2-(4-Amino­benzene­sulfonamido)-4,6-dimethyl­pyrimidin-1-ium 2-carb­oxy-4,6-dinitro­phenolate

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536813005631

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o472

doi:10.1107/S1600536813005631

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2-(4-Aminobenzenesulfonamido)-4,6-dimethylpyrimidin-1-ium 2-carboxy-4,6-dinitrophenolate

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 20 February 2013; accepted 26 February 2013; online 2 March 2013)

In the structure of the phenolate salt of the sulfa drug sulfamethazine with 3,5-dinitrosalicylic acid, C₁₂H₁₅N₄O₂S⁺·C₇H₃N₂O₇⁻, the dihedral angle between the pyrimidine and benzene rings of the cation is 59.70 (17)°. In the crystal, cation–anion hydrogen-bonding interactions involving pyrimidine–carboxy N⁺—H⋯O and amine–carboxy N—H⋯O pairs give a cyclic R₂²(8) motif while secondary N—H⋯O hydrogen bonds between the aniline group and both sulfone and nitro O-atom acceptors give a two-dimensional structure extending in (001).

Related literature

For background to sulfamethazine and its co-crystals, see: O'Neil (2001 ); Caira (2007 ); Ghosh et al. (2011 ). For similar structures, see: Caira (1991 ); Lynch et al. (2000 ); Smith & Wermuth (2013 ). For structures of 3,5-dinitrosalicylic acid salts, see: Smith et al. (2003 ). For graph-set analysis, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₅N₄O₂S⁺·C₇H₃N₂O₇⁻
M_r = 506.46
Monoclinic, P 2₁ /c
a = 8.1691 (3) Å
b = 32.0736 (9) Å
c = 8.9869 (3) Å
β = 112.258 (5)°
V = 2179.23 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 200 K
0.40 × 0.35 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.918, T_max = 0.980
14977 measured reflections
4264 independent reflections
3645 reflections with I > \2s(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.158
S = 1.10
4264 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O11	0.88	1.75	2.617 (4)	168
N2A—H2A⋯O12	0.78	1.95	2.729 (4)	170
O12—H12⋯O2	0.96	1.52	2.416 (5)	154
N41A—H41A⋯O51ⁱ	0.81	2.50	3.248 (5)	153
N41A—H42A⋯O12Aⁱⁱ	0.81	2.46	3.202 (4)	152
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813005631/nk2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005631/nk2201Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813005631/nk2201Isup3.cml

checkCIF report

Comment top

The drug sulfamethazine (or sulfadimidine) [4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide] (O'Neil, 2001) has been used as a model for co-crystal formation (Caira, 2007; Ghosh et al., 2011), commonly forming 1:1 adducts with carboxylic acids, predominently the benzoic analogues but including some amides. The structures of a number of these have been reported, e.g. anthranilic acid and 4-aminobenzoic acid (Caira, 1991), 2,4-dinitrobenzoic acid (Lynch et al., 2000), as well as benzamide, 4-hydroxybenzamide and picolinamide (Ghosh et al., 2011). In all of these co-crystals, heterodimers are formed through a cyclic intermolecular hydrogen-bonding motif [graph set R²₂(8) (Bernstein et al., 1995)], involving amine N—H···O_carboxyl and carboxylic acid O—H···N_pyrimidine pairs.

However, there are no examples of the structures of proton-transfer salts of sulfamethazine with carboxylic acids so we looked at the products from the 1:1 stoichiometric reactions with some strong acids. Crystalline materials were obtained from the 5-nitrosalicylic acid and picric acid reactions, namely the anhydrous (1:1) carboxylate and picrate salts, respectively (Smith & Wermuth, 2013). With 3,5-dinitrosalicylic acid (DNSA), the poorly-formed anhydrous 1:1 salt of the title compound, C₁₂H₁₅N₄O₂S⁺ C₇H₃N₂O₇^-, was obtained, and the structure is reported herein. DNSA has been particularly useful in providing crystalline proton-transfer salts with both aliphatic and aromatic amines, the majority of which have been picrates, in which an anti-related acidic proton is retained on the carboxylic acid group rather than on the phenolic group (Smith et al., 2003).

