Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044054/sj2353sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044054/sj2353Isup2.hkl |
CCDC reference: 663767
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.004 Å
- R factor = 0.043
- wR factor = 0.136
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.55 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
In a 50 mL flask provided with magnetic stirrer were placed 4-hydrazinocarbonyl-2-methyl-2H-pyrazole-3-sulfonic acid amide (1.10 g, 5 mmol), 2-chloro-benzaldehyde (0.84 g, 6 mmol) and anhydrous ethanol (10 mL). The reaction mixture was heated to reflux for 3 h, allowed to cool to room temperature. The white solid was filtered and recrystallized from a dimethylformamide-ethanol mixture to give the title compound (yield 94%). Colourless crystals of (I) suitable for X-ray structure analysis were grown from the mixture of tetrahydrofuran and petroleum ether (v/v, 1:6).
The H atom bound to N3 was found in a difference Fourier map and its coordinates were refined with Uiso(H) = 1.2Ueq(N). All other H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms
Pyrazole derivatives are important compounds with versatile industrial and medical applications (Liang & He, 2005; Wang et al., 2004). We report here the molecular structure of (I). In the title compound, all bond lengths and angles are within normal ranges (Allen et al., 1987) and the molecules are stabilized by intra and intermolecular hydrogen bonds (Table 1). Short intermolecular distances between the centroids, Cg1, of two adjacent pyrazole ring suggest π— π stacking interactions [Cg1···Cg1iii = 3.4664 (13) Å, iii = 2 - x, 2 - y, -z].
For biological and pharmaceutical activity of pyrazoles, see: Liang & He (2005); Wang et al. (2004). For the preparation of derivatives of pyrazoles, see: Zou et al. (2005). For reference structural data, see: Allen et al. (1987).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
Fig. 1. The structure of (I). showing 50% probability displacement ellipsoids and the atom-numbering scheme. | |
Fig. 2. The crystal packing of (I) with hydrogen bonds drawn as dashed lines. |
C12H12ClN5O3S | Z = 2 |
Mr = 341.78 | F(000) = 352 |
Triclinic, P1 | Dx = 1.545 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4272 (6) Å | Cell parameters from 2721 reflections |
b = 9.0905 (7) Å | θ = 2.2–28.3° |
c = 10.4381 (7) Å | µ = 0.42 mm−1 |
α = 89.525 (1)° | T = 292 K |
β = 66.852 (1)° | Block, colorless |
γ = 87.722 (1)° | 0.10 × 0.10 × 0.08 mm |
V = 734.66 (9) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 2421 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
φ and ω scans | h = −10→9 |
4684 measured reflections | k = −11→11 |
2843 independent reflections | l = −12→8 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0737P)2 + 0.1888P] where P = (Fo2 + 2Fc2)/3 |
2843 reflections | (Δ/σ)max = 0.011 |
209 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C12H12ClN5O3S | γ = 87.722 (1)° |
