Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108011888/em3013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108011888/em3013Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108011888/em3013IIsup3.hkl |
CCDC references: 692661; 692662
For related literature, see: Allen (2002); Bernstein et al. (1995); Caira (1992); Cinacchi & Prampolini (2003); Frisk & Hultman (1965); Gelbrich et al. (2007); Liu et al. (1994); Nabert-Bock (1958); Rambaud et al. (1985).
Sulfasymazine was supplied by Lederle (now Wyeth–Lederle Pharma). Single crystals suitable for diffraction were prepared by slowly cooling a saturated acetonitrile solution of the commercial product. Sulfatriazine monohydrate was supplied by Stickstoffwerke Linz; single crystals of anhydrous sulfatriazine were prepared by dissolving sulfatriazine monohydrate in acetonitrile and allowing the solution to evaporate slowly to dryness.
All H atoms were identified in a difference map. Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip (C—H = 0.98 Å). The H atoms of CH2 (C—H = 0.99 Å) and benzene (C—H = 0.95 Å) groups were positioned geometricallly. The Uiso(H) parameters were set at 1.5Ueq(C) for CH3 H atoms and 1.2Ueq(C) for other C-bound H atoms. H atoms attached to N atoms were refined with restrained distances [N—H = 0.88 (2) Å] and their Uiso parameters were refined freely.
For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2008).
C13H17N5O2S | F(000) = 648 |
Mr = 307.38 | Dx = 1.413 Mg m−3 |
Monoclinic, P21/n | Melting point = 188–190 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3257 (2) Å | Cell parameters from 2906 reflections |
b = 16.7918 (4) Å | θ = 2.9–26.0° |
c = 9.8600 (2) Å | µ = 0.24 mm−1 |
β = 110.693 (1)° | T = 120 K |
V = 1444.42 (6) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Bruker–Nonius KappaCCD diffractometer | 2805 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2342 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.0°, θmin = 3.3° |
ϕ & ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −20→20 |
Tmin = 0.932, Tmax = 0.954 | l = −12→12 |
17818 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0629P)2 + 0.9906P] where P = (Fo2 + 2Fc2)/3 |
2805 reflections | (Δ/σ)max < 0.001 |
204 parameters | Δρmax = 0.84 e Å−3 |
3 restraints | Δρmin = −0.57 e Å−3 |
C13H17N5O2S | V = 1444.42 (6) Å3 |
Mr = 307.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.3257 (2) Å | µ = 0.24 mm−1 |
b = 16.7918 (4) Å | T = 120 K |
c = 9.8600 (2) Å | 0.20 × 0.20 × 0.20 mm |
β = 110.693 (1)° |
Bruker–Nonius KappaCCD diffractometer | 2805 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 2342 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.954 | Rint = 0.055 |
17818 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 3 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.84 e Å−3 |
2805 reflections | Δρmin = −0.57 e Å−3 |
