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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o597.
Published online 2009 February 25. doi:  10.1107/S160053680900614X
PMCID: PMC2968658

Benzyl 2-(4-bromo­anilino)-4,4-dimethyl-6-oxocyclo­hex-1-enecarbodithio­ate: first triclinic polymorph

Abstract

The six-membered cyclo­hexene ring in the title compound, C22H22BrNOS2, adopts an envelope conformation, with the C atom bearing the two methyl groups representing the flap. This atom deviates by 0.686 (4) Å from the plane passing through the other five atoms of the ring (r.m.s. deviation = 0.025 Å). The mol­ecular conformation is stabilized by an intra­molecular N—H(...)S hydrogen bond.

Related literature

For previous work on this topic, see: El Ashry et al. (2005a [triangle],b [triangle], 2006 [triangle], 2008a [triangle],b [triangle]); El Ashry, Kassem et al. (2009 [triangle]). For the use of enamines in heterocyclic synthesis, see: Tominaga (1989 [triangle]); Tominaga et al. (1991 [triangle]). For another triclinic polymorph of the title compound, see El Ashry, Amer et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o597-scheme1.jpg

Experimental

Crystal data

  • C22H22BrNOS2
  • M r = 460.44
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o597-efi1.jpg
  • a = 9.3030 (3) Å
  • b = 9.8099 (3) Å
  • c = 12.3538 (4) Å
  • α = 73.464 (2)°
  • β = 72.391 (2)°
  • γ = 89.916 (2)°
  • V = 1025.73 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.22 mm−1
  • T = 100 K
  • 0.40 × 0.04 × 0.04 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.684, T max = 0.917
  • 9757 measured reflections
  • 4709 independent reflections
  • 3490 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.077
  • S = 0.99
  • 4709 reflections
  • 250 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.38 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/S160053680900614X/bt2876sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900614X/bt2876Isup2.hkl

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

Acknowledgments

We thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The enaminodithiocarboxylates are a class of compounds of crucial significance for designing functionalized molecules that are suitable for studying the biological activity of potentially useful chemicals. They are also important reactants in the synthesis of heterocyclic compounds (Tominaga, 1989; Tominaga et al., 1991). Our interest in such class of compounds revolves around new glycosyl donors (El Ashry et al., 2005a, 2005b, 2006, 2008a, 2008b, El Ashry, Kassem et al.2009). The title compound is to be used in a model study to understand the scope of the reaction that uses cyclic enaminones. A possibility exists that the representative title compound can lead to a fused cyclized product.

Experimental

To a solution of 3-(4-bromoanilino)-5,5-dimethyl-cyclohex-2-en-1-one (0.1 mol) in DMSO (20 ml) and sodium hydroxide (0.1 mol) in water (1 ml) was added carbon disulphide (0.3 mol). The mixture was kept at 263 K for 20 min. Benzyl bromide (0.1 mol) was added. The mixture was left for 24 h, after which it was quenched with water (200 ml) and then acidified with 10% hydrochloric acid. The resulting precipitate was collected by filtration, dried and purified on a silica gel column (30% ethyl acetate in hexane) to give orange crystals (40% yield, mp 458 K). HRMS for C22H22BrNOS2, calc.: 459.0326, found, m/z: 459.0316.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The methyl groups were allowed to rotate but not to tip.

The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.88±0.01 Å; its isotropic displacement parameter was freely refined.

Figures

Fig. 1.
Anisotropic displacement ellipsoid plot (Barbour, 2001) plot of C22H22BrNOS2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C22H22BrNOS2Z = 2
Mr = 460.44F(000) = 472
Triclinic, P1Dx = 1.491 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.3030 (3) ÅCell parameters from 2124 reflections
b = 9.8099 (3) Åθ = 2.4–25.2°
c = 12.3538 (4) ŵ = 2.22 mm1
α = 73.464 (2)°T = 100 K
β = 72.391 (2)°Prism, yellow
γ = 89.916 (2)°0.40 × 0.04 × 0.04 mm
V = 1025.73 (6) Å3

Data collection

Bruker SMART APEX diffractometer4709 independent reflections
Radiation source: fine-focus sealed tube3490 reflections with I > 2σ(I)
graphiteRint = 0.039
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→12
Tmin = 0.684, Tmax = 0.917k = −12→12
9757 measured reflectionsl = −16→15