Mr = 341.78 | V = 734.66 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4272 (6) Å | Mo Kα radiation |
b = 9.0905 (7) Å | µ = 0.42 mm−1 |
c = 10.4381 (7) Å | T = 292 K |
α = 89.525 (1)° | 0.10 × 0.10 × 0.08 mm |
β = 66.852 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 2421 reflections with I > 2σ(I) |
4684 measured reflections | Rint = 0.051 |
2843 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.32 e Å−3 |
2843 reflections | Δρmin = −0.29 e Å−3 |
209 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 | ||
C1 | 1.4090 (3) | 0.9541 (3) | −0.1318 (3) | 0.0513 (6) | |
H1A | 1.4523 | 1.0053 | −0.2188 | 0.077* | |
H1B | 1.4896 | 0.8758 | −0.1332 | 0.077* | |
H1C | 1.3944 | 1.0214 | −0.0572 | 0.077* | |
C2 | 1.1438 (3) | 0.8013 (2) | −0.0105 (2) | 0.0305 (4) | |
C3 | 0.9973 (3) | 0.7766 (2) | −0.0376 (2) | 0.0324 (5) | |
C4 | 1.0236 (3) | 0.8610 (3) | −0.1570 (2) | 0.0403 (5) | |
H4 | 0.9460 | 0.8673 | −0.2004 | 0.048* | |
C5 | 0.8395 (3) | 0.6899 (2) | 0.0232 (2) | 0.0356 (5) | |
C6 | 0.6552 (3) | 0.4574 (3) | 0.3040 (2) | 0.0414 (5) | |
H6 | 0.7386 | 0.4629 | 0.3411 | 0.050* | |
C7 | 0.5040 (3) | 0.3680 (3) | 0.3721 (2) | 0.0425 (5) | |
C8 | 0.4960 (4) | 0.2636 (3) | 0.4734 (3) | 0.0520 (7) | |
C9 | 0.3514 (5) | 0.1801 (3) | 0.5337 (3) | 0.0724 (10) | |
H9 | 0.3483 | 0.1104 | 0.6003 | 0.087* | |
C10 | 0.2140 (5) | 0.1986 (4) | 0.4970 (4) | 0.0782 (11) | |
H10 | 0.1185 | 0.1408 | 0.5373 | 0.094* | |
C11 | 0.2164 (4) | 0.3036 (4) | 0.3995 (3) | 0.0703 (9) | |
H11 | 0.1214 | 0.3182 | 0.3760 | 0.084* | |
C12 | 0.3606 (3) | 0.3868 (3) | 0.3372 (3) | 0.0521 (6) | |
H12 | 0.3620 | 0.4565 | 0.2710 | 0.062* | |
Cl1 | 0.66414 (13) | 0.23836 (9) | 0.52817 (8) | 0.0729 (3) | |
N1 | 1.2424 (2) | 0.8929 (2) | −0.11050 (19) | 0.0377 (4) | |
N2 | 1.1702 (3) | 0.9306 (2) | −0.2012 (2) | 0.0451 (5) | |
N3 | 0.8156 (3) | 0.6116 (2) | 0.1381 (2) | 0.0413 (5) | |
H3A | 0.894 (4) | 0.615 (3) | 0.174 (3) | 0.050* | |
N4 | 0.6715 (2) | 0.5276 (2) | 0.1936 (2) | 0.0393 (4) | |
N5 | 1.3822 (3) | 0.6394 (3) | 0.0437 (3) | 0.0551 (6) | |
H5A | 1.371 (4) | 0.572 (4) | 0.004 (3) | 0.066* | |
H5B | 1.475 (4) | 0.675 (4) | 0.028 (3) | 0.066* | |
O1 | 1.0830 (2) | 0.6507 (2) | 0.2113 (2) | 0.0637 (6) | |
O2 | 1.2641 (2) | 0.8658 (2) | 0.17484 (19) | 0.0550 (5) | |
O3 | 0.7372 (2) | 0.6923 (2) | −0.03414 (19) | 0.0569 (5) | |
S1 | 1.21556 (7) | 0.74039 (6) | 0.12003 (6) | 0.0396 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0446 (14) | 0.0509 (14) | 0.0628 (16) | −0.0168 (11) | −0.0246 (12) | 0.0050 (12) |
C2 | 0.0267 (10) | 0.0327 (10) | 0.0325 (10) | 0.0012 (8) | −0.0121 (8) | 0.0012 (8) |
C3 | 0.0299 (10) | 0.0334 (11) | 0.0344 (11) | 0.0002 (8) | −0.0134 (9) | 0.0011 (9) |
C4 | 0.0391 (12) | 0.0452 (13) | 0.0420 (12) | −0.0045 (9) | −0.0216 (10) | 0.0079 (10) |
C5 | 0.0274 (10) | 0.0409 (12) | 0.0407 (12) | −0.0031 (9) | −0.0156 (9) | 0.0033 (9) |
C6 | 0.0435 (13) | 0.0424 (12) | 0.0401 (12) | −0.0063 (10) | −0.0180 (10) | 0.0042 (10) |
C7 | 0.0501 (14) | 0.0370 (12) | 0.0351 (12) | −0.0075 (10) | −0.0106 (10) | 0.0022 (9) |
C8 | 0.0724 (18) | 0.0412 (13) | 0.0387 (13) | −0.0043 (12) | −0.0176 (12) | 0.0018 (11) |
C9 | 0.104 (3) | 0.0474 (16) | 0.0473 (16) | −0.0239 (17) | −0.0087 (17) | 0.0134 (13) |
C10 | 0.076 (2) | 0.069 (2) | 0.068 (2) | −0.0373 (18) | −0.0023 (18) | 0.0075 (16) |
C11 | 0.0557 (17) | 0.077 (2) | 0.070 (2) | −0.0231 (15) | −0.0139 (15) | 0.0018 (16) |
C12 | 0.0501 (15) | 0.0539 (15) | 0.0490 (15) | −0.0129 (12) | −0.0151 (12) | 0.0061 (12) |
Cl1 | 0.1105 (7) | 0.0599 (5) | 0.0602 (5) | 0.0084 (4) | −0.0475 (5) | 0.0067 (3) |
N1 | 0.0360 (10) | 0.0388 (10) | 0.0397 (10) | −0.0068 (8) | −0.0161 (8) | 0.0026 (8) |
N2 | 0.0490 (11) | 0.0476 (11) | 0.0429 (11) | −0.0113 (9) | −0.0219 (9) | 0.0111 (9) |
N3 | 0.0345 (10) | 0.0506 (11) | 0.0438 (11) | −0.0116 (8) | −0.0200 (9) | 0.0111 (9) |
N4 | 0.0362 (10) | 0.0415 (10) | 0.0409 (10) | −0.0093 (8) | −0.0153 (8) | 0.0044 (8) |
N5 | 0.0396 (12) | 0.0471 (13) | 0.0931 (19) | 0.0038 (10) | −0.0418 (13) | −0.0099 (12) |
O1 | 0.0450 (10) | 0.0969 (15) | 0.0610 (12) | −0.0200 (10) | −0.0326 (9) | 0.0362 (11) |
O2 | 0.0611 (11) | 0.0611 (11) | 0.0556 (11) | 0.0016 (9) | −0.0368 (9) | −0.0085 (9) |
O3 | 0.0403 (9) | 0.0845 (14) | 0.0577 (11) | −0.0222 (9) | −0.0305 (9) | 0.0270 (10) |
S1 | 0.0339 (3) | 0.0472 (4) | 0.0441 (4) | −0.0034 (2) | −0.0224 (3) | 0.0067 (3) |
C1—N1 | 1.465 (3) | C8—C9 | 1.386 (4) |
C1—H1A | 0.9600 | C8—Cl1 | 1.731 (3) |
C1—H1B | 0.9600 | C9—C10 | 1.360 (5) |
C1—H1C | 0.9600 | C9—H9 | 0.9300 |
C2—N1 | 1.353 (3) | C10—C11 | 1.384 (5) |
C2—C3 | 1.397 (3) | C10—H10 | 0.9300 |
C2—S1 | 1.772 (2) | C11—C12 | 1.384 (4) |
C3—C4 | 1.404 (3) | C11—H11 | 0.9300 |
C3—C5 | 1.484 (3) | C12—H12 | 0.9300 |
C4—N2 | 1.323 (3) | N1—N2 | 1.347 (3) |
C4—H4 | 0.9300 | N3—N4 | 1.381 (3) |
C5—O3 | 1.227 (3) | N3—H3A | 0.87 (3) |
C5—N3 | 1.340 (3) | N5—S1 | 1.575 (2) |
C6—N4 | 1.274 (3) | N5—H5A | 0.77 (3) |
C6—C7 | 1.466 (3) | N5—H5B | 0.82 (3) |
C6—H6 | 0.9300 | O1—S1 | 1.4292 (19) |
C7—C12 | 1.397 (4) | O2—S1 | 1.4235 (18) |
C7—C8 | 1.398 (3) | ||
N1—C1—H1A | 109.5 | C10—C9—H9 | 119.5 |
N1—C1—H1B | 109.5 | C8—C9—H9 | 119.5 |
H1A—C1—H1B | 109.5 | C9—C10—C11 | 119.9 (3) |
N1—C1—H1C | 109.5 | C9—C10—H10 | 120.0 |
H1A—C1—H1C | 109.5 | C11—C10—H10 | 120.0 |
H1B—C1—H1C | 109.5 | C12—C11—C10 | 119.8 (3) |
N1—C2—C3 | 106.98 (18) | C12—C11—H11 | 120.1 |
N1—C2—S1 | 119.13 (15) | C10—C11—H11 | 120.1 |
C3—C2—S1 | 133.89 (16) | C11—C12—C7 | 121.1 (3) |
C2—C3—C4 | 103.20 (18) | C11—C12—H12 | 119.5 |
C2—C3—C5 | 137.5 (2) | C7—C12—H12 | 119.5 |
C4—C3—C5 | 119.3 (2) | N2—N1—C2 | 112.22 (17) |
N2—C4—C3 | 112.9 (2) | N2—N1—C1 | 117.85 (19) |
N2—C4—H4 | 123.6 | C2—N1—C1 | 129.9 (2) |
C3—C4—H4 | 123.6 | C4—N2—N1 | 104.69 (18) |
O3—C5—N3 | 122.8 (2) | C5—N3—N4 | 118.87 (19) |
O3—C5—C3 | 118.8 (2) | C5—N3—H3A | 117.9 (18) |
N3—C5—C3 | 118.38 (19) | N4—N3—H3A | 123.2 (18) |
N4—C6—C7 | 119.6 (2) | C6—N4—N3 | 115.7 (2) |
N4—C6—H6 | 120.2 | S1—N5—H5A | 116 (2) |
C7—C6—H6 | 120.2 | S1—N5—H5B | 117 (2) |
C12—C7—C8 | 117.7 (2) | H5A—N5—H5B | 124 (3) |
C12—C7—C6 | 119.9 (2) | O2—S1—O1 | 119.36 (12) |
C8—C7—C6 | 122.4 (3) | O2—S1—N5 | 108.30 (12) |
C9—C8—C7 | 120.5 (3) | O1—S1—N5 | 108.40 (14) |
C9—C8—Cl1 | 118.7 (2) | O2—S1—C2 | 107.99 (10) |
C7—C8—Cl1 | 120.9 (2) | O1—S1—C2 | 105.91 (10) |
C10—C9—C8 | 120.9 (3) | N5—S1—C2 | 106.13 (12) |
N1—C2—C3—C4 | −0.4 (2) | C10—C11—C12—C7 | −0.7 (5) |
S1—C2—C3—C4 | 179.24 (18) | C8—C7—C12—C11 | −0.9 (4) |
N1—C2—C3—C5 | 178.8 (2) | C6—C7—C12—C11 | 179.8 (2) |
S1—C2—C3—C5 | −1.6 (4) | C3—C2—N1—N2 | 0.3 (2) |
C2—C3—C4—N2 | 0.3 (3) | S1—C2—N1—N2 | −179.38 (15) |
C5—C3—C4—N2 | −178.99 (19) | C3—C2—N1—C1 | 180.0 (2) |
C2—C3—C5—O3 | −177.8 (2) | S1—C2—N1—C1 | 0.3 (3) |
C4—C3—C5—O3 | 1.2 (3) | C3—C4—N2—N1 | −0.2 (3) |
C2—C3—C5—N3 | 1.8 (4) | C2—N1—N2—C4 | −0.1 (3) |
C4—C3—C5—N3 | −179.2 (2) | C1—N1—N2—C4 | −179.8 (2) |
N4—C6—C7—C12 | −15.3 (3) | O3—C5—N3—N4 | 1.2 (4) |
N4—C6—C7—C8 | 165.4 (2) | C3—C5—N3—N4 | −178.40 (19) |
C12—C7—C8—C9 | 1.5 (4) | C7—C6—N4—N3 | 178.6 (2) |
C6—C7—C8—C9 | −179.2 (2) | C5—N3—N4—C6 | −179.1 (2) |
C12—C7—C8—Cl1 | −177.30 (19) | N1—C2—S1—O2 | 49.18 (19) |
C6—C7—C8—Cl1 | 2.0 (3) | C3—C2—S1—O2 | −130.4 (2) |
C7—C8—C9—C10 | −0.6 (4) | N1—C2—S1—O1 | 178.13 (18) |
Cl1—C8—C9—C10 | 178.2 (3) | C3—C2—S1—O1 | −1.4 (3) |
C8—C9—C10—C11 | −1.0 (5) | N1—C2—S1—N5 | −66.77 (19) |
C9—C10—C11—C12 | 1.6 (5) | C3—C2—S1—N5 | 113.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.87 (3) | 1.83 (3) | 2.685 (3) | 166 (3) |
N5—H5B···O3i | 0.82 (3) | 2.05 (3) | 2.835 (3) | 160 (3) |
N5—H5A···N4ii | 0.77 (3) | 2.42 (3) | 3.105 (3) | 149 (3) |
N5—H5A···O3ii | 0.77 (3) | 2.58 (3) | 3.231 (3) | 144 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H12ClN5O3S |
Mr | 341.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 292 |
a, b, c (Å) | 8.4272 (6), 9.0905 (7), 10.4381 (7) |
α, β, γ (°) | 89.525 (1), 66.852 (1), 87.722 (1) |
V (Å3) | 734.66 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.10 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4684, 2843, 2421 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.136, 1.11 |
No. of reflections | 2843 |
No. of parameters | 209 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.29 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.87 (3) | 1.83 (3) | 2.685 (3) | 166 (3) |
N5—H5B···O3i | 0.82 (3) | 2.05 (3) | 2.835 (3) | 160 (3) |
N5—H5A···N4ii | 0.77 (3) | 2.42 (3) | 3.105 (3) | 149 (3) |
N5—H5A···O3ii | 0.77 (3) | 2.58 (3) | 3.231 (3) | 144 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z. |
Pyrazole derivatives are important compounds with versatile industrial and medical applications (Liang & He, 2005; Wang et al., 2004). We report here the molecular structure of (I). In the title compound, all bond lengths and angles are within normal ranges (Allen et al., 1987) and the molecules are stabilized by intra and intermolecular hydrogen bonds (Table 1). Short intermolecular distances between the centroids, Cg1, of two adjacent pyrazole ring suggest π— π stacking interactions [Cg1···Cg1iii = 3.4664 (13) Å, iii = 2 - x, 2 - y, -z].