3,5-Di­nitro­benzoic acid–di­methyl sulfoxide (1/1)

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

doi:10.1107/S1600536805003818

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o609-o611

https://doi.org/10.1107/S1600536805003818

3,5-Dinitrobenzoic acid–dimethyl sulfoxide (1/1)

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

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

(Received 1 February 2005; accepted 2 February 2005; online 12 February 2005)

The title complex, C₇H₄N₂O₆·C₂H₆OS, involves an intermolecular hydrogen-bond motif between the carboxyl and the sulfoxide groups. This motif has precedence in the Cambridge Structural Database, and is shown here to be more favourable than a possible carboxylic acid homodimer.

Comment

As part of ongoing research into the crystallization preferences of crystalline complexes, the growth of a previously reported three-component crystalline complex (Pedireddi et al., 1996 ) was attempted. The solvent dimethyl sulfoxide (DMSO) was used to aid dissolution of the components. In several instances, the crystallization unexpectedly resulted in single crystals of the title adduct, (I). The asymmetric unit consists of one molecule each of 3,5-dinitrobenzoic acid (3,5-DNBA) and DMSO (Fig. 1).

Previously reported crystallizations of 3,5-DNBA indicate a dimorphic nature for this substance. Two monoclinic polymorphs have been reported (Prince et al., 1991 ) and both exhibit the common carboxylic acid dimer hydrogen-bond motif. The interaction between 3,5-DNBA and DMSO described here involves a hydrogen bond between the carboxyl moiety of the acid and the sulfoxide group of the solvent (Fig. 2). It is interesting, therefore, that the title complex represents the disruption of the carboxylic acid dimer by the introduction of the sulfoxide moiety upon complexation.

A search of the Cambridge Structural Database (CSD, Version 5.25, Update 3; Allen, 2002 ) reveals precedence for this acid–DMSO interaction. Searching for structures which contain both a carboxyl moiety and a DMSO molecule among all organic structures for which three-dimensional coordinates have been determined resulted in 37 hits. Of those, 29 complexes exhibit an O—H⋯O=S hydrogen bond which is shorter than the sum of the van der Waals radii of the two O atoms. The apparent substantial likelihood of the formation of this motif indicates a potential utility for crystal engineering experimental design.

Crystal packing results in what may be perceived as alternating sheets of 3,5-DNBA and DMSO stacking along [001] (Figs. 3 and 4).

Figure 1
The asymmetric unit of (I

), showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993

Figure 2
Crystal packing diagram, showing the intermolecular hydrogen-bonding interactions as dashed lines.

Figure 3
Crystal packing diagram, showing sheets stacking along [001], as viewed along [010]. Dashed lines indicate hydrogen bonds.

Figure 4
Crystal packing diagram showing sheets stacking along [001], as viewed along [100].

Experimental

All starting components were obtained from Sigma Aldrich Ltd. 3,5-Dinitrobenzoic acid (357 mg) and 0.5 equivalents of anthracene (150 mg) were heated to reflux in benzene (ca 50 ml). To dissolve the solids fully, a small quantity of DMSO (ca 2 ml) was added to the slurry. The resulting solution was allowed to cool and evaporate slowly over a period of 24 h. Crystals were observed before all the solvent had evaporated; a single crystal was harvested from this saturated solution for X-ray diffraction analysis.

Crystal data

C₇H₄N₂O₆·C₂H₆OS
M_r = 290.25
Orthorhombic, Pbca
a = 10.0156 (2) Å
b = 12.0767 (2) Å
c = 20.6483 (5) Å
V = 2497.52 (9) Å³
Z = 8
D_x = 1.544 Mg m⁻³
Mo Kα radiation
Cell parameters from 11 611 reflections
θ = 1.0–27.5°
μ = 0.29 mm⁻¹
T = 260 (2) K
Plate, yellow
0.23 × 0.23 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Thin-slice ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.873, T_max = 0.970
16 897 measured reflections
2856 independent reflections
2114 reflections with I > 2σ(I)
R_int = 0.050
θ_max = 27.5°
h = −12 → 13
k = −15 → 15
l = −26 → 26

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.134
S = 1.03
2856 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0672P)² + 1.1187P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.40 e Å⁻³

All H atoms bonded to C atoms were placed geometrically and refined using a riding model. The U_iso values for methyl H atoms were taken as 1.5U_eq of the carrier atom. For all other H atoms, U_iso(H) = 1.2U_eq(carrier atom). The C—H distances of the methyl groups were fixed at 0.96 Å; all other C—H distances were fixed at 0.93 Å. The O—H H atom was located from difference Fourier maps and fixed at an O—H bond distance of 1.00 Å.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); 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, global. DOI: https://doi.org/10.1107/S1600536805003818/jh6000sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805003818/jh6000Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (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-dinitrobenzoic acid–dimethyl sulfoxide (1/1) top