204 parameters |
Experimental. Thermomicroscopic investigations were performed using a Reichert Thermovar polarized light microscope (Reichert, Vienna, Austria) equipped with a Kofler hot stage (Reichert, Vienna, Austria). |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.43317 (5) | 0.21502 (3) | 0.62389 (5) | 0.01829 (16) | |
O1 | 0.53740 (15) | 0.16874 (8) | 0.73809 (15) | 0.0233 (3) | |
O2 | 0.47689 (16) | 0.29344 (8) | 0.59530 (16) | 0.0244 (3) | |
N1 | −0.16295 (19) | 0.23374 (11) | 0.71105 (19) | 0.0217 (4) | |
H1A | −0.229 (3) | 0.2670 (14) | 0.651 (3) | 0.038 (7)* | |
H1B | −0.204 (3) | 0.1869 (11) | 0.715 (3) | 0.031 (6)* | |
N2 | 0.39968 (19) | 0.16916 (10) | 0.46775 (18) | 0.0199 (4) | |
H2 | 0.383 (3) | 0.2026 (14) | 0.397 (2) | 0.041 (7)* | |
N3 | 0.33623 (18) | 0.04459 (10) | 0.53926 (18) | 0.0205 (4) | |
N4 | 0.24030 (19) | −0.05390 (10) | 0.35607 (19) | 0.0241 (4) | |
N5 | 0.31081 (18) | 0.07315 (10) | 0.29414 (18) | 0.0212 (4) | |
C1 | 0.2574 (2) | 0.21997 (11) | 0.6502 (2) | 0.0172 (4) | |
C2 | 0.2227 (2) | 0.16509 (12) | 0.7403 (2) | 0.0194 (4) | |
H2A | 0.2943 | 0.1249 | 0.7882 | 0.023* | |
C3 | 0.0824 (2) | 0.16987 (12) | 0.7593 (2) | 0.0210 (4) | |
H3 | 0.0586 | 0.1333 | 0.8218 | 0.025* | |
C4 | −0.0241 (2) | 0.22824 (11) | 0.6871 (2) | 0.0191 (4) | |
C5 | 0.0120 (2) | 0.28208 (11) | 0.5962 (2) | 0.0213 (4) | |
H5 | −0.0602 | 0.3217 | 0.5466 | 0.026* | |
C6 | 0.1521 (2) | 0.27816 (11) | 0.5776 (2) | 0.0203 (4) | |
H6 | 0.1762 | 0.3150 | 0.5156 | 0.024* | |
C7 | 0.3466 (2) | 0.09213 (11) | 0.4345 (2) | 0.0187 (4) | |
C8 | 0.2575 (2) | −0.00074 (12) | 0.2614 (2) | 0.0225 (4) | |
C9 | 0.2824 (2) | −0.02833 (12) | 0.4936 (2) | 0.0214 (4) | |
C10 | 0.2137 (3) | −0.02522 (15) | 0.1051 (2) | 0.0340 (5) | |
H10A | 0.1208 | 0.0045 | 0.0464 | 0.041* | |
H10B | 0.1879 | −0.0826 | 0.0963 | 0.041* | |
C11 | 0.3400 (4) | −0.01014 (16) | 0.0440 (3) | 0.0488 (7) | |
H11A | 0.3032 | −0.0243 | −0.0590 | 0.073* | |
H11B | 0.4297 | −0.0427 | 0.0965 | 0.073* | |
H11C | 0.3685 | 0.0463 | 0.0553 | 0.073* | |
C12 | 0.2667 (2) | −0.08498 (12) | 0.6058 (2) | 0.0263 (5) | |
H12A | 0.3512 | −0.0755 | 0.6990 | 0.032* | |
H12B | 0.2760 | −0.1403 | 0.5752 | 0.032* | |
C13 | 0.1138 (3) | −0.07543 (13) | 0.6278 (2) | 0.0297 (5) | |
H13A | 0.1101 | −0.1118 | 0.7042 | 0.044* | |
H13B | 0.0299 | −0.0879 | 0.5372 | 0.044* | |
H13C | 0.1032 | −0.0204 | 0.6561 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0174 (3) | 0.0192 (3) | 0.0207 (3) | −0.00228 (18) | 0.0098 (2) | −0.00277 (18) |
O1 | 0.0175 (7) | 0.0301 (8) | 0.0224 (7) | 0.0006 (6) | 0.0071 (6) | −0.0003 (6) |
O2 | 0.0244 (7) | 0.0209 (7) | 0.0330 (8) | −0.0067 (6) | 0.0163 (7) | −0.0036 (6) |
N1 | 0.0179 (8) | 0.0207 (9) | 0.0292 (10) | −0.0021 (7) | 0.0116 (8) | −0.0037 (7) |
N2 | 0.0255 (9) | 0.0184 (8) | 0.0196 (8) | −0.0012 (7) | 0.0128 (7) | −0.0011 (7) |
