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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2459.
Published online 2009 September 12. doi:  10.1107/S1600536809036320
PMCID: PMC2970403

n-Butyl 2-(2,4-dichloro­anilino)-4,4-dimethyl-6-oxocyclo­hex-1-enecarbo­dithio­ate

Abstract

The cyclo­hexene ring in the title compound, C19H23Cl2NOS2, adopts an envelope conformation, with the C atom bearing the two methyl groups representing the flap. This atom deviates by 0.630 (2) Å from the plane passing through the other five atoms of the ring (r.m.s. deviation = 0.020 Å). The mol­ecular conformation is stabilized by an intra­molecular N—H(...)S hydrogen bond.

Related literature

For the crystal structures of the n-undeca­nyl and 2-hydroxy­ethyl analogues, see: El Ashry et al. (2009a [triangle],b [triangle]).

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Object name is e-65-o2459-scheme1.jpg

Experimental

Crystal data

  • C19H23Cl2NOS2
  • M r = 416.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2459-efi1.jpg
  • a = 9.0321 (1) Å
  • b = 19.4422 (2) Å
  • c = 11.4700 (1) Å
  • β = 100.331 (1)°
  • V = 1981.52 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.55 mm−1
  • T = 123 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.853, T max = 0.947
  • 18747 measured reflections
  • 4554 independent reflections
  • 4279 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.070
  • S = 1.00
  • 4554 reflections
  • 230 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036320/ci2904sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036320/ci2904Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the University of Karachi and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

A cooled (283 K) solution of (2,4-dichloroanilino)-4,4-dimethyl-6-oxocyclohex-1-ene (0.2 mol) and sodium hydroxide (0.2 mol) in DMSO (30 ml) and water (2 ml), was treated with carbon disulfide (0.3 mol). After 40 min, n-bromobutane (0.15 mol) was added and the reaction mixture was left overnight. The mixture was then diluted with water (200 ml) and acidified with 10% hydrochloric acid. The product was purified on silica gel column chromatography to give yellow crystals when recrystallized from ethanol (m.p. 401 K).

Refinement

The N-bound H atom was located in a difference Fourier map and was refined freely. C-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 to 1.5Ueq(C).

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) plot of C19H23Cl2NOS2 at the 70% probability level; H atoms are drawn as spheres of arbitrary radius.

