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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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[O'Neil, M. J. (2001). Editor. The Merck Index, 13th ed. p. 1588. Whitehouse Station, NJ: Merck & Co. Inc.]); Caira (2007[Caira, M. R. (2007). Mol. Pharm. 4, 310-316.]); Ghosh et al. (2011[Ghosh, S., Bag, P. P. & Reddy, C. M. (2011). Cryst. Growth Des. 11, 3489-3503.]). For similar structures, see: Caira (1991[Caira, M. R. (1991). J. Crystallogr. Spectrosc. Res. 21, 641-648.]); Lynch et al. (2000[Lynch, D. E., Sandhu, P. & Parsons, S. (2000). Aust. J. Chem. 53, 383-387.]); Smith & Wermuth (2013[Smith, G. & Wermuth, U. D. (2013). Acta Cryst. C69. Submitted.]). For structures of 3,5-dinitro­salicylic acid salts, see: Smith et al. (2003[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2003). Aust. J. Chem. 56, 707-713.]). For graph-set analysis, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C12H15N4O2S+·C7H3N2O7

  • Mr = 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[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.918, Tmax = 0.980

  • 14977 measured reflections

  • 4264 independent reflections

  • 3645 reflections with I > \2s(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 0.158

  • S = 1.10

  • 4264 reflections

  • 318 parameters

  • H-atom parameters constrained

  • Δρmax = 0.87 e Å−3

  • Δρmin = −0.51 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: PLATON.

Supporting information


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···Ocarboxyl and carboxylic acid O—H···Npyrimidine 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.

Refinement top

Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods but their positional and isotropic displacement parameters were subsequently allowed to ride in the refinement with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included at calculated positions [C—H (aromatic) = 0.93 Å or C—H (methyl) = 0.96 Å] and also treated as riding, with Uiso(H) = 1.2Ueq(C)aromatic or 1.5Ueq (C)methyl.