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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 0.99w = 1/[σ2(Fo2) + (0.0236P)2 + 0.5453P] where P = (Fo2 + 2Fc2)/3
4709 reflections(Δ/σ)max = 0.001
250 parametersΔρmax = 0.47 e Å3
1 restraintΔρmin = −0.37 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
Br10.36770 (4)0.20219 (3)1.10143 (3)0.02491 (9)
S10.64466 (8)1.01099 (7)0.25672 (6)0.01823 (16)
S20.74397 (8)0.76685 (8)0.41055 (6)0.02190 (17)
O10.3727 (2)1.0432 (2)0.34593 (18)0.0319 (5)
N10.4826 (3)0.6419 (2)0.6181 (2)0.0182 (5)
H10.5775 (16)0.658 (3)0.571 (2)0.035 (10)*
C10.3918 (3)0.7277 (3)0.5732 (2)0.0153 (6)
C20.2258 (3)0.7000 (3)0.6438 (2)0.0181 (6)
H2A0.20560.75090.70480.022*
H2B0.20240.59660.68600.022*
C30.1189 (3)0.7459 (3)0.5701 (2)0.0179 (6)
C40.1689 (3)0.9016 (3)0.5000 (2)0.0196 (6)
H4A0.10960.93250.44430.024*
H4B0.14370.95940.55600.024*
C50.3345 (3)0.9339 (3)0.4300 (2)0.0192 (6)
C60.4459 (3)0.8392 (3)0.4637 (2)0.0149 (6)
C70.1277 (3)0.6549 (3)0.4872 (3)0.0267 (7)
H7A0.05470.68320.44390.040*
H7B0.10400.55400.53400.040*
H7C0.23020.66890.43040.040*
C8−0.0436 (3)0.7327 (3)0.6537 (3)0.0256 (7)
H8A−0.11170.76620.60670.038*
H8B−0.04830.79090.70720.038*
H8C−0.07470.63260.70070.038*
C90.6016 (3)0.8658 (3)0.3878 (2)0.0158 (6)
C100.8407 (3)0.9962 (3)0.1768 (2)0.0211 (6)
H10A0.90901.01310.22040.025*
H10B0.85310.90040.16550.025*
C110.8740 (3)1.1104 (3)0.0584 (2)0.0198 (6)
C120.8062 (3)1.0952 (3)−0.0244 (3)0.0243 (7)
H120.73921.0127−0.00550.029*
C130.8346 (3)1.1978 (3)−0.1334 (3)0.0290 (7)
H130.78811.1855−0.18910.035*
C140.9310 (4)1.3184 (3)−0.1609 (3)0.0306 (8)
H140.95111.3891−0.23580.037*
C150.9979 (4)1.3362 (3)−0.0802 (3)0.0306 (8)
H151.06371.4194−0.09920.037*
C160.9693 (3)1.2323 (3)0.0298 (3)0.0250 (7)
H161.01561.24550.08530.030*
C170.4444 (3)0.5381 (3)0.7324 (2)0.0168 (6)
C180.3865 (3)0.5766 (3)0.8354 (2)0.0203 (6)
H180.36490.67240.83080.024*
C190.3599 (3)0.4755 (3)0.9452 (3)0.0212 (6)
H190.31880.50131.01630.025*
C200.3937 (3)0.3364 (3)0.9507 (2)0.0197 (6)
C210.4509 (3)0.2970 (3)0.8484 (2)0.0202 (6)
