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Acta Cryst. (2009). E65, o600    [ doi:10.1107/S1600536809006175 ]

n-Undecanyl 2-(4-bromoanilino)-4,4-dimethyl-6-oxocyclohex-1-enecarbodithioate

E. S. H. El Ashry, M. R. Amer, M. R. Shah and S. W. Ng

Abstract top

The six-membered cyclohexene ring in the title compound, C26H38BrNOS2, adopts an envelope conformation, with the C atom bearing the two methyl groups representing the flap. This atom deviates by 0.651 (3) Å from the plane passing through the other five atoms of the ring (r.m.s. deviation = 0.051 Å). The molecular conformation is stabilized by an N-H...S hydrogen bond. The title compound is isomorphous with n-undecanyl 2-(4-chloroanilino)-4,4-dimethyl-6-oxocyclohex-1-enecarbodithioate.

Related literature top

For background, see: El Ashry et al. (2009a). For the isomorphous n-undecanyl 2-(4-chloroanilino)-4,4-dimethyl-6-oxocyclohex-1-enylcarbodithioate, see: El Ashry et al. (2009b).

Experimental top

To a solution of (4-bromophenylamino)-5,5-dimethyl-cyclohex-2-en-1-one (0.1 mol) in DMSO (20 ml) and sodium hydroxide (0.4 g) in water (1 ml), carbon disulfide (0.3 mol) was added in the course of 30 minutes. The mixture was stirred for 20 min at 283 K, and then 1-bromoundecane (0.1 mol) was added drop wise at room temperature for 30 min. The reaction mixture was left for 24 h and then diluted with water (200 ml) and acidified with 10% hydrochloric acid. The resulting precipitate was collected by filtration, dried and purified on silica gel column (40% ethyl acetate in hexane) to give yellow crystal (38% yield; mp.410 K).

