4-Amino-N-(4,6-dimethyl-pyrimidin-2-yl)benzene-sulfonamide-2-nitro-benzoic acid (1/1).

In the asymmetric unit of the title co-crystal, C(12)H(14)N(4)O(2)S·C(7)H(5)NO(4), the sulfamethazine and 2-nitro-benzoic acid mol-ecules form a heterodimer through inter-molecular amide-carb-oxy-lic acid N-H⋯O and carb-oxy-lic acid-pyrimidine O-H⋯N hydrogen-bond pairs, giving a cyclic motif [graph set R(2) (2)(8)]. The dihedral angle between the two aromatic ring systems in the sulfamethazine mol-ecule is 88.96 (18)° and the nitro group of the acid is 50% rotationally disordered. Secondary aniline N-H⋯O(sulfone) hydrogen-bonding associations give a two-dimensional structure lying parallel to the ab plane.

Related literature

For background to sulfamethazole as a model for co-crystal formation, see: Caira (2007 ▶); Ghosh et al. (2011 ▶). For structures of 1:1 adducts of sulfamethazine with nitro­benzoic acid analogues, see: Lynch et al. (2000 ▶); Smith & Wermuth (2012 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C12H14N4O2S·C7H5NO4

M = 445.46

Orthorhombic,

a = 14.2945 (4) Å

b = 8.0115 (3) Å

c = 19.0962 (5) Å

V = 2186.91 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 200 K

0.30 × 0.21 × 0.12 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.964, T max = 0.980

5541 measured reflections

2777 independent reflections

2587 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.099

S = 1.04

2777 reflections

286 parameters

29 restraints

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 565 Friedel pairs

Flack parameter: 0.08 (9)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000779/gg2106sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000779/gg2106Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000779/gg2106Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H14N4O2S·C7H5NO4	F(000) = 928
Mr = 445.46	Dx = 1.353 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3011 reflections
a = 14.2945 (4) Å	θ = 3.1–28.8°
b = 8.0115 (3) Å	µ = 0.19 mm−1
c = 19.0962 (5) Å	T = 200 K
V = 2186.91 (12) Å3	Plate, yellow
Z = 4	0.30 × 0.21 × 0.12 mm