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
[Figure 1] 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.
[Figure 2] 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+·C7H3N2O7F(000) = 1048
Mr = 506.46Dx = 1.544 Mg m3
Monoclinic, P21/cMelting point = 457–458 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.1691 (3) ÅCell parameters from 4751 reflections
b = 32.0736 (9) Åθ = 3.1–28.8°
c = 8.9869 (3) ŵ = 0.22 mm1
β = 112.258 (5)°T = 200 K
V = 2179.23 (15) Å3Plate, yellow
Z = 40.40 × 0.35 × 0.20 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
4264 independent reflections
Radiation source: Enhance (Mo) X-ray source3645 reflections with I > \2s(I)
Graphite monochromatorRint = 0.039
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.1°
ω scansh = 710
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 3939
Tmin = 0.918, Tmax = 0.980l = 1111
14977 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0472P)2 + 4.2454P]
where P = (Fo2 + 2Fc2)/3
4264 reflections(Δ/σ)max = 0.010
318 parametersΔρmax = 0.87 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C12H15N4O2S+·C7H3N2O7V = 2179.23 (15) Å3
Mr = 506.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1691 (3) ŵ = 0.22 mm1
b = 32.0736 (9) ÅT = 200 K
c = 8.9869 (3) Å0.40 × 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)
Tmin = 0.918, Tmax = 0.980Rint = 0.039
14977 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 1.10Δρmax = 0.87 e Å3
4264 reflectionsΔρmin = 0.51 e Å3
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
xyzUiso*/Ueq
S1A0.33370 (9)0.09248 (2)0.49476 (9)0.0225 (2)
O11A0.4293 (3)0.11377 (7)0.6420 (3)0.0308 (7)
O12A0.1986 (3)0.06331 (7)0.4858 (3)0.0300 (7)
N1A0.0333 (4)0.16571 (9)0.1560 (3)0.0347 (9)
N2A0.2414 (3)0.13221 (8)0.3706 (3)0.0279 (8)
N3A0.0595 (4)0.09249 (9)0.1533 (3)0.0318 (8)
N41A0.8562 (4)0.00864 (9)0.2912 (4)0.0352 (9)
C2A0.1081 (4)0.12918 (10)0.2241 (4)0.0271 (9)
C4A0.0789 (5)0.09197 (13)0.0121 (4)0.0394 (11)
C5A0.1668 (5)0.12839 (15)0.0589 (4)0.0487 (13)
C6A0.1059 (5)0.16547 (14)0.0136 (4)0.0460 (14)
C11A0.4832 (4)0.06863 (9)0.4269 (4)0.0209 (8)
C21A0.4332 (4)0.03461 (10)0.3223 (4)0.0281 (9)
C31A0.5563 (4)0.01481 (10)0.2778 (4)0.0306 (10)
C41A0.7336 (4)0.02831 (9)0.3364 (4)0.0257 (9)
C42A0.1332 (6)0.05060 (14)0.0664 (5)0.0582 (16)
C51A0.7806 (4)0.06280 (10)0.4394 (4)0.0279 (9)
C61A0.6577 (4)0.08258 (9)0.4841 (4)0.0250 (9)
C62A0.1833 (7)0.20700 (16)0.0541 (6)0.0709 (17)
O20.5067 (5)0.25084 (9)0.7126 (4)0.0712 (11)
O110.1194 (4)0.24106 (9)0.2706 (4)0.0589 (11)
O120.2967 (4)0.21077 (8)0.4967 (4)0.0606 (10)
O310.8156 (5)0.34132 (12)0.8480 (5)0.0813 (16)
O320.6599 (6)0.30963 (12)0.9593 (4)0.0868 (16)
O510.3439 (7)0.42888 (10)0.4234 (4)0.0993 (19)
O520.1099 (6)0.39640 (11)0.2632 (5)0.0763 (16)
N30.6791 (5)0.32438 (11)0.8427 (5)0.0557 (15)
N50.2539 (7)0.39791 (10)0.3752 (5)0.0568 (16)
C10.3126 (5)0.28407 (11)0.4776 (5)0.0429 (11)