Refinement top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) plot of C26H38BrNOS2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
n-Undecanyl 2-(4-bromoanilino)-4,4-dimethyl-6-oxocyclohex-1-enecarbodithioate top
Crystal data top
C26H38BrNOS2Z = 2
Mr = 524.60F(000) = 552
Triclinic, P1Dx = 1.296 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0469 (2) ÅCell parameters from 3369 reflections
b = 11.8346 (3) Åθ = 2.7–27.3°
c = 14.9374 (3) ŵ = 1.70 mm−1
α = 95.863 (1)°T = 100 K
β = 95.414 (2)°Chip, orange
γ = 106.595 (1)°0.45 × 0.15 × 0.05 mm
V = 1344.70 (5) Å3
Data collection top
Bruker SMART APEX
diffractometer		6149 independent reflections
Radiation source: fine-focus sealed tube4426 reflections with I > 2σ(I)
graphiteRint = 0.028
ω scansθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.768, Tmax = 0.920k = −15→15
12608 measured reflectionsl = −18→19
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) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0482P)2 + 0.562P]
where P = (Fo2 + 2Fc2)/3
6149 reflections(Δ/σ)max = 0.001
287 parametersΔρmax = 0.60 e Å−3
1 restraintΔρmin = −0.73 e Å−3
Crystal data top
C26H38BrNOS2γ = 106.595 (1)°
Mr = 524.60V = 1344.70 (5) Å3
Triclinic, P1Z = 2
a = 8.0469 (2) ÅMo Kα radiation
b = 11.8346 (3) ŵ = 1.70 mm−1
c = 14.9374 (3) ÅT = 100 K
α = 95.863 (1)°0.45 × 0.15 × 0.05 mm
β = 95.414 (2)°
Data collection top
Bruker SMART APEX
diffractometer		6149 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4426 reflections with I > 2σ(I)
Tmin = 0.768, Tmax = 0.920Rint = 0.028
12608 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104Δρmax = 0.60 e Å−3
S = 1.02Δρmin = −0.73 e Å−3
6149 reflectionsAbsolute structure: ?
287 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.20125 (4)0.40758 (3)1.043527 (19)0.04841 (12)
S10.63664 (8)0.25017 (5)0.39673 (4)0.01981 (14)
S20.39769 (8)0.15843 (5)0.52739 (4)0.02570 (15)
N10.4559 (3)0.34432 (19)0.67717 (14)0.0227 (5)
H10.417 (4)0.2707 (13)0.6491 (19)0.043 (9)*
O10.7716 (2)0.47491 (15)0.43470 (11)0.0243 (4)
C10.7367 (3)0.4886 (2)0.51245 (15)0.0176 (5)
C20.8229 (3)0.6079 (2)0.56838 (15)0.0197 (5)
H2A0.76690.66580.54590.024*
H2B0.94710.63430.55800.024*
C30.8164 (3)0.6126 (2)0.67035 (16)0.0196 (5)
C40.6285 (3)0.5481 (2)0.68353 (16)0.0194 (5)
H4A0.62160.54630.74920.023*
H4B0.55100.59360.66120.023*
C50.5629 (3)0.4234 (2)0.63549 (15)0.0171 (5)
C60.6129 (3)0.3925 (2)0.54951 (15)0.0172 (5)
C70.9431 (3)0.5538 (2)0.71398 (17)0.0267 (6)
H7A1.06310.59810.70680.040*
H7B0.91620.47170.68450.040*
H7C0.93160.55390.77870.040*
C80.8613 (3)0.7423 (2)0.71367 (18)0.0287 (6)
H8A0.77590.77840.68750.043*
H8B0.97860.78620.70200.043*
H8C0.85830.74530.77930.043*
C90.5497 (3)0.2747 (2)0.49803 (16)0.0190 (5)
C100.5389 (3)0.0919 (2)0.36124 (17)0.0244 (5)
H10A0.54760.04770.41340.029*