N3 | 0.0209 (8) | 0.0199 (8) | 0.0227 (8) | 0.0013 (7) | 0.0100 (7) | 0.0003 (7) |
N4 | 0.0201 (9) | 0.0219 (9) | 0.0303 (9) | 0.0000 (7) | 0.0090 (7) | −0.0050 (7) |
N5 | 0.0198 (8) | 0.0235 (9) | 0.0219 (8) | 0.0009 (7) | 0.0096 (7) | −0.0031 (7) |
C1 | 0.0171 (9) | 0.0186 (9) | 0.0174 (9) | −0.0018 (7) | 0.0081 (8) | −0.0037 (7) |
C2 | 0.0199 (10) | 0.0189 (9) | 0.0195 (9) | 0.0026 (8) | 0.0073 (8) | 0.0009 (7) |
C3 | 0.0239 (10) | 0.0206 (10) | 0.0211 (10) | −0.0010 (8) | 0.0111 (8) | 0.0022 (8) |
C4 | 0.0182 (9) | 0.0206 (9) | 0.0198 (9) | −0.0034 (8) | 0.0085 (8) | −0.0089 (8) |
C5 | 0.0224 (10) | 0.0185 (10) | 0.0222 (10) | 0.0031 (8) | 0.0069 (8) | 0.0006 (8) |
C6 | 0.0233 (10) | 0.0194 (10) | 0.0207 (10) | −0.0006 (8) | 0.0109 (8) | 0.0009 (8) |
C7 | 0.0155 (9) | 0.0205 (10) | 0.0217 (9) | 0.0023 (7) | 0.0087 (8) | −0.0013 (8) |
C8 | 0.0165 (9) | 0.0245 (11) | 0.0277 (11) | 0.0008 (8) | 0.0094 (8) | −0.0053 (8) |
C9 | 0.0173 (9) | 0.0188 (10) | 0.0293 (10) | 0.0032 (8) | 0.0098 (8) | −0.0005 (8) |
C10 | 0.0298 (12) | 0.0394 (13) | 0.0290 (12) | −0.0007 (10) | 0.0056 (10) | −0.0124 (10) |
C11 | 0.087 (2) | 0.0386 (14) | 0.0298 (12) | −0.0228 (14) | 0.0320 (14) | −0.0077 (11) |
C12 | 0.0281 (11) | 0.0182 (10) | 0.0332 (12) | 0.0006 (8) | 0.0118 (9) | 0.0037 (9) |
C13 | 0.0316 (12) | 0.0289 (12) | 0.0320 (12) | 0.0024 (9) | 0.0156 (10) | 0.0077 (9) |
S1—O1 | 1.4293 (15) | C3—H3 | 0.9500 |
S1—O2 | 1.4355 (14) | C4—C5 | 1.396 (3) |
S1—N2 | 1.6495 (16) | C5—C6 | 1.384 (3) |
S1—C1 | 1.7492 (19) | C5—H5 | 0.9500 |
N1—C4 | 1.399 (2) | C6—H6 | 0.9500 |
N1—H1A | 0.884 (17) | C8—C10 | 1.506 (3) |
N1—H1B | 0.883 (16) | C9—C12 | 1.504 (3) |
N2—C7 | 1.382 (3) | C10—C11 | 1.522 (3) |
N2—H2 | 0.869 (17) | C10—H10A | 0.9900 |
N3—C7 | 1.335 (3) | C10—H10B | 0.9900 |
N3—C9 | 1.340 (3) | C11—H11A | 0.9800 |
N4—C8 | 1.342 (3) | C11—H11B | 0.9800 |
N4—C9 | 1.342 (3) | C11—H11C | 0.9800 |
N5—C8 | 1.333 (3) | C12—C13 | 1.525 (3) |
N5—C7 | 1.343 (2) | C12—H12A | 0.9900 |
C1—C6 | 1.391 (3) | C12—H12B | 0.9900 |
C1—C2 | 1.396 (3) | C13—H13A | 0.9800 |
C2—C3 | 1.388 (3) | C13—H13B | 0.9800 |
C2—H2A | 0.9500 | C13—H13C | 0.9800 |
C3—C4 | 1.398 (3) | ||
O1—S1—O2 | 119.48 (9) | N3—C7—N5 | 126.57 (18) |
O1—S1—N2 | 109.47 (9) | N3—C7—N2 | 119.60 (17) |
O2—S1—N2 | 102.60 (9) | N5—C7—N2 | 113.83 (17) |
O1—S1—C1 | 108.73 (9) | N5—C8—N4 | 125.23 (18) |
O2—S1—C1 | 109.35 (9) | N5—C8—C10 | 116.44 (19) |
N2—S1—C1 | 106.39 (9) | N4—C8—C10 | 118.33 (19) |
C4—N1—H1A | 113.4 (18) | N3—C9—N4 | 124.95 (19) |
C4—N1—H1B | 113.2 (16) | N3—C9—C12 | 116.97 (18) |
H1A—N1—H1B | 112 (2) | N4—C9—C12 | 118.08 (18) |
C7—N2—S1 | 126.28 (14) | C8—C10—C11 | 113.04 (19) |
C7—N2—H2 | 117.8 (18) | C8—C10—H10A | 109.0 |
S1—N2—H2 | 111.9 (18) | C11—C10—H10A | 109.0 |
C7—N3—C9 | 114.07 (17) | C8—C10—H10B | 109.0 |
C8—N4—C9 | 115.21 (17) | C11—C10—H10B | 109.0 |
