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The title compound, C28H22Cl2N4O4S2, was prepared from triethyl­amine and N-(α,4-dichloro­benzyl­idene­amino)-p-toluene­sulfonamide and proved to be a 1,4-dihydro-s-tetra­zine derivative. In the mol­ecule, which possesses a crystallographically imposed inversion centre, the tetra­zine ring is essentially planar.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027510/cv6561sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027510/cv6561Isup2.hkl
Contains datablock I

CCDC reference: 287533

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](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

Comment top

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].

Experimental top

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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atomic labelling and 30% probability displacement ellipsoids. Unlabelled atoms and atoms labelled with a superscript i are related to labelled atoms by the symmetry operator (−x + 1, −y − 1, −z).
3,6-Bis(p-chlorophenyl)-1,4-bis(p-tolylsulfonyl)-1,4-dihydro-1,2,4,5-tetrazine top
Crystal data top
C28H22Cl2N4O4S2F(000) = 1264
Mr = 613.52Dx = 1.504 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 19.313 (8) Åθ = 9.6–14.0°
b = 7.007 (4) ŵ = 0.44 mm1
c = 20.998 (4) ÅT = 292 K
β = 107.50 (2)°Prism, yellow
V = 2710 (2) Å30.35 × 0.30 × 0.20 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer
1847 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
Graphite monochromatorθmax = 25.2°, θmin = 2.0°
ω/2θ scansh = 122
Absorption correction: ψ scan
(North et al., 1968)
k = 08
Tmin = 0.862, Tmax = 0.918l = 2524
2676 measured reflections3 standard reflections every 60 min
2441 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C28H22Cl2N4O4S2V = 2710 (2) Å3
Mr = 613.52Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.313 (8) ŵ = 0.44 mm1
b = 7.007 (4) ÅT = 292 K
c = 20.998 (4) Å0.35 × 0.30 × 0.20 mm
β = 107.50 (2)°
Data collection top
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 = 0.9183 standard reflections every 60 min
2676 measured reflections intensity decay: none
2441 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.06Δρmax = 0.27 e Å3
2441 reflectionsΔρmin = 0.31 e Å3
182 parameters
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
xyzUiso*/Ueq
S10.615717 (11)0.50949 (3)0.061408 (9)0.03628 (6)
Cl10.394923 (15)0.13415 (4)0.288325 (13)0.07011 (9)
O10.60225 (3)0.40575 (10)0.12169 (3)0.04904 (19)
O20.64711 (3)0.69385 (9)0.05535 (3)0.04824 (19)
N10.53136 (3)0.54226 (9)0.04975 (3)0.03170 (18)
N20.54267 (3)0.66244 (10)0.00697 (3)0.03303 (19)
C10.47014 (5)0.05914 (13)0.10269 (4)0.0393 (2)
H10.48630.00800.05990.047*
C20.44798 (5)0.06073 (14)0.15686 (4)0.0468 (3)
H20.44960.19240.15090.056*
C30.42349 (4)0.01604 (14)0.21981 (4)0.0428 (3)
C40.42157 (5)0.21006 (15)0.22960 (4)0.0451 (3)
H40.40500.26040.27250.054*
C50.44448 (5)0.32905 (13)0.17506 (4)0.0416 (3)
H50.44370.46050.18120.050*
C60.46862 (4)0.25434 (12)0.11113 (4)0.0319 (2)
C70.48729 (4)0.37899 (11)0.05161 (4)0.0302 (2)
C80.66008 (4)0.36568 (12)0.00616 (4)0.0356 (2)
C90.69457 (5)0.44631 (15)0.06747 (5)0.0504 (3)
H90.69860.57820.07200.061*
C100.72299 (5)0.32950 (16)0.12190 (5)0.0547 (3)
H100.74640.38390.16320.066*
C110.71746 (5)0.13358 (15)0.11642 (5)0.0498 (3)
C120.68422 (5)0.05736 (15)0.05421 (5)0.0547 (3)
H120.68140.07460.04950.066*
C130.65523 (5)0.16943 (13)0.00091 (5)0.0441 (3)
H130.63270.11450.04230.053*
C140.74702 (6)0.00749 (19)0.17576 (6)0.0744 (4)
H14A0.79180.04850.17410.112*
H14B0.75560.08160.21580.112*
H14C0.71260.09170.17550.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.03913 (9)0.04191 (11)0.03045 (8)0.00304 (9)0.01446 (7)0.00201 (8)