C20.4505 (6)0.28519 (11)0.6290 (5)0.0462 (15)
C30.5295 (6)0.32354 (12)0.6872 (5)0.0456 (14)
C40.4725 (6)0.36005 (11)0.6024 (5)0.0483 (15)
C50.3300 (6)0.35804 (11)0.4587 (5)0.0485 (14)
C60.2494 (6)0.32095 (11)0.3902 (5)0.0464 (15)
C110.2342 (6)0.24260 (11)0.4069 (6)0.0489 (15)
H1A0.070500.189200.207200.0420*
H2A0.261200.153400.417600.0330*
H5A0.265600.127300.154500.0580*
H21A0.316600.025400.282900.0340*
H31A0.522400.007800.208000.0370*
H41A0.835600.015500.262400.0420*
H42A0.959600.014300.342400.0420*
H43A0.177400.033600.001900.0870*
H44A0.033000.037200.076800.0870*
H45A0.224200.054300.171000.0870*
H51A0.896600.072400.477900.0330*
H61A0.690900.105400.553000.0300*
H63A0.159400.226700.031800.1070*
H64A0.308800.204200.110100.1070*
H65A0.131100.216600.127400.1070*
H40.528800.385300.641300.0580*
H60.156800.320500.290200.0560*
H120.389700.219000.595200.0730*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0178 (4)0.0252 (4)0.0234 (4)0.0015 (3)0.0066 (3)0.0017 (3)
O11A0.0251 (11)0.0396 (13)0.0253 (12)0.0024 (10)0.0069 (10)0.0038 (10)
O12A0.0210 (11)0.0346 (12)0.0356 (13)0.0023 (9)0.0122 (10)0.0024 (10)
N1A0.0303 (15)0.0369 (15)0.0354 (16)0.0092 (13)0.0108 (13)0.0082 (13)
N2A0.0235 (13)0.0207 (13)0.0324 (15)0.0026 (10)0.0026 (12)0.0014 (11)
N3A0.0270 (14)0.0381 (15)0.0263 (14)0.0019 (12)0.0057 (12)0.0023 (12)
N41A0.0307 (15)0.0290 (14)0.0512 (18)0.0007 (12)0.0215 (14)0.0033 (13)
C2A0.0186 (15)0.0354 (17)0.0270 (16)0.0058 (13)0.0083 (13)0.0074 (13)
C4A0.0289 (18)0.061 (2)0.0254 (17)0.0095 (17)0.0071 (14)0.0030 (17)
C5A0.031 (2)0.079 (3)0.0253 (18)0.003 (2)0.0016 (16)0.0090 (19)
C6A0.0322 (19)0.068 (3)0.034 (2)0.0196 (19)0.0082 (17)0.0169 (19)
C11A0.0166 (14)0.0206 (14)0.0250 (15)0.0019 (11)0.0072 (12)0.0044 (12)
C21A0.0212 (15)0.0263 (16)0.0347 (18)0.0045 (13)0.0082 (14)0.0025 (13)
C31A0.0294 (17)0.0221 (15)0.0396 (19)0.0044 (13)0.0123 (15)0.0081 (14)
C41A0.0272 (16)0.0236 (15)0.0284 (16)0.0042 (13)0.0129 (14)0.0064 (13)
C42A0.060 (3)0.067 (3)0.033 (2)0.024 (2)0.001 (2)0.004 (2)
C51A0.0195 (15)0.0312 (16)0.0329 (17)0.0036 (13)0.0098 (13)0.0001 (14)
C61A0.0220 (15)0.0237 (15)0.0271 (16)0.0026 (12)0.0067 (13)0.0022 (12)
C62A0.065 (3)0.076 (3)0.059 (3)0.040 (3)0.009 (2)0.028 (3)
O20.074 (2)0.0400 (16)0.072 (2)0.0168 (16)0.0036 (18)0.0058 (15)
O110.068 (2)0.0378 (16)0.0570 (19)0.0118 (14)0.0079 (17)0.0055 (14)
O120.076 (2)0.0265 (13)0.0627 (19)0.0072 (14)0.0075 (17)0.0003 (13)
O310.055 (2)0.092 (3)0.107 (3)0.006 (2)0.042 (2)0.017 (2)
O320.116 (3)0.083 (3)0.055 (2)0.032 (2)0.025 (2)0.0023 (19)
O510.220 (5)0.0320 (17)0.057 (2)0.005 (2)0.065 (3)0.0031 (15)
O520.096 (3)0.067 (2)0.085 (3)0.039 (2)0.056 (2)0.041 (2)
N30.065 (3)0.0376 (19)0.074 (3)0.0023 (18)0.037 (2)0.0111 (18)
N50.116 (4)0.0297 (18)0.050 (2)0.010 (2)0.060 (2)0.0088 (16)
C10.055 (2)0.0275 (18)0.053 (2)0.0116 (17)0.028 (2)0.0029 (16)
C20.059 (3)0.0238 (17)0.065 (3)0.0117 (17)0.034 (2)0.0045 (17)