C8—N5—C7 | 113.96 (17) | H10A—C10—H10B | 107.8 |
C6—C1—C2 | 120.70 (18) | C10—C11—H11A | 109.5 |
C6—C1—S1 | 119.04 (15) | C10—C11—H11B | 109.5 |
C2—C1—S1 | 120.24 (15) | H11A—C11—H11B | 109.5 |
C3—C2—C1 | 119.35 (18) | C10—C11—H11C | 109.5 |
C3—C2—H2A | 120.3 | H11A—C11—H11C | 109.5 |
C1—C2—H2A | 120.3 | H11B—C11—H11C | 109.5 |
C2—C3—C4 | 120.38 (18) | C9—C12—C13 | 112.14 (17) |
C2—C3—H3 | 119.8 | C9—C12—H12A | 109.2 |
C4—C3—H3 | 119.8 | C13—C12—H12A | 109.2 |
C5—C4—C3 | 119.47 (18) | C9—C12—H12B | 109.2 |
C5—C4—N1 | 120.90 (18) | C13—C12—H12B | 109.2 |
C3—C4—N1 | 119.59 (18) | H12A—C12—H12B | 107.9 |
C6—C5—C4 | 120.52 (18) | C12—C13—H13A | 109.5 |
C6—C5—H5 | 119.7 | C12—C13—H13B | 109.5 |
C4—C5—H5 | 119.7 | H13A—C13—H13B | 109.5 |
C5—C6—C1 | 119.57 (18) | C12—C13—H13C | 109.5 |
C5—C6—H6 | 120.2 | H13A—C13—H13C | 109.5 |
C1—C6—H6 | 120.2 | H13B—C13—H13C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.88 (2) | 2.64 (2) | 3.298 (2) | 132 (2) |
N1—H1B···N4ii | 0.88 (2) | 2.33 (2) | 3.121 (2) | 149 (2) |
N1—H1B···O1i | 0.88 (2) | 2.52 (2) | 3.098 (2) | 124 (2) |
N2—H2···N1iii | 0.87 (2) | 2.03 (2) | 2.891 (2) | 171 (2) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z+1; (iii) x+1/2, −y+1/2, z−1/2. |
C11H13N5O4S | Z = 2 |
Mr = 311.32 | F(000) = 324 |
Triclinic, P1 | Dx = 1.550 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1566 (3) Å | Cell parameters from 2381 reflections |
b = 8.6577 (4) Å | θ = 2.9–27.5° |
c = 10.5410 (4) Å | µ = 0.27 mm−1 |
α = 97.180 (3)° | T = 120 K |
β = 103.374 (2)° | Block, colourless |
γ = 109.255 (2)° | 0.30 × 0.20 × 0.20 mm |
V = 667.06 (5) Å3 |
Bruker–Nonius KappaCCD diffractometer | 2448 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2122 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.9° |
ϕ & ω scans | h = −9→9 |
Absorption correction: multi-scan SADABS V2007/2 (Sheldrick, 2007) | k = −10→10 |
Tmin = 0.914, Tmax = 0.948 | l = −12→12 |
7268 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)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.157 | w = 1/[σ2(Fo2) + (0.0941P)2 + 0.2249P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2448 reflections | Δρmax = 0.43 e Å−3 |
203 parameters | Δρmin = −0.61 e Å−3 |
3 restraints | Extinction correction: SHELXL, Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.047 (12) |
C11H13N5O4S | γ = 109.255 (2)° |
Mr = 311.32 | V = 667.06 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1566 (3) Å | Mo Kα radiation |
b = 8.6577 (4) Å | µ = 0.27 mm−1 |
c = 10.5410 (4) Å | T = 120 K |
α = 97.180 (3)° | 0.30 × 0.20 × 0.20 mm |
β = 103.374 (2)° |
Bruker–Nonius KappaCCD diffractometer | 2448 independent reflections |
Absorption correction: multi-scan SADABS V2007/2 (Sheldrick, 2007) | 2122 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 0.948 | Rint = 0.073 |