With the title salt, the phenolate anion is found (Fig. 1), providing a variant of the R²₂(8) cation–anion hydrogen-bonding interaction as found in the non-transfer co-crystal structures, the difference arising from the presence of the transferred acid proton on the pyrimidine nitrogen (N1A). The slight asymmetry in the N1A···O and N2A···O hydrogen bond distances [2.622 (5) and 2.732 (4) Å] (Table 1) is comparable with those in the non-transfer co-crystals. In the DNSA anion, the anti-related acid proton forms the usual intramolecular hydrogen bond with the phenolate O-atom (Smith et al., 2003). Both H-atoms of the aniline group of the cation participate in intermolecular N—H···O hydrogen-bonding interactions with both sulfone and nitro O-atom acceptors, giving extensions along the a and b axes respectively, giving a two-dimensional structure lying along (001) (Fig. 2).

In the sulfamethazine cation, the dihedral angle between the pyrimidinium and phenyl rings is 59.70 (17)°, similar to that found in the picrate salt [58.18 (7)°] (Smith & Wermuth, 2013), but significantly smaller than commonly found with the adduct structures, e.g. 70.3 (4)° in the 2,4-dinitrobenzoic acid co-crystal (Lynch et al., 2000). The two interacting pyrimidine–DNSA moieties are close to coplanar [inter-ring dihedral angle 12.2 (2)°].

Related literature top

For background to sulfamethazine and its co-crystals, see: O'Neil (2001); Caira (2007); Ghosh et al. (2011). For similar structures, see: Caira (1991); Lynch et al. (2000); Smith & Wermuth (2013). For structures of 3,5-dinitrosalicylic acid salts, see: Smith et al. (2003). For graph-set analysis, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by the reaction of 1 mmol quantities of 4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (sulfamethazine) with 3,5-dinitrosalicylic in 50 ml of 50% ethanol–water with 10 min refluxing. Partial evaporation of the solvent gave poorly-formed yellow crystal plates (m.p. 457–458 K) from which a specimen was cleaved for the X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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 (Spek, 2009).

Figures top

	Fig. 1. Molecular conformation and atom-numbering scheme for the title compound, with inter-species hydrogen bonds shown as a dashed lines. Non-H atoms are shown as 40% probability displacement ellipsoids.
	Fig. 2. The two-dimensional network structure viewed down c, showing hydrogen-bonding associations as dashed lines. Non-associative H atoms are omitted.

2-(4-Aminobenzenesulfonamido)-4,6-dimethylpyrimidin-1-ium 2-carboxy-4,6-dinitrophenolate top

Crystal data top

C₁₂H₁₅N₄O₂S⁺·C₇H₃N₂O₇⁻	F(000) = 1048
M_r = 506.46	D_x = 1.544 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 457–458 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.1691 (3) Å	Cell parameters from 4751 reflections
b = 32.0736 (9) Å	θ = 3.1–28.8°
c = 8.9869 (3) Å	µ = 0.22 mm⁻¹
β = 112.258 (5)°	T = 200 K
V = 2179.23 (15) Å³	Plate, yellow
Z = 4	0.40 × 0.35 × 0.20 mm

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	4264 independent reflections
Radiation source: Enhance (Mo) X-ray source	3645 reflections with I > \2s(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −7→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −39→39
T_min = 0.918, T_max = 0.980	l = −11→11
14977 measured 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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0472P)² + 4.2454P] where P = (F_o² + 2F_c²)/3
4264 reflections	(Δ/σ)_max = 0.010
318 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₂H₁₅N₄O₂S⁺·C₇H₃N₂O₇⁻	V = 2179.23 (15) Å³
M_r = 506.46	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1691 (3) Å	µ = 0.22 mm⁻¹
b = 32.0736 (9) Å	T = 200 K
c = 8.9869 (3) Å	0.40 × 0.35 × 0.20 mm
β = 112.258 (5)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	4264 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	3645 reflections with I > \2s(I)
T_min = 0.918, T_max = 0.980	R_int = 0.039
14977 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.10	Δρ_max = 0.87 e Å⁻³
4264 reflections	Δρ_min = −0.51 e Å⁻³
318 parameters

