The title triazole compound, C
15H
8Cl
4N
4S·C
3H
7NO, has been obtained as an unexpected product when attempting to prepare Schiff bases of thiocarbohydrazide (TCH). The triazole ring is planar within 0.004 (8) Å because of conjugation. The dihedral angles between the 1,2,4-triazole ring and the two benzene rings are 24.9 (2) and 70.0 (2)°. The interplanar angle between the two benzene rings is 83.4 (2)°. The packing of the molecules is stabilized both by van der Waals interactions and by N—H
O intermolecular hydrogen bonds between the triazole N atom and the carbonyl O atom of the dimethylformamide solvent molecule.
Supporting information
CCDC reference: 270431
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.005 Å
- R factor = 0.031
- wR factor = 0.039
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for N3 - N4 .. 5.06 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for C5 - C6 .. 5.64 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C16
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N5
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.00
From the CIF: _reflns_number_total 3377
Count of symmetry unique reflns 2085
Completeness (_total/calc) 161.97%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1292
Fraction of Friedel pairs measured 0.620
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 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
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: APEX2; program(s) used to refine structure: APEX2; molecular graphics: APEX2; software used to prepare material for publication: APEX2.
3-(2,4-Dichlorophenyl)-4-[(1E)-(2,4-dichlorophenyl)methyleneamino]-
4,5-dihydro-1
H-1,2,4-triazole-5-thione dimethylformamide solvate
top
Crystal data top
C15H8Cl4N4S·C3H7NO | Dx = 1.462 Mg m−3 |
Mr = 491.21 | Melting point = 491–495 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2c -2ac | Cell parameters from 2025 reflections |
a = 11.3496 (19) Å | θ = 4.2–20.3° |
b = 18.016 (3) Å | µ = 0.64 mm−1 |
c = 10.9165 (18) Å | T = 273 K |
V = 2232.2 (6) Å3 | Block, pale yellow |
Z = 4 | 0.27 × 0.16 × 0.09 mm |
F(000) = 1000 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 1956 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 25.0°, θmin = 4.3° |
Detector resolution: 8.26 pixels mm-1 | h = −10→13 |
φ and ω scans | k = −21→21 |
9843 measured reflections | l = −10→12 |
3377 independent reflections | |
Refinement top
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.039 | w = 1/[σ2(Fo2) + (0.0165P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.82 | (Δ/σ)max < 0.001 |