7268 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 3 restraints |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.43 e Å−3 |
2448 reflections | Δρmin = −0.61 e Å−3 |
203 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.25571 (7) | 0.78437 (7) | 0.40711 (5) | 0.0156 (3) | |
O1 | 0.3490 (2) | 0.8722 (2) | 0.54379 (16) | 0.0208 (4) | |
O2 | 0.3282 (2) | 0.6771 (2) | 0.34282 (17) | 0.0212 (4) | |
O3 | −0.1273 (2) | 0.6577 (2) | −0.08832 (16) | 0.0203 (4) | |
O4 | 0.3625 (2) | 1.1247 (2) | −0.04302 (17) | 0.0219 (4) | |
N1 | −0.5182 (3) | 0.4070 (3) | 0.3306 (2) | 0.0213 (5) | |
H1A | −0.569 (4) | 0.311 (3) | 0.273 (3) | 0.033 (8)* | |
H1B | −0.585 (3) | 0.463 (3) | 0.346 (3) | 0.025 (7)* | |
N2 | 0.2664 (3) | 0.9441 (2) | 0.32898 (19) | 0.0171 (5) | |
H2 | 0.367 (3) | 1.027 (3) | 0.370 (3) | 0.029 (8)* | |
N3 | 0.0650 (2) | 0.7873 (2) | 0.12208 (19) | 0.0162 (5) | |
N4 | 0.1115 (3) | 0.8860 (2) | −0.07328 (19) | 0.0184 (5) | |
N5 | 0.3155 (3) | 1.0390 (2) | 0.1415 (2) | 0.0183 (5) | |
C1 | 0.0286 (3) | 0.6738 (3) | 0.3880 (2) | 0.0152 (5) | |
C2 | −0.0537 (3) | 0.5101 (3) | 0.3105 (2) | 0.0174 (5) | |
H2A | 0.0155 | 0.4599 | 0.2714 | 0.021* | |
C3 | −0.2350 (3) | 0.4221 (3) | 0.2911 (2) | 0.0169 (5) | |
H3 | −0.2911 | 0.3114 | 0.2376 | 0.020* | |
C4 | −0.3383 (3) | 0.4948 (3) | 0.3500 (2) | 0.0165 (5) | |
C5 | −0.2505 (3) | 0.6584 (3) | 0.4324 (2) | 0.0180 (5) | |
H5 | −0.3176 | 0.7081 | 0.4747 | 0.022* | |
C6 | −0.0687 (3) | 0.7456 (3) | 0.4515 (2) | 0.0182 (5) | |
H6 | −0.0100 | 0.8546 | 0.5078 | 0.022* | |
C7 | 0.2143 (3) | 0.9217 (3) | 0.1915 (2) | 0.0153 (5) | |
C8 | 0.0221 (3) | 0.7810 (3) | −0.0082 (2) | 0.0154 (5) | |
C9 | 0.2577 (3) | 1.0113 (3) | 0.0085 (2) | 0.0158 (5) | |
C10 | −0.2354 (3) | 0.5375 (3) | −0.0266 (2) | 0.0230 (6) | |
H10A | −0.3402 | 0.4536 | −0.0959 | 0.034* | |
H10B | −0.2776 | 0.5960 | 0.0369 | 0.034* | |
H10C | −0.1611 | 0.4818 | 0.0207 | 0.034* | |
C11 | 0.3104 (4) | 1.1010 (3) | −0.1879 (2) | 0.0251 (6) | |
H11A | 0.3966 | 1.1917 | −0.2135 | 0.038* | |
H11B | 0.1882 | 1.1023 | −0.2197 | 0.038* | |
H11C | 0.3115 | 0.9930 | −0.2279 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0124 (4) | 0.0172 (4) | 0.0139 (4) | 0.0029 (3) | 0.0021 (2) | 0.0030 (2) |
O1 | 0.0173 (9) | 0.0247 (9) | 0.0122 (9) | 0.0004 (7) | −0.0003 (7) | 0.0040 (7) |
O2 | 0.0164 (9) | 0.0238 (9) | 0.0244 (10) | 0.0076 (7) | 0.0076 (7) | 0.0052 (7) |
O3 | 0.0183 (9) | 0.0181 (9) | 0.0154 (9) | −0.0007 (7) | 0.0010 (7) | −0.0003 (7) |
O4 | 0.0234 (9) | 0.0215 (9) | 0.0165 (9) | 0.0024 (7) | 0.0063 (7) | 0.0051 (7) |
N1 | 0.0147 (10) | 0.0192 (11) | 0.0265 (12) | 0.0034 (9) | 0.0053 (9) | 0.0020 (9) |
N2 | 0.0155 (10) | 0.0150 (10) | 0.0130 (10) | −0.0015 (8) | 0.0009 (8) | 0.0013 (8) |
N3 | 0.0136 (10) | 0.0140 (10) | 0.0168 (11) | 0.0021 (8) | 0.0020 (8) | 0.0013 (8) |
N4 | 0.0170 (10) | 0.0185 (11) | 0.0165 (11) | 0.0047 (8) | 0.0032 (8) | 0.0009 (8) |
