2-Chloro-N'-[4-(dimethyl-amino)-benzyl-idene]-N-[4-(3-methyl-3-phenyl-cyclo-but-yl)-1,3-thia-zol-2-yl]acetohydrazide.

The mol-ecular conformation of the title compound, C(25)H(27)ClN(4)OS, is stabilized by an intra-molecular benzyl-idine C-H⋯N(thia-zole) hydrogen bond. The thiazole ring makes dihedral angles of 12.0 (3) and 20.4 (2)°, respectively, with the phenyl and benzene rings, while the phenyl and benzene rings make a dihedral angle of 22.6 (2)°. The crystal packing involves weak inter-molecular thia-zole C-H⋯O(carbon-yl) and methyl C-H⋯π hydrogen-bonding associations.

Related literature

For applications of related compounds, see: Brown et al. (1974 ▶); Dehmlow & Schmidt (1990 ▶); Foerster et al. (1979) ▶; Roger et al. (1977 ▶); Sawhney et al. (1978) ▶; Slip et al. (1974) ▶; Suzuki et al. (1979) ▶. For background to Schiff bases, see: Costamagna et al. (1992 ▶); Fita et al. (2005 ▶); Sridharan et al. (2004 ▶). For related structures, see: Dinçer et al. (2004 ▶); Demir et al. (2006 ▶); Özdemir et al. (2004 ▶); Soylu et al. (2005 ▶); Xu et al. (1994 ▶). For bond-length data, see: Allen (1984 ▶).

Experimental

Crystal data

C25H27ClN4OS

M = 467.02

Monoclinic,

a = 9.0194 (5) Å

b = 26.7946 (11) Å

c = 13.1773 (7) Å

β = 132.054 (3)°

V = 2364.6 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 296 K

0.62 × 0.36 × 0.02 mm

Data collection

Stoe IPDS 2 CCD diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.533, T max = 0.896

22742 measured reflections

4446 independent reflections

2250 reflections with I > 2σ(I)

R int = 0.143

Refinement

R[F 2 > 2σ(F 2)] = 0.070

wR(F 2) = 0.121

S = 1.01

4446 reflections

292 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.17 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049962/zs2082sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049962/zs2082Isup2.hkl

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

C25H27ClN4OS	F(000) = 984
Mr = 467.02	Dx = 1.312 Mg m−3
Monoclinic, P21/c	Melting point: 420 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.0194 (5) Å	Cell parameters from 14801 reflections
b = 26.7946 (11) Å	θ = 1.5–26.2°
c = 13.1773 (7) Å	µ = 0.28 mm−1
β = 132.054 (3)°	T = 296 K
V = 2364.6 (2) Å3	Plate, brown
Z = 4	0.62 × 0.36 × 0.02 mm