Crystal data top

C₇H₄N₂O₆·C₂H₆OS	D_x = 1.544 Mg m⁻³
M_r = 290.25	Melting point: not measured K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 10.0156 (2) Å	Cell parameters from 11611 reflections
b = 12.0767 (2) Å	θ = 1.0–27.5°
c = 20.6483 (5) Å	µ = 0.29 mm⁻¹
V = 2497.52 (9) Å³	T = 260 K
Z = 8	Plate, yellow
F(000) = 1200	0.23 × 0.23 × 0.12 mm

Data collection top

Nonius–Kappa CCD diffractometer	2114 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Thin–slice ω and φ scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (SORTAV; Blessing 1995)	h = −12→13
T_min = 0.873, T_max = 0.970	k = −15→15
16897 measured reflections	l = −26→26
2856 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0672P)² + 1.1187P] where P = (F_o² + 2F_c²)/3
2856 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.60 e Å⁻³
1 restraint	Δρ_min = −0.40 e Å⁻³

Special details top

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	0.41031 (17)	−0.05040 (14)	0.15161 (8)	0.0526 (4)
O2	0.28020 (17)	−0.15088 (14)	0.08622 (9)	0.0553 (5)
H2A	0.284 (4)	−0.208 (3)	0.1197 (15)	0.117 (14)*
O3	0.5018 (2)	0.37105 (15)	−0.02034 (10)	0.0713 (6)
O4	0.5381 (2)	0.31999 (16)	0.07821 (10)	0.0642 (5)
O5	0.27367 (19)	0.12356 (17)	−0.16760 (8)	0.0618 (5)
O6	0.2394 (2)	−0.04496 (16)	−0.13742 (9)	0.0643 (5)
C1	0.35291 (19)	0.02206 (16)	0.04847 (10)	0.0354 (4)
N1	0.49347 (19)	0.30483 (16)	0.02397 (11)	0.0478 (5)
N2	0.27320 (18)	0.05110 (18)	−0.12700 (9)	0.0456 (5)
C2	0.41434 (19)	0.12320 (18)	0.06069 (10)	0.0375 (5)
H2	0.4482	0.1391	0.1016	0.045*
C3	0.42432 (19)	0.19929 (17)	0.01149 (10)	0.0375 (5)
C4	0.3761 (2)	0.17989 (17)	−0.05049 (10)	0.0385 (5)
H4	0.3828	0.2327	−0.0831	0.046*
C5	0.31788 (19)	0.07820 (17)	−0.06102 (10)	0.0367 (5)
C6	0.30450 (19)	−0.00084 (18)	−0.01318 (10)	0.0369 (5)
H6	0.2637	−0.0684	−0.0221	0.044*
C7	0.3500 (2)	−0.06314 (18)	0.10160 (10)	0.0398 (5)
S1	0.06085 (6)	0.16639 (5)	0.18509 (3)	0.04586 (19)
O7	0.20480 (17)	0.19557 (15)	0.16814 (9)	0.0581 (5)
C8	0.0644 (3)	0.0223 (2)	0.20131 (15)	0.0641 (7)
H8A	0.0720	−0.0177	0.1613	0.096*
H8B	−0.0165	0.0011	0.2230	0.096*
H8C	0.1395	0.0055	0.2284	0.096*
C9	0.0355 (3)	0.2154 (3)	0.26485 (14)	0.0688 (8)
H9A	0.0434	0.2946	0.2654	0.103*
H9B	0.1014	0.1837	0.2931	0.103*
H9C	−0.0520	0.1944	0.2793	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0591 (10)	0.0608 (10)	0.0378 (9)	−0.0014 (8)	−0.0088 (7)	0.0056 (8)
O2	0.0572 (10)	0.0523 (10)	0.0563 (10)	−0.0128 (8)	−0.0177 (8)	0.0165 (8)
O3	0.0949 (15)	0.0464 (10)	0.0726 (13)	−0.0167 (10)	−0.0046 (11)	0.0084 (9)
O4	0.0642 (11)	0.0684 (12)	0.0600 (12)	−0.0216 (9)	−0.0089 (9)	−0.0114 (9)
O5	0.0707 (12)	0.0784 (12)	0.0362 (9)	0.0107 (10)	−0.0072 (8)	0.0069 (9)
O6	0.0764 (13)	0.0694 (12)	0.0471 (10)	−0.0071 (10)	−0.0109 (9)	−0.0148 (9)
C1	0.0285 (9)	0.0418 (11)	0.0360 (11)	0.0047 (8)	0.0006 (8)	0.0007 (8)
N1	0.0428 (10)	0.0434 (10)	0.0571 (12)	−0.0025 (8)	0.0025 (9)	−0.0058 (9)
N2	0.0401 (10)	0.0602 (12)	0.0364 (10)	0.0068 (9)	−0.0032 (8)	−0.0037 (9)
C2	0.0335 (10)	0.0460 (11)	0.0329 (10)	0.0052 (9)	0.0001 (8)	−0.0050 (9)
C3	0.0329 (10)	0.0378 (10)	0.0418 (11)	0.0026 (8)	0.0020 (8)	−0.0042 (9)
C4	0.0357 (10)	0.0415 (11)	0.0384 (11)	0.0065 (9)	0.0023 (8)	0.0044 (9)
C5	0.0318 (9)	0.0469 (11)	0.0313 (10)	0.0053 (9)	−0.0013 (8)	−0.0037 (9)
C6	0.0315 (9)	0.0405 (10)	0.0386 (11)	0.0015 (8)	−0.0001 (8)	−0.0022 (9)
C7	0.0347 (10)	0.0465 (12)	0.0382 (11)	0.0044 (9)	0.0014 (9)	0.0036 (9)
S1	0.0476 (3)	0.0501 (3)	0.0399 (3)	0.0041 (2)	0.0004 (2)	0.0081 (2)
O7	0.0498 (10)	0.0589 (10)	0.0656 (11)	0.0066 (8)	0.0140 (8)	0.0232 (9)
C8	0.0721 (18)	0.0475 (14)	0.0727 (18)	−0.0040 (13)	0.0059 (14)	0.0033 (13)
C9	0.0781 (19)	0.0703 (18)	0.0581 (17)	−0.0043 (15)	0.0164 (14)	−0.0099 (14)