N5 | 0.0172 (10) | 0.0181 (10) | 0.0176 (11) | 0.0049 (8) | 0.0048 (8) | 0.0023 (8) |
C1 | 0.0125 (11) | 0.0151 (11) | 0.0134 (11) | 0.0013 (9) | 0.0016 (8) | 0.0019 (9) |
C2 | 0.0180 (12) | 0.0175 (12) | 0.0161 (12) | 0.0067 (10) | 0.0058 (9) | 0.0002 (9) |
C3 | 0.0197 (12) | 0.0137 (11) | 0.0148 (12) | 0.0036 (9) | 0.0050 (9) | 0.0021 (9) |
C4 | 0.0149 (11) | 0.0174 (12) | 0.0154 (12) | 0.0042 (10) | 0.0025 (9) | 0.0057 (9) |
C5 | 0.0161 (12) | 0.0199 (12) | 0.0197 (13) | 0.0078 (10) | 0.0068 (9) | 0.0040 (10) |
C6 | 0.0214 (12) | 0.0142 (11) | 0.0164 (12) | 0.0057 (10) | 0.0037 (9) | 0.0004 (9) |
C7 | 0.0135 (11) | 0.0152 (11) | 0.0164 (12) | 0.0061 (9) | 0.0030 (9) | 0.0018 (9) |
C8 | 0.0155 (11) | 0.0150 (12) | 0.0155 (12) | 0.0076 (9) | 0.0027 (9) | 0.0009 (9) |
C9 | 0.0164 (12) | 0.0164 (11) | 0.0157 (12) | 0.0076 (9) | 0.0052 (9) | 0.0022 (9) |
C10 | 0.0215 (13) | 0.0181 (12) | 0.0198 (13) | −0.0008 (10) | 0.0030 (10) | −0.0010 (10) |
C11 | 0.0273 (14) | 0.0314 (14) | 0.0151 (13) | 0.0066 (11) | 0.0080 (10) | 0.0086 (11) |
S1—O2 | 1.4359 (17) | N5—C9 | 1.335 (3) |
S1—O1 | 1.4388 (17) | C1—C6 | 1.390 (3) |
S1—N2 | 1.684 (2) | C1—C2 | 1.399 (3) |
S1—C1 | 1.731 (2) | C2—C3 | 1.373 (3) |
O3—C8 | 1.334 (3) | C2—H2A | 0.9500 |
O3—C10 | 1.453 (3) | C3—C4 | 1.409 (3) |
O4—C9 | 1.335 (3) | C3—H3 | 0.9500 |
O4—C11 | 1.455 (3) | C4—C5 | 1.417 (3) |
N1—C4 | 1.363 (3) | C5—C6 | 1.377 (3) |
N1—H1A | 0.876 (18) | C5—H5 | 0.9500 |
N1—H1B | 0.869 (17) | C6—H6 | 0.9500 |
N2—C7 | 1.382 (3) | C10—H10A | 0.9800 |
N2—H2 | 0.861 (18) | C10—H10B | 0.9800 |
N3—C8 | 1.326 (3) | C10—H10C | 0.9800 |
N3—C7 | 1.346 (3) | C11—H11A | 0.9800 |
N4—C8 | 1.334 (3) | C11—H11B | 0.9800 |
N4—C9 | 1.334 (3) | C11—H11C | 0.9800 |
N5—C7 | 1.331 (3) | ||
O2—S1—O1 | 118.76 (10) | C3—C4—C5 | 118.8 (2) |
O2—S1—N2 | 108.57 (10) | C6—C5—C4 | 120.4 (2) |
O1—S1—N2 | 101.73 (10) | C6—C5—H5 | 119.8 |
O2—S1—C1 | 109.19 (11) | C4—C5—H5 | 119.8 |
O1—S1—C1 | 110.64 (11) | C5—C6—C1 | 119.8 (2) |
N2—S1—C1 | 107.14 (11) | C5—C6—H6 | 120.1 |
C8—O3—C10 | 117.52 (18) | C1—C6—H6 | 120.1 |
C9—O4—C11 | 116.97 (19) | N5—C7—N3 | 126.7 (2) |
C4—N1—H1A | 118 (2) | N5—C7—N2 | 116.0 (2) |
C4—N1—H1B | 117.8 (19) | N3—C7—N2 | 117.3 (2) |
H1A—N1—H1B | 119 (3) | N3—C8—O3 | 118.9 (2) |
C7—N2—S1 | 122.97 (16) | N3—C8—N4 | 127.8 (2) |
C7—N2—H2 | 115 (2) | O3—C8—N4 | 113.3 (2) |
S1—N2—H2 | 108 (2) | N4—C9—N5 | 127.0 (2) |
C8—N3—C7 | 112.6 (2) | N4—C9—O4 | 119.3 (2) |
C8—N4—C9 | 112.7 (2) | N5—C9—O4 | 113.7 (2) |
C7—N5—C9 | 113.2 (2) | O3—C10—H10A | 109.5 |
C6—C1—C2 | 120.7 (2) | O3—C10—H10B | 109.5 |
C6—C1—S1 | 120.33 (18) | H10A—C10—H10B | 109.5 |
C2—C1—S1 | 118.98 (18) | O3—C10—H10C | 109.5 |
C3—C2—C1 | 119.8 (2) | H10A—C10—H10C | 109.5 |
C3—C2—H2A | 120.1 | H10B—C10—H10C | 109.5 |
C1—C2—H2A | 120.1 | O4—C11—H11A | 109.5 |
C2—C3—C4 | 120.5 (2) | O4—C11—H11B | 109.5 |
C2—C3—H3 | 119.8 | H11A—C11—H11B | 109.5 |