Crystal data

C19H23Cl2NOS2F(000) = 872
Mr = 416.40Dx = 1.396 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9957 reflections
a = 9.0321 (1) Åθ = 2.5–28.2°
b = 19.4422 (2) ŵ = 0.55 mm1
c = 11.4700 (1) ÅT = 123 K
β = 100.331 (1)°Block, yellow
V = 1981.52 (3) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer4554 independent reflections
Radiation source: fine-focus sealed tube4279 reflections with I > 2σ(I)
graphiteRint = 0.016
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→11
Tmin = 0.853, Tmax = 0.947k = −25→25
18747 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0405P)2 + 0.9836P] where P = (Fo2 + 2Fc2)/3
4554 reflections(Δ/σ)max = 0.001
230 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.25 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.66246 (3)0.420713 (17)0.99199 (3)0.02548 (8)
Cl21.25630 (3)0.391875 (17)1.00782 (3)0.02572 (8)
S10.17044 (3)0.547076 (14)0.56447 (2)0.01521 (7)
S20.45310 (3)0.595199 (14)0.71292 (3)0.01818 (8)
O10.18119 (12)0.41970 (5)0.52118 (12)0.0435 (3)
N10.65717 (11)0.47990 (5)0.74995 (8)0.01551 (19)
H10.625 (2)0.5237 (10)0.7584 (16)0.033 (4)*
C10.31311 (14)0.40793 (6)0.56335 (11)0.0194 (2)
C20.37252 (13)0.33742 (6)0.54278 (10)0.0176 (2)
H2A0.41180.33810.46760.021*
H2B0.28780.30440.53310.021*
C30.49613 (12)0.31158 (6)0.64090 (10)0.0150 (2)
C40.61567 (12)0.36787 (6)0.66192 (10)0.0163 (2)
H4A0.69250.35470.73120.020*
H4B0.66620.36980.59220.020*
C50.55899 (12)0.43880 (6)0.68327 (9)0.0133 (2)
C60.41136 (12)0.46044 (6)0.63000 (10)0.0141 (2)
C70.56586 (14)0.24599 (6)0.60044 (11)0.0203 (2)
H7A0.60510.25540.52770.030*
H7B0.48900.21000.58510.030*
H7C0.64820.23060.66260.030*
C80.43521 (15)0.29707 (7)0.75460 (11)0.0246 (3)
H8A0.35900.26070.73970.037*
H8B0.38980.33900.78000.037*
H8C0.51780.28220.81700.037*
C90.80208 (12)0.45912 (6)0.81146 (10)0.0144 (2)
C100.81793 (13)0.43077 (6)0.92496 (10)0.0160 (2)
C110.95775 (13)0.40992 (6)0.98561 (10)0.0171 (2)
H110.96810.39021.06240.021*
C121.08177 (13)0.41848 (6)0.93158 (10)0.0171 (2)
C131.07029 (13)0.44805 (6)0.82040 (10)0.0187 (2)
H131.15720.45430.78560.022*
C140.92928 (13)0.46846 (6)0.76063 (10)0.0169 (2)
H140.91980.48890.68450.020*
C150.35496 (12)0.53004 (6)0.63903 (9)0.0140 (2)