Oxford Diffraction Gemini-S CCD-detector diffractometer	2777 independent reflections
Radiation source: Enhance (Mo) X-ray source	2587 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −17→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→9
Tmin = 0.964, Tmax = 0.980	l = −23→8
5541 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0555P)2 + 0.5356P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2777 reflections	Δρmax = 0.29 e Å−3
286 parameters	Δρmin = −0.21 e Å−3
29 restraints	Absolute structure: Flack (1983), 565 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (9)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.44672 (4)	1.02307 (8)	0.75273 (5)	0.0249 (2)
O11A	0.35295 (13)	0.9968 (3)	0.72869 (13)	0.0342 (7)
O12A	0.50151 (14)	1.1513 (3)	0.72083 (12)	0.0326 (7)
N1A	0.47662 (18)	1.1033 (3)	0.95152 (15)	0.0352 (8)
N2A	0.43078 (16)	1.0714 (3)	0.83654 (14)	0.0288 (8)
N3A	0.59047 (17)	1.0898 (3)	0.86027 (15)	0.0334 (8)
N41A	0.65507 (17)	0.3924 (3)	0.7489 (2)	0.0538 (12)
C2A	0.5032 (2)	1.0887 (4)	0.88442 (16)	0.0273 (9)
C4A	0.6585 (2)	1.1028 (4)	0.9085 (2)	0.0392 (11)
C5A	0.6372 (3)	1.1216 (5)	0.9787 (2)	0.0497 (14)
C6A	0.5446 (3)	1.1221 (5)	0.99900 (19)	0.0429 (11)
C11A	0.50792 (17)	0.8370 (3)	0.75032 (18)	0.0262 (8)
C21A	0.60295 (19)	0.8371 (4)	0.73347 (16)	0.0286 (9)
C31A	0.6509 (2)	0.6892 (4)	0.73148 (18)	0.0312 (9)
C41A	0.60616 (19)	0.5374 (3)	0.7475 (2)	0.0324 (9)
C42A	0.7565 (2)	1.0928 (6)	0.8819 (3)	0.0592 (15)
C51A	0.5098 (2)	0.5407 (4)	0.76412 (18)	0.0323 (9)
C61A	0.46169 (19)	0.6885 (4)	0.76475 (17)	0.0289 (9)
C62A	0.5143 (3)	1.1416 (7)	1.0737 (2)	0.0663 (16)
O11	0.28633 (18)	0.8862 (4)	0.90536 (17)	0.0639 (10)
O12	0.30259 (17)	1.0522 (4)	0.99775 (15)	0.0505 (9)
O21	0.2682 (14)	0.800 (3)	1.1121 (18)	0.083 (5)	0.500
O22	0.1915 (11)	1.0471 (16)	1.1479 (5)	0.095 (4)	0.500
O23	0.1968 (11)	0.9621 (18)	1.1692 (5)	0.095 (4)	0.500
O24	0.2837 (14)	0.842 (3)	1.1026 (18)	0.083 (5)	0.500
N2	0.2084 (2)	0.9099 (6)	1.1124 (2)	0.0668 (14)
C1	0.1619 (2)	0.9013 (4)	0.98691 (19)	0.0378 (10)
C2	0.1370 (2)	0.8973 (5)	1.05718 (19)	0.0408 (11)
C3	0.0460 (2)	0.8689 (5)	1.0792 (2)	0.0503 (14)
C4	−0.0216 (3)	0.8434 (6)	1.0290 (3)	0.0613 (16)
C5	0.0011 (3)	0.8421 (7)	0.9596 (3)	0.0680 (18)
C6	0.0926 (3)	0.8725 (6)	0.9385 (2)	0.0580 (14)
C11	0.2569 (2)	0.9455 (5)	0.95931 (19)	0.0387 (11)
H2A	0.37560	1.03330	0.85240	0.0350*
H5A	0.68450	1.13390	1.01170	0.0600*
H21A	0.63350	0.93690	0.72370	0.0340*
H31A	0.71390	0.68900	0.71940	0.0380*
H41A	0.71650	0.38280	0.73590	0.0650*
H42A	0.62490	0.30460	0.75470	0.0650*
H43A	0.78730	0.99840	0.90250	0.0890*
H44A	0.78950	1.19300	0.89420	0.0890*
H45A	0.75570	1.08070	0.83190	0.0890*
H51A	0.47880	0.44180	0.77470	0.0390*
H61A	0.39800	0.68950	0.77480	0.0350*
H62A	0.44730	1.13730	1.07620	0.0990*
H63A	0.53580	1.24710	1.09130	0.0990*
H64A	0.54040	1.05310	1.10130	0.0990*
H3	0.03110	0.86720	1.12660	0.0600*
H4	−0.08350	0.82690	1.04260	0.0740*
H5	−0.04480	0.82070	0.92630	0.0820*
H6	0.10710	0.87350	0.89100	0.0690*
H12	0.36150	1.06900	0.98230	0.0760*

	U11	U22	U33	U12	U13	U23
S1A	0.0215 (3)	0.0274 (3)	0.0259 (3)	0.0012 (2)	−0.0003 (3)	−0.0001 (4)
O11A	0.0246 (10)	0.0395 (11)	0.0385 (13)	0.0037 (8)	−0.0055 (10)	−0.0031 (10)
O12A	0.0320 (11)	0.0301 (11)	0.0357 (12)	−0.0002 (8)	0.0019 (10)	0.0056 (11)
N1A	0.0352 (14)	0.0415 (16)	0.0289 (14)	−0.0063 (12)	0.0044 (12)	−0.0024 (13)
N2A	0.0196 (12)	0.0357 (13)	0.0312 (14)	−0.0001 (10)	0.0047 (11)	−0.0042 (12)
N3A	0.0287 (13)	0.0381 (15)	0.0334 (15)	−0.0045 (11)	0.0021 (12)	−0.0023 (13)
N41A	0.0292 (12)	0.0281 (13)	0.104 (3)	0.0001 (10)	0.0144 (19)	0.000 (2)
C2A	0.0290 (15)	0.0261 (15)	0.0267 (16)	−0.0033 (12)	0.0013 (13)	−0.0014 (13)
C4A	0.0333 (17)	0.0414 (18)	0.043 (2)	−0.0065 (14)	−0.0031 (17)	−0.0012 (17)
C5A	0.047 (2)	0.063 (3)	0.039 (2)	−0.0157 (18)	−0.0120 (18)	0.003 (2)
C6A	0.048 (2)	0.050 (2)	0.0306 (18)	−0.0159 (17)	0.0001 (16)	−0.0002 (17)
C11A	0.0234 (12)	0.0310 (14)	0.0242 (13)	0.0008 (10)	−0.0014 (14)	−0.0014 (15)
C21A	0.0236 (13)	0.0308 (14)	0.0314 (17)	−0.0061 (11)	0.0053 (12)	0.0009 (13)
C31A	0.0209 (13)	0.0333 (15)	0.0395 (19)	0.0001 (11)	0.0049 (13)	−0.0029 (14)
C41A	0.0264 (13)	0.0318 (14)	0.0391 (17)	−0.0005 (11)	0.0013 (17)	0.0005 (17)
C42A	0.0316 (19)	0.079 (3)	0.067 (3)	−0.007 (2)	−0.006 (2)	−0.008 (3)
C51A	0.0278 (14)	0.0282 (14)	0.041 (2)	−0.0072 (11)	0.0010 (15)	−0.0015 (15)
C61A	0.0190 (12)	0.0346 (15)	0.033 (2)	−0.0056 (10)	0.0014 (13)	−0.0021 (14)
C62A	0.080 (3)	0.090 (3)	0.029 (2)	−0.017 (3)	0.001 (2)	−0.004 (2)
O11	0.0497 (15)	0.092 (2)	0.0499 (18)	−0.0238 (14)	0.0210 (14)	−0.0240 (17)
O12	0.0360 (13)	0.0713 (17)	0.0443 (16)	−0.0111 (12)	0.0148 (12)	−0.0126 (15)
O21	0.054 (6)	0.123 (10)	0.073 (8)	0.001 (7)	−0.004 (4)	0.065 (6)
O22	0.060 (3)	0.186 (12)	0.039 (5)	−0.011 (7)	0.000 (5)	−0.033 (6)
O23	0.060 (3)	0.186 (12)	0.039 (5)	−0.011 (7)	0.000 (5)	−0.033 (6)
O24	0.054 (6)	0.123 (10)	0.073 (8)	0.001 (7)	−0.004 (4)	0.065 (6)
N2	0.0385 (19)	0.125 (3)	0.037 (2)	−0.011 (2)	0.0077 (17)	0.001 (2)
C1	0.0342 (16)	0.046 (2)	0.0333 (18)	−0.0038 (14)	0.0065 (16)	0.0044 (17)
C2	0.0335 (17)	0.052 (2)	0.037 (2)	−0.0019 (15)	0.0062 (16)	0.0041 (17)
C3	0.043 (2)	0.070 (3)	0.038 (2)	−0.0094 (18)	0.0142 (18)	0.003 (2)
C4	0.036 (2)	0.088 (3)	0.060 (3)	−0.020 (2)	0.010 (2)	−0.001 (3)
C5	0.042 (2)	0.113 (4)	0.049 (3)	−0.023 (2)	−0.008 (2)	0.006 (3)
C6	0.043 (2)	0.096 (3)	0.035 (2)	−0.015 (2)	0.0038 (17)	0.005 (2)
C11	0.0347 (18)	0.048 (2)	0.0335 (19)	−0.0029 (15)	0.0057 (16)	−0.0002 (17)

S1A—O11A	1.432 (2)	C21A—C31A	1.369 (4)
S1A—O12A	1.428 (2)	C31A—C41A	1.408 (4)
S1A—N2A	1.662 (3)	C41A—C51A	1.414 (4)
S1A—C11A	1.729 (2)	C51A—C61A	1.369 (4)
O11—C11	1.210 (5)	C5A—H5A	0.9300
O12—C11	1.302 (5)	C21A—H21A	0.9300
O21—N2	1.23 (2)	C31A—H31A	0.9300
O22—N2	1.314 (13)	C42A—H45A	0.9600
O23—N2	1.174 (11)	C42A—H43A	0.9600
O24—N2	1.22 (2)	C42A—H44A	0.9600
O12—H12	0.9000	C51A—H51A	0.9300
N1A—C6A	1.338 (5)	C61A—H61A	0.9300
N1A—C2A	1.342 (4)	C62A—H62A	0.9600
N2A—C2A	1.388 (4)	C62A—H63A	0.9600
N3A—C2A	1.330 (4)	C62A—H64A	0.9600
N3A—C4A	1.343 (4)	C1—C6	1.375 (5)
N41A—C41A	1.356 (3)	C1—C11	1.499 (4)
N2A—H2A	0.9000	C1—C2	1.389 (5)
N41A—H41A	0.9200	C2—C3	1.386 (4)
N41A—H42A	0.8300	C3—C4	1.376 (6)
N2—C2	1.471 (5)	C4—C5	1.365 (8)
C4A—C42A	1.492 (4)	C5—C6	1.390 (6)
C4A—C5A	1.383 (5)	C3—H3	0.9300
C5A—C6A	1.379 (6)	C4—H4	0.9300
C6A—C62A	1.499 (5)	C5—H5	0.9300
C11A—C21A	1.396 (4)	C6—H6	0.9300
C11A—C61A	1.389 (4)
O11A—S1A—O12A	118.83 (14)	C11A—C21A—H21A	120.00
O11A—S1A—N2A	102.39 (13)	C31A—C21A—H21A	120.00
O11A—S1A—C11A	109.77 (13)	C21A—C31A—H31A	120.00
O12A—S1A—N2A	108.56 (13)	C41A—C31A—H31A	120.00
O12A—S1A—C11A	109.35 (13)	H43A—C42A—H44A	109.00
N2A—S1A—C11A	107.21 (15)	C4A—C42A—H44A	109.00
C2A—N1A—C6A	116.8 (3)	C4A—C42A—H43A	109.00
S1A—N2A—C2A	123.7 (2)	H44A—C42A—H45A	109.00
C2A—N3A—C4A	116.2 (3)	H43A—C42A—H45A	109.00
C2A—N2A—H2A	118.00	C4A—C42A—H45A	109.00
S1A—N2A—H2A	111.00	C61A—C51A—H51A	120.00
C41A—N41A—H41A	124.00	C41A—C51A—H51A	120.00
H41A—N41A—H42A	118.00	C11A—C61A—H61A	120.00
C41A—N41A—H42A	117.00	C51A—C61A—H61A	120.00
O24—N2—C2	118.1 (16)	H63A—C62A—H64A	110.00
O23—N2—C2	126.1 (8)	C6A—C62A—H62A	109.00
O21—N2—O22	137.0 (16)	C6A—C62A—H63A	109.00
O21—N2—C2	115.5 (15)	H62A—C62A—H63A	109.00
O22—N2—C2	107.4 (7)	H62A—C62A—H64A	110.00
N1A—C2A—N3A	126.6 (3)	C6A—C62A—H64A	109.00
N1A—C2A—N2A	115.3 (3)	C2—C1—C11	125.3 (3)
N2A—C2A—N3A	118.2 (3)	C6—C1—C11	117.1 (3)
N3A—C4A—C5A	120.9 (3)	C2—C1—C6	117.5 (3)
C5A—C4A—C42A	122.9 (4)	N2—C2—C3	116.4 (3)
N3A—C4A—C42A	116.2 (4)	C1—C2—C3	122.5 (3)
C4A—C5A—C6A	119.0 (4)	N2—C2—C1	120.9 (3)
N1A—C6A—C5A	120.4 (3)	C2—C3—C4	118.2 (4)
N1A—C6A—C62A	116.6 (4)	C3—C4—C5	120.7 (4)
C5A—C6A—C62A	123.0 (4)	C4—C5—C6	120.3 (4)
C21A—C11A—C61A	120.6 (2)	C1—C6—C5	120.8 (4)
S1A—C11A—C61A	119.5 (2)	O11—C11—C1	121.4 (3)
S1A—C11A—C21A	119.9 (2)	O12—C11—C1	114.3 (3)
C11A—C21A—C31A	119.5 (3)	O11—C11—O12	124.3 (3)
C21A—C31A—C41A	120.9 (3)	C2—C3—H3	121.00
C31A—C41A—C51A	118.4 (2)	C4—C3—H3	121.00
N41A—C41A—C31A	120.7 (3)	C3—C4—H4	120.00
N41A—C41A—C51A	120.9 (3)	C5—C4—H4	120.00
C41A—C51A—C61A	120.5 (3)	C4—C5—H5	120.00
C11A—C61A—C51A	120.0 (3)	C6—C5—H5	120.00
C4A—C5A—H5A	121.00	C1—C6—H6	120.00
C6A—C5A—H5A	120.00	C5—C6—H6	120.00
O11A—S1A—N2A—C2A	172.1 (2)	O23—N2—C2—C3	−31.7 (11)
O12A—S1A—N2A—C2A	−61.5 (3)	O24—N2—C2—C1	−36.8 (15)
C11A—S1A—N2A—C2A	56.6 (3)	O24—N2—C2—C3	138.5 (14)
O11A—S1A—C11A—C21A	145.0 (3)	O22—N2—C2—C3	−67.6 (7)
O11A—S1A—C11A—C61A	−34.6 (3)	O23—N2—C2—C1	153.1 (9)
O12A—S1A—C11A—C21A	13.0 (3)	C42A—C4A—C5A—C6A	−177.1 (4)
O12A—S1A—C11A—C61A	−166.6 (3)	N3A—C4A—C5A—C6A	1.8 (5)
N2A—S1A—C11A—C21A	−104.5 (3)	C4A—C5A—C6A—N1A	0.5 (6)
N2A—S1A—C11A—C61A	75.9 (3)	C4A—C5A—C6A—C62A	180.0 (4)
O24—O21—N2—O23	−106 (6)	C61A—C11A—C21A—C31A	−0.3 (5)
O24—O21—N2—C2	102 (6)	S1A—C11A—C61A—C51A	−178.9 (3)
O24—O21—N2—O22	−74 (7)	S1A—C11A—C21A—C31A	−179.8 (3)
O23—O22—N2—C2	127.6 (15)	C21A—C11A—C61A—C51A	1.5 (5)
O23—O22—N2—O21	−56 (3)	C11A—C21A—C31A—C41A	−1.2 (5)
O23—O22—N2—O24	−82 (3)	C21A—C31A—C41A—N41A	−176.6 (3)
O22—O23—N2—C2	−69.3 (18)	C21A—C31A—C41A—C51A	1.5 (5)
O22—O23—N2—O24	120 (2)	C31A—C41A—C51A—C61A	−0.2 (5)
O22—O23—N2—O21	142.5 (18)	N41A—C41A—C51A—C61A	177.9 (3)
O21—O24—N2—O22	124 (5)	C41A—C51A—C61A—C11A	−1.3 (5)
O21—O24—N2—O23	83 (6)	C6—C1—C2—N2	173.8 (4)
O21—O24—N2—C2	−88 (6)	C6—C1—C2—C3	−1.2 (6)
C2A—N1A—C6A—C62A	178.9 (4)	C11—C1—C2—N2	−10.5 (6)
C6A—N1A—C2A—N2A	−179.3 (3)	C11—C1—C2—C3	174.5 (4)
C6A—N1A—C2A—N3A	0.5 (5)	C2—C1—C6—C5	0.6 (6)
C2A—N1A—C6A—C5A	−1.7 (5)	C11—C1—C6—C5	−175.6 (4)
S1A—N2A—C2A—N1A	−170.5 (2)	C2—C1—C11—O11	149.7 (4)
S1A—N2A—C2A—N3A	9.7 (4)	C2—C1—C11—O12	−30.9 (5)
C4A—N3A—C2A—N2A	−178.5 (3)	C6—C1—C11—O11	−34.5 (5)
C2A—N3A—C4A—C5A	−2.9 (5)	C6—C1—C11—O12	144.8 (4)
C4A—N3A—C2A—N1A	1.8 (5)	N2—C2—C3—C4	−175.0 (4)
C2A—N3A—C4A—C42A	176.1 (3)	C1—C2—C3—C4	0.2 (6)
O21—N2—C2—C3	115.3 (15)	C2—C3—C4—C5	1.6 (7)
O22—N2—C2—C1	117.1 (7)	C3—C4—C5—C6	−2.3 (8)
O21—N2—C2—C1	−60.0 (15)	C4—C5—C6—C1	1.2 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···N1A	0.90	1.77	2.671 (4)	180
N2A—H2A···O11	0.90	2.01	2.862 (4)	158
N41A—H41A···O11Ai	0.92	2.18	2.990 (3)	147
N41A—H42A···O12Aii	0.83	2.24	2.973 (3)	146
C3—H3···O12Aiii	0.93	2.54	3.289 (4)	138
C21A—H21A···O12A	0.93	2.55	2.915 (4)	104
C31A—H31A···O11Ai	0.93	2.49	3.250 (4)	139
C51A—H51A···O12Aii	0.93	2.57	3.230 (4)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12⋯N1A	0.90	1.77	2.671 (4)	180
N2A—H2A⋯O11	0.90	2.01	2.862 (4)	158
N41A—H41A⋯O11A i	0.92	2.18	2.990 (3)	147
N41A—H42A⋯O12A ii	0.83	2.24	2.973 (3)	146

Symmetry codes: (i) ; (ii) .