Cl10.07286 (15)0.08009 (17)0.05599 (12)0.02454 (14)0.01728 (11)0.03874 (12)
O10.0478 (3)0.0685 (4)0.0356 (3)0.0046 (3)0.0197 (2)0.0124 (3)
O20.0551 (3)0.0425 (3)0.0505 (3)0.0114 (3)0.0209 (2)0.0049 (3)
N10.0384 (3)0.0285 (3)0.0286 (3)0.0003 (3)0.0106 (2)0.0022 (3)
N20.0403 (3)0.0299 (3)0.0284 (3)0.0009 (3)0.0096 (2)0.0023 (3)
C10.0488 (4)0.0359 (4)0.0325 (4)0.0004 (4)0.0111 (3)0.0003 (4)
C20.0600 (5)0.0309 (4)0.0506 (4)0.0031 (4)0.0185 (4)0.0069 (4)
C30.0403 (4)0.0514 (5)0.0386 (4)0.0127 (4)0.0147 (3)0.0164 (4)
C40.0487 (5)0.0548 (5)0.0294 (4)0.0061 (4)0.0083 (3)0.0008 (4)
C50.0542 (5)0.0348 (5)0.0324 (4)0.0009 (4)0.0078 (3)0.0023 (4)
C60.0332 (4)0.0332 (4)0.0296 (3)0.0009 (3)0.0100 (3)0.0026 (3)
C70.0344 (4)0.0264 (4)0.0277 (3)0.0035 (3)0.0064 (3)0.0019 (3)
C80.0337 (3)0.0362 (4)0.0394 (4)0.0001 (3)0.0146 (3)0.0029 (3)
C90.0602 (5)0.0388 (5)0.0452 (5)0.0031 (5)0.0051 (4)0.0039 (4)
C100.0561 (5)0.0592 (6)0.0409 (5)0.0057 (5)0.0028 (4)0.0007 (5)
C110.0350 (4)0.0562 (6)0.0607 (5)0.0083 (4)0.0180 (3)0.0160 (5)
C120.0451 (5)0.0371 (5)0.0804 (6)0.0024 (4)0.0165 (4)0.0059 (5)
C130.0369 (4)0.0406 (5)0.0532 (5)0.0005 (4)0.0111 (4)0.0075 (4)
C140.0555 (6)0.0868 (8)0.0798 (7)0.0148 (6)0.0186 (5)0.0383 (6)
Geometric parameters (Å, º) top
S1—O11.4143 (8)C5—H50.9300
S1—O21.4163 (11)C6—C71.4778 (12)
S1—N11.7339 (10)C7—N2i1.2743 (12)
S1—C81.7411 (11)C8—C91.3801 (13)
Cl1—C31.7333 (12)C8—C131.3832 (15)
N1—C71.4195 (13)C9—C101.3784 (15)
N1—N21.4209 (11)C9—H90.9300
N2—C7i1.2743 (12)C10—C111.3790 (17)
C1—C21.3746 (14)C10—H100.9300
C1—C61.3783 (15)C11—C121.3782 (15)
C1—H10.9300C11—C141.4937 (16)
C2—C31.3728 (13)C12—C131.3712 (15)
C2—H20.9300C12—H120.9300
C3—C41.3738 (16)C13—H130.9300
C4—C51.3775 (14)C14—H14A0.9599
C4—H40.9300C14—H14B0.9599
C5—C61.3847 (12)C14—H14C0.9599
O1—S1—O2120.51 (5)N2i—C7—N1124.38 (7)
O1—S1—N1105.47 (5)N2i—C7—C6115.99 (8)
O2—S1—N1105.16 (6)N1—C7—C6119.42 (8)
O1—S1—C8110.17 (5)C9—C8—C13120.34 (9)
O2—S1—C8111.24 (5)C9—C8—S1120.29 (8)
N1—S1—C8102.39 (5)C13—C8—S1119.15 (7)
C7—N1—N2116.13 (7)C10—C9—C8119.37 (10)
C7—N1—S1118.07 (7)C10—C9—H9120.3
N2—N1—S1106.42 (5)C8—C9—H9120.3
C7i—N2—N1119.49 (7)C9—C10—C11121.36 (10)
C2—C1—C6120.71 (8)C9—C10—H10119.3
C2—C1—H1119.6C11—C10—H10119.3
C6—C1—H1119.6C12—C11—C10117.84 (10)
C3—C2—C1119.25 (9)C12—C11—C14120.91 (10)
C3—C2—H2120.4C10—C11—C14121.25 (10)
C1—C2—H2120.4C13—C12—C11122.26 (10)
C2—C3—C4121.19 (9)C13—C12—H12118.9
C2—C3—Cl1119.52 (8)C11—C12—H12118.9
C4—C3—Cl1119.29 (7)C12—C13—C8118.79 (9)
C3—C4—C5119.15 (9)C12—C13—H13120.6
C3—C4—H4120.4C8—C13—H13120.6
C5—C4—H4120.4C11—C14—H14A109.5
C4—C5—C6120.50 (9)C11—C14—H14B109.5
C4—C5—H5119.7H14A—C14—H14B109.5
C6—C5—H5119.7C11—C14—H14C109.5
C1—C6—C5119.19 (8)H14A—C14—H14C109.5
C1—C6—C7119.18 (8)H14B—C14—H14C109.5
C5—C6—C7121.46 (8)
O1—S1—N1—C753.02 (7)S1—N1—C7—C656.14 (8)
O2—S1—N1—C7178.61 (5)C1—C6—C7—N2i46.78 (11)
C8—S1—N1—C762.27 (7)C5—C6—C7—N2i128.34 (9)
O1—S1—N1—N2174.34 (5)C1—C6—C7—N1138.25 (8)
O2—S1—N1—N245.97 (6)C5—C6—C7—N146.63 (11)
C8—S1—N1—N270.38 (6)O1—S1—C8—C9163.88 (8)
C7—N1—N2—C7i1.08 (10)O2—S1—C8—C927.57 (10)
S1—N1—N2—C7i134.78 (7)N1—S1—C8—C984.31 (9)
C6—C1—C2—C30.63 (14)O1—S1—C8—C1321.41 (9)
C1—C2—C3—C40.76 (15)O2—S1—C8—C13157.71 (8)
C1—C2—C3—Cl1179.60 (7)N1—S1—C8—C1390.41 (9)
C2—C3—C4—C50.20 (14)C13—C8—C9—C101.20 (15)
Cl1—C3—C4—C5179.84 (7)S1—C8—C9—C10173.46 (8)
C3—C4—C5—C60.50 (14)C8—C9—C10—C110.21 (17)
C2—C1—C6—C50.05 (14)C9—C10—C11—C121.71 (16)
C2—C1—C6—C7175.18 (8)C9—C10—C11—C14178.78 (10)
C4—C5—C6—C10.62 (14)C10—C11—C12—C131.88 (16)
C4—C5—C6—C7174.50 (8)C14—C11—C12—C13178.61 (10)
N2—N1—C7—N2i1.14 (11)C11—C12—C13—C80.53 (15)
S1—N1—C7—N2i129.34 (7)C9—C8—C13—C121.04 (14)
N2—N1—C7—C6175.66 (6)S1—C8—C13—C12173.67 (8)
Symmetry code: (i) x+1, y1, z.