C160.14330 (13)0.63819 (6)0.58501 (10)0.0162 (2)
H16A0.24110.66180.58850.019*
H16B0.07370.65610.51500.019*
C170.08095 (13)0.65650 (6)0.69585 (10)0.0169 (2)
H17A0.15750.64620.76690.020*
H17B−0.00890.62800.69940.020*
C180.03800 (14)0.73269 (6)0.69634 (11)0.0226 (2)
H18A0.12540.76090.68460.027*
H18B−0.04510.74180.62920.027*
C19−0.01100 (17)0.75431 (7)0.81137 (13)0.0308 (3)
H19A−0.03740.80330.80740.046*
H19B0.07160.74640.87800.046*
H19C−0.09880.72720.82270.046*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01664 (14)0.03539 (18)0.02576 (15)−0.00287 (11)0.00749 (11)0.00779 (12)
Cl20.01535 (14)0.03229 (17)0.02687 (16)0.00715 (11)−0.00338 (11)0.00089 (12)
S10.01301 (13)0.01582 (14)0.01536 (13)0.00136 (9)−0.00128 (10)−0.00127 (9)
S20.01510 (14)0.01493 (14)0.02250 (15)−0.00004 (10)−0.00210 (11)−0.00381 (10)
O10.0189 (5)0.0256 (5)0.0756 (8)0.0054 (4)−0.0192 (5)−0.0213 (5)
N10.0130 (4)0.0142 (5)0.0177 (5)−0.0003 (3)−0.0015 (3)−0.0014 (4)
C10.0162 (5)0.0169 (5)0.0229 (6)0.0000 (4)−0.0023 (4)−0.0034 (4)
C20.0170 (5)0.0148 (5)0.0188 (5)−0.0003 (4)−0.0028 (4)−0.0027 (4)
C30.0135 (5)0.0141 (5)0.0162 (5)−0.0014 (4)0.0000 (4)0.0001 (4)
C40.0123 (5)0.0148 (5)0.0210 (5)−0.0003 (4)0.0012 (4)−0.0022 (4)
C50.0128 (5)0.0150 (5)0.0125 (5)−0.0017 (4)0.0028 (4)0.0006 (4)
C60.0122 (5)0.0145 (5)0.0150 (5)−0.0011 (4)0.0008 (4)−0.0008 (4)
C70.0188 (5)0.0145 (5)0.0259 (6)−0.0003 (4)−0.0010 (4)−0.0021 (4)
C80.0264 (6)0.0257 (6)0.0225 (6)−0.0027 (5)0.0066 (5)0.0050 (5)
C90.0124 (5)0.0139 (5)0.0156 (5)−0.0009 (4)−0.0009 (4)−0.0023 (4)
C100.0138 (5)0.0169 (5)0.0175 (5)−0.0024 (4)0.0035 (4)−0.0003 (4)
C110.0181 (6)0.0169 (5)0.0153 (5)−0.0003 (4)0.0002 (4)0.0009 (4)
C120.0128 (5)0.0178 (5)0.0186 (5)0.0025 (4)−0.0028 (4)−0.0027 (4)
C130.0142 (5)0.0239 (6)0.0183 (5)−0.0002 (4)0.0037 (4)−0.0027 (4)
C140.0169 (5)0.0197 (5)0.0137 (5)−0.0016 (4)0.0010 (4)−0.0012 (4)
C150.0126 (5)0.0166 (5)0.0125 (5)−0.0006 (4)0.0013 (4)0.0003 (4)
C160.0176 (5)0.0144 (5)0.0158 (5)0.0018 (4)0.0007 (4)0.0019 (4)
C170.0156 (5)0.0163 (5)0.0184 (5)0.0011 (4)0.0020 (4)−0.0009 (4)
C180.0224 (6)0.0180 (6)0.0251 (6)0.0033 (4)−0.0016 (5)−0.0030 (4)
C190.0309 (7)0.0264 (7)0.0340 (7)0.0087 (5)0.0030 (6)−0.0091 (6)