Special details top

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

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
S1A	0.33370 (9)	0.09248 (2)	0.49476 (9)	0.0225 (2)
O11A	0.4293 (3)	0.11377 (7)	0.6420 (3)	0.0308 (7)
O12A	0.1986 (3)	0.06331 (7)	0.4858 (3)	0.0300 (7)
N1A	0.0333 (4)	0.16571 (9)	0.1560 (3)	0.0347 (9)
N2A	0.2414 (3)	0.13221 (8)	0.3706 (3)	0.0279 (8)
N3A	0.0595 (4)	0.09249 (9)	0.1533 (3)	0.0318 (8)
N41A	0.8562 (4)	0.00864 (9)	0.2912 (4)	0.0352 (9)
C2A	0.1081 (4)	0.12918 (10)	0.2241 (4)	0.0271 (9)
C4A	−0.0789 (5)	0.09197 (13)	0.0121 (4)	0.0394 (11)
C5A	−0.1668 (5)	0.12839 (15)	−0.0589 (4)	0.0487 (13)
C6A	−0.1059 (5)	0.16547 (14)	0.0136 (4)	0.0460 (14)
C11A	0.4832 (4)	0.06863 (9)	0.4269 (4)	0.0209 (8)
C21A	0.4332 (4)	0.03461 (10)	0.3223 (4)	0.0281 (9)
C31A	0.5563 (4)	0.01481 (10)	0.2778 (4)	0.0306 (10)
C41A	0.7336 (4)	0.02831 (9)	0.3364 (4)	0.0257 (9)
C42A	−0.1332 (6)	0.05060 (14)	−0.0664 (5)	0.0582 (16)
C51A	0.7806 (4)	0.06280 (10)	0.4394 (4)	0.0279 (9)
C61A	0.6577 (4)	0.08258 (9)	0.4841 (4)	0.0250 (9)
C62A	−0.1833 (7)	0.20700 (16)	−0.0541 (6)	0.0709 (17)
O2	0.5067 (5)	0.25084 (9)	0.7126 (4)	0.0712 (11)
O11	0.1194 (4)	0.24106 (9)	0.2706 (4)	0.0589 (11)
O12	0.2967 (4)	0.21077 (8)	0.4967 (4)	0.0606 (10)
O31	0.8156 (5)	0.34132 (12)	0.8480 (5)	0.0813 (16)
O32	0.6599 (6)	0.30963 (12)	0.9593 (4)	0.0868 (16)
O51	0.3439 (7)	0.42888 (10)	0.4234 (4)	0.0993 (19)
O52	0.1099 (6)	0.39640 (11)	0.2632 (5)	0.0763 (16)
N3	0.6791 (5)	0.32438 (11)	0.8427 (5)	0.0557 (15)
N5	0.2539 (7)	0.39791 (10)	0.3752 (5)	0.0568 (16)
C1	0.3126 (5)	0.28407 (11)	0.4776 (5)	0.0429 (11)
C2	0.4505 (6)	0.28519 (11)	0.6290 (5)	0.0462 (15)
C3	0.5295 (6)	0.32354 (12)	0.6872 (5)	0.0456 (14)
C4	0.4725 (6)	0.36005 (11)	0.6024 (5)	0.0483 (15)
C5	0.3300 (6)	0.35804 (11)	0.4587 (5)	0.0485 (14)
C6	0.2494 (6)	0.32095 (11)	0.3902 (5)	0.0464 (15)
C11	0.2342 (6)	0.24260 (11)	0.4069 (6)	0.0489 (15)
H1A	0.07050	0.18920	0.20720	0.0420*
H2A	0.26120	0.15340	0.41760	0.0330*
H5A	−0.26560	0.12730	−0.15450	0.0580*
H21A	0.31660	0.02540	0.28290	0.0340*
H31A	0.52240	−0.00780	0.20800	0.0370*
H41A	0.83560	−0.01550	0.26240	0.0420*
H42A	0.95960	0.01430	0.34240	0.0420*
H43A	−0.17740	0.03360	−0.00190	0.0870*
H44A	−0.03300	0.03720	−0.07680	0.0870*
H45A	−0.22420	0.05430	−0.17100	0.0870*
H51A	0.89660	0.07240	0.47790	0.0330*
H61A	0.69090	0.10540	0.55300	0.0300*
H63A	−0.15940	0.22670	0.03180	0.1070*
H64A	−0.30880	0.20420	−0.11010	0.1070*
H65A	−0.13110	0.21660	−0.12740	0.1070*
H4	0.52880	0.38530	0.64130	0.0580*
H6	0.15680	0.32050	0.29020	0.0560*