C4—C3—H3 | 119.8 | O4—C11—H11C | 109.5 |
N1—C4—C3 | 120.3 (2) | H11A—C11—H11C | 109.5 |
N1—C4—C5 | 120.9 (2) | H11B—C11—H11C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N5i | 0.88 (2) | 2.34 (2) | 3.206 (3) | 172 (3) |
N1—H1B···O2ii | 0.87 (2) | 2.19 (2) | 2.998 (3) | 154 (3) |
N2—H2···O1iii | 0.86 (2) | 2.11 (2) | 2.899 (2) | 152 (3) |
Symmetry codes: (i) x−1, y−1, z; (ii) x−1, y, z; (iii) −x+1, −y+2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H17N5O2S | C11H13N5O4S |
Mr | 307.38 | 311.32 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 9.3257 (2), 16.7918 (4), 9.8600 (2) | 8.1566 (3), 8.6577 (4), 10.5410 (4) |
α, β, γ (°) | 90, 110.693 (1), 90 | 97.180 (3), 103.374 (2), 109.255 (2) |
V (Å3) | 1444.42 (6) | 667.06 (5) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.27 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 | 0.30 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) | Multi-scan SADABS V2007/2 (Sheldrick, 2007) |
Tmin, Tmax | 0.932, 0.954 | 0.914, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17818, 2805, 2342 | 7268, 2448, 2122 |
Rint | 0.055 | 0.073 |
(sin θ/λ)max (Å−1) | 0.617 | 0.606 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.114, 1.01 | 0.052, 0.157, 1.09 |
No. of reflections | 2805 | 2448 |
No. of parameters | 204 | 203 |
No. of restraints | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.84, −0.57 | 0.43, −0.61 |
Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Bruker, 1998) and Mercury (Bruno et al., 2002), publCIF (Westrip, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.884 (17) | 2.64 (2) | 3.298 (2) | 132 (2) |
N1—H1B···N4ii | 0.883 (16) | 2.329 (19) | 3.121 (2) | 149 (2) |
N1—H1B···O1i | 0.883 (16) | 2.52 (2) | 3.098 (2) | 124.0 (19) |
N2—H2···N1iii | 0.869 (17) | 2.029 (18) | 2.891 (2) | 171 (2) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z+1; (iii) x+1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N5i | 0.876 (18) | 2.336 (19) | 3.206 (3) | 172 (3) |
N1—H1B···O2ii | 0.869 (17) | 2.19 (2) | 2.998 (3) | 154 (3) |
N2—H2···O1iii | 0.861 (18) | 2.11 (2) | 2.899 (2) | 152 (3) |
Symmetry codes: (i) x−1, y−1, z; (ii) x−1, y, z; (iii) −x+1, −y+2, −z+1. |
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Structurally related compounds may form isomorphous crystal structures. For example a series of 22 isostructural 4,4'-disubstituted benzenesulfonamidobenzenes have been identitified (Gelbrich et al., 2007). Sulfasymazine, (I), and sulfatriazine, (II), are closely related historical drugs of the sulfonamide family with antibacterial properties (Frisk & Hultman, 1965, Nabert-Bock, 1958). These compounds differ only in the nature of R, but their crystal structures display very different packing arrangements despite the fact that the O atoms in the methoxy substituents of (II) do not take part in hydrogen bonding.