Geometric parameters (Å, º) top

O1—C7	1.206 (3)	C3—C4	1.388 (3)
O2—C7	1.309 (3)	C4—C5	1.377 (3)
O2—H2A	0.974 (19)	C4—H4	0.9300
O3—N1	1.218 (3)	C5—C6	1.380 (3)
O4—N1	1.220 (3)	C6—H6	0.9300
O5—N2	1.212 (3)	S1—O7	1.5249 (18)
O6—N2	1.228 (3)	S1—C9	1.768 (3)
C1—C6	1.390 (3)	S1—C8	1.772 (3)
C1—C2	1.391 (3)	C8—H8A	0.9600
C1—C7	1.504 (3)	C8—H8B	0.9600
N1—C3	1.473 (3)	C8—H8C	0.9600
N2—C5	1.471 (3)	C9—H9A	0.9600
C2—C3	1.373 (3)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600

C7—O2—H2A	112 (2)	C5—C6—C1	118.95 (19)
C6—C1—C2	119.68 (19)	C5—C6—H6	120.5
C6—C1—C7	121.67 (19)	C1—C6—H6	120.5
C2—C1—C7	118.49 (18)	O1—C7—O2	125.4 (2)
O3—N1—O4	124.5 (2)	O1—C7—C1	121.8 (2)
O3—N1—C3	118.0 (2)	O2—C7—C1	112.78 (18)
O4—N1—C3	117.6 (2)	O7—S1—C9	105.79 (13)
O5—N2—O6	124.2 (2)	O7—S1—C8	104.57 (12)
O5—N2—C5	118.6 (2)	C9—S1—C8	98.93 (15)
O6—N2—C5	117.17 (19)	S1—C8—H8A	109.5
C3—C2—C1	119.06 (19)	S1—C8—H8B	109.5
C3—C2—H2	120.5	H8A—C8—H8B	109.5
C1—C2—H2	120.5	S1—C8—H8C	109.5
C2—C3—C4	122.94 (19)	H8A—C8—H8C	109.5
C2—C3—N1	118.92 (19)	H8B—C8—H8C	109.5
C4—C3—N1	118.10 (19)	S1—C9—H9A	109.5
C5—C4—C3	116.34 (19)	S1—C9—H9B	109.5
C5—C4—H4	121.8	H9A—C9—H9B	109.5
C3—C4—H4	121.8	S1—C9—H9C	109.5
C4—C5—C6	123.02 (19)	H9A—C9—H9C	109.5
C4—C5—N2	118.28 (19)	H9B—C9—H9C	109.5
C6—C5—N2	118.65 (19)

C6—C1—C2—C3	0.9 (3)	O5—N2—C5—C4	−9.2 (3)
C7—C1—C2—C3	176.37 (18)	O6—N2—C5—C4	169.85 (19)
C1—C2—C3—C4	−0.2 (3)	O5—N2—C5—C6	173.41 (19)
C1—C2—C3—N1	−177.95 (17)	O6—N2—C5—C6	−7.6 (3)
O3—N1—C3—C2	179.7 (2)	C4—C5—C6—C1	−0.7 (3)
O4—N1—C3—C2	−0.5 (3)	N2—C5—C6—C1	176.65 (17)
O3—N1—C3—C4	1.9 (3)	C2—C1—C6—C5	−0.4 (3)
O4—N1—C3—C4	−178.4 (2)	C7—C1—C6—C5	−175.80 (17)
C2—C3—C4—C5	−0.8 (3)	C6—C1—C7—O1	168.0 (2)
N1—C3—C4—C5	176.96 (17)	C2—C1—C7—O1	−7.5 (3)
C3—C4—C5—C6	1.2 (3)	C6—C1—C7—O2	−9.9 (3)
C3—C4—C5—N2	−176.09 (17)	C2—C1—C7—O2	174.69 (18)

Acknowledgements

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

References

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 & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pedireddi, V. R., Jones, W., Chorlton, A. P. & Docherty, R. (1996). Chem. Commun. p. 987. CrossRef Google Scholar
Prince, P., Fronczek, F. R. & Gandour, R. D. (1991). Acta Cryst. C47, 895–898. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1993). XP. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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