H12	0.38970	0.21900	0.59520	0.0730*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0178 (4)	0.0252 (4)	0.0234 (4)	0.0015 (3)	0.0066 (3)	0.0017 (3)
O11A	0.0251 (11)	0.0396 (13)	0.0253 (12)	0.0024 (10)	0.0069 (10)	−0.0038 (10)
O12A	0.0210 (11)	0.0346 (12)	0.0356 (13)	−0.0023 (9)	0.0122 (10)	0.0024 (10)
N1A	0.0303 (15)	0.0369 (15)	0.0354 (16)	0.0092 (13)	0.0108 (13)	0.0082 (13)
N2A	0.0235 (13)	0.0207 (13)	0.0324 (15)	0.0026 (10)	0.0026 (12)	−0.0014 (11)
N3A	0.0270 (14)	0.0381 (15)	0.0263 (14)	−0.0019 (12)	0.0057 (12)	0.0023 (12)
N41A	0.0307 (15)	0.0290 (14)	0.0512 (18)	0.0007 (12)	0.0215 (14)	−0.0033 (13)
C2A	0.0186 (15)	0.0354 (17)	0.0270 (16)	0.0058 (13)	0.0083 (13)	0.0074 (13)
C4A	0.0289 (18)	0.061 (2)	0.0254 (17)	−0.0095 (17)	0.0071 (14)	0.0030 (17)
C5A	0.031 (2)	0.079 (3)	0.0253 (18)	0.003 (2)	−0.0016 (16)	0.0090 (19)
C6A	0.0322 (19)	0.068 (3)	0.034 (2)	0.0196 (19)	0.0082 (17)	0.0169 (19)
C11A	0.0166 (14)	0.0206 (14)	0.0250 (15)	0.0019 (11)	0.0072 (12)	0.0044 (12)
C21A	0.0212 (15)	0.0263 (16)	0.0347 (18)	−0.0045 (13)	0.0082 (14)	−0.0025 (13)
C31A	0.0294 (17)	0.0221 (15)	0.0396 (19)	−0.0044 (13)	0.0123 (15)	−0.0081 (14)
C41A	0.0272 (16)	0.0236 (15)	0.0284 (16)	0.0042 (13)	0.0129 (14)	0.0064 (13)
C42A	0.060 (3)	0.067 (3)	0.033 (2)	−0.024 (2)	0.001 (2)	−0.004 (2)
C51A	0.0195 (15)	0.0312 (16)	0.0329 (17)	−0.0036 (13)	0.0098 (13)	−0.0001 (14)
C61A	0.0220 (15)	0.0237 (15)	0.0271 (16)	−0.0026 (12)	0.0067 (13)	−0.0022 (12)
C62A	0.065 (3)	0.076 (3)	0.059 (3)	0.040 (3)	0.009 (2)	0.028 (3)
O2	0.074 (2)	0.0400 (16)	0.072 (2)	0.0168 (16)	−0.0036 (18)	0.0058 (15)
O11	0.068 (2)	0.0378 (16)	0.0570 (19)	0.0118 (14)	0.0079 (17)	0.0055 (14)
O12	0.076 (2)	0.0265 (13)	0.0627 (19)	0.0072 (14)	0.0075 (17)	0.0003 (13)
O31	0.055 (2)	0.092 (3)	0.107 (3)	0.006 (2)	0.042 (2)	−0.017 (2)
O32	0.116 (3)	0.083 (3)	0.055 (2)	−0.032 (2)	0.025 (2)	−0.0023 (19)
O51	0.220 (5)	0.0320 (17)	0.057 (2)	−0.005 (2)	0.065 (3)	0.0031 (15)
O52	0.096 (3)	0.067 (2)	0.085 (3)	0.039 (2)	0.056 (2)	0.041 (2)
N3	0.065 (3)	0.0376 (19)	0.074 (3)	0.0023 (18)	0.037 (2)	−0.0111 (18)
N5	0.116 (4)	0.0297 (18)	0.050 (2)	0.010 (2)	0.060 (2)	0.0088 (16)
C1	0.055 (2)	0.0275 (18)	0.053 (2)	0.0116 (17)	0.028 (2)	0.0029 (16)
C2	0.059 (3)	0.0238 (17)	0.065 (3)	0.0117 (17)	0.034 (2)	0.0045 (17)
C3	0.059 (3)	0.036 (2)	0.050 (2)	0.0036 (18)	0.030 (2)	−0.0050 (17)
C4	0.080 (3)	0.0228 (17)	0.064 (3)	−0.0029 (18)	0.052 (3)	−0.0022 (17)
C5	0.085 (3)	0.0319 (19)	0.048 (2)	0.016 (2)	0.047 (2)	0.0092 (17)
C6	0.071 (3)	0.0259 (18)	0.064 (3)	0.0116 (18)	0.050 (2)	0.0054 (17)
C11	0.060 (3)	0.0249 (18)	0.070 (3)	0.0087 (18)	0.034 (2)	0.0028 (18)

