Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027510/cv6561sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027510/cv6561Isup2.hkl |
CCDC reference: 287533
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.105
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for S1 - O2 .. 12.66 su
Alert level C PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C8 - C13 .. 6.09 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C11 - C12 .. 5.21 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C12 - C13 .. 5.70 su PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C28 H22 Cl2 N4 O4 S2
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 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 4 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 1 ALERT type 4 Improvement, methodology, query or suggestion
The title compound was obtained by adding N-(p-tolylsulfonyl)-α-chloro-(4-chlorophenyl)hydrazone dropwise to triethylamine using tetrahydrofuran as solvent at 265 K. [Quantities of reagents?] The resulting preciptate was filtered and recrystallized [Solvent?] to afford the title compound. A solution of the compound in butan-2-one was concentrated gradually at room temperature to afford yellow crystals of (I) suitable for X-ray diffraction (m.p. 453–454.5 K).
H atoms were placed in calculated positions and refined using a riding model. They were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl H atoms) times the equivalent isotropic displacement parameters of their parent atoms, and C—H distances were set to 0.93 Å for the aromatic H atoms and 0.96 Å for those of the methyl groups.
Data collection: CAD4 (Enraf–Nonius, 1994); cell refinement: CAD4; data reduction: XCAD4, PSI and EAC (Enraf–Nonius, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C28H22Cl2N4O4S2 | F(000) = 1264 |
Mr = 613.52 | Dx = 1.504 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 19.313 (8) Å | θ = 9.6–14.0° |
b = 7.007 (4) Å | µ = 0.44 mm−1 |
c = 20.998 (4) Å | T = 292 K |
β = 107.50 (2)° | Prism, yellow |
V = 2710 (2) Å3 | 0.35 × 0.30 × 0.20 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 1847 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 25.2°, θmin = 2.0° |
ω/2θ scans | h = −1→22 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→8 |
Tmin = 0.862, Tmax = 0.918 | l = −25→24 |
2676 measured reflections | 3 standard reflections every 60 min |
2441 independent reflections | intensity decay: none |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0466P)2 + 3.219P] where P = (Fo2 + 2Fc2)/3 |
2441 reflections | (Δ/σ)max = 0.002 |
182 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C28H22Cl2N4O4S2 | V = 2710 (2) Å3 |
Mr = 613.52 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.313 (8) Å | µ = 0.44 mm−1 |
b = 7.007 (4) Å | T = 292 K |
c = 20.998 (4) Å | 0.35 × 0.30 × 0.20 mm |
β = 107.50 (2)° |
Enraf–Nonius CAD-4 diffractometer | 1847 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.037 |