Stoe IPDS 2 CCD diffractometer	4446 independent reflections
Radiation source: fine-focus sealed tube	2250 reflections with I > 2σ(I)
graphite	Rint = 0.143
Detector resolution: 6.67 pixels mm-1	θmax = 25.6°, θmin = 1.5°
rotation method scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −32→32
Tmin = 0.533, Tmax = 0.896	l = −16→16
22742 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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0287P)2] where P = (Fo2 + 2Fc2)/3
4446 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.17 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
Cl1	0.45265 (18)	0.13475 (4)	0.49349 (10)	0.0796 (4)
N1	0.2748 (4)	0.14808 (12)	−0.0565 (3)	0.0585 (9)
N2	0.3574 (4)	0.12803 (12)	0.1519 (3)	0.0563 (8)
N3	0.3105 (4)	0.07697 (12)	0.1292 (3)	0.0552 (8)
N4	0.1455 (6)	−0.15632 (14)	−0.0154 (4)	0.0862 (12)
O1	0.4501 (5)	0.18872 (11)	0.3042 (3)	0.0788 (9)
S1	0.43474 (18)	0.22208 (4)	0.11117 (10)	0.0743 (4)
C1	−0.1810 (5)	0.05376 (17)	−0.5909 (3)	0.0609 (11)
H1	−0.1777	0.0674	−0.6542	0.073*
C2	−0.2743 (6)	0.00874 (17)	−0.6195 (4)	0.0700 (12)
H2	−0.3308	−0.0079	−0.7004	0.084*
C3	−0.2841 (6)	−0.01176 (17)	−0.5289 (5)	0.0764 (13)
H3	−0.3498	−0.0419	−0.5488	0.092*
C4	−0.1959 (6)	0.01272 (18)	−0.4082 (4)	0.0755 (13)
H4	−0.2012	−0.0011	−0.3460	0.091*
C5	−0.1001 (6)	0.05746 (17)	−0.3794 (4)	0.0661 (11)
H5	−0.0396	0.0733	−0.2970	0.079*
C6	−0.0916 (5)	0.07958 (15)	−0.4710 (3)	0.0529 (10)
C7	0.0148 (5)	0.12898 (15)	−0.4359 (3)	0.0572 (10)
C8	−0.0100 (6)	0.15109 (18)	−0.5534 (4)	0.0809 (14)
H8A	0.0609	0.1822	−0.5249	0.121*
H8B	−0.1491	0.1567	−0.6305	0.121*
H8C	0.0427	0.1283	−0.5786	0.121*
C9	0.2381 (5)	0.13060 (16)	−0.3001 (3)	0.0628 (11)
H9A	0.2754	0.1036	−0.2377	0.075*
H9B	0.3309	0.1330	−0.3138	0.075*
C10	−0.0258 (5)	0.16916 (15)	−0.3724 (4)	0.0661 (11)
H10A	−0.0808	0.1557	−0.3352	0.079*
H10B	−0.1051	0.1970	−0.4330	0.079*
C11	0.2018 (5)	0.18072 (15)	−0.2618 (3)	0.0617 (11)
H11	0.2369	0.2089	−0.2896	0.074*
C12	0.2851 (5)	0.18755 (15)	−0.1199 (3)	0.0596 (11)
C13	0.3684 (6)	0.22920 (15)	−0.0435 (4)	0.0731 (12)
H13	0.3875	0.2584	−0.0716	0.088*
C14	0.3471 (5)	0.16094 (14)	0.0637 (3)	0.0543 (10)
C15	0.4014 (5)	0.14549 (16)	0.2682 (3)	0.0563 (10)
C16	0.3891 (6)	0.10708 (15)	0.3459 (3)	0.0599 (11)
H16A	0.4799	0.0798	0.3731	0.072*
H16B	0.2547	0.0937	0.2877	0.072*
C17	0.3002 (5)	0.05152 (15)	0.0428 (4)	0.0593 (11)
H17	0.3185	0.0671	−0.0112	0.071*
C18	0.2602 (5)	−0.00161 (14)	0.0285 (3)	0.0507 (9)
C19	0.2467 (6)	−0.02964 (16)	−0.0652 (3)	0.0650 (12)
H19	0.2626	−0.0139	−0.1203	0.078*
C20	0.2104 (6)	−0.08041 (16)	−0.0799 (4)	0.0677 (12)
H20	0.2008	−0.0977	−0.1453	0.081*
C21	0.2381 (5)	−0.02730 (16)	0.1094 (3)	0.0607 (11)
H21	0.2465	−0.0097	0.1740	0.073*
C22	0.2044 (6)	−0.07735 (16)	0.0970 (4)	0.0646 (11)
H22	0.1921	−0.0929	0.1541	0.077*
C23	0.1877 (5)	−0.10629 (16)	0.0009 (4)	0.0597 (11)
C24	0.1179 (8)	−0.18412 (18)	−0.1206 (5)	0.1007 (17)
H24A	0.0632	−0.2163	−0.1301	0.151*
H24B	0.2443	−0.1881	−0.0961	0.151*
H24C	0.0279	−0.1664	−0.2056	0.151*
C25	0.1709 (7)	−0.18470 (19)	0.0877 (5)	0.1005 (17)
H25A	0.3076	−0.1828	0.1720	0.151*
H25B	0.1362	−0.2189	0.0593	0.151*
H25C	0.0859	−0.1714	0.1008	0.151*