Geometric parameters (Å, º) top

S1A—O11A	1.430 (3)	C6A—C62A	1.501 (7)
S1A—O12A	1.426 (3)	C11A—C61A	1.393 (5)
S1A—N2A	1.673 (3)	C11A—C21A	1.397 (4)
S1A—C11A	1.736 (3)	C21A—C31A	1.371 (5)
O2—C2	1.314 (5)	C31A—C41A	1.409 (5)
O11—C11	1.230 (6)	C41A—C51A	1.400 (4)
O12—C11	1.281 (5)	C51A—C61A	1.370 (5)
O31—N3	1.225 (6)	C5A—H5A	0.9300
O32—N3	1.213 (6)	C21A—H21A	0.9300
O51—N5	1.214 (6)	C31A—H31A	0.9300
O52—N5	1.226 (7)	C42A—H45A	0.9600
O12—H12	0.9600	C42A—H43A	0.9600
N1A—C6A	1.352 (5)	C42A—H44A	0.9600
N1A—C2A	1.356 (4)	C51A—H51A	0.9300
N2A—C2A	1.357 (4)	C61A—H61A	0.9300
N3A—C4A	1.342 (5)	C62A—H63A	0.9600
N3A—C2A	1.325 (4)	C62A—H64A	0.9600
N41A—C41A	1.369 (5)	C62A—H65A	0.9600
N1A—H1A	0.8800	C1—C6	1.406 (5)
N2A—H2A	0.7800	C1—C11	1.508 (5)
N41A—H42A	0.8100	C1—C2	1.400 (6)
N41A—H41A	0.8100	C2—C3	1.396 (6)
N3—C3	1.467 (6)	C3—C4	1.378 (5)
N5—C5	1.494 (5)	C4—C5	1.374 (6)
C4A—C5A	1.393 (6)	C5—C6	1.386 (5)
C4A—C42A	1.489 (6)	C4—H4	0.9300
C5A—C6A	1.357 (6)	C6—H6	0.9300

