Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033880/sg2181sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033880/sg2181Isup2.hkl |
CCDC reference: 657777
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.111
- Data-to-parameter ratio = 13.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 400 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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
1-(3,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanoxime (0.01 mol) was treated with triethylamine (0.0105 mol) and 40 ml trichloromethane, then the mixture was refluxed for 20 h. The resulting product was filtered off and dried in vacuo. The residue was purified by silica gel flash chromatography using a gradient from a 3:1 mixture of petroleum ether:ethyl acetate as eluent. (72% yield). mp 421–423 K. 1H NMR (CDCl3, 600 MHz) δ: 8.35 (s, 1H), 7.95 (s, 1H), 7.93–7.54 (m, 3H), 6.28 (s, 1H), 5.52 (s, 2H). IR (KBr) cm-1: 3337, 3098, 2945, 2852, 1743, 1508. Anal. Calc. for C12H11Cl2N5O2 (Mr=328.1): C 43.92, H 3.38, N 21.34; Found C 44.25, H 3.19, N 21.78.
All H atoms were placed in calculated positions, with N—H = 0.86 and C—H = 0.93–0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2(1.5 for methyl groups) times Ueq(C,N).
The derivatives of 1H-1,2,4-triazoles have been reported to possess various biological activities (Xu et al., 2002). In a search for new triazole compounds with better biological activity, the title compound, (I), was synthesized. We report here the crystal structure of (I).
Bond lengths and angles of the triazole rings are in agreement with those in previous reports (Çoruh et al., 2003; Li et al., 2005). The N=C bond length [N4=C7 = 1.285 (4) Å] are close to the value reported in the literature (Puviarasan et al., 1999). Atoms Cl1/Cl2/O1/N4/C7/C8/C11 lies in the benzene ring (C1/C2/C3/C4/C5/C6) plane, and the deviations from the least-squares plane through the ring atoms are all smaller than 0.046 (2) Å. The dihedral angle between the plane of benzene and triazole (N1/N2/N3/C9/C10) ring is 89.79 (2)°. Intermolecular hydrogen bonds N—H···N and C—H···O link the molecules into zigzag chains running in the [101] direction. The crystal packing (Fig. 2) is further stabilized by van der Waals forces.
For the crystal structures of related compounds, see: Çoruh et al. (2003); Li et al. (2005); Puviarasan et al. (1999). For details of the biological activities of triazole compounds, see: Xu et al. (2002).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
C12H11Cl2N5O2 | Z = 2 |
Mr = 328.16 | F(000) = 336 |
Triclinic, P1 | Dx = 1.522 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.016 (2) Å | Cell parameters from 1527 reflections |
b = 8.430 (2) Å | θ = 2.9–26.3° |
c = 14.721 (4) Å | µ = 0.47 mm−1 |
α = 101.501 (4)° | T = 294 K |
β = 100.057 (4)° | Block, white |
γ = 93.977 (4)° | 0.30 × 0.20 × 0.18 mm |
V = 716.1 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 2497 independent reflections |
Radiation source: fine-focus sealed tube | 1863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→6 |