	U11	U22	U33	U12	U13	U23
Cl1	0.1198 (9)	0.0642 (8)	0.0901 (7)	0.0022 (7)	0.0849 (7)	−0.0016 (6)
N1	0.0693 (19)	0.050 (2)	0.0533 (17)	−0.0062 (16)	0.0399 (16)	−0.0047 (15)
N2	0.070 (2)	0.041 (2)	0.0609 (18)	−0.0027 (16)	0.0450 (17)	−0.0051 (15)
N3	0.0614 (19)	0.0405 (19)	0.0599 (18)	−0.0059 (15)	0.0391 (16)	−0.0039 (15)
N4	0.133 (3)	0.040 (2)	0.096 (3)	−0.015 (2)	0.081 (3)	−0.0071 (19)
O1	0.124 (2)	0.048 (2)	0.0852 (18)	−0.0129 (18)	0.0785 (18)	−0.0124 (15)
S1	0.1041 (8)	0.0462 (7)	0.0685 (6)	−0.0156 (6)	0.0561 (6)	−0.0103 (5)
C1	0.057 (2)	0.065 (3)	0.054 (2)	0.004 (2)	0.0342 (19)	0.000 (2)
C2	0.061 (3)	0.058 (3)	0.069 (3)	0.001 (2)	0.034 (2)	−0.011 (2)
C3	0.067 (3)	0.048 (3)	0.096 (3)	−0.001 (2)	0.047 (3)	0.004 (2)
C4	0.083 (3)	0.071 (3)	0.079 (3)	0.002 (3)	0.057 (3)	0.016 (2)
C5	0.076 (3)	0.064 (3)	0.062 (2)	−0.001 (2)	0.048 (2)	0.004 (2)
C6	0.052 (2)	0.059 (3)	0.053 (2)	0.007 (2)	0.0370 (19)	0.0055 (18)
C7	0.060 (2)	0.058 (3)	0.0501 (19)	−0.003 (2)	0.0356 (19)	0.0014 (18)
C8	0.087 (3)	0.083 (4)	0.065 (2)	−0.016 (3)	0.048 (2)	0.008 (2)
C9	0.063 (2)	0.067 (3)	0.056 (2)	−0.003 (2)	0.039 (2)	−0.0031 (19)
C10	0.071 (3)	0.053 (3)	0.065 (2)	−0.001 (2)	0.042 (2)	0.003 (2)
C11	0.069 (3)	0.052 (3)	0.057 (2)	−0.009 (2)	0.039 (2)	0.0017 (18)
C12	0.064 (2)	0.050 (3)	0.055 (2)	−0.008 (2)	0.035 (2)	0.0020 (18)
C13	0.098 (3)	0.043 (3)	0.069 (2)	−0.017 (2)	0.052 (2)	−0.0034 (19)
C14	0.058 (2)	0.042 (2)	0.054 (2)	−0.0026 (18)	0.0336 (19)	−0.0028 (17)
C15	0.064 (2)	0.052 (3)	0.060 (2)	0.002 (2)	0.044 (2)	−0.0001 (19)
C16	0.071 (3)	0.053 (3)	0.066 (2)	0.005 (2)	0.050 (2)	−0.0013 (18)
C17	0.070 (3)	0.045 (3)	0.062 (2)	0.000 (2)	0.045 (2)	0.0029 (19)
C18	0.055 (2)	0.041 (2)	0.0541 (19)	0.0010 (18)	0.0355 (18)	−0.0001 (17)
C19	0.089 (3)	0.051 (3)	0.058 (2)	−0.001 (2)	0.051 (2)	−0.0007 (19)
C20	0.099 (3)	0.048 (3)	0.065 (2)	−0.001 (2)	0.059 (2)	−0.0039 (19)
C21	0.072 (3)	0.053 (3)	0.063 (2)	−0.007 (2)	0.048 (2)	−0.0086 (19)
C22	0.078 (3)	0.054 (3)	0.069 (2)	−0.010 (2)	0.052 (2)	−0.001 (2)
C23	0.062 (2)	0.048 (3)	0.062 (2)	−0.002 (2)	0.038 (2)	−0.0016 (19)
C24	0.133 (4)	0.051 (3)	0.114 (4)	−0.012 (3)	0.081 (3)	−0.015 (3)
C25	0.127 (4)	0.065 (4)	0.111 (3)	−0.012 (3)	0.081 (3)	0.012 (3)

Cl1—C16	1.779 (3)	C9—C11	1.545 (5)
N1—C14	1.292 (4)	C9—H9A	0.9700
N1—C12	1.389 (5)	C9—H9B	0.9700
N2—C15	1.382 (4)	C10—C11	1.558 (5)
N2—N3	1.404 (4)	C10—H10A	0.9700
N2—C14	1.412 (5)	C10—H10B	0.9700
N3—C17	1.276 (4)	C11—C12	1.487 (5)
N4—C23	1.371 (5)	C11—H11	0.9800
N4—C25	1.435 (5)	C12—C13	1.345 (5)
N4—C24	1.441 (6)	C13—H13	0.9300
O1—C15	1.217 (4)	C15—C16	1.508 (5)
S1—C13	1.707 (4)	C16—H16A	0.9700
S1—C14	1.743 (4)	C16—H16B	0.9700
C1—C2	1.371 (6)	C17—C18	1.450 (5)
C1—C6	1.385 (5)	C17—H17	0.9300
C1—H1	0.9300	C18—C19	1.379 (5)
C2—C3	1.370 (6)	C18—C21	1.392 (5)
C2—H2	0.9300	C19—C20	1.382 (5)
C3—C4	1.378 (6)	C19—H19	0.9300
C3—H3	0.9300	C20—C23	1.396 (5)
C4—C5	1.374 (6)	C20—H20	0.9300
C4—H4	0.9300	C21—C22	1.360 (5)
C5—C6	1.392 (5)	C21—H21	0.9300
C5—H5	0.9300	C22—C23	1.405 (5)
C6—C7	1.514 (5)	C22—H22	0.9300
C7—C8	1.528 (5)	C24—H24A	0.9600
C7—C10	1.550 (5)	C24—H24B	0.9600
C7—C9	1.560 (5)	C24—H24C	0.9600
C8—H8A	0.9600	C25—H25A	0.9600
C8—H8B	0.9600	C25—H25B	0.9600
C8—H8C	0.9600	C25—H25C	0.9600
C14—N1—C12	110.6 (3)	C12—C11—H11	110.9
C15—N2—N3	112.8 (3)	C9—C11—H11	110.9
C15—N2—C14	120.9 (3)	C10—C11—H11	110.9
N3—N2—C14	126.1 (3)	C13—C12—N1	114.2 (3)
C17—N3—N2	122.9 (3)	C13—C12—C11	127.0 (4)
C23—N4—C25	121.3 (4)	N1—C12—C11	118.8 (3)
C23—N4—C24	120.5 (4)	C12—C13—S1	112.0 (3)
C25—N4—C24	116.9 (4)	C12—C13—H13	124.0
C13—S1—C14	87.95 (19)	S1—C13—H13	124.0
C2—C1—C6	122.3 (4)	N1—C14—N2	122.9 (3)
C2—C1—H1	118.9	N1—C14—S1	115.2 (3)
C6—C1—H1	118.9	N2—C14—S1	121.8 (3)
C3—C2—C1	119.9 (4)	O1—C15—N2	121.0 (4)
C3—C2—H2	120.0	O1—C15—C16	123.8 (3)
C1—C2—H2	120.0	N2—C15—C16	115.2 (3)
C2—C3—C4	119.4 (4)	C15—C16—Cl1	110.0 (3)
C2—C3—H3	120.3	C15—C16—H16A	109.7
C4—C3—H3	120.3	Cl1—C16—H16A	109.7
C5—C4—C3	120.3 (4)	C15—C16—H16B	109.7
C5—C4—H4	119.9	Cl1—C16—H16B	109.7
C3—C4—H4	119.9	H16A—C16—H16B	108.2
C4—C5—C6	121.5 (4)	N3—C17—C18	120.2 (4)
C4—C5—H5	119.3	N3—C17—H17	119.9
C6—C5—H5	119.3	C18—C17—H17	119.9
C1—C6—C5	116.6 (4)	C19—C18—C21	116.4 (4)
C1—C6—C7	123.4 (3)	C19—C18—C17	121.1 (4)
C5—C6—C7	120.0 (3)	C21—C18—C17	122.5 (4)
C6—C7—C8	113.4 (3)	C18—C19—C20	122.1 (4)
C6—C7—C10	116.2 (3)	C18—C19—H19	118.9
C8—C7—C10	110.5 (4)	C20—C19—H19	118.9
C6—C7—C9	116.2 (3)	C19—C20—C23	121.6 (4)
C8—C7—C9	110.6 (3)	C19—C20—H20	119.2
C10—C7—C9	87.2 (3)	C23—C20—H20	119.2
C7—C8—H8A	109.5	C22—C21—C18	122.0 (4)
C7—C8—H8B	109.5	C22—C21—H21	119.0
H8A—C8—H8B	109.5	C18—C21—H21	119.0
C7—C8—H8C	109.5	C21—C22—C23	122.2 (4)
H8A—C8—H8C	109.5	C21—C22—H22	118.9
H8B—C8—H8C	109.5	C23—C22—H22	118.9
C11—C9—C7	90.3 (3)	N4—C23—C20	122.3 (4)
C11—C9—H9A	113.6	N4—C23—C22	122.1 (4)
C7—C9—H9A	113.6	C20—C23—C22	115.6 (4)
C11—C9—H9B	113.6	N4—C24—H24A	109.5
C7—C9—H9B	113.6	N4—C24—H24B	109.5
H9A—C9—H9B	110.9	H24A—C24—H24B	109.5
C7—C10—C11	90.2 (3)	N4—C24—H24C	109.5
C7—C10—H10A	113.6	H24A—C24—H24C	109.5
C11—C10—H10A	113.6	H24B—C24—H24C	109.5
C7—C10—H10B	113.6	N4—C25—H25A	109.5
C11—C10—H10B	113.6	N4—C25—H25B	109.5
H10A—C10—H10B	110.9	H25A—C25—H25B	109.5
C12—C11—C9	118.6 (3)	N4—C25—H25C	109.5
C12—C11—C10	116.1 (3)	H25A—C25—H25C	109.5
C9—C11—C10	87.5 (3)	H25B—C25—H25C	109.5
C15—N2—N3—C17	−167.2 (3)	C11—C12—C13—S1	177.2 (3)
C14—N2—N3—C17	18.0 (5)	C14—S1—C13—C12	0.9 (3)
C6—C1—C2—C3	1.1 (6)	C12—N1—C14—N2	−179.4 (3)
C1—C2—C3—C4	−1.4 (7)	C12—N1—C14—S1	−0.1 (4)
C2—C3—C4—C5	0.5 (7)	C15—N2—C14—N1	−168.1 (4)
C3—C4—C5—C6	0.9 (7)	N3—N2—C14—N1	6.4 (6)
C2—C1—C6—C5	0.2 (6)	C15—N2—C14—S1	12.6 (5)
C2—C1—C6—C7	179.1 (4)	N3—N2—C14—S1	−172.9 (3)
C4—C5—C6—C1	−1.2 (6)	C13—S1—C14—N1	−0.5 (3)
C4—C5—C6—C7	179.8 (4)	C13—S1—C14—N2	178.8 (3)
C1—C6—C7—C8	7.8 (5)	N3—N2—C15—O1	178.1 (4)
C5—C6—C7—C8	−173.3 (4)	C14—N2—C15—O1	−6.8 (6)
C1—C6—C7—C10	137.5 (4)	N3—N2—C15—C16	−0.4 (4)
C5—C6—C7—C10	−43.6 (5)	C14—N2—C15—C16	174.7 (3)
C1—C6—C7—C9	−122.0 (4)	O1—C15—C16—Cl1	0.7 (5)
C5—C6—C7—C9	56.8 (5)	N2—C15—C16—Cl1	179.2 (3)
C6—C7—C9—C11	−134.4 (3)	N2—N3—C17—C18	177.1 (3)
C8—C7—C9—C11	94.4 (4)	N3—C17—C18—C19	179.4 (3)
C10—C7—C9—C11	−16.5 (3)	N3—C17—C18—C21	−2.1 (6)
C6—C7—C10—C11	134.3 (3)	C21—C18—C19—C20	0.9 (6)
C8—C7—C10—C11	−94.7 (3)	C17—C18—C19—C20	179.5 (4)
C9—C7—C10—C11	16.3 (3)	C18—C19—C20—C23	−0.8 (6)
C7—C9—C11—C12	134.9 (3)	C19—C18—C21—C22	−0.1 (6)
C7—C9—C11—C10	16.4 (3)	C17—C18—C21—C22	−178.7 (4)
C7—C10—C11—C12	−137.2 (3)	C18—C21—C22—C23	−0.7 (6)
C7—C10—C11—C9	−16.5 (3)	C25—N4—C23—C20	164.4 (4)
C14—N1—C12—C13	0.8 (5)	C24—N4—C23—C20	−1.5 (7)
C14—N1—C12—C11	−177.7 (3)	C25—N4—C23—C22	−17.7 (7)
C9—C11—C12—C13	140.8 (4)	C24—N4—C23—C22	176.3 (4)
C10—C11—C12—C13	−117.0 (5)	C19—C20—C23—N4	177.9 (4)
C9—C11—C12—N1	−40.9 (5)	C19—C20—C23—C22	0.0 (6)
C10—C11—C12—N1	61.3 (5)	C21—C22—C23—N4	−177.2 (4)
N1—C12—C13—S1	−1.2 (5)	C21—C22—C23—C20	0.8 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N1	0.93	2.21	2.838 (5)	124.
C13—H13···O1i	0.93	2.50	3.374 (5)	157.
C16—H16A···Cg1ii	0.97	2.57	3.493	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N1	0.93	2.21	2.838 (5)	124
C13—H13⋯O1i	0.93	2.50	3.374 (5)	157
C16—H16A⋯Cg1ii	0.97	2.57	3.493	159

Symmetry codes: (i) ; (ii) .