O11A—S1A—O12A	120.36 (15)	C6A—C5A—H5A	121.00
O11A—S1A—N2A	101.75 (13)	C4A—C5A—H5A	121.00
O11A—S1A—C11A	108.98 (16)	C11A—C21A—H21A	120.00
O12A—S1A—N2A	108.57 (14)	C31A—C21A—H21A	120.00
O12A—S1A—C11A	108.88 (15)	C41A—C31A—H31A	120.00
N2A—S1A—C11A	107.50 (14)	C21A—C31A—H31A	120.00
C11—O12—H12	110.00	C4A—C42A—H43A	109.00
C2A—N1A—C6A	119.7 (3)	C4A—C42A—H45A	110.00
S1A—N2A—C2A	125.8 (2)	C4A—C42A—H44A	109.00
C2A—N3A—C4A	117.2 (3)	H44A—C42A—H45A	109.00
C6A—N1A—H1A	120.00	H43A—C42A—H44A	110.00
C2A—N1A—H1A	120.00	H43A—C42A—H45A	109.00
C2A—N2A—H2A	121.00	C61A—C51A—H51A	120.00
S1A—N2A—H2A	111.00	C41A—C51A—H51A	120.00
H41A—N41A—H42A	116.00	C51A—C61A—H61A	120.00
C41A—N41A—H42A	117.00	C11A—C61A—H61A	120.00
C41A—N41A—H41A	117.00	H64A—C62A—H65A	109.00
O31—N3—C3	117.6 (4)	C6A—C62A—H64A	109.00
O32—N3—C3	118.8 (4)	C6A—C62A—H65A	110.00
O31—N3—O32	123.6 (5)	H63A—C62A—H64A	110.00
O51—N5—C5	116.2 (4)	H63A—C62A—H65A	109.00
O52—N5—C5	117.8 (4)	C6A—C62A—H63A	109.00
O51—N5—O52	126.1 (4)	C2—C1—C6	120.8 (3)
N2A—C2A—N3A	120.9 (3)	C2—C1—C11	119.3 (3)
N1A—C2A—N3A	123.3 (3)	C6—C1—C11	120.0 (4)
N1A—C2A—N2A	115.8 (3)	O2—C2—C3	120.9 (4)
C5A—C4A—C42A	121.4 (3)	C1—C2—C3	118.3 (3)
N3A—C4A—C42A	116.9 (4)	O2—C2—C1	120.8 (3)
N3A—C4A—C5A	121.7 (4)	N3—C3—C2	118.2 (4)
C4A—C5A—C6A	118.9 (3)	C2—C3—C4	122.0 (4)
N1A—C6A—C5A	118.9 (4)	N3—C3—C4	119.7 (4)
N1A—C6A—C62A	116.9 (4)	C3—C4—C5	117.9 (4)
C5A—C6A—C62A	124.2 (4)	N5—C5—C6	118.3 (4)
C21A—C11A—C61A	119.8 (3)	C4—C5—C6	123.3 (4)
S1A—C11A—C21A	121.0 (3)	N5—C5—C4	118.4 (3)
S1A—C11A—C61A	119.1 (2)	C1—C6—C5	117.5 (4)
C11A—C21A—C31A	119.9 (3)	O11—C11—C1	119.8 (4)
C21A—C31A—C41A	120.8 (3)	O12—C11—C1	115.7 (4)
C31A—C41A—C51A	118.4 (3)	O11—C11—O12	124.5 (4)
N41A—C41A—C51A	120.8 (3)	C3—C4—H4	121.00
N41A—C41A—C31A	120.8 (3)	C5—C4—H4	121.00
C41A—C51A—C61A	120.8 (3)	C1—C6—H6	121.00
C11A—C61A—C51A	120.3 (3)	C5—C6—H6	121.00

