; Allen, 2002 ), when searching for structures which contain both a carboxyl group and a DMSO molecule among all organic structures for which three-dimensional coordinates have been determined. The hydrogen-bond interaction in the crystal structure is presented in Fig. 2.

The title complex packs in a monoclinic unit cell in the space group P2₁/c. Crystal packing results in alternating sheets of acid and DMSO molecules stacking along [010]. (Figs. 3 and 4).

The experiment reported here represents a successful demonstration of the methodological approach of crystal engineering: observation of a particular heteromolecular hydrogen-bonding interaction, evaluation of the abundance of the interaction in the CSD, and application of this information to the design of a novel crystalline molecular complex. The demonstrated robustness of this hydrogen-bond motif indicates a potential utility for future crystal engineering experiment design.

Figure 1
The asymmetric unit (XP; Sheldrick, 1993

) of (I

), showing displacement ellipsoids at the 50% probability level.

Figure 2
Part of the crystal packing (DIAMOND; Brandenburg, 1999

), showing intermolecular hydrogen-bond interactions as dashed lines.

Figure 3
The crystal packing (DIAMOND; Brandenburg, 1999

), viewed along [100], showing sheets stacking along [010].

Figure 4
The crystal packing (DIAMOND; Brandenburg, 1999

), viewed along [001], showing sheets stacking along [010].

Experimental

All starting components were obtained from Sigma Aldrich Ltd. 4-Methyl-3,5-dinitrobenzoic acid (64 mg) was dissolved in excess DMSO with gentle heating. The resulting solution was allowed to cool and evaporate slowly over a period of one week. From the solids that precipitated, a single crystal was harvested for subsequent XRD analysis.

Crystal data

C₈H₆N₂O₆·C₂H₆OS
M_r = 304.28
Monoclinic, P2₁/c
a = 6.9483 (2) Å
b = 22.4844 (5) Å
c = 8.2364 (2) Å
β = 92.765 (1)°
V = 1285.26 (6) Å³
Z = 4
D_x = 1.572 Mg m⁻³
Mo Kα radiation
Cell parameters from 7863 reflections
θ = 1.0–27.5°
μ = 0.29 mm⁻¹
T = 180 (2) K
Plate, colourless
0.35 × 0.32 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Thin-slice ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.901, T_max = 0.976
9790 measured reflections
2930 independent reflections
2263 reflections with I > 2σ(I)
R_int = 0.043
θ_max = 27.5°
h = −9 → 9
k = −29 → 29
l = −7 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.102
S = 1.06
2930 reflections
187 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0398P)² + 0.6419P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.33 e Å⁻³

All H atoms bonded to carbon were positioned geometrically and refined using a riding model, with U_iso = 1.5U_eq for methyl H atoms and U_iso(H) = 1.2U_eq(carrier atom) for all other H atoms. The C—H distances of the methyl groups were fixed at 0.98 Å; all other C—H distances were fixed at 0.95 Å. The O—H H atom was located in a difference Fourier map and refined isotropically.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: XP (Sheldrick, 1993 ) and DIAMOND (Brandenburg, 1999 )(software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, wj0440. DOI: https://doi.org/10.1107/S1600536805008779/hg6157sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805008779/hg6157Isup2.hkl

Computing details top

Data collection: Collect (Nonius B.V. 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SIR92 (Altomare et al. 1994); program(s) used to refine structure: SHELXL97 (Sheldrick 1997); software used to prepare material for publication: SHELXL97.

3,5-dinitro-4-methylbenzoic acid dimethyl sulfoxide top

Crystal data top

C₈H₆N₂O₆·C₂H₆OS	F(000) = 632
M_r = 304.28	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/c	Melting point: not measured K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.9483 (2) Å	Cell parameters from 7863 reflections
b = 22.4844 (5) Å	θ = 1.0–27.5°
c = 8.2364 (2) Å	µ = 0.29 mm⁻¹
β = 92.765 (1)°	T = 180 K
V = 1285.26 (6) Å³	Plate, colourless
Z = 4	0.35 × 0.32 × 0.10 mm

Data collection top

Nonius Kappa CCD diffractometer	2263 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Thin–slice ω and φ scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan Sortav (Blessing 1995)	h = −9→9
T_min = 0.901, T_max = 0.976	k = −29→29
9790 measured reflections	l = −7→10
2930 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0398P)² + 0.6419P] where P = (F_o² + 2F_c²)/3
2930 reflections	(Δ/σ)_max < 0.001
187 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.33 e Å⁻³

Special details top

Experimental. The –COOH hydrogen atom was located and its position was refined satisfactorily.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and

goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.6815 (2)	−0.08681 (6)	1.20349 (17)	0.0350 (3)
H1	0.664 (3)	−0.1248 (8)	1.257 (3)	0.042*
O2	0.6761 (3)	−0.13533 (6)	0.96732 (18)	0.0454 (4)
O3	0.9171 (2)	0.11314 (7)	1.22899 (18)	0.0390 (4)
O4	0.8000 (2)	0.17390 (6)	1.0462 (2)	0.0426 (4)
O5	0.7981 (3)	−0.01287 (8)	0.4786 (2)	0.0610 (5)
O6	0.6390 (2)	0.06916 (8)	0.4873 (2)	0.0501 (4)
N1	0.8439 (2)	0.12389 (7)	1.0941 (2)	0.0278 (4)
N2	0.7299 (3)	0.02850 (8)	0.5517 (2)	0.0334 (4)
C1	0.7264 (2)	−0.03097 (8)	0.9698 (2)	0.0213 (4)
C2	0.7674 (2)	0.01946 (8)	1.0625 (2)	0.0214 (4)
H2	0.7716	0.0174	1.1778	0.026*
C3	0.8021 (2)	0.07289 (8)	0.9847 (2)	0.0221 (4)
C4	0.7989 (3)	0.07983 (8)	0.8157 (2)	0.0238 (4)
C5	0.7521 (2)	0.02758 (8)	0.7310 (2)	0.0237 (4)
C6	0.7207 (2)	−0.02672 (8)	0.8024 (2)	0.0241 (4)
H6	0.6954	−0.0609	0.7371	0.029*
C7	0.6912 (3)	−0.09025 (8)	1.0459 (2)	0.0239 (4)
C8	0.8514 (3)	0.13656 (9)	0.7308 (3)	0.0340 (5)
H8A	0.9031	0.1270	0.6253	0.051*
H8B	0.9488	0.1581	0.7976	0.051*
H8C	0.7363	0.1614	0.7142	0.051*
S1	0.32344 (7)	0.17405 (2)	0.45368 (6)	0.02639 (14)
O7	0.3552 (2)	0.18195 (6)	0.63648 (16)	0.0319 (3)
C9	0.5251 (3)	0.20847 (10)	0.3685 (3)	0.0368 (5)
H9A	0.6407	0.1846	0.3934	0.055*
H9B	0.5429	0.2484	0.4147	0.055*
H9C	0.5029	0.2115	0.2504	0.055*
C10	0.1463 (3)	0.22803 (9)	0.3945 (3)	0.0350 (5)
H10A	0.0234	0.2176	0.4408	0.052*
H10B	0.1300	0.2290	0.2757	0.052*
H10C	0.1878	0.2673	0.4344	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0579 (9)	0.0267 (7)	0.0208 (7)	−0.0060 (7)	0.0045 (6)	0.0032 (6)
O2	0.0836 (12)	0.0235 (8)	0.0293 (9)	−0.0053 (7)	0.0061 (8)	−0.0017 (6)
O3	0.0488 (9)	0.0370 (8)	0.0305 (9)	−0.0036 (7)	−0.0061 (7)	−0.0084 (7)
O4	0.0565 (10)	0.0216 (7)	0.0497 (10)	0.0047 (7)	0.0024 (8)	−0.0023 (7)
O5	0.1171 (16)	0.0419 (10)	0.0243 (9)	−0.0021 (10)	0.0078 (9)	−0.0072 (7)
O6	0.0561 (10)	0.0609 (11)	0.0323 (9)	0.0060 (8)	−0.0078 (7)	0.0193 (8)
N1	0.0285 (8)	0.0258 (9)	0.0294 (9)	−0.0013 (7)	0.0036 (7)	−0.0045 (7)
N2	0.0421 (10)	0.0379 (10)	0.0201 (9)	−0.0112 (8)	−0.0003 (7)	0.0032 (8)
C1	0.0195 (8)	0.0243 (9)	0.0201 (9)	0.0030 (7)	0.0013 (7)	0.0022 (7)
C2	0.0194 (8)	0.0275 (9)	0.0174 (9)	0.0024 (7)	0.0012 (6)	−0.0004 (7)
C3	0.0194 (8)	0.0223 (9)	0.0245 (10)	0.0010 (7)	0.0009 (7)	−0.0034 (7)
C4	0.0213 (9)	0.0254 (10)	0.0248 (10)	0.0016 (7)	0.0004 (7)	0.0019 (7)
C5	0.0245 (9)	0.0305 (10)	0.0160 (9)	−0.0002 (7)	0.0004 (7)	0.0016 (7)
C6	0.0249 (9)	0.0245 (10)	0.0227 (10)	0.0012 (7)	0.0005 (7)	−0.0018 (7)
C7	0.0262 (9)	0.0247 (9)	0.0210 (10)	0.0021 (7)	0.0026 (7)	0.0017 (8)
C8	0.0390 (11)	0.0287 (10)	0.0341 (12)	−0.0042 (9)	0.0005 (9)	0.0083 (9)
S1	0.0386 (3)	0.0196 (2)	0.0209 (3)	−0.00201 (19)	0.00083 (19)	0.00087 (18)
O7	0.0510 (9)	0.0263 (7)	0.0185 (7)	−0.0026 (6)	0.0034 (6)	0.0016 (5)
C9	0.0389 (12)	0.0421 (13)	0.0297 (12)	0.0006 (9)	0.0054 (9)	0.0085 (9)
C10	0.0364 (11)	0.0317 (11)	0.0363 (12)	−0.0017 (9)	−0.0025 (9)	0.0039 (9)