Tmin = 0.873, Tmax = 0.921 | k = −10→5 |
3665 measured reflections | l = −17→17 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0587P)2 + 0.1094P] where P = (Fo2 + 2Fc2)/3 |
2497 reflections | (Δ/σ)max = 0.004 |
191 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C12H11Cl2N5O2 | γ = 93.977 (4)° |
Mr = 328.16 | V = 716.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.016 (2) Å | Mo Kα radiation |
b = 8.430 (2) Å | µ = 0.47 mm−1 |
c = 14.721 (4) Å | T = 294 K |
α = 101.501 (4)° | 0.30 × 0.20 × 0.18 mm |
β = 100.057 (4)° |
Bruker SMART CCD area-detector diffractometer | 2497 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1863 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 0.921 | Rint = 0.019 |
3665 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
2497 reflections | Δρmin = −0.23 e Å−3 |
191 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 | ||
Cl1 | 1.29314 (11) | −0.19171 (9) | 0.01383 (5) | 0.0566 (2) | |
Cl2 | 0.87282 (14) | −0.36122 (8) | 0.07119 (6) | 0.0773 (3) | |
O1 | 0.5256 (3) | 0.19831 (19) | 0.37808 (11) | 0.0459 (4) | |
O2 | 0.2410 (3) | 0.2024 (2) | 0.45331 (12) | 0.0561 (5) | |
N1 | 0.6867 (3) | 0.4563 (2) | 0.29428 (14) | 0.0410 (5) | |
N2 | 0.5955 (4) | 0.4215 (2) | 0.20095 (15) | 0.0516 (6) | |
N3 | 0.4610 (5) | 0.6417 (3) | 0.27541 (19) | 0.0683 (7) | |
N4 | 0.6348 (3) | 0.0963 (2) | 0.31413 (13) | 0.0396 (5) | |
N5 | 0.3195 (3) | −0.0440 (2) | 0.37867 (14) | 0.0458 (5) | |
H5 | 0.4090 | −0.0934 | 0.3457 | 0.055* | |
C1 | 1.1004 (4) | 0.1653 (3) | 0.19469 (17) | 0.0454 (6) | |
H1 | 1.1468 | 0.2754 | 0.2195 | 0.054* | |
C2 | 1.2155 (4) | 0.0786 (3) | 0.13105 (17) | 0.0467 (6) | |
H2 | 1.3387 | 0.1304 | 0.1141 | 0.056* | |
C3 | 1.1487 (4) | −0.0836 (3) | 0.09290 (16) | 0.0404 (6) | |
C4 | 0.9628 (4) | −0.1587 (3) | 0.11822 (17) | 0.0427 (6) | |
C5 | 0.8491 (4) | −0.0720 (3) | 0.18221 (17) | 0.0417 (6) | |
H5A | 0.7253 | −0.1238 | 0.1988 | 0.050* | |
C6 | 0.9175 (4) | 0.0918 (3) | 0.22214 (15) | 0.0354 (5) | |
C7 | 0.7949 (4) | 0.1808 (3) | 0.29180 (15) | 0.0369 (5) | |
C8 | 0.8565 (4) | 0.3608 (3) | 0.33421 (19) | 0.0482 (6) | |
H8A | 0.8673 | 0.3800 | 0.4021 | 0.058* | |
H8B | 1.0037 | 0.3952 | 0.3220 | 0.058* | |
C9 | 0.6048 (5) | 0.5866 (3) | 0.3364 (2) | 0.0624 (8) | |
H9 | 0.6438 | 0.6330 | 0.4006 | 0.075* | |
C10 | 0.4608 (5) | 0.5358 (3) | 0.1939 (2) | 0.0580 (7) | |
H10 | 0.3718 | 0.5433 | 0.1368 | 0.070* | |
C11 | 0.3497 (4) | 0.1160 (3) | 0.40575 (16) | 0.0417 (6) | |
C12 | 0.1374 (5) | −0.1376 (3) | 0.4038 (2) | 0.0616 (8) | |
H12A | 0.1642 | −0.1271 | 0.4710 | 0.092* | |
H12B | 0.1316 | −0.2501 | 0.3734 | 0.092* | |
H12C | −0.0044 | −0.0975 | 0.3835 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0555 (4) | 0.0657 (5) | 0.0554 (4) | 0.0165 (3) | 0.0292 (3) | 0.0097 (3) |
Cl2 | 0.0810 (6) | 0.0403 (4) | 0.1080 (7) | −0.0039 (3) | 0.0551 (5) | −0.0184 (4) |
O1 | 0.0534 (10) | 0.0356 (9) | 0.0479 (10) | 0.0124 (7) | 0.0190 (8) | −0.0032 (7) |
O2 | 0.0617 (11) | 0.0552 (11) | 0.0528 (10) | 0.0217 (9) | 0.0260 (9) | −0.0035 (8) |
N1 | 0.0464 (12) | 0.0286 (10) | 0.0475 (12) | 0.0063 (8) | 0.0165 (9) | −0.0001 (8) |
N2 | 0.0702 (15) | 0.0400 (12) | 0.0470 (13) | 0.0127 (11) | 0.0180 (11) | 0.0063 (10) |
N3 | 0.0821 (18) | 0.0472 (14) | 0.0761 (17) | 0.0288 (13) | 0.0179 (14) | 0.0045 (13) |
N4 | 0.0458 (12) | 0.0331 (11) | 0.0412 (11) | 0.0143 (9) | 0.0155 (9) | 0.0012 (8) |
N5 | 0.0538 (13) | 0.0392 (12) | 0.0514 (12) | 0.0166 (9) | 0.0264 (10) | 0.0080 (9) |
C1 | 0.0487 (15) | 0.0377 (13) | 0.0485 (14) | 0.0001 (11) | 0.0099 (12) | 0.0075 (11) |
C2 | 0.0441 (14) | 0.0474 (15) | 0.0504 (15) | −0.0014 (11) | 0.0162 (12) | 0.0106 (12) |
C3 | 0.0394 (13) | 0.0477 (15) | 0.0368 (12) | 0.0117 (11) | 0.0118 (10) | 0.0094 (11) |
C4 | 0.0449 (14) | 0.0342 (13) | 0.0490 (14) | 0.0074 (10) | 0.0149 (11) | 0.0029 (11) |
C5 | 0.0392 (13) | 0.0343 (13) | 0.0520 (14) | 0.0039 (10) | 0.0182 (11) | 0.0022 (11) |
C6 | 0.0353 (13) | 0.0332 (12) | 0.0373 (12) | 0.0083 (10) | 0.0048 (10) | 0.0070 (10) |
C7 | 0.0361 (13) | 0.0312 (12) | 0.0401 (13) | 0.0080 (10) | 0.0031 (10) | 0.0023 (10) |
C8 | 0.0440 (15) | 0.0357 (14) | 0.0576 (16) | 0.0055 (11) | 0.0076 (12) | −0.0054 (11) |
C9 | 0.077 (2) | 0.0445 (16) | 0.0593 (17) | 0.0199 (14) | 0.0163 (15) | −0.0105 (13) |
C10 | 0.0747 (19) | 0.0424 (16) | 0.0625 (18) | 0.0124 (14) | 0.0167 (15) | 0.0188 (13) |
C11 | 0.0429 (14) | 0.0489 (15) | 0.0342 (12) | 0.0145 (11) | 0.0086 (11) | 0.0065 (11) |
C12 | 0.0643 (18) | 0.0607 (18) | 0.0730 (19) | 0.0128 (14) | 0.0342 (15) | 0.0255 (15) |
Cl1—C3 | 1.727 (2) | C1—H1 | 0.9300 |
Cl2—C4 | 1.719 (2) | C2—C3 | 1.373 (3) |
O1—C11 | 1.388 (3) | C2—H2 | 0.9300 |
O1—N4 | 1.424 (2) | C3—C4 | 1.390 (3) |
O2—C11 | 1.213 (3) | C4—C5 | 1.382 (3) |
N1—C9 | 1.320 (3) | C5—C6 | 1.391 (3) |
N1—N2 | 1.352 (3) | C5—H5A | 0.9300 |
N1—C8 | 1.460 (3) | C6—C7 | 1.481 (3) |
N2—C10 | 1.309 (3) | C7—C8 | 1.514 (3) |
N3—C9 | 1.312 (4) | C8—H8A | 0.9700 |
N3—C10 | 1.345 (4) | C8—H8B | 0.9700 |
N4—C7 | 1.285 (3) | C9—H9 | 0.9300 |
N5—C11 | 1.318 (3) | C10—H10 | 0.9300 |
N5—C12 | 1.448 (3) | C12—H12A | 0.9600 |
N5—H5 | 0.8600 | C12—H12B | 0.9600 |
C1—C2 | 1.384 (3) | C12—H12C | 0.9600 |
C1—C6 | 1.385 (3) | ||
C11—O1—N4 | 113.69 (16) | C1—C6—C7 | 122.5 (2) |
C9—N1—N2 | 109.4 (2) | C5—C6—C7 | 119.6 (2) |
C9—N1—C8 | 129.2 (2) | N4—C7—C6 | 116.11 (19) |
N2—N1—C8 | 121.33 (18) | N4—C7—C8 | 122.3 (2) |
C10—N2—N1 | 102.3 (2) | C6—C7—C8 | 121.6 (2) |
C9—N3—C10 | 102.4 (2) | N1—C8—C7 | 110.93 (19) |
C7—N4—O1 | 110.06 (18) | N1—C8—H8A | 109.5 |
C11—N5—C12 | 120.7 (2) | C7—C8—H8A | 109.5 |
C11—N5—H5 | 119.6 | N1—C8—H8B | 109.5 |
C12—N5—H5 | 119.6 | C7—C8—H8B | 109.5 |
C2—C1—C6 | 121.4 (2) | H8A—C8—H8B | 108.0 |
C2—C1—H1 | 119.3 | N3—C9—N1 | 110.9 (3) |
C6—C1—H1 | 119.3 | N3—C9—H9 | 124.6 |
C3—C2—C1 | 120.2 (2) | N1—C9—H9 | 124.6 |
C3—C2—H2 | 119.9 | N2—C10—N3 | 114.9 (3) |
C1—C2—H2 | 119.9 | N2—C10—H10 | 122.5 |
C2—C3—C4 | 119.2 (2) | N3—C10—H10 | 122.5 |
C2—C3—Cl1 | 120.16 (19) | O2—C11—N5 | 127.4 (2) |
C4—C3—Cl1 | 120.65 (19) | O2—C11—O1 | 114.8 (2) |
C5—C4—C3 | 120.4 (2) | N5—C11—O1 | 117.73 (19) |
C5—C4—Cl2 | 119.09 (19) | N5—C12—H12A | 109.5 |
C3—C4—Cl2 | 120.48 (18) | N5—C12—H12B | 109.5 |
C4—C5—C6 | 120.8 (2) | H12A—C12—H12B | 109.5 |
C4—C5—H5A | 119.6 | N5—C12—H12C | 109.5 |
C6—C5—H5A | 119.6 | H12A—C12—H12C | 109.5 |
C1—C6—C5 | 117.9 (2) | H12B—C12—H12C | 109.5 |
C9—N1—N2—C10 | −0.4 (3) | C1—C6—C7—N4 | −177.0 (2) |
C8—N1—N2—C10 | −177.9 (2) | C5—C6—C7—N4 | 2.8 (3) |
C11—O1—N4—C7 | 179.96 (19) | C1—C6—C7—C8 | 2.7 (3) |
C6—C1—C2—C3 | 0.5 (4) | C5—C6—C7—C8 | −177.5 (2) |
C1—C2—C3—C4 | 0.7 (4) | C9—N1—C8—C7 | 141.5 (3) |
C1—C2—C3—Cl1 | −179.79 (19) | N2—N1—C8—C7 | −41.6 (3) |
C2—C3—C4—C5 | −1.1 (4) | N4—C7—C8—N1 | −74.3 (3) |
Cl1—C3—C4—C5 | 179.40 (18) | C6—C7—C8—N1 | 106.1 (2) |
C2—C3—C4—Cl2 | 179.50 (19) | C10—N3—C9—N1 | 0.2 (3) |
Cl1—C3—C4—Cl2 | 0.0 (3) | N2—N1—C9—N3 | 0.1 (3) |
C3—C4—C5—C6 | 0.3 (4) | C8—N1—C9—N3 | 177.3 (2) |
Cl2—C4—C5—C6 | 179.70 (19) | N1—N2—C10—N3 | 0.6 (3) |
C2—C1—C6—C5 | −1.3 (4) | C9—N3—C10—N2 | −0.6 (4) |
C2—C1—C6—C7 | 178.5 (2) | C12—N5—C11—O2 | 1.3 (4) |
C4—C5—C6—C1 | 0.9 (3) | C12—N5—C11—O1 | −179.1 (2) |
C4—C5—C6—C7 | −178.9 (2) | N4—O1—C11—O2 | −173.63 (18) |
O1—N4—C7—C6 | −177.40 (17) | N4—O1—C11—N5 | 6.7 (3) |
O1—N4—C7—C8 | 2.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N3i | 0.86 | 2.33 | 3.035 (3) | 139 |
C9—H9···O2ii | 0.93 | 2.28 | 3.191 (3) | 167 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H11Cl2N5O2 |
Mr | 328.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 6.016 (2), 8.430 (2), 14.721 (4) |
α, β, γ (°) | 101.501 (4), 100.057 (4), 93.977 (4) |
V (Å3) | 716.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.30 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.873, 0.921 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3665, 2497, 1863 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.111, 1.04 |
No. of reflections | 2497 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.23 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N3i | 0.86 | 2.33 | 3.035 (3) | 139.0 |
C9—H9···O2ii | 0.93 | 2.28 | 3.191 (3) | 167.3 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1. |
The derivatives of 1H-1,2,4-triazoles have been reported to possess various biological activities (Xu et al., 2002). In a search for new triazole compounds with better biological activity, the title compound, (I), was synthesized. We report here the crystal structure of (I).
Bond lengths and angles of the triazole rings are in agreement with those in previous reports (Çoruh et al., 2003; Li et al., 2005). The N=C bond length [N4=C7 = 1.285 (4) Å] are close to the value reported in the literature (Puviarasan et al., 1999). Atoms Cl1/Cl2/O1/N4/C7/C8/C11 lies in the benzene ring (C1/C2/C3/C4/C5/C6) plane, and the deviations from the least-squares plane through the ring atoms are all smaller than 0.046 (2) Å. The dihedral angle between the plane of benzene and triazole (N1/N2/N3/C9/C10) ring is 89.79 (2)°. Intermolecular hydrogen bonds N—H···N and C—H···O link the molecules into zigzag chains running in the [101] direction. The crystal packing (Fig. 2) is further stabilized by van der Waals forces.