H10B0.41370.07500.33800.029*
C110.6358 (3)0.0527 (2)0.28703 (16)0.0239 (5)
H11A0.75990.06930.31210.029*
H11B0.5864−0.03440.26990.029*
C120.6282 (3)0.1122 (2)0.20152 (16)0.0257 (6)
H12A0.50430.09840.17710.031*
H12B0.68270.19910.21760.031*
C130.7204 (3)0.0665 (2)0.12828 (17)0.0269 (6)
H13A0.6626−0.01980.11050.032*
H13B0.84290.07710.15370.032*
C140.7206 (4)0.1286 (2)0.04413 (17)0.0285 (6)
H14A0.59810.11590.01760.034*
H14B0.77480.21530.06220.034*
C150.8177 (4)0.0858 (3)−0.02797 (17)0.0303 (6)
H15A0.7686−0.0016−0.04330.036*
H15B0.94210.1036−0.00290.036*
C160.8069 (4)0.1428 (2)−0.11419 (17)0.0283 (6)
H16A0.85770.2301−0.09890.034*
H16B0.68220.1263−0.13840.034*
C170.9010 (4)0.0991 (3)−0.18796 (17)0.0292 (6)
H17A1.02670.1187−0.16480.035*
H17B0.85370.0114−0.20160.035*
C180.8831 (3)0.1527 (2)−0.27507 (17)0.0275 (6)
H18A0.75720.1372−0.29610.033*
H18B0.93630.2401−0.26180.033*
C190.9672 (3)0.1054 (3)−0.35106 (17)0.0289 (6)
H19A0.91860.0176−0.36250.035*
H19B1.09440.1251−0.33170.035*
C200.9383 (4)0.1558 (3)−0.4385 (2)0.0415 (7)
H20A0.99460.1220−0.48530.062*
H20B0.98900.2426−0.42820.062*
H20C0.81260.1355−0.45860.062*
C210.3982 (3)0.3639 (2)0.76329 (16)0.0223 (5)
C220.2948 (3)0.4369 (3)0.77828 (18)0.0321 (6)
H220.26310.47800.73130.039*
C230.2372 (4)0.4502 (3)0.86191 (18)0.0358 (7)
H230.16670.50110.87280.043*
C240.2825 (3)0.3895 (3)0.92928 (17)0.0302 (6)
C250.3827 (4)0.3158 (3)0.91502 (19)0.0395 (7)
H250.41170.27350.96190.047*
C260.4422 (4)0.3029 (2)0.83136 (18)0.0342 (7)
H260.51320.25220.82100.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0475 (2)0.0680 (3)0.02154 (15)0.00315 (17)0.01392 (13)0.00077 (14)
S10.0220 (3)0.0169 (3)0.0192 (3)0.0037 (2)0.0035 (2)0.0015 (2)
S20.0276 (3)0.0168 (3)0.0307 (3)0.0012 (3)0.0111 (3)0.0029 (3)
N10.0266 (11)0.0189 (11)0.0226 (11)0.0046 (9)0.0089 (9)0.0035 (9)
O10.0282 (9)0.0220 (9)0.0202 (9)0.0019 (8)0.0076 (7)0.0037 (7)
C10.0145 (11)0.0183 (12)0.0199 (12)0.0048 (9)0.0012 (9)0.0028 (9)
C20.0210 (12)0.0176 (12)0.0196 (12)0.0035 (10)0.0021 (9)0.0046 (9)
C30.0167 (11)0.0206 (12)0.0199 (12)0.0038 (10)0.0016 (9)0.0015 (10)
C40.0197 (12)0.0206 (12)0.0181 (11)0.0052 (10)0.0039 (9)0.0039 (9)
C50.0130 (11)0.0190 (12)0.0203 (11)0.0060 (9)0.0004 (9)0.0052 (9)
C60.0166 (11)0.0161 (12)0.0188 (11)0.0042 (9)0.0017 (9)0.0045 (9)
C70.0203 (12)0.0363 (15)0.0223 (13)0.0068 (11)0.0011 (10)0.0052 (11)
C80.0284 (14)0.0232 (14)0.0290 (14)0.0002 (11)0.0056 (11)−0.0017 (11)
C90.0181 (11)0.0215 (12)0.0191 (11)0.0080 (10)0.0020 (9)0.0051 (10)
C100.0287 (13)0.0166 (12)0.0244 (13)0.0024 (11)0.0029 (10)0.0001 (10)
C110.0282 (13)0.0164 (12)0.0252 (13)0.0055 (11)0.0023 (10)−0.0015 (10)
C120.0285 (14)0.0245 (13)0.0217 (13)0.0062 (11)0.0009 (10)−0.0014 (10)
C130.0279 (14)0.0251 (14)0.0242 (13)0.0050 (11)0.0006 (10)−0.0018 (11)
C140.0322 (14)0.0279 (14)0.0247 (13)0.0093 (12)0.0025 (11)0.0011 (11)