C30.059 (3)0.036 (2)0.050 (2)0.0036 (18)0.030 (2)0.0050 (17)
C40.080 (3)0.0228 (17)0.064 (3)0.0029 (18)0.052 (3)0.0022 (17)
C50.085 (3)0.0319 (19)0.048 (2)0.016 (2)0.047 (2)0.0092 (17)
C60.071 (3)0.0259 (18)0.064 (3)0.0116 (18)0.050 (2)0.0054 (17)
C110.060 (3)0.0249 (18)0.070 (3)0.0087 (18)0.034 (2)0.0028 (18)
Geometric parameters (Å, º) top
S1A—O11A1.430 (3)C6A—C62A1.501 (7)
S1A—O12A1.426 (3)C11A—C61A1.393 (5)
S1A—N2A1.673 (3)C11A—C21A1.397 (4)
S1A—C11A1.736 (3)C21A—C31A1.371 (5)
O2—C21.314 (5)C31A—C41A1.409 (5)
O11—C111.230 (6)C41A—C51A1.400 (4)
O12—C111.281 (5)C51A—C61A1.370 (5)
O31—N31.225 (6)C5A—H5A0.9300
O32—N31.213 (6)C21A—H21A0.9300
O51—N51.214 (6)C31A—H31A0.9300
O52—N51.226 (7)C42A—H45A0.9600
O12—H120.9600C42A—H43A0.9600
N1A—C6A1.352 (5)C42A—H44A0.9600
N1A—C2A1.356 (4)C51A—H51A0.9300
N2A—C2A1.357 (4)C61A—H61A0.9300
N3A—C4A1.342 (5)C62A—H63A0.9600
N3A—C2A1.325 (4)C62A—H64A0.9600
N41A—C41A1.369 (5)C62A—H65A0.9600
N1A—H1A0.8800C1—C61.406 (5)
N2A—H2A0.7800C1—C111.508 (5)
N41A—H42A0.8100C1—C21.400 (6)
N41A—H41A0.8100C2—C31.396 (6)
N3—C31.467 (6)C3—C41.378 (5)
N5—C51.494 (5)C4—C51.374 (6)
C4A—C5A1.393 (6)C5—C61.386 (5)
C4A—C42A1.489 (6)C4—H40.9300
C5A—C6A1.357 (6)C6—H60.9300
O11A—S1A—O12A120.36 (15)C6A—C5A—H5A121.00
O11A—S1A—N2A101.75 (13)C4A—C5A—H5A121.00
O11A—S1A—C11A108.98 (16)C11A—C21A—H21A120.00
O12A—S1A—N2A108.57 (14)C31A—C21A—H21A120.00
O12A—S1A—C11A108.88 (15)C41A—C31A—H31A120.00
N2A—S1A—C11A107.50 (14)C21A—C31A—H31A120.00
C11—O12—H12110.00C4A—C42A—H43A109.00
C2A—N1A—C6A119.7 (3)C4A—C42A—H45A110.00
S1A—N2A—C2A125.8 (2)C4A—C42A—H44A109.00
C2A—N3A—C4A117.2 (3)H44A—C42A—H45A109.00
C6A—N1A—H1A120.00H43A—C42A—H44A110.00
C2A—N1A—H1A120.00H43A—C42A—H45A109.00
C2A—N2A—H2A121.00C61A—C51A—H51A120.00
S1A—N2A—H2A111.00C41A—C51A—H51A120.00
H41A—N41A—H42A116.00C51A—C61A—H61A120.00
C41A—N41A—H42A117.00C11A—C61A—H61A120.00
C41A—N41A—H41A117.00H64A—C62A—H65A109.00
O31—N3—C3117.6 (4)C6A—C62A—H64A109.00
O32—N3—C3118.8 (4)C6A—C62A—H65A110.00
O31—N3—O32123.6 (5)H63A—C62A—H64A110.00
O51—N5—C5116.2 (4)H63A—C62A—H65A109.00
O52—N5—C5117.8 (4)C6A—C62A—H63A109.00
O51—N5—O52126.1 (4)C2—C1—C6120.8 (3)
N2A—C2A—N3A120.9 (3)C2—C1—C11119.3 (3)
N1A—C2A—N3A123.3 (3)C6—C1—C11120.0 (4)
N1A—C2A—N2A115.8 (3)O2—C2—C3120.9 (4)
C5A—C4A—C42A121.4 (3)C1—C2—C3118.3 (3)
N3A—C4A—C42A116.9 (4)O2—C2—C1120.8 (3)
N3A—C4A—C5A121.7 (4)N3—C3—C2118.2 (4)
C4A—C5A—C6A118.9 (3)C2—C3—C4122.0 (4)
N1A—C6A—C5A118.9 (4)N3—C3—C4119.7 (4)
N1A—C6A—C62A116.9 (4)C3—C4—C5117.9 (4)
C5A—C6A—C62A124.2 (4)N5—C5—C6118.3 (4)
C21A—C11A—C61A119.8 (3)C4—C5—C6123.3 (4)
S1A—C11A—C21A121.0 (3)N5—C5—C4118.4 (3)
S1A—C11A—C61A119.1 (2)C1—C6—C5117.5 (4)
C11A—C21A—C31A119.9 (3)O11—C11—C1119.8 (4)
C21A—C31A—C41A120.8 (3)O12—C11—C1115.7 (4)
C31A—C41A—C51A118.4 (3)O11—C11—O12124.5 (4)
N41A—C41A—C51A120.8 (3)C3—C4—H4121.00
N41A—C41A—C31A120.8 (3)C5—C4—H4121.00
C41A—C51A—C61A120.8 (3)C1—C6—H6121.00