Tmin = 0.862, Tmax = 0.918 | 3 standard reflections every 60 min |
2676 measured reflections | intensity decay: none |
2441 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
2441 reflections | Δρmin = −0.31 e Å−3 |
182 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 | 0.615717 (11) | −0.50949 (3) | −0.061408 (9) | 0.03628 (6) | |
Cl1 | 0.394923 (15) | 0.13415 (4) | −0.288325 (13) | 0.07011 (9) | |
O1 | 0.60225 (3) | −0.40575 (10) | −0.12169 (3) | 0.04904 (19) | |
O2 | 0.64711 (3) | −0.69385 (9) | −0.05535 (3) | 0.04824 (19) | |
N1 | 0.53136 (3) | −0.54226 (9) | −0.04975 (3) | 0.03170 (18) | |
N2 | 0.54267 (3) | −0.66244 (10) | 0.00697 (3) | 0.03303 (19) | |
C1 | 0.47014 (5) | −0.05914 (13) | −0.10269 (4) | 0.0393 (2) | |
H1 | 0.4863 | −0.0080 | −0.0599 | 0.047* | |
C2 | 0.44798 (5) | 0.06073 (14) | −0.15686 (4) | 0.0468 (3) | |
H2 | 0.4496 | 0.1924 | −0.1509 | 0.056* | |
C3 | 0.42349 (4) | −0.01604 (14) | −0.21981 (4) | 0.0428 (3) | |
C4 | 0.42157 (5) | −0.21006 (15) | −0.22960 (4) | 0.0451 (3) | |
H4 | 0.4050 | −0.2604 | −0.2725 | 0.054* | |
C5 | 0.44448 (5) | −0.32905 (13) | −0.17506 (4) | 0.0416 (3) | |
H5 | 0.4437 | −0.4605 | −0.1812 | 0.050* | |
C6 | 0.46862 (4) | −0.25434 (12) | −0.11113 (4) | 0.0319 (2) | |
C7 | 0.48729 (4) | −0.37899 (11) | −0.05161 (4) | 0.0302 (2) | |
C8 | 0.66008 (4) | −0.36568 (12) | 0.00616 (4) | 0.0356 (2) | |
C9 | 0.69457 (5) | −0.44631 (15) | 0.06747 (5) | 0.0504 (3) | |
H9 | 0.6986 | −0.5782 | 0.0720 | 0.061* | |
C10 | 0.72299 (5) | −0.32950 (16) | 0.12190 (5) | 0.0547 (3) | |
H10 | 0.7464 | −0.3839 | 0.1632 | 0.066* | |
C11 | 0.71746 (5) | −0.13358 (15) | 0.11642 (5) | 0.0498 (3) | |
C12 | 0.68422 (5) | −0.05736 (15) | 0.05421 (5) | 0.0547 (3) | |
H12 | 0.6814 | 0.0746 | 0.0495 | 0.066* | |
C13 | 0.65523 (5) | −0.16943 (13) | −0.00091 (5) | 0.0441 (3) | |
H13 | 0.6327 | −0.1145 | −0.0423 | 0.053* | |
C14 | 0.74702 (6) | −0.00749 (19) | 0.17576 (6) | 0.0744 (4) | |
H14A | 0.7918 | 0.0485 | 0.1741 | 0.112* | |
H14B | 0.7556 | −0.0816 | 0.2158 | 0.112* | |
H14C | 0.7126 | 0.0917 | 0.1755 | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03913 (9) | 0.04191 (11) | 0.03045 (8) | 0.00304 (9) | 0.01446 (7) | 0.00201 (8) |
Cl1 | 0.07286 (15) | 0.08009 (17) | 0.05599 (12) | 0.02454 (14) | 0.01728 (11) | 0.03874 (12) |
O1 | 0.0478 (3) | 0.0685 (4) | 0.0356 (3) | 0.0046 (3) | 0.0197 (2) | 0.0124 (3) |
O2 | 0.0551 (3) | 0.0425 (3) | 0.0505 (3) | 0.0114 (3) | 0.0209 (2) | −0.0049 (3) |
N1 | 0.0384 (3) | 0.0285 (3) | 0.0286 (3) | −0.0003 (3) | 0.0106 (2) | 0.0022 (3) |
N2 | 0.0403 (3) | 0.0299 (3) | 0.0284 (3) | −0.0009 (3) | 0.0096 (2) | 0.0023 (3) |
C1 | 0.0488 (4) | 0.0359 (4) | 0.0325 (4) | −0.0004 (4) | 0.0111 (3) | −0.0003 (4) |
C2 | 0.0600 (5) | 0.0309 (4) | 0.0506 (4) | 0.0031 (4) | 0.0185 (4) | 0.0069 (4) |
C3 | 0.0403 (4) | 0.0514 (5) | 0.0386 (4) | 0.0127 (4) | 0.0147 (3) | 0.0164 (4) |
C4 | 0.0487 (5) | 0.0548 (5) | 0.0294 (4) | 0.0061 (4) | 0.0083 (3) | 0.0008 (4) |
C5 | 0.0542 (5) | 0.0348 (5) | 0.0324 (4) | 0.0009 (4) | 0.0078 (3) | −0.0023 (4) |
C6 | 0.0332 (4) | 0.0332 (4) | 0.0296 (3) | −0.0009 (3) | 0.0100 (3) | 0.0026 (3) |
C7 | 0.0344 (4) | 0.0264 (4) | 0.0277 (3) | −0.0035 (3) | 0.0064 (3) | −0.0019 (3) |
C8 | 0.0337 (3) | 0.0362 (4) | 0.0394 (4) | 0.0001 (3) | 0.0146 (3) | 0.0029 (3) |
C9 | 0.0602 (5) | 0.0388 (5) | 0.0452 (5) | −0.0031 (5) | 0.0051 (4) | 0.0039 (4) |
C10 | 0.0561 (5) | 0.0592 (6) | 0.0409 (5) | −0.0057 (5) | 0.0028 (4) | 0.0007 (5) |
C11 | 0.0350 (4) | 0.0562 (6) | 0.0607 (5) | −0.0083 (4) | 0.0180 (3) | −0.0160 (5) |
C12 | 0.0451 (5) | 0.0371 (5) | 0.0804 (6) | −0.0024 (4) | 0.0165 (4) | −0.0059 (5) |
C13 | 0.0369 (4) | 0.0406 (5) | 0.0532 (5) | −0.0005 (4) | 0.0111 (4) | 0.0075 (4) |
C14 | 0.0555 (6) | 0.0868 (8) | 0.0798 (7) | −0.0148 (6) | 0.0186 (5) | −0.0383 (6) |
S1—O1 | 1.4143 (8) | C5—H5 | 0.9300 |
S1—O2 | 1.4163 (11) | C6—C7 | 1.4778 (12) |
S1—N1 | 1.7339 (10) | C7—N2i | 1.2743 (12) |
S1—C8 | 1.7411 (11) | C8—C9 | 1.3801 (13) |
Cl1—C3 | 1.7333 (12) | C8—C13 | 1.3832 (15) |
N1—C7 | 1.4195 (13) | C9—C10 | 1.3784 (15) |
N1—N2 | 1.4209 (11) | C9—H9 | 0.9300 |
N2—C7i | 1.2743 (12) | C10—C11 | 1.3790 (17) |
C1—C2 | 1.3746 (14) | C10—H10 | 0.9300 |
C1—C6 | 1.3783 (15) | C11—C12 | 1.3782 (15) |
C1—H1 | 0.9300 | C11—C14 | 1.4937 (16) |
C2—C3 | 1.3728 (13) | C12—C13 | 1.3712 (15) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.3738 (16) | C13—H13 | 0.9300 |
C4—C5 | 1.3775 (14) | C14—H14A | 0.9599 |
C4—H4 | 0.9300 | C14—H14B | 0.9599 |
C5—C6 | 1.3847 (12) | C14—H14C | 0.9599 |
O1—S1—O2 | 120.51 (5) | N2i—C7—N1 | 124.38 (7) |
O1—S1—N1 | 105.47 (5) | N2i—C7—C6 | 115.99 (8) |
O2—S1—N1 | 105.16 (6) | N1—C7—C6 | 119.42 (8) |
O1—S1—C8 | 110.17 (5) | C9—C8—C13 | 120.34 (9) |
O2—S1—C8 | 111.24 (5) | C9—C8—S1 | 120.29 (8) |
N1—S1—C8 | 102.39 (5) | C13—C8—S1 | 119.15 (7) |
C7—N1—N2 | 116.13 (7) | C10—C9—C8 | 119.37 (10) |
C7—N1—S1 | 118.07 (7) | C10—C9—H9 | 120.3 |
N2—N1—S1 | 106.42 (5) | C8—C9—H9 | 120.3 |
C7i—N2—N1 | 119.49 (7) | C9—C10—C11 | 121.36 (10) |
C2—C1—C6 | 120.71 (8) | C9—C10—H10 | 119.3 |
C2—C1—H1 | 119.6 | C11—C10—H10 | 119.3 |
C6—C1—H1 | 119.6 | C12—C11—C10 | 117.84 (10) |
C3—C2—C1 | 119.25 (9) | C12—C11—C14 | 120.91 (10) |
C3—C2—H2 | 120.4 | C10—C11—C14 | 121.25 (10) |
C1—C2—H2 | 120.4 | C13—C12—C11 | 122.26 (10) |
C2—C3—C4 | 121.19 (9) | C13—C12—H12 | 118.9 |
C2—C3—Cl1 | 119.52 (8) | C11—C12—H12 | 118.9 |
C4—C3—Cl1 | 119.29 (7) | C12—C13—C8 | 118.79 (9) |
C3—C4—C5 | 119.15 (9) | C12—C13—H13 | 120.6 |
C3—C4—H4 | 120.4 | C8—C13—H13 | 120.6 |
C5—C4—H4 | 120.4 | C11—C14—H14A | 109.5 |
C4—C5—C6 | 120.50 (9) | C11—C14—H14B | 109.5 |
C4—C5—H5 | 119.7 | H14A—C14—H14B | 109.5 |
C6—C5—H5 | 119.7 | C11—C14—H14C | 109.5 |
C1—C6—C5 | 119.19 (8) | H14A—C14—H14C | 109.5 |
C1—C6—C7 | 119.18 (8) | H14B—C14—H14C | 109.5 |
C5—C6—C7 | 121.46 (8) | ||
O1—S1—N1—C7 | −53.02 (7) | S1—N1—C7—C6 | 56.14 (8) |
O2—S1—N1—C7 | 178.61 (5) | C1—C6—C7—N2i | 46.78 (11) |
C8—S1—N1—C7 | 62.27 (7) | C5—C6—C7—N2i | −128.34 (9) |
O1—S1—N1—N2 | 174.34 (5) | C1—C6—C7—N1 | −138.25 (8) |
O2—S1—N1—N2 | 45.97 (6) | C5—C6—C7—N1 | 46.63 (11) |
C8—S1—N1—N2 | −70.38 (6) | O1—S1—C8—C9 | −163.88 (8) |
C7—N1—N2—C7i | 1.08 (10) | O2—S1—C8—C9 | −27.57 (10) |
S1—N1—N2—C7i | 134.78 (7) | N1—S1—C8—C9 | 84.31 (9) |
C6—C1—C2—C3 | 0.63 (14) | O1—S1—C8—C13 | 21.41 (9) |
C1—C2—C3—C4 | −0.76 (15) | O2—S1—C8—C13 | 157.71 (8) |
C1—C2—C3—Cl1 | 179.60 (7) | N1—S1—C8—C13 | −90.41 (9) |
C2—C3—C4—C5 | 0.20 (14) | C13—C8—C9—C10 | 1.20 (15) |
Cl1—C3—C4—C5 | 179.84 (7) | S1—C8—C9—C10 | −173.46 (8) |
C3—C4—C5—C6 | 0.50 (14) | C8—C9—C10—C11 | 0.21 (17) |
C2—C1—C6—C5 | 0.05 (14) | C9—C10—C11—C12 | −1.71 (16) |
C2—C1—C6—C7 | −175.18 (8) | C9—C10—C11—C14 | 178.78 (10) |
C4—C5—C6—C1 | −0.62 (14) | C10—C11—C12—C13 | 1.88 (16) |
C4—C5—C6—C7 | 174.50 (8) | C14—C11—C12—C13 | −178.61 (10) |
N2—N1—C7—N2i | −1.14 (11) | C11—C12—C13—C8 | −0.53 (15) |
S1—N1—C7—N2i | −129.34 (7) | C9—C8—C13—C12 | −1.04 (14) |
N2—N1—C7—C6 | −175.66 (6) | S1—C8—C13—C12 | 173.67 (8) |
Symmetry code: (i) −x+1, −y−1, −z. |
Experimental details
Crystal data | |
Chemical formula | C28H22Cl2N4O4S2 |
Mr | 613.52 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 292 |
a, b, c (Å) | 19.313 (8), 7.007 (4), 20.998 (4) |
β (°) | 107.50 (2) |
V (Å3) | 2710 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.35 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.862, 0.918 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2676, 2441, 1847 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.105, 1.06 |
No. of reflections | 2441 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.31 |
Computer programs: CAD4 (Enraf–Nonius, 1994), XCAD4, PSI and EAC (Enraf–Nonius, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
S1—O1 | 1.4143 (8) | N1—C7 | 1.4195 (13) |
S1—O2 | 1.4163 (11) | N1—N2 | 1.4209 (11) |
S1—N1 | 1.7339 (10) | N2—C7i | 1.2743 (12) |
S1—C8 | 1.7411 (11) | C6—C7 | 1.4778 (12) |
Cl1—C3 | 1.7333 (12) | ||
O1—S1—O2 | 120.51 (5) | N2—N1—S1 | 106.42 (5) |
N1—S1—C8 | 102.39 (5) | C7i—N2—N1 | 119.49 (7) |
C7—N1—N2 | 116.13 (7) | N2i—C7—N1 | 124.38 (7) |
C7—N1—N2—C7i | 1.08 (10) | N2—N1—C7—N2i | −1.14 (11) |
Symmetry code: (i) −x+1, −y−1, −z. |
s-Tetrazine derivatives, possessing a wide range of biological activities, are widely used in pesticides and herbicides (Sauer, 1996). In a continuation of our study into the structure–activity relationships of s-tetrazine derivatives (Hu et al., 2002, 2004), we have obtained the title compound, (I), as a product of the reaction of triethylamine and N-(p-tolylsulfonyl)-α-chloro-(4-chlorophenyl)-hydrazone.
The title compound was shown to be a 1,4-dihydro-s-tetrazine derivative. The molecule of (I) possesses a crystallographically imposed inversion centre (Fig. 1). Selected bond lengths and angles are listed in the Table 1. The central tetrazine ring has an essentially planar conformation, as shown by the minimal deviation [0.0123 (12) Å] of atom N1 from the N2/C7/N2i/C7i plane [symmetry code: (i) −x + 1, −y − 1, −z].