Geometric parameters (Å, º) top

O1—C7	1.305 (2)	C4—C8	1.508 (3)
O1—H1	0.972 (16)	C5—C6	1.377 (3)
O2—C7	1.204 (2)	C6—H6	0.9500
O3—N1	1.224 (2)	C8—H8A	0.9800
O4—N1	1.225 (2)	C8—H8B	0.9800
O5—N2	1.217 (2)	C8—H8C	0.9800
O6—N2	1.218 (2)	S1—O7	1.5215 (14)
N1—C3	1.479 (2)	S1—C9	1.775 (2)
N2—C5	1.478 (2)	S1—C10	1.780 (2)
C1—C6	1.380 (2)	C9—H9A	0.9800
C1—C2	1.389 (2)	C9—H9B	0.9800
C1—C7	1.498 (2)	C9—H9C	0.9800
C2—C3	1.388 (2)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C3—C4	1.399 (3)	C10—H10C	0.9800
C4—C5	1.397 (3)

C7—O1—H1	114.4 (14)	O2—C7—O1	125.24 (17)
O3—N1—O4	124.04 (17)	O2—C7—C1	122.39 (17)
O3—N1—C3	117.46 (16)	O1—C7—C1	112.37 (16)
O4—N1—C3	118.48 (16)	C4—C8—H8A	109.5
O5—N2—O6	124.34 (19)	C4—C8—H8B	109.5
O5—N2—C5	117.38 (17)	H8A—C8—H8B	109.5
O6—N2—C5	118.22 (18)	C4—C8—H8C	109.5
C6—C1—C2	119.19 (17)	H8A—C8—H8C	109.5
C6—C1—C7	118.82 (16)	H8B—C8—H8C	109.5
C2—C1—C7	121.99 (16)	O7—S1—C9	105.10 (9)
C3—C2—C1	119.23 (17)	O7—S1—C10	104.89 (9)
C3—C2—H2	120.4	C9—S1—C10	98.23 (10)
C1—C2—H2	120.4	S1—C9—H9A	109.5
C2—C3—C4	124.11 (17)	S1—C9—H9B	109.5
C2—C3—N1	115.04 (16)	H9A—C9—H9B	109.5
C4—C3—N1	120.86 (16)	S1—C9—H9C	109.5
C5—C4—C3	113.27 (16)	H9A—C9—H9C	109.5
C5—C4—C8	122.37 (17)	H9B—C9—H9C	109.5
C3—C4—C8	124.27 (17)	S1—C10—H10A	109.5
C6—C5—C4	124.78 (17)	S1—C10—H10B	109.5
C6—C5—N2	115.35 (16)	H10A—C10—H10B	109.5
C4—C5—N2	119.86 (16)	S1—C10—H10C	109.5
C5—C6—C1	119.36 (17)	H10A—C10—H10C	109.5
C5—C6—H6	120.3	H10B—C10—H10C	109.5
C1—C6—H6	120.3

C6—C1—C2—C3	−0.2 (2)	C3—C4—C5—N2	175.91 (16)
C7—C1—C2—C3	178.84 (15)	C8—C4—C5—N2	−7.4 (3)
C1—C2—C3—C4	0.0 (3)	O5—N2—C5—C6	−42.7 (2)
C1—C2—C3—N1	179.89 (15)	O6—N2—C5—C6	134.65 (19)
O3—N1—C3—C2	27.8 (2)	O5—N2—C5—C4	138.3 (2)
O4—N1—C3—C2	−150.75 (16)	O6—N2—C5—C4	−44.4 (2)
O3—N1—C3—C4	−152.29 (17)	C4—C5—C6—C1	3.0 (3)
O4—N1—C3—C4	29.2 (2)	N2—C5—C6—C1	−175.97 (16)
C2—C3—C4—C5	1.5 (3)	C2—C1—C6—C5	−1.2 (3)
N1—C3—C4—C5	−178.39 (15)	C7—C1—C6—C5	179.72 (16)
C2—C3—C4—C8	−175.10 (17)	C6—C1—C7—O2	7.2 (3)
N1—C3—C4—C8	5.0 (3)	C2—C1—C7—O2	−171.82 (18)
C3—C4—C5—C6	−3.1 (3)	C6—C1—C7—O1	−173.54 (16)
C8—C4—C5—C6	173.63 (18)	C2—C1—C7—O1	7.4 (2)

Acknowledgements

We are grateful for funding from the Pfizer Institute for Pharmaceutical Materials Science (AVT and WJ). We thank Dr J. E. Davies for the data collection and structure determination.

References

Abthorpe, M., Trask, A. V. & Jones, W. (2005) Acta Cryst. E61, o609–o611. CrossRef IUCr Journals Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. (1999). DIAMOND. Version 2.1c. Crystal Impact GbR, Bonn, Germany. Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1993). XP. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.