H210.47320.20140.85310.024*
C220.4755 (3)0.3981 (3)0.7388 (2)0.0202 (6)
H220.51370.37150.66780.024*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02959 (18)0.02257 (16)0.01791 (15)−0.00197 (12)−0.00961 (12)0.00337 (12)
S10.0185 (4)0.0162 (3)0.0149 (3)0.0032 (3)−0.0018 (3)−0.0005 (3)
S20.0162 (4)0.0236 (4)0.0205 (4)0.0054 (3)−0.0041 (3)−0.0002 (3)
O10.0258 (12)0.0285 (12)0.0251 (12)0.0089 (10)−0.0013 (9)0.0094 (9)
N10.0154 (13)0.0186 (12)0.0158 (12)0.0009 (10)−0.0043 (10)0.0014 (10)
C10.0181 (15)0.0129 (13)0.0176 (14)0.0016 (11)−0.0075 (12)−0.0066 (11)
C20.0177 (15)0.0172 (14)0.0153 (14)0.0004 (11)−0.0040 (11)−0.0001 (11)
C30.0163 (15)0.0191 (14)0.0175 (14)0.0018 (12)−0.0060 (12)−0.0035 (12)
C40.0173 (15)0.0186 (14)0.0209 (15)0.0046 (12)−0.0054 (12)−0.0036 (12)
C50.0205 (15)0.0197 (15)0.0154 (14)0.0034 (12)−0.0049 (12)−0.0027 (12)
C60.0153 (14)0.0166 (13)0.0126 (13)0.0035 (11)−0.0060 (11)−0.0023 (11)
C70.0238 (17)0.0280 (16)0.0337 (18)0.0017 (13)−0.0137 (14)−0.0124 (14)
C80.0162 (15)0.0254 (16)0.0288 (17)0.0011 (13)−0.0051 (13)−0.0004 (13)
C90.0185 (14)0.0148 (13)0.0134 (13)0.0004 (11)−0.0048 (11)−0.0034 (11)
C100.0168 (15)0.0216 (15)0.0199 (15)0.0026 (12)−0.0010 (12)−0.0036 (12)
C110.0167 (15)0.0192 (14)0.0190 (15)0.0046 (12)0.0003 (12)−0.0052 (12)
C120.0210 (16)0.0254 (16)0.0224 (16)−0.0034 (13)−0.0029 (13)−0.0051 (13)
C130.0250 (17)0.0389 (19)0.0197 (16)0.0040 (14)−0.0079 (13)−0.0026 (14)
C140.0350 (19)0.0254 (17)0.0206 (16)0.0059 (15)−0.0027 (14)0.0032 (13)
C150.0343 (19)0.0179 (15)0.0315 (18)−0.0040 (14)−0.0017 (15)−0.0042 (14)
C160.0258 (17)0.0248 (16)0.0229 (16)0.0013 (13)−0.0054 (13)−0.0072 (13)
C170.0150 (14)0.0180 (14)0.0160 (14)−0.0014 (11)−0.0068 (11)−0.0009 (11)
C180.0227 (16)0.0164 (14)0.0236 (15)0.0029 (12)−0.0106 (13)−0.0054 (12)
C190.0236 (16)0.0234 (15)0.0189 (15)0.0034 (13)−0.0095 (12)−0.0067 (12)
C200.0191 (15)0.0189 (14)0.0165 (14)−0.0018 (12)−0.0072 (12)0.0033 (12)
C210.0220 (16)0.0139 (14)0.0232 (15)0.0014 (12)−0.0076 (12)−0.0026 (12)
C220.0207 (15)0.0221 (15)0.0151 (14)0.0040 (12)−0.0037 (12)−0.0035 (12)