3377 reflections | Δρmax = 0.22 e Å−3 |
264 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (4) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.00511 (8) | 0.13674 (5) | 0.09675 (7) | 0.0666 (2) | |
Cl1 | −0.27397 (9) | 0.36750 (5) | 0.74596 (7) | 0.0881 (3) | |
Cl2 | −0.20235 (9) | 0.14720 (5) | 0.42729 (8) | 0.0995 (3) | |
Cl3 | 0.22577 (10) | 0.41118 (5) | 0.15381 (8) | 0.0980 (3) | |
Cl4 | 0.56605 (9) | 0.46671 (5) | 0.48244 (9) | 0.0998 (3) | |
N1 | 0.1006 (3) | 0.26706 (14) | 0.3018 (2) | 0.0551 (7) | |
N2 | 0.1659 (3) | 0.23067 (13) | 0.2115 (2) | 0.0489 (7) | |
N3 | 0.2378 (3) | 0.16563 (13) | 0.0686 (2) | 0.0646 (8) | |
H3 | 0.2453 | 0.1341 | 0.0099 | 0.077* | |
N4 | 0.3297 (2) | 0.20839 (15) | 0.1100 (2) | 0.0604 (7) | |
C1 | −0.1561 (3) | 0.23127 (15) | 0.4887 (3) | 0.0517 (8) | |
C2 | −0.2236 (3) | 0.26120 (18) | 0.5818 (3) | 0.0580 (9) | |
H2 | −0.2892 | 0.2361 | 0.6118 | 0.070* | |
C3 | −0.1913 (3) | 0.32934 (19) | 0.6294 (2) | 0.0563 (9) | |
C4 | −0.0967 (3) | 0.36713 (18) | 0.5825 (3) | 0.0584 (8) | |
H4 | −0.0774 | 0.4138 | 0.6128 | 0.070* | |
C5 | −0.0304 (3) | 0.33594 (17) | 0.4905 (3) | 0.0555 (8) | |
H5 | 0.0343 | 0.3617 | 0.4600 | 0.067* | |
C6 | −0.0582 (3) | 0.26644 (17) | 0.4420 (2) | 0.0455 (8) | |
C7 | 0.0142 (3) | 0.23342 (18) | 0.3463 (2) | 0.0544 (9) | |
H7 | −0.0042 | 0.1862 | 0.3176 | 0.065* | |
C8 | 0.4330 (3) | 0.27936 (18) | 0.3519 (3) | 0.0625 (9) | |
H8 | 0.4464 | 0.2288 | 0.3621 | 0.075* | |
C9 | 0.4981 (3) | 0.3292 (2) | 0.4178 (3) | 0.0671 (9) | |
H9 | 0.5551 | 0.3125 | 0.4725 | 0.080* | |
C10 | 0.4790 (3) | 0.4044 (2) | 0.4029 (3) | 0.0637 (9) | |
C11 | 0.3949 (3) | 0.4297 (2) | 0.3243 (3) | 0.0684 (10) | |
H11 | 0.3821 | 0.4804 | 0.3152 | 0.082* | |
C12 | 0.3284 (3) | 0.37882 (18) | 0.2577 (3) | 0.0570 (8) | |
C13 | 0.3470 (3) | 0.30292 (17) | 0.2700 (3) | 0.0478 (8) | |
C14 | 0.2825 (3) | 0.24782 (17) | 0.1956 (3) | 0.0513 (9) | |
C15 | 0.1341 (3) | 0.17703 (16) | 0.1276 (3) | 0.0514 (8) | |
C16 | 0.6339 (6) | −0.0243 (3) | 0.3608 (4) | 0.128 (2) | |
H16 | 0.5713 | −0.0235 | 0.4157 | 0.154* | |
C17 | 0.5406 (4) | 0.0734 (2) | 0.2456 (4) | 0.1180 (15) | |
H17A | 0.4770 | 0.0675 | 0.3027 | 0.177* | |
H17B | 0.5123 | 0.0646 | 0.1639 | 0.177* | |
H17C | 0.5712 | 0.1230 | 0.2512 | 0.177* | |
C18 | 0.7274 (4) | 0.0194 (2) | 0.1837 (4) | 0.1153 (14) | |
H18A | 0.7895 | −0.0125 | 0.2120 | 0.173* | |
H18B | 0.7576 | 0.0687 | 0.1722 | 0.173* | |
H18C | 0.6975 | 0.0010 | 0.1072 | 0.173* | |
N5 | 0.6328 (3) | 0.02090 (18) | 0.2740 (3) | 0.0728 (8) | |