Geometric parameters (Å, °)

Cl1—C101.7287 (11)C8—H8A0.98
Cl2—C121.7387 (12)C8—H8B0.98
S1—C151.7628 (11)C8—H8C0.98
S1—C161.8094 (12)C9—C141.3903 (16)
S2—C151.6851 (11)C9—C101.3973 (16)
O1—C11.2244 (16)C10—C111.3885 (16)
N1—C51.3291 (14)C11—C121.3840 (17)
N1—C91.4293 (14)C11—H110.95
N1—H10.911 (18)C12—C131.3856 (17)
C1—C61.4733 (15)C13—C141.3916 (16)
C1—C21.5061 (16)C13—H130.95
C2—C31.5214 (15)C14—H140.95
C2—H2A0.99C16—C171.5222 (16)
C2—H2B0.99C16—H16A0.99
C3—C41.5258 (15)C16—H16B0.99
C3—C81.5300 (16)C17—C181.5315 (16)
C3—C71.5307 (16)C17—H17A0.99
C4—C51.5063 (15)C17—H17B0.99
C4—H4A0.99C18—C191.5240 (19)
C4—H4B0.99C18—H18A0.99
C5—C61.4269 (15)C18—H18B0.99
C6—C151.4562 (15)C19—H19A0.98
C7—H7A0.98C19—H19B0.98
C7—H7B0.98C19—H19C0.98
C7—H7C0.98
C15—S1—C16105.02 (5)C14—C9—N1120.57 (10)
C5—N1—C9124.86 (10)C10—C9—N1120.21 (10)
C5—N1—H1115.5 (11)C11—C10—C9120.93 (10)
C9—N1—H1119.6 (11)C11—C10—Cl1118.85 (9)
O1—C1—C6121.90 (11)C9—C10—Cl1120.22 (9)
O1—C1—C2117.19 (11)C12—C11—C10118.49 (10)
C6—C1—C2120.90 (10)C12—C11—H11120.8
C1—C2—C3114.80 (9)C10—C11—H11120.8
C1—C2—H2A108.6C11—C12—C13121.94 (11)
C3—C2—H2A108.6C11—C12—Cl2118.20 (9)
C1—C2—H2B108.6C13—C12—Cl2119.85 (9)
C3—C2—H2B108.6C12—C13—C14118.85 (11)
H2A—C2—H2B107.5C12—C13—H13120.6
C2—C3—C4106.54 (9)C14—C13—H13120.6
C2—C3—C8111.29 (10)C9—C14—C13120.55 (11)
C4—C3—C8110.49 (10)C9—C14—H14119.7
C2—C3—C7109.76 (9)C13—C14—H14119.7
C4—C3—C7109.11 (9)C6—C15—S2125.12 (8)
C8—C3—C7109.58 (10)C6—C15—S1116.90 (8)
C5—C4—C3115.52 (9)S2—C15—S1117.97 (6)
C5—C4—H4A108.4C17—C16—S1114.63 (8)
C3—C4—H4A108.4C17—C16—H16A108.6
C5—C4—H4B108.4S1—C16—H16A108.6
C3—C4—H4B108.4C17—C16—H16B108.6
H4A—C4—H4B107.5S1—C16—H16B108.6
N1—C5—C6123.03 (10)H16A—C16—H16B107.6
N1—C5—C4115.65 (10)C16—C17—C18111.18 (10)
C6—C5—C4121.26 (10)C16—C17—H17A109.4
C5—C6—C15123.74 (10)C18—C17—H17A109.4
C5—C6—C1116.59 (10)C16—C17—H17B109.4
C15—C6—C1119.67 (10)C18—C17—H17B109.4
C3—C7—H7A109.5H17A—C17—H17B108.0
C3—C7—H7B109.5C19—C18—C17112.52 (11)
H7A—C7—H7B109.5C19—C18—H18A109.1
C3—C7—H7C109.5C17—C18—H18A109.1
H7A—C7—H7C109.5C19—C18—H18B109.1
H7B—C7—H7C109.5C17—C18—H18B109.1
C3—C8—H8A109.5H18A—C18—H18B107.8
C3—C8—H8B109.5C18—C19—H19A109.5
H8A—C8—H8B109.5C18—C19—H19B109.5
C3—C8—H8C109.5H19A—C19—H19B109.5
H8A—C8—H8C109.5C18—C19—H19C109.5
H8B—C8—H8C109.5H19A—C19—H19C109.5
C14—C9—C10119.20 (10)H19B—C19—H19C109.5
O1—C1—C2—C3−149.43 (13)C14—C9—C10—C11−2.07 (17)
C6—C1—C2—C331.47 (16)N1—C9—C10—C11179.58 (10)
C1—C2—C3—C4−52.05 (13)C14—C9—C10—Cl1178.25 (9)
C1—C2—C3—C868.46 (13)N1—C9—C10—Cl1−0.10 (15)
C1—C2—C3—C7−170.06 (10)C9—C10—C11—C120.65 (17)
C2—C3—C4—C552.18 (12)Cl1—C10—C11—C12−179.66 (9)
C8—C3—C4—C5−68.83 (13)C10—C11—C12—C131.04 (17)
C7—C3—C4—C5170.62 (9)C10—C11—C12—Cl2−179.71 (9)
C9—N1—C5—C6175.52 (10)C11—C12—C13—C14−1.26 (18)
C9—N1—C5—C4−7.29 (16)Cl2—C12—C13—C14179.50 (9)
C3—C4—C5—N1151.63 (10)C10—C9—C14—C131.84 (17)
C3—C4—C5—C6−31.13 (15)N1—C9—C14—C13−179.82 (10)
N1—C5—C6—C152.50 (17)C12—C13—C14—C9−0.21 (17)
C4—C5—C6—C15−174.53 (10)C5—C6—C15—S2−0.17 (16)
N1—C5—C6—C1−177.12 (10)C1—C6—C15—S2179.44 (9)
C4—C5—C6—C15.84 (15)C5—C6—C15—S1178.79 (8)
O1—C1—C6—C5174.85 (13)C1—C6—C15—S1−1.60 (14)
C2—C1—C6—C5−6.09 (16)C16—S1—C15—C6−175.86 (8)
O1—C1—C6—C15−4.79 (19)C16—S1—C15—S23.18 (8)
C2—C1—C6—C15174.27 (10)C15—S1—C16—C17−89.34 (9)
C5—N1—C9—C1495.10 (14)S1—C16—C17—C18−170.96 (8)
C5—N1—C9—C10−86.58 (14)C16—C17—C18—C19−174.62 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···S20.91 (2)2.08 (2)2.885 (1)147 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2904).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • El Ashry, E. S. H., Amer, M. R., Shah, M. R. & Ng, S. W. (2009a). Acta Cryst. E65, o601. [PMC free article] [PubMed]
  • El Ashry, E. S. H., Amer, M. R., Shah, M. R. & Ng, S. W. (2009b). Acta Cryst. E65, o602. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography