(±)-1,2-Bis(N'-benzoyl-thio-ureido)cyclo-hexa-ne.

In the title compound, C(22)H(24)N(4)O(2)S(2), the two thio-urea segments of the side-arm groups are inclined at a dihedral angle of 73.09 (9)°. The central cyclo-hexane bridge adopts a chair conformation. The mol-ecule is stabilized by N-H⋯O intra-molecular hydrogen bonds forming S(6) rings, and N-H⋯O and N-H⋯S inter-molecular hydrogen bonds forming infinite chains developing parallel to the b axis.

Related literature

For related structures, see: Yusof et al. (2008 ▶); Thiam et al. (2008 ▶). For bond-length data, see Allen et al. (1987 ▶). For a description of hydrogen-bonding patterns, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C22H24N4O2S2

M = 440.57

Monoclinic,

a = 19.725 (6) Å

b = 11.054 (3) Å

c = 20.700 (5) Å

β = 91.252 (9)°

V = 4512 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.26 mm−1

T = 298 K

0.45 × 0.39 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.891, T max = 0.950

16892 measured reflections

4212 independent reflections

3334 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.145

S = 1.11

4212 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014991/dn2675sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014991/dn2675Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811014991/dn2675Isup3.cml

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

C22H24N4O2S2	F(000) = 1856
Mr = 440.57	Dx = 1.297 Mg m−3
Monoclinic, C2/c	Melting point = 495.3–497.3 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 19.725 (6) Å	Cell parameters from 4375 reflections
b = 11.054 (3) Å	θ = 2.0–25.2°
c = 20.700 (5) Å	µ = 0.26 mm−1
β = 91.252 (9)°	T = 298 K
V = 4512 (2) Å3	Block, colourless
Z = 8	0.45 × 0.39 × 0.20 mm

Bruker SMART APEX CCD area-detector diffractometer	4212 independent reflections
Radiation source: fine-focus sealed tube	3334 reflections with I > 2σ(I)
graphite	Rint = 0.043
Detector resolution: 83.66 pixels mm-1	θmax = 25.5°, θmin = 2.0°
ω scans	h = −23→23
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→13
Tmin = 0.891, Tmax = 0.950	l = −24→25
16892 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0596P)2 + 4.3773P] where P = (Fo2 + 2Fc2)/3
4212 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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	0.02397 (4)	0.38387 (8)	0.42308 (5)	0.0633 (3)
S2	0.02746 (4)	0.92533 (8)	0.41333 (4)	0.0586 (3)
O1	−0.09838 (10)	0.7174 (2)	0.36607 (12)	0.0702 (7)
O2	0.14844 (9)	0.71111 (18)	0.56241 (9)	0.0492 (5)
N1	−0.07970 (10)	0.5330 (2)	0.41058 (11)	0.0468 (6)
H1A	−0.1004	0.4730	0.4279	0.056*
N2	0.02222 (10)	0.6069 (2)	0.37479 (11)	0.0454 (6)
H2A	0.0001	0.6723	0.3664	0.054*
N3	0.12087 (11)	0.7590 (2)	0.43944 (10)	0.0450 (6)
H3A	0.1456	0.7217	0.4678	0.054*
N4	0.08148 (11)	0.86601 (19)	0.52667 (10)	0.0410 (5)
H4A	0.0591	0.9281	0.5394	0.049*
C1	−0.21028 (19)	0.5515 (3)	0.4688 (2)	0.0898 (13)
H1B	−0.1791	0.4990	0.4881	0.108*
C2	−0.2756 (2)	0.5544 (4)	0.4898 (3)	0.124 (2)
H2B	−0.2884	0.5035	0.5231	0.149*
C3	−0.32249 (19)	0.6311 (5)	0.4623 (3)	0.1007 (17)
H3B	−0.3668	0.6324	0.4767	0.121*
C4	−0.3036 (2)	0.7045 (5)	0.4142 (2)	0.1030 (17)
H4B	−0.3352	0.7564	0.3951	0.124*
C5	−0.23709 (17)	0.7038 (4)	0.39271 (18)	0.0871 (13)
H5A	−0.2245	0.7565	0.3601	0.104*
C6	−0.19050 (14)	0.6265 (3)	0.41907 (15)	0.0523 (8)
C7	−0.11937 (14)	0.6315 (3)	0.39623 (14)	0.0477 (7)
C8	−0.01047 (13)	0.5160 (3)	0.40108 (13)	0.0440 (6)
C9	0.09410 (13)	0.6023 (3)	0.35922 (13)	0.0446 (6)
H9A	0.1160	0.5420	0.3874	0.054*
C10	0.10317 (15)	0.5628 (3)	0.28926 (15)	0.0606 (8)
H10A	0.0819	0.4846	0.2825	0.073*
H10B	0.0810	0.6205	0.2605	0.073*
C11	0.17797 (17)	0.5547 (4)	0.27354 (17)	0.0723 (10)
H11A	0.1993	0.4919	0.2997	0.087*
H11B	0.1827	0.5330	0.2285	0.087*
C12	0.21279 (16)	0.6735 (4)	0.28648 (16)	0.0701 (10)
H12A	0.1947	0.7342	0.2570	0.084*
H12B	0.2609	0.6652	0.2786	0.084*
C13	0.20305 (14)	0.7155 (4)	0.35590 (15)	0.0631 (9)
H13A	0.2238	0.7944	0.3619	0.076*
H13B	0.2255	0.6594	0.3853	0.076*
C14	0.12781 (12)	0.7232 (3)	0.37194 (12)	0.0434 (6)
H14A	0.1061	0.7845	0.3442	0.052*
C15	0.07964 (13)	0.8440 (2)	0.46047 (12)	0.0419 (6)
C16	0.11438 (12)	0.8012 (2)	0.57403 (13)	0.0398 (6)
C17	0.10748 (12)	0.8470 (3)	0.64079 (13)	0.0419 (6)
C18	0.10957 (15)	0.9688 (3)	0.65517 (14)	0.0526 (7)
H18A	0.1143	1.0253	0.6223	0.063*
C19	0.10464 (18)	1.0065 (3)	0.71809 (17)	0.0713 (10)
H19A	0.1066	1.0886	0.7278	0.086*
C20	0.09689 (18)	0.9240 (4)	0.76659 (17)	0.0742 (10)
H20A	0.0933	0.9504	0.8090	0.089*
C21	0.09432 (17)	0.8037 (4)	0.75319 (15)	0.0673 (9)
H21A	0.0884	0.7482	0.7863	0.081*
C22	0.10055 (15)	0.7639 (3)	0.69031 (14)	0.0546 (8)
H22A	0.1001	0.6815	0.6813	0.065*

	U11	U22	U33	U12	U13	U23
S1	0.0446 (4)	0.0520 (5)	0.0936 (7)	0.0080 (3)	0.0057 (4)	0.0092 (4)
S2	0.0634 (5)	0.0719 (6)	0.0406 (4)	0.0246 (4)	0.0012 (3)	0.0038 (4)
O1	0.0475 (12)	0.0653 (15)	0.0982 (18)	0.0125 (11)	0.0131 (12)	0.0236 (13)
O2	0.0491 (11)	0.0522 (12)	0.0463 (11)	0.0115 (9)	−0.0001 (9)	−0.0018 (9)
N1	0.0325 (11)	0.0479 (13)	0.0602 (15)	0.0014 (10)	0.0076 (10)	0.0023 (11)
N2	0.0320 (11)	0.0500 (13)	0.0544 (14)	0.0050 (10)	0.0054 (10)	0.0016 (11)
N3	0.0399 (12)	0.0545 (14)	0.0405 (13)	0.0060 (11)	0.0009 (10)	−0.0002 (11)
N4	0.0438 (12)	0.0408 (12)	0.0387 (12)	0.0064 (10)	0.0041 (9)	0.0007 (10)
C1	0.067 (2)	0.060 (2)	0.144 (4)	0.0126 (18)	0.050 (2)	0.012 (2)
C2	0.086 (3)	0.073 (3)	0.217 (6)	0.002 (2)	0.090 (4)	0.002 (3)
C3	0.045 (2)	0.112 (4)	0.147 (5)	−0.008 (2)	0.030 (2)	−0.065 (3)
C4	0.051 (2)	0.175 (5)	0.083 (3)	0.042 (3)	−0.009 (2)	−0.032 (3)
C5	0.053 (2)	0.141 (4)	0.067 (2)	0.036 (2)	0.0017 (17)	0.002 (2)
C6	0.0376 (15)	0.0555 (18)	0.064 (2)	0.0017 (13)	0.0041 (13)	−0.0204 (15)
C7	0.0389 (14)	0.0502 (18)	0.0541 (18)	0.0014 (13)	0.0022 (13)	−0.0044 (14)
C8	0.0365 (13)	0.0499 (16)	0.0456 (16)	0.0021 (12)	0.0004 (11)	−0.0064 (13)
C9	0.0335 (13)	0.0547 (17)	0.0459 (16)	0.0058 (12)	0.0061 (11)	−0.0004 (13)
C10	0.0539 (18)	0.072 (2)	0.0557 (19)	0.0005 (16)	0.0075 (14)	−0.0163 (16)
C11	0.060 (2)	0.100 (3)	0.057 (2)	0.018 (2)	0.0176 (16)	−0.0145 (19)
C12	0.0414 (16)	0.111 (3)	0.059 (2)	0.0034 (18)	0.0204 (14)	−0.005 (2)
C13	0.0391 (16)	0.093 (3)	0.0574 (19)	−0.0060 (16)	0.0096 (13)	−0.0071 (18)
C14	0.0352 (13)	0.0594 (18)	0.0358 (14)	0.0029 (12)	0.0063 (11)	−0.0006 (13)
C15	0.0370 (13)	0.0480 (16)	0.0411 (15)	−0.0013 (12)	0.0077 (11)	0.0026 (13)
C16	0.0327 (13)	0.0414 (15)	0.0453 (15)	−0.0023 (11)	0.0028 (11)	0.0035 (12)
C17	0.0343 (13)	0.0500 (16)	0.0413 (15)	0.0019 (12)	−0.0009 (11)	0.0017 (13)
C18	0.0573 (17)	0.0518 (18)	0.0485 (17)	0.0038 (14)	−0.0049 (13)	−0.0018 (14)
C19	0.089 (3)	0.064 (2)	0.061 (2)	0.0148 (19)	−0.0099 (18)	−0.0170 (18)
C20	0.082 (2)	0.096 (3)	0.0451 (19)	0.016 (2)	0.0042 (17)	−0.018 (2)
C21	0.073 (2)	0.088 (3)	0.0418 (18)	−0.0025 (19)	0.0034 (15)	0.0087 (17)
C22	0.0590 (18)	0.0589 (19)	0.0457 (17)	−0.0045 (15)	−0.0003 (14)	0.0005 (15)