O2 | 0.7162 (3) | −0.07169 (16) | 0.3788 (3) | 0.1423 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0620 (6) | 0.0695 (6) | 0.0683 (5) | −0.0083 (6) | −0.0023 (5) | −0.0048 (5) |
Cl1 | 0.0889 (8) | 0.0945 (6) | 0.0807 (6) | 0.0131 (6) | 0.0349 (6) | −0.0027 (6) |
Cl2 | 0.1101 (8) | 0.0854 (6) | 0.1030 (7) | −0.0443 (6) | 0.0330 (6) | −0.0216 (6) |
Cl3 | 0.1051 (9) | 0.0747 (6) | 0.1143 (7) | −0.0006 (7) | −0.0458 (7) | 0.0275 (6) |
Cl4 | 0.0958 (8) | 0.0850 (7) | 0.1187 (7) | −0.0008 (6) | −0.0282 (7) | −0.0327 (6) |
N1 | 0.0433 (18) | 0.0665 (19) | 0.0555 (18) | 0.0002 (17) | 0.0063 (14) | −0.0065 (15) |
N2 | 0.048 (2) | 0.0521 (17) | 0.0468 (16) | −0.0032 (15) | 0.0050 (14) | 0.0003 (14) |
N3 | 0.071 (2) | 0.0633 (18) | 0.0592 (16) | −0.0022 (18) | 0.0149 (16) | −0.0107 (14) |
N4 | 0.060 (2) | 0.0586 (17) | 0.0624 (17) | −0.0092 (17) | 0.0097 (17) | −0.0015 (15) |
C1 | 0.047 (2) | 0.0575 (19) | 0.0504 (19) | −0.0061 (19) | −0.0018 (18) | 0.0051 (17) |
C2 | 0.047 (2) | 0.074 (2) | 0.0536 (18) | −0.003 (2) | 0.0086 (18) | 0.0124 (18) |
C3 | 0.051 (3) | 0.065 (2) | 0.053 (2) | 0.007 (2) | 0.0091 (18) | 0.0067 (18) |
C4 | 0.060 (2) | 0.057 (2) | 0.0583 (19) | 0.001 (2) | 0.0044 (18) | −0.0018 (19) |
C5 | 0.041 (2) | 0.066 (2) | 0.0584 (19) | −0.0057 (19) | 0.0075 (17) | 0.0051 (18) |
C6 | 0.044 (2) | 0.046 (2) | 0.0460 (18) | 0.0017 (18) | −0.0011 (17) | 0.0057 (16) |
C7 | 0.062 (3) | 0.049 (2) | 0.052 (2) | −0.002 (2) | 0.002 (2) | 0.0012 (17) |
C8 | 0.060 (3) | 0.051 (2) | 0.076 (2) | 0.005 (2) | 0.002 (2) | 0.0072 (19) |
C9 | 0.059 (3) | 0.068 (3) | 0.074 (2) | 0.007 (2) | −0.017 (2) | −0.001 (2) |
C10 | 0.059 (3) | 0.065 (3) | 0.066 (2) | −0.001 (2) | 0.004 (2) | −0.013 (2) |
C11 | 0.068 (3) | 0.052 (2) | 0.085 (2) | 0.009 (2) | −0.011 (2) | 0.0038 (19) |
C12 | 0.049 (2) | 0.057 (2) | 0.065 (2) | 0.0035 (19) | −0.0038 (19) | 0.0066 (18) |
C13 | 0.041 (2) | 0.053 (2) | 0.0493 (18) | 0.0013 (19) | 0.0072 (17) | 0.0022 (17) |
C14 | 0.050 (3) | 0.051 (2) | 0.053 (2) | 0.003 (2) | 0.0069 (19) | 0.0039 (17) |
C15 | 0.056 (2) | 0.049 (2) | 0.0488 (19) | 0.0019 (19) | 0.0085 (18) | 0.0025 (16) |
C16 | 0.226 (8) | 0.079 (4) | 0.078 (3) | −0.053 (4) | −0.054 (4) | 0.018 (3) |
C17 | 0.107 (4) | 0.128 (3) | 0.119 (3) | 0.023 (3) | −0.003 (3) | 0.002 (3) |
C18 | 0.112 (4) | 0.106 (3) | 0.127 (3) | −0.003 (3) | 0.015 (3) | −0.003 (3) |
N5 | 0.076 (3) | 0.073 (2) | 0.069 (2) | −0.005 (2) | −0.007 (2) | −0.0114 (19) |
O2 | 0.219 (4) | 0.092 (2) | 0.116 (2) | −0.010 (3) | −0.074 (2) | 0.0385 (19) |
Geometric parameters (Å, º) top
S1—C15 | 1.668 (3) | C7—H7 | 0.9300 |
Cl1—C3 | 1.724 (3) | C8—C9 | 1.367 (4) |
Cl2—C1 | 1.738 (3) | C8—C13 | 1.390 (4) |
Cl3—C12 | 1.727 (3) | C8—H8 | 0.9300 |
Cl4—C10 | 1.729 (3) | C9—C10 | 1.382 (4) |
N1—C7 | 1.251 (3) | C9—H9 | 0.9300 |
N1—N2 | 1.397 (3) | C10—C11 | 1.362 (4) |
N2—C14 | 1.369 (4) | C11—C12 | 1.392 (4) |
N2—C15 | 1.380 (3) | C11—H11 | 0.9300 |
N3—C15 | 1.357 (3) | C12—C13 | 1.390 (4) |
N3—N4 | 1.374 (3) | C13—C14 | 1.476 (4) |
N3—H3 | 0.8600 | C16—N5 | 1.250 (4) |
N4—C14 | 1.291 (3) | C16—O2 | 1.280 (6) |
C1—C6 | 1.378 (3) | C16—H16 | 0.9300 |
C1—C2 | 1.383 (4) | C17—N5 | 1.445 (4) |
C2—C3 | 1.382 (4) | C17—H17A | 0.9600 |
C2—H2 | 0.9300 | C17—H17B | 0.9600 |
C3—C4 | 1.370 (4) | C17—H17C | 0.9600 |
C4—C5 | 1.375 (4) | C18—N5 | 1.458 (4) |
C4—H4 | 0.9300 | C18—H18A | 0.9600 |
C5—C6 | 1.396 (3) | C18—H18B | 0.9600 |
C5—H5 | 0.9300 | C18—H18C | 0.9600 |
C6—C7 | 1.456 (4) | | |
| | | |
C7—N1—N2 | 117.5 (3) | C11—C10—Cl4 | 120.0 (3) |
C14—N2—C15 | 109.1 (3) | C9—C10—Cl4 | 119.2 (3) |
C14—N2—N1 | 119.8 (3) | C10—C11—C12 | 119.2 (3) |
C15—N2—N1 | 131.2 (3) | C10—C11—H11 | 120.4 |
C15—N3—N4 | 114.7 (2) | C12—C11—H11 | 120.4 |
C15—N3—H3 | 122.6 | C13—C12—C11 | 121.0 (3) |
N4—N3—H3 | 122.6 | C13—C12—Cl3 | 119.8 (3) |
C14—N4—N3 | 103.4 (3) | C11—C12—Cl3 | 119.1 (3) |
C6—C1—C2 | 122.7 (3) | C12—C13—C8 | 118.0 (3) |
C6—C1—Cl2 | 120.1 (2) | C12—C13—C14 | 122.2 (3) |
C2—C1—Cl2 | 117.2 (3) | C8—C13—C14 | 119.8 (3) |
C3—C2—C1 | 118.4 (3) | N4—C14—N2 | 111.7 (3) |
C3—C2—H2 | 120.8 | N4—C14—C13 | 124.2 (3) |
C1—C2—H2 | 120.8 | N2—C14—C13 | 124.1 (3) |
C4—C3—C2 | 120.6 (3) | N3—C15—N2 | 101.2 (3) |
C4—C3—Cl1 | 120.3 (3) | N3—C15—S1 | 126.8 (3) |
C2—C3—Cl1 | 119.1 (3) | N2—C15—S1 | 132.0 (3) |
C3—C4—C5 | 119.9 (3) | N5—C16—O2 | 123.9 (6) |
C3—C4—H4 | 120.0 | N5—C16—H16 | 118.0 |
C5—C4—H4 | 120.0 | O2—C16—H16 | 118.0 |
C4—C5—C6 | 121.3 (3) | N5—C17—H17A | 109.5 |
C4—C5—H5 | 119.3 | N5—C17—H17B | 109.5 |
C6—C5—H5 | 119.3 | H17A—C17—H17B | 109.5 |
C1—C6—C5 | 117.0 (3) | N5—C17—H17C | 109.5 |
C1—C6—C7 | 122.2 (3) | H17A—C17—H17C | 109.5 |
C5—C6—C7 | 120.7 (3) | H17B—C17—H17C | 109.5 |
N1—C7—C6 | 121.5 (3) | N5—C18—H18A | 109.5 |
N1—C7—H7 | 119.2 | N5—C18—H18B | 109.5 |
C6—C7—H7 | 119.2 | H18A—C18—H18B | 109.5 |
C9—C8—C13 | 121.2 (3) | N5—C18—H18C | 109.5 |
C9—C8—H8 | 119.4 | H18A—C18—H18C | 109.5 |
C13—C8—H8 | 119.4 | H18B—C18—H18C | 109.5 |
C8—C9—C10 | 119.8 (3) | C16—N5—C17 | 126.6 (5) |
C8—C9—H9 | 120.1 | C16—N5—C18 | 119.5 (4) |
C10—C9—H9 | 120.1 | C17—N5—C18 | 113.6 (3) |
C11—C10—C9 | 120.8 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O2i | 0.86 | 1.87 | 2.726 (2) | 172 |
Symmetry code: (i) −x+1, −y, z−1/2. |