N2A—S1A—C11A—C61A	89.7 (3)	S1A—C11A—C21A—C31A	−176.2 (3)
O11A—S1A—N2A—C2A	−165.7 (3)	C61A—C11A—C21A—C31A	0.7 (5)
O11A—S1A—C11A—C21A	157.1 (3)	C21A—C11A—C61A—C51A	−0.7 (5)
O12A—S1A—C11A—C21A	24.1 (3)	S1A—C11A—C61A—C51A	176.4 (3)
O12A—S1A—C11A—C61A	−152.9 (3)	C11A—C21A—C31A—C41A	0.0 (5)
O12A—S1A—N2A—C2A	−37.7 (3)	C21A—C31A—C41A—N41A	−179.7 (3)
C11A—S1A—N2A—C2A	79.9 (3)	C21A—C31A—C41A—C51A	−0.9 (5)
O11A—S1A—C11A—C61A	−19.9 (3)	C31A—C41A—C51A—C61A	1.0 (5)
N2A—S1A—C11A—C21A	−93.4 (3)	N41A—C41A—C51A—C61A	179.7 (3)
C2A—N1A—C6A—C62A	179.4 (4)	C41A—C51A—C61A—C11A	−0.2 (5)
C6A—N1A—C2A—N3A	4.6 (6)	C6—C1—C2—O2	178.3 (5)
C6A—N1A—C2A—N2A	−176.9 (3)	C6—C1—C2—C3	−3.2 (7)
C2A—N1A—C6A—C5A	−0.6 (6)	C11—C1—C2—O2	−3.0 (7)
S1A—N2A—C2A—N1A	169.1 (2)	C11—C1—C2—C3	175.5 (4)
S1A—N2A—C2A—N3A	−12.3 (5)	C2—C1—C6—C5	0.8 (7)
C4A—N3A—C2A—N1A	−4.6 (5)	C11—C1—C6—C5	−178.0 (4)
C2A—N3A—C4A—C42A	−179.8 (4)	C2—C1—C11—O11	−176.3 (5)
C4A—N3A—C2A—N2A	176.9 (3)	C2—C1—C11—O12	3.0 (7)
C2A—N3A—C4A—C5A	0.9 (6)	C6—C1—C11—O11	2.5 (7)
O32—N3—C3—C4	125.6 (5)	C6—C1—C11—O12	−178.3 (4)
O31—N3—C3—C4	−52.1 (6)	O2—C2—C3—N3	1.2 (7)
O32—N3—C3—C2	−55.2 (6)	O2—C2—C3—C4	−179.6 (5)
O31—N3—C3—C2	127.1 (5)	C1—C2—C3—N3	−177.4 (4)
O51—N5—C5—C6	−168.2 (5)	C1—C2—C3—C4	1.9 (7)
O52—N5—C5—C4	−167.5 (5)	N3—C3—C4—C5	−178.9 (4)
O52—N5—C5—C6	10.2 (7)	C2—C3—C4—C5	1.9 (7)
O51—N5—C5—C4	14.1 (7)	C3—C4—C5—N5	173.0 (5)
N3A—C4A—C5A—C6A	2.8 (6)	C3—C4—C5—C6	−4.6 (8)
C42A—C4A—C5A—C6A	−176.5 (4)	N5—C5—C6—C1	−174.3 (4)
C4A—C5A—C6A—N1A	−2.9 (6)	C4—C5—C6—C1	3.3 (8)
C4A—C5A—C6A—C62A	177.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O11	0.88	1.75	2.617 (4)	168
N2A—H2A···O12	0.78	1.95	2.729 (4)	170
O12—H12···O2	0.96	1.52	2.416 (5)	154
N41A—H41A···O51ⁱ	0.81	2.50	3.248 (5)	153
N41A—H42A···O12Aⁱⁱ	0.81	2.46	3.202 (4)	152
C5A—H5A···O11Aⁱⁱⁱ	0.93	2.51	3.408 (5)	163
C51A—H51A···O12Aⁱⁱ	0.93	2.46	3.280 (4)	147
C61A—H61A···O11A	0.93	2.56	2.916 (4)	103
C62A—H63A···O11	0.96	2.51	3.218 (6)	131
C62A—H64A···O2ⁱⁱⁱ	0.96	2.29	2.960 (7)	127

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₄O₂S⁺·C₇H₃N₂O₇⁻
M_r	506.46
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	8.1691 (3), 32.0736 (9), 8.9869 (3)
β (°)	112.258 (5)
V (Å³)	2179.23 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.40 × 0.35 × 0.20

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.918, 0.980
No. of measured, independent and observed [I > \2s(I)] reflections	14977, 4264, 3645
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.158, 1.10
No. of reflections	4264
No. of parameters	318
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.51

Computer programs: CrysAlis PRO (Agilent, 2012), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O11	0.88	1.75	2.617 (4)	168
N2A—H2A···O12	0.78	1.95	2.729 (4)	170
O12—H12···O2	0.96	1.52	2.416 (5)	154
N41A—H41A···O51ⁱ	0.81	2.50	3.248 (5)	153
N41A—H42A···O12Aⁱⁱ	0.81	2.46	3.202 (4)	152

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z.

Acknowledgements

The authors acknowledge financial support from the Australian Reseach Council, the Science and Engineering Faculty and the University Library, Queensland University of Technology.

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Caira, M. R. (1991). J. Crystallogr. Spectrosc. Res. 21, 641–648. CSD CrossRef CAS Web of Science Google Scholar
Caira, M. R. (2007). Mol. Pharm. 4, 310–316. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
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O'Neil, M. J. (2001). Editor. The Merck Index, 13th ed. p. 1588. Whitehouse Station, NJ: Merck & Co. Inc. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G. & Wermuth, U. D. (2013). Acta Cryst. C69. Submitted. CrossRef IUCr Journals Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-(4-Amino­benzene­sulfonamido)-4,6-di­methyl­pyrimidin-1-ium 2-carb­­oxy-4,6-di­nitro­phenolate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-(4-Aminobenzenesulfonamido)-4,6-dimethylpyrimidin-1-ium 2-carboxy-4,6-dinitrophenolate