S1—C8	1.670 (3)	C9—C14	1.513 (4)
S2—C15	1.666 (3)	C9—C10	1.527 (4)
O1—C7	1.215 (3)	C9—H9A	0.9800
O2—C16	1.228 (3)	C10—C11	1.521 (4)
N1—C7	1.370 (4)	C10—H10A	0.9700
N1—C8	1.397 (3)	C10—H10B	0.9700
N1—H1A	0.8600	C11—C12	1.504 (5)
N2—C8	1.318 (3)	C11—H11A	0.9700
N2—C9	1.462 (3)	C11—H11B	0.9700
N2—H2A	0.8600	C12—C13	1.526 (4)
N3—C15	1.323 (3)	C12—H12A	0.9700
N3—C14	1.462 (3)	C12—H12B	0.9700
N3—H3A	0.8600	C13—C14	1.530 (4)
N4—C16	1.366 (3)	C13—H13A	0.9700
N4—C15	1.392 (3)	C13—H13B	0.9700
N4—H4A	0.8600	C14—H14A	0.9800
C1—C2	1.369 (5)	C16—C17	1.481 (4)
C1—C6	1.385 (5)	C17—C18	1.379 (4)
C1—H1B	0.9300	C17—C22	1.386 (4)
C2—C3	1.369 (7)	C18—C19	1.373 (4)
C2—H2B	0.9300	C18—H18A	0.9300
C3—C4	1.342 (7)	C19—C20	1.367 (5)
C3—H3B	0.9300	C19—H19A	0.9300
C4—C5	1.394 (5)	C20—C21	1.359 (5)
C4—H4B	0.9300	C20—H20A	0.9300
C5—C6	1.360 (5)	C21—C22	1.382 (4)
C5—H5A	0.9300	C21—H21A	0.9300
C6—C7	1.491 (4)	C22—H22A	0.9300
C7—N1—C8	129.2 (2)	C12—C11—C10	110.6 (3)
C7—N1—H1A	115.4	C12—C11—H11A	109.5
C8—N1—H1A	115.4	C10—C11—H11A	109.5
C8—N2—C9	123.4 (2)	C12—C11—H11B	109.5
C8—N2—H2A	118.3	C10—C11—H11B	109.5
C9—N2—H2A	118.3	H11A—C11—H11B	108.1
C15—N3—C14	125.3 (2)	C11—C12—C13	111.5 (3)
C15—N3—H3A	117.4	C11—C12—H12A	109.3
C14—N3—H3A	117.4	C13—C12—H12A	109.3
C16—N4—C15	128.1 (2)	C11—C12—H12B	109.3
C16—N4—H4A	116.0	C13—C12—H12B	109.3
C15—N4—H4A	116.0	H12A—C12—H12B	108.0
C2—C1—C6	120.2 (4)	C12—C13—C14	111.3 (2)
C2—C1—H1B	119.9	C12—C13—H13A	109.4
C6—C1—H1B	119.9	C14—C13—H13A	109.4
C1—C2—C3	121.0 (5)	C12—C13—H13B	109.4
C1—C2—H2B	119.5	C14—C13—H13B	109.4
C3—C2—H2B	119.5	H13A—C13—H13B	108.0
C4—C3—C2	119.1 (4)	N3—C14—C9	110.8 (2)
C4—C3—H3B	120.5	N3—C14—C13	109.5 (2)
C2—C3—H3B	120.5	C9—C14—C13	109.8 (2)
C3—C4—C5	120.8 (4)	N3—C14—H14A	108.9
C3—C4—H4B	119.6	C9—C14—H14A	108.9
C5—C4—H4B	119.6	C13—C14—H14A	108.9
C6—C5—C4	120.5 (4)	N3—C15—N4	116.4 (2)
C6—C5—H5A	119.8	N3—C15—S2	124.6 (2)
C4—C5—H5A	119.8	N4—C15—S2	119.00 (19)
C5—C6—C1	118.4 (3)	O2—C16—N4	122.5 (2)
C5—C6—C7	118.8 (3)	O2—C16—C17	121.5 (2)
C1—C6—C7	122.7 (3)	N4—C16—C17	116.0 (2)
O1—C7—N1	122.3 (3)	C18—C17—C22	119.4 (3)
O1—C7—C6	121.7 (3)	C18—C17—C16	122.2 (3)
N1—C7—C6	116.0 (3)	C22—C17—C16	118.4 (3)