As can be seen in Figs. 1 and 2, the molecules of (I) and (II) adopt slightly different conformations. The S1—N2—C7—N3 torsion angle is 8.4 (3)° in sulfasymazine and 39.7 (3)° in sulfatriazine, and the methoxy and ethyl substitutents adopt different conformations relative to the triazine ring. It is well known that the low-energy conformations differ for ethyl and methoxy substituents on phenyl rings, with ethyl substituents preferentially lying out of plane (with a minimum energy when the Car—Car—CEt—CEt torsion angle is 90°), and methoxy substituents prefentially lying in-plane (Cinacchi & Prampolini, 2003). The N4—C8—C10—C11 and N4—C9—C12—C13 torsion angles in sulfasymazine are 128.1 (2) and 93.2 (2)°, respectively, whereas the equivalent torsion angles in sulfatriazine, N4—C8—O3—C10 and N4—C9—O4—C11, are 179.4 (2) and 1.2 (3)°, respectively; thus the methoxy and ethyl groups adopt approximately the low-energy conformation expected for each compound.
Both (I) and (II) have three potential hydrogen-bond donors, all of which are employed in both structures. In sulfasymazine, one of the amine H atoms bifurcates to form hydrogen bonds to both an N atom in the triazine ring and an O atom of the sulfone. The crystal structure of (I) displays an infinite three-dimensional hydrogen-bonded network, where each molecule is connected to five others. The two N—H···N interactions result in layers which contain dimers with a central R22(24) ring, and four such rings are linked by a larger ring, the graph-set notation (Bernstein et al., 1995) of which is R66(32) (Fig. 3a). Each layer is connected to those above and below it by NH2···O2S hydrogen bonding (Fig. 3b) with rather long H···O distances (see Table 1). This type of hydrogen bonding, where each of the H atoms in the NH2 group is hydrogen bonded to an O atom in the same sulfone group, is not novel but is unusual. In the Cambridge Structural Database (Version 5.29 of 2007; Allen, 2002), this feature is found in only one other N1-substituted sulfonamide, a 1:1 cocrystal of sulfadimidine with aspirin (Caira, 1992). A simplified hydrogen-bonded diagram of the overall three-dimensional hydrogen-bonded network is shown in Fig. 3(c), where each molecule has been collapsed to a point and hydrogen bonds are represented by arrows (which point to the hydrogen-bond acceptor). The rings are off-set such that atom N3 lies directly above the centre of the other ring, and atoms C9 and C7 eclipse each other. The shortest hydrogen bond in the structure is that between the amide H atom and amine N atom, at 2.029 (18) Å.
Sulfatriazine, on the other hand, exhibits a two-dimensional hydrogen-bonding pattern, which is composed of two layers of molecules. Each layer (Fig. 4a) consists of R44(26) rings that result from two interactions, both involving the NH2 group as a hydrogen-bond donor; HNH···O═S and HNH···Ntriazine. The sulfonamide units of each layer are linked by dimeric SNH···O═S contacts to those of the other layer, resulting in R22(8) rings and additionally in R44(24) rings (Fig. 4b). A visualization of the overall double-layer topology where each molecule of (II) is hydrogen bonded to five other molecules is given in Fig. 4(c). The triazine rings, which are aligned parallel to each other on the outer faces of the double layer, slot together with the triazine rings of the adjacent double layer. The triazine rings do not, however, show any π stacking; the rings are off-set by more than the width of a triazine ring. The sulfonamide dimer formed by the mutual donation of the amide H atom to the sulfonamide O atom of the other molecule is also seen in at least four other crystal structures of sulfonamides (Rambaud et al., 1985; Giuseppetti et al., 1977; Patel et al., 1983; Liu et al., 1994), plus a series of isomorphous crystal structures of 22 related sulfonamides (Gelbrich et al., 2007).
Polymorphism in sulfonamides is a well known phenomenon, and one reason for this is the number of possible combinations between potential hydrogen-bond donor and acceptor groups. Thermomicroscopic analysis of pure sulfasymazine showed the substance to melt without change at 461–463 K. Sulfatriazine showed decomposition upon melting at 442 K, also without previous transformation. However, for sulfatriazine, two crystal morphologies with different melting points have been observed: needles and rods (405–408 K), and rhombuses and prisms (431–439 K) (Kuhnert-Branstätter et al., 1970), in addition to the monohydrate which is present in the commercial product. From hot stage microscopy experiments we have confirmed the existence of needles that melt at 412 K, but we did not obtain single crystals of this form. Thus the possibility of isostructural polymorphs of (I) and (II) cannot be discounted, although this would probably require the energy of a higher conformation of either the methoxy or the ethyl groups being overcome.