Geometric parameters (Å, °)

Br1—C201.895 (3)C8—H8C0.9800
S1—C91.763 (3)C10—C111.511 (4)
S1—C101.820 (3)C10—H10A0.9900
S2—C91.686 (3)C10—H10B0.9900
O1—C51.224 (3)C11—C161.384 (4)
N1—C11.321 (3)C11—C121.394 (4)
N1—C171.427 (3)C12—C131.383 (4)
N1—H10.884 (10)C12—H120.9500
C1—C61.424 (3)C13—C141.382 (4)
C1—C21.506 (4)C13—H130.9500
C2—C31.527 (4)C14—C151.373 (4)
C2—H2A0.9900C14—H140.9500
C2—H2B0.9900C15—C161.396 (4)
C3—C41.518 (4)C15—H150.9500
C3—C71.524 (4)C16—H160.9500
C3—C81.532 (4)C17—C181.382 (4)
C4—C51.504 (4)C17—C221.388 (4)
C4—H4A0.9900C18—C191.385 (4)
C4—H4B0.9900C18—H180.9500
C5—C61.465 (4)C19—C201.388 (4)
C6—C91.444 (4)C19—H190.9500
C7—H7A0.9800C20—C211.379 (4)
C7—H7B0.9800C21—C221.385 (4)
C7—H7C0.9800C21—H210.9500
C8—H8A0.9800C22—H220.9500
C8—H8B0.9800
C9—S1—C10104.06 (13)C6—C9—S1116.85 (19)
C1—N1—C17127.3 (2)S2—C9—S1117.21 (16)
C1—N1—H1113 (2)C11—C10—S1104.63 (18)
C17—N1—H1120 (2)C11—C10—H10A110.8
N1—C1—C6122.4 (2)S1—C10—H10A110.8
N1—C1—C2116.2 (2)C11—C10—H10B110.8
C6—C1—C2121.4 (2)S1—C10—H10B110.8
C1—C2—C3114.7 (2)H10A—C10—H10B108.9
C1—C2—H2A108.6C16—C11—C12118.4 (3)
C3—C2—H2A108.6C16—C11—C10121.7 (3)
C1—C2—H2B108.6C12—C11—C10119.9 (3)
C3—C2—H2B108.6C13—C12—C11121.2 (3)
H2A—C2—H2B107.6C13—C12—H12119.4
C4—C3—C7111.0 (2)C11—C12—H12119.4
C4—C3—C2106.0 (2)C14—C13—C12119.6 (3)
C7—C3—C2111.0 (2)C14—C13—H13120.2
C4—C3—C8109.5 (2)C12—C13—H13120.2
C7—C3—C8109.9 (2)C15—C14—C13120.1 (3)
C2—C3—C8109.4 (2)C15—C14—H14119.9
C5—C4—C3115.2 (2)C13—C14—H14119.9
C5—C4—H4A108.5C14—C15—C16120.2 (3)
C3—C4—H4A108.5C14—C15—H15119.9
C5—C4—H4B108.5C16—C15—H15119.9
C3—C4—H4B108.5C11—C16—C15120.4 (3)
H4A—C4—H4B107.5C11—C16—H16119.8
O1—C5—C6121.5 (3)C15—C16—H16119.8
O1—C5—C4117.6 (2)C18—C17—C22120.1 (2)
C6—C5—C4120.9 (2)C18—C17—N1121.1 (2)
C1—C6—C9124.3 (2)C22—C17—N1118.6 (2)
C1—C6—C5116.5 (2)C17—C18—C19120.0 (3)
C9—C6—C5119.2 (2)C17—C18—H18120.0
C3—C7—H7A109.5C19—C18—H18120.0
C3—C7—H7B109.5C18—C19—C20119.4 (3)
H7A—C7—H7B109.5C18—C19—H19120.3
C3—C7—H7C109.5C20—C19—H19120.3
H7A—C7—H7C109.5C21—C20—C19120.9 (3)
H7B—C7—H7C109.5C21—C20—Br1120.2 (2)
C3—C8—H8A109.5C19—C20—Br1118.9 (2)
C3—C8—H8B109.5C20—C21—C22119.4 (3)
H8A—C8—H8B109.5C20—C21—H21120.3
C3—C8—H8C109.5C22—C21—H21120.3
H8A—C8—H8C109.5C21—C22—C17120.1 (3)
H8B—C8—H8C109.5C21—C22—H22120.0
C6—C9—S2125.9 (2)C17—C22—H22120.0
C17—N1—C1—C6172.3 (3)C10—S1—C9—S24.9 (2)
C17—N1—C1—C2−8.4 (4)C9—S1—C10—C11174.14 (19)
N1—C1—C2—C3−152.6 (2)S1—C10—C11—C16109.1 (3)
C6—C1—C2—C326.7 (4)S1—C10—C11—C12−69.9 (3)
C1—C2—C3—C4−53.7 (3)C16—C11—C12—C131.0 (4)
C1—C2—C3—C766.9 (3)C10—C11—C12—C13−179.9 (3)
C1—C2—C3—C8−171.7 (2)C11—C12—C13—C14−0.5 (5)
C7—C3—C4—C5−68.6 (3)C12—C13—C14—C15−0.2 (5)
C2—C3—C4—C552.0 (3)C13—C14—C15—C160.3 (5)
C8—C3—C4—C5169.9 (2)C12—C11—C16—C15−0.8 (4)
C3—C4—C5—O1158.1 (3)C10—C11—C16—C15−179.9 (3)
C3—C4—C5—C6−23.4 (4)C14—C15—C16—C110.2 (5)
N1—C1—C6—C93.5 (4)C1—N1—C17—C18−58.6 (4)
C2—C1—C6—C9−175.8 (2)C1—N1—C17—C22125.4 (3)
N1—C1—C6—C5−174.7 (2)C22—C17—C18—C190.2 (4)
C2—C1—C6—C56.0 (4)N1—C17—C18—C19−175.6 (2)
O1—C5—C6—C1170.7 (3)C17—C18—C19—C200.8 (4)
C4—C5—C6—C1−7.8 (4)C18—C19—C20—C21−1.1 (4)
O1—C5—C6—C9−7.6 (4)C18—C19—C20—Br1176.4 (2)
C4—C5—C6—C9173.9 (2)C19—C20—C21—C220.3 (4)
C1—C6—C9—S23.1 (4)Br1—C20—C21—C22−177.1 (2)
C5—C6—C9—S2−178.7 (2)C20—C21—C22—C170.7 (4)
C1—C6—C9—S1−179.3 (2)C18—C17—C22—C21−1.0 (4)
C5—C6—C9—S1−1.2 (3)N1—C17—C22—C21174.9 (2)
C10—S1—C9—C6−172.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···S20.88 (1)2.10 (2)2.905 (2)151 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2876).

References

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