Experimental details

Crystal data
Chemical formulaC28H22Cl2N4O4S2
Mr613.52
Crystal system, space groupMonoclinic, C2/c
Temperature (K)292
a, b, c (Å)19.313 (8), 7.007 (4), 20.998 (4)
β (°) 107.50 (2)
V3)2710 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.44
Crystal size (mm)0.35 × 0.30 × 0.20
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.862, 0.918
No. of measured, independent and
observed [I > 2σ(I)] reflections
2676, 2441, 1847
Rint0.037
(sin θ/λ)max1)0.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.105, 1.06
No. of reflections2441
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
S1—O11.4143 (8)N1—C71.4195 (13)
S1—O21.4163 (11)N1—N21.4209 (11)
S1—N11.7339 (10)N2—C7i1.2743 (12)
S1—C81.7411 (11)C6—C71.4778 (12)
Cl1—C31.7333 (12)
O1—S1—O2120.51 (5)N2—N1—S1106.42 (5)
N1—S1—C8102.39 (5)C7i—N2—N1119.49 (7)
C7—N1—N2116.13 (7)N2i—C7—N1124.38 (7)
C7—N1—N2—C7i1.08 (10)N2—N1—C7—N2i1.14 (11)
Symmetry code: (i) x+1, y1, z.
 

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