N2—C8—N1	116.4 (2)	C19—C18—C17	119.9 (3)
N2—C8—S1	125.4 (2)	C19—C18—H18A	120.0
N1—C8—S1	118.2 (2)	C17—C18—H18A	120.0
N2—C9—C14	110.8 (2)	C20—C19—C18	120.4 (3)
N2—C9—C10	110.7 (2)	C20—C19—H19A	119.8
C14—C9—C10	110.9 (2)	C18—C19—H19A	119.8
N2—C9—H9A	108.1	C21—C20—C19	120.4 (3)
C14—C9—H9A	108.1	C21—C20—H20A	119.8
C10—C9—H9A	108.1	C19—C20—H20A	119.8
C11—C10—C9	110.8 (2)	C20—C21—C22	120.0 (3)
C11—C10—H10A	109.5	C20—C21—H21A	120.0
C9—C10—H10A	109.5	C22—C21—H21A	120.0
C11—C10—H10B	109.5	C21—C22—C17	119.8 (3)
C9—C10—H10B	109.5	C21—C22—H22A	120.1
H10A—C10—H10B	108.1	C17—C22—H22A	120.1
C6—C1—C2—C3	−0.2 (7)	C15—N3—C14—C13	132.9 (3)
C1—C2—C3—C4	−0.2 (8)	N2—C9—C14—N3	58.4 (3)
C2—C3—C4—C5	−0.5 (7)	C10—C9—C14—N3	−178.2 (2)
C3—C4—C5—C6	1.5 (7)	N2—C9—C14—C13	179.4 (2)
C4—C5—C6—C1	−1.8 (6)	C10—C9—C14—C13	−57.2 (3)
C4—C5—C6—C7	−178.0 (4)	C12—C13—C14—N3	177.7 (3)
C2—C1—C6—C5	1.2 (6)	C12—C13—C14—C9	55.9 (4)
C2—C1—C6—C7	177.2 (4)	C14—N3—C15—N4	−178.8 (2)
C8—N1—C7—O1	7.3 (5)	C14—N3—C15—S2	0.5 (4)
C8—N1—C7—C6	−173.5 (3)	C16—N4—C15—N3	−8.8 (4)
C5—C6—C7—O1	16.3 (5)	C16—N4—C15—S2	171.9 (2)
C1—C6—C7—O1	−159.7 (3)	C15—N4—C16—O2	0.5 (4)
C5—C6—C7—N1	−162.9 (3)	C15—N4—C16—C17	179.7 (2)
C1—C6—C7—N1	21.1 (4)	O2—C16—C17—C18	138.7 (3)
C9—N2—C8—N1	−177.5 (2)	N4—C16—C17—C18	−40.5 (3)
C9—N2—C8—S1	2.1 (4)	O2—C16—C17—C22	−39.6 (4)
C7—N1—C8—N2	0.2 (4)	N4—C16—C17—C22	141.3 (3)
C7—N1—C8—S1	−179.4 (2)	C22—C17—C18—C19	−0.1 (4)
C8—N2—C9—C14	−143.0 (3)	C16—C17—C18—C19	−178.4 (3)
C8—N2—C9—C10	93.5 (3)	C17—C18—C19—C20	−0.7 (5)
N2—C9—C10—C11	−178.4 (3)	C18—C19—C20—C21	0.3 (5)
C14—C9—C10—C11	58.1 (4)	C19—C20—C21—C22	0.9 (5)
C9—C10—C11—C12	−56.7 (4)	C20—C21—C22—C17	−1.8 (5)
C10—C11—C12—C13	55.7 (4)	C18—C17—C22—C21	1.4 (4)
C11—C12—C13—C14	−55.7 (4)	C16—C17—C22—C21	179.7 (3)
C15—N3—C14—C9	−105.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.01	2.677 (3)	134
N3—H3A···O2	0.86	1.96	2.645 (3)	136
N1—H1A···O2i	0.86	2.26	3.077 (3)	159
N4—H4A···S2ii	0.86	2.56	3.405 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.01	2.677 (3)	134
N3—H3A⋯O2	0.86	1.96	2.645 (3)	136
N1—H1A⋯O2i	0.86	2.26	3.077 (3)	159
N4—H4A⋯S2ii	0.86	2.56	3.405 (3)	166

Symmetry codes: (i) ; (ii) .