C11A—C61A—C51A120.3 (3)C5—C6—H6121.00
N2A—S1A—C11A—C61A89.7 (3)S1A—C11A—C21A—C31A176.2 (3)
O11A—S1A—N2A—C2A165.7 (3)C61A—C11A—C21A—C31A0.7 (5)
O11A—S1A—C11A—C21A157.1 (3)C21A—C11A—C61A—C51A0.7 (5)
O12A—S1A—C11A—C21A24.1 (3)S1A—C11A—C61A—C51A176.4 (3)
O12A—S1A—C11A—C61A152.9 (3)C11A—C21A—C31A—C41A0.0 (5)
O12A—S1A—N2A—C2A37.7 (3)C21A—C31A—C41A—N41A179.7 (3)
C11A—S1A—N2A—C2A79.9 (3)C21A—C31A—C41A—C51A0.9 (5)
O11A—S1A—C11A—C61A19.9 (3)C31A—C41A—C51A—C61A1.0 (5)
N2A—S1A—C11A—C21A93.4 (3)N41A—C41A—C51A—C61A179.7 (3)
C2A—N1A—C6A—C62A179.4 (4)C41A—C51A—C61A—C11A0.2 (5)
C6A—N1A—C2A—N3A4.6 (6)C6—C1—C2—O2178.3 (5)
C6A—N1A—C2A—N2A176.9 (3)C6—C1—C2—C33.2 (7)
C2A—N1A—C6A—C5A0.6 (6)C11—C1—C2—O23.0 (7)
S1A—N2A—C2A—N1A169.1 (2)C11—C1—C2—C3175.5 (4)
S1A—N2A—C2A—N3A12.3 (5)C2—C1—C6—C50.8 (7)
C4A—N3A—C2A—N1A4.6 (5)C11—C1—C6—C5178.0 (4)
C2A—N3A—C4A—C42A179.8 (4)C2—C1—C11—O11176.3 (5)
C4A—N3A—C2A—N2A176.9 (3)C2—C1—C11—O123.0 (7)
C2A—N3A—C4A—C5A0.9 (6)C6—C1—C11—O112.5 (7)
O32—N3—C3—C4125.6 (5)C6—C1—C11—O12178.3 (4)
O31—N3—C3—C452.1 (6)O2—C2—C3—N31.2 (7)
O32—N3—C3—C255.2 (6)O2—C2—C3—C4179.6 (5)
O31—N3—C3—C2127.1 (5)C1—C2—C3—N3177.4 (4)
O51—N5—C5—C6168.2 (5)C1—C2—C3—C41.9 (7)
O52—N5—C5—C4167.5 (5)N3—C3—C4—C5178.9 (4)
O52—N5—C5—C610.2 (7)C2—C3—C4—C51.9 (7)
O51—N5—C5—C414.1 (7)C3—C4—C5—N5173.0 (5)
N3A—C4A—C5A—C6A2.8 (6)C3—C4—C5—C64.6 (8)
C42A—C4A—C5A—C6A176.5 (4)N5—C5—C6—C1174.3 (4)
C4A—C5A—C6A—N1A2.9 (6)C4—C5—C6—C13.3 (8)
C4A—C5A—C6A—C62A177.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O110.881.752.617 (4)168
N2A—H2A···O120.781.952.729 (4)170
O12—H12···O20.961.522.416 (5)154
N41A—H41A···O51i0.812.503.248 (5)153
N41A—H42A···O12Aii0.812.463.202 (4)152
C5A—H5A···O11Aiii0.932.513.408 (5)163
C51A—H51A···O12Aii0.932.463.280 (4)147
C61A—H61A···O11A0.932.562.916 (4)103
C62A—H63A···O110.962.513.218 (6)131
C62A—H64A···O2iii0.962.292.960 (7)127
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y, z; (iii) x1, y, z1.

Experimental details

Crystal data
Chemical formulaC12H15N4O2S+·C7H3N2O7
Mr506.46
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)8.1691 (3), 32.0736 (9), 8.9869 (3)
β (°) 112.258 (5)
V3)2179.23 (15)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.40 × 0.35 × 0.20
Data collection
DiffractometerOxford Diffraction Gemini-S CCD-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.918, 0.980
No. of measured, independent and
observed [I > \2s(I)] reflections
14977, 4264, 3645
Rint0.039
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.158, 1.10
No. of reflections4264
No. of parameters318
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1A—H1A···O110.881.752.617 (4)168
N2A—H2A···O120.781.952.729 (4)170
O12—H12···O20.961.522.416 (5)154
N41A—H41A···O51i0.812.503.248 (5)153
N41A—H42A···O12Aii0.812.463.202 (4)152
Symmetry codes: (i) x+1, y1/2, 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

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