C150.0319 (15)0.0364 (16)0.0232 (14)0.0118 (13)0.0024 (11)0.0028 (12)
C160.0295 (14)0.0286 (14)0.0263 (14)0.0084 (12)0.0031 (11)0.0016 (11)
C170.0281 (14)0.0340 (15)0.0247 (13)0.0076 (12)0.0029 (11)0.0051 (11)
C180.0272 (13)0.0244 (14)0.0287 (14)0.0039 (11)0.0044 (11)0.0042 (11)
C190.0242 (13)0.0350 (15)0.0283 (14)0.0080 (12)0.0050 (11)0.0093 (12)
C200.0422 (17)0.052 (2)0.0341 (16)0.0140 (15)0.0125 (13)0.0174 (14)
C210.0205 (12)0.0229 (13)0.0200 (12)0.0001 (10)0.0048 (10)0.0025 (10)
C220.0301 (14)0.0501 (18)0.0248 (14)0.0212 (14)0.0083 (11)0.0132 (13)
C230.0282 (14)0.058 (2)0.0278 (14)0.0222 (14)0.0086 (12)0.0060 (14)
C240.0271 (14)0.0384 (16)0.0191 (13)−0.0008 (12)0.0069 (10)0.0032 (11)
C250.060 (2)0.0362 (17)0.0251 (14)0.0145 (16)0.0092 (14)0.0122 (13)
C260.0531 (18)0.0269 (15)0.0288 (15)0.0181 (14)0.0102 (13)0.0094 (12)
Geometric parameters (Å, °) top
Br1—C241.898 (3)C12—H12B0.9900
S1—C91.758 (2)C13—C141.520 (4)
S1—C101.813 (2)C13—H13A0.9900
S2—C91.687 (2)C13—H13B0.9900
N1—C51.328 (3)C14—C151.517 (4)
N1—C211.427 (3)C14—H14A0.9900
N1—H10.882 (10)C14—H14B0.9900
O1—C11.226 (3)C15—C161.520 (4)
C1—C61.475 (3)C15—H15A0.9900
C1—C21.505 (3)C15—H15B0.9900
C2—C31.525 (3)C16—C171.523 (4)
C2—H2A0.9900C16—H16A0.9900
C2—H2B0.9900C16—H16B0.9900
C3—C71.524 (3)C17—C181.517 (4)
C3—C41.529 (3)C17—H17A0.9900
C3—C81.530 (3)C17—H17B0.9900
C4—C51.496 (3)C18—C191.514 (4)
C4—H4A0.9900C18—H18A0.9900
C4—H4B0.9900C18—H18B0.9900
C5—C61.425 (3)C19—C201.516 (4)
C6—C91.447 (3)C19—H19A0.9900
C7—H7A0.9800C19—H19B0.9900
C7—H7B0.9800C20—H20A0.9800
C7—H7C0.9800C20—H20B0.9800
C8—H8A0.9800C20—H20C0.9800
C8—H8B0.9800C21—C221.376 (4)
C8—H8C0.9800C21—C261.381 (4)
C10—C111.521 (3)C22—C231.382 (4)
C10—H10A0.9900C22—H220.9500
C10—H10B0.9900C23—C241.375 (4)
C11—C121.524 (3)C23—H230.9500
C11—H11A0.9900C24—C251.361 (4)
C11—H11B0.9900C25—C261.389 (4)
C12—C131.517 (3)C25—H250.9500
C12—H12A0.9900C26—H260.9500
C9—S1—C10103.12 (11)C12—C13—H13A108.8
C5—N1—C21127.6 (2)C14—C13—H13A108.8
C5—N1—H1117 (2)C12—C13—H13B108.8
C21—N1—H1116 (2)C14—C13—H13B108.8
O1—C1—C6121.4 (2)H13A—C13—H13B107.7
O1—C1—C2117.4 (2)C15—C14—C13113.7 (2)
C6—C1—C2121.1 (2)C15—C14—H14A108.8
C1—C2—C3115.96 (19)C13—C14—H14A108.8
C1—C2—H2A108.3C15—C14—H14B108.8
C3—C2—H2A108.3C13—C14—H14B108.8
C1—C2—H2B108.3H14A—C14—H14B107.7
C3—C2—H2B108.3C14—C15—C16113.2 (2)
H2A—C2—H2B107.4C14—C15—H15A108.9
C2—C3—C7111.1 (2)C16—C15—H15A108.9
C2—C3—C4107.11 (19)C14—C15—H15B108.9
C7—C3—C4110.6 (2)C16—C15—H15B108.9
C2—C3—C8109.5 (2)H15A—C15—H15B107.7
C7—C3—C8109.9 (2)C15—C16—C17113.9 (2)
C4—C3—C8108.6 (2)C15—C16—H16A108.8
C5—C4—C3113.52 (19)C17—C16—H16A108.8
C5—C4—H4A108.9C15—C16—H16B108.8
C3—C4—H4A108.9C17—C16—H16B108.8
C5—C4—H4B108.9H16A—C16—H16B107.7
C3—C4—H4B108.9C18—C17—C16113.4 (2)
H4A—C4—H4B107.7C18—C17—H17A108.9
N1—C5—C6122.4 (2)C16—C17—H17A108.9
N1—C5—C4116.4 (2)C18—C17—H17B108.9
C6—C5—C4121.3 (2)C16—C17—H17B108.9
C5—C6—C9124.1 (2)H17A—C17—H17B107.7
C5—C6—C1116.5 (2)C19—C18—C17114.3 (2)
C9—C6—C1119.4 (2)C19—C18—H18A108.7
C3—C7—H7A109.5C17—C18—H18A108.7
C3—C7—H7B109.5C19—C18—H18B108.7
H7A—C7—H7B109.5C17—C18—H18B108.7
C3—C7—H7C109.5H18A—C18—H18B107.6
H7A—C7—H7C109.5C18—C19—C20112.9 (2)
H7B—C7—H7C109.5C18—C19—H19A109.0
C3—C8—H8A109.5C20—C19—H19A109.0
C3—C8—H8B109.5C18—C19—H19B109.0
H8A—C8—H8B109.5C20—C19—H19B109.0
C3—C8—H8C109.5H19A—C19—H19B107.8
H8A—C8—H8C109.5C19—C20—H20A109.5
H8B—C8—H8C109.5C19—C20—H20B109.5
C6—C9—S2125.08 (18)H20A—C20—H20B109.5
C6—C9—S1117.86 (17)C19—C20—H20C109.5
S2—C9—S1117.06 (14)H20A—C20—H20C109.5
C11—C10—S1108.50 (16)H20B—C20—H20C109.5
C11—C10—H10A110.0C22—C21—C26120.0 (2)
S1—C10—H10A110.0C22—C21—N1121.8 (2)
C11—C10—H10B110.0C26—C21—N1118.1 (2)
S1—C10—H10B110.0C21—C22—C23119.9 (3)
H10A—C10—H10B108.4C21—C22—H22120.1
C12—C11—C10115.1 (2)C23—C22—H22120.1
C12—C11—H11A108.5C24—C23—C22119.6 (3)
C10—C11—H11A108.5C24—C23—H23120.2
C12—C11—H11B108.5C22—C23—H23120.2
C10—C11—H11B108.5C25—C24—C23121.1 (3)
H11A—C11—H11B107.5C25—C24—Br1119.6 (2)
C13—C12—C11113.1 (2)C23—C24—Br1119.3 (2)
C13—C12—H12A109.0C24—C25—C26119.5 (3)
C11—C12—H12A109.0C24—C25—H25120.3
C13—C12—H12B109.0C26—C25—H25120.3
C11—C12—H12B109.0C21—C26—C25119.9 (3)
H12A—C12—H12B107.8C21—C26—H26120.0
C12—C13—C14113.6 (2)C25—C26—H26120.0
O1—C1—C2—C3−164.4 (2)C10—S1—C9—C6174.90 (18)
C6—C1—C2—C316.5 (3)C10—S1—C9—S2−5.28 (17)
C1—C2—C3—C774.2 (3)C9—S1—C10—C11−166.51 (17)
C1—C2—C3—C4−46.7 (3)S1—C10—C11—C12−61.2 (2)
C1—C2—C3—C8−164.2 (2)C10—C11—C12—C13−177.7 (2)
C2—C3—C4—C555.8 (3)C11—C12—C13—C14−177.6 (2)
C7—C3—C4—C5−65.4 (3)C12—C13—C14—C15178.2 (2)
C8—C3—C4—C5174.0 (2)C13—C14—C15—C16176.2 (2)
C21—N1—C5—C6179.2 (2)C14—C15—C16—C17−179.0 (2)
C21—N1—C5—C4−1.1 (4)C15—C16—C17—C18177.6 (2)
C3—C4—C5—N1144.6 (2)C16—C17—C18—C19−176.8 (2)
C3—C4—C5—C6−35.7 (3)C17—C18—C19—C20176.9 (2)
N1—C5—C6—C91.9 (4)C5—N1—C21—C2265.1 (4)
C4—C5—C6—C9−177.8 (2)C5—N1—C21—C26−117.8 (3)
N1—C5—C6—C1−178.2 (2)C26—C21—C22—C230.9 (4)
C4—C5—C6—C12.1 (3)N1—C21—C22—C23177.9 (2)
O1—C1—C6—C5−171.3 (2)C21—C22—C23—C24−0.6 (4)
C2—C1—C6—C57.8 (3)C22—C23—C24—C25−0.3 (4)
O1—C1—C6—C98.6 (3)C22—C23—C24—Br1−179.5 (2)
C2—C1—C6—C9−172.3 (2)C23—C24—C25—C260.9 (4)
C5—C6—C9—S24.4 (3)Br1—C24—C25—C26−179.9 (2)
C1—C6—C9—S2−175.45 (17)C22—C21—C26—C25−0.3 (4)
C5—C6—C9—S1−175.79 (18)N1—C21—C26—C25−177.4 (2)
C1—C6—C9—S14.4 (3)C24—C25—C26—C21−0.6 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S20.88 (1)2.11 (2)2.876 (2)146 (3)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S20.88 (1)2.11 (2)2.876 (2)146 (3)
Acknowledgements top

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

references
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