Literature DB >> 21522635

2-[3-((Z)-2-{4-[Bis(2-chloro-eth-yl)amino]-phen-yl}ethen-yl)-5,5-dimethyl-cyclo-hex-2-en-1-yl-idene]propane-dinitrile.

Li Liu, Ying Shao, Jie-Ping Shi, Hong-Wen Hu, Guo-Yuan Lu.

Abstract

The highly conjugated title compound, C(23)H(25)Cl(2)N(3), is nearly planar (the mean deviation from the plane being 0.049 Å), except for the -C(CH(3))(2) group on the cyclo-hexene ring and the two CH(2)Cl groups. The cyclo-hexene ring has an envelope configuration. In the crystal, the packing is stabilized by C-H⋯Cl inter-actions and C-H⋯π inter-actions involving the benzene ring.

Entities: CellLine Chemical Disease Gene Species

Year: 2010 PMID： 21522635 PMCID： PMC3050295 DOI： 10.1107/S1600536810051068

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

The title compound was prepared by the Knoevenagel reaction, see: Bai et al. (2006 ▶); Samyn et al. (2001 ▶). It is an intermediate for the preparation of non-linear optical materials, see: Kwon et al. (2006 ▶); Shu et al. (1998 ▶); Chun et al. (2001 ▶); Zheng et al. (2000 ▶). For a related structure, see Kolev et al. (2005 ▶).

Experimental

Crystal data

C23H25Cl2N3 M = 414.36 Triclinic, a = 9.106 (7) Å b = 10.819 (9) Å c = 13.325 (4) Å α = 70.052 (6)° β = 70.02 (1)° γ = 65.11 (1)° V = 1088.8 (13) Å3 Z = 2 Mo Kα radiation μ = 0.31 mm−1 T = 295 K 0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.926, T max = 0.955 5376 measured reflections 3695 independent reflections 3130 reflections with I > 2σ(I) R int = 0.108

Refinement

R[F 2 > 2σ(F 2)] = 0.052 wR(F 2) = 0.149 S = 1.08 3695 reflections 253 parameters H-atom parameters constrained Δρmax = 0.40 e Å−3 Δρmin = −0.45 e Å−3 Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051068/fl2317sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051068/fl2317Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₂₃H₂₅Cl₂N₃	Z = 2
M_r = 414.36	F(000) = 436
Triclinic, P1	D_x = 1.264 Mg m⁻³
Hall symbol: -P 1	Melting point: 462(2) K
a = 9.106 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.819 (9) Å	Cell parameters from 3172 reflections
c = 13.325 (4) Å	θ = 2.4–28.3°
α = 70.052 (6)°	µ = 0.31 mm⁻¹
β = 70.02 (1)°	T = 295 K
γ = 65.11 (1)°	Block, red
V = 1088.8 (13) Å³	0.25 × 0.20 × 0.15 mm

Bruker SMART CCD area-detector diffractometer	3695 independent reflections
Radiation source: fine-focus sealed tube	3130 reflections with I > 2σ(I)
graphite	R_int = 0.108
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→9
T_min = 0.926, T_max = 0.955	k = −12→12
5376 measured reflections	l = −15→15

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0923P)² + 0.0577P] where P = (F_o² + 2F_c²)/3
3695 reflections	(Δ/σ)_max < 0.001
253 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.45 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	U_iso*/U_eq
Cl1	0.94296 (7)	0.45978 (6)	0.17603 (5)	0.0391 (2)
Cl2	1.69804 (7)	0.19448 (6)	0.30464 (5)	0.0455 (2)
N1	1.2573 (2)	0.45672 (17)	0.23659 (13)	0.0238 (4)
C6	0.8407 (2)	0.95499 (19)	0.75122 (15)	0.0215 (4)
H6A	0.9244	0.8771	0.7786	0.026*
C7	0.8134 (2)	0.9638 (2)	0.65538 (15)	0.0208 (4)
C14	1.1692 (2)	0.55189 (19)	0.30229 (15)	0.0216 (4)
C5	0.7456 (2)	1.0609 (2)	0.81253 (15)	0.0210 (4)
C12	0.9649 (2)	0.7739 (2)	0.33495 (16)	0.0231 (4)
H12A	0.8866	0.8586	0.3097	0.028*
C10	0.9014 (2)	0.8540 (2)	0.50045 (16)	0.0224 (4)
H10A	0.8225	0.9330	0.4692	0.027*
C16	1.1131 (2)	0.6197 (2)	0.47076 (16)	0.0229 (4)
H16A	1.1352	0.5974	0.5392	0.027*
C11	0.9938 (2)	0.7485 (2)	0.43735 (15)	0.0215 (4)
C9	0.9138 (2)	0.8536 (2)	0.59796 (16)	0.0222 (4)
H9A	0.9928	0.7767	0.6308	0.027*
C13	1.0470 (2)	0.6794 (2)	0.26958 (15)	0.0231 (4)
H13	1.0211	0.7003	0.2026	0.028*
C21	0.7696 (2)	1.0458 (2)	0.91198 (16)	0.0240 (4)
C23	0.6733 (3)	1.1514 (2)	0.97320 (16)	0.0281 (5)
C15	1.1987 (2)	0.5248 (2)	0.40534 (16)	0.0229 (4)
H15A	1.2781	0.4407	0.4302	0.028*
C4	0.6212 (2)	1.1924 (2)	0.76371 (16)	0.0238 (4)
H4A	0.6762	1.2596	0.7189	0.029*
H4B	0.5353	1.2329	0.8223	0.029*
C19	1.3873 (2)	0.3277 (2)	0.27018 (16)	0.0241 (4)
H19A	1.4040	0.2599	0.2312	0.029*
H19B	1.3531	0.2894	0.3481	0.029*
N3	0.5935 (3)	1.2370 (2)	1.02102 (15)	0.0399 (5)
C8	0.6800 (2)	1.0893 (2)	0.60875 (16)	0.0252 (4)
H8A	0.6307	1.0594	0.5713	0.030*
H8B	0.7312	1.1548	0.5544	0.030*
C3	0.5410 (2)	1.1659 (2)	0.69367 (16)	0.0236 (4)
C17	1.2492 (3)	0.4899 (2)	0.12292 (16)	0.0261 (5)
H17A	1.3614	0.4675	0.0772	0.031*
H17B	1.1921	0.5898	0.1000	0.031*
C18	1.1606 (3)	0.4119 (2)	0.10506 (18)	0.0323 (5)
H18A	1.2152	0.3121	0.1304	0.039*
H18B	1.1691	0.4308	0.0271	0.039*
N2	0.9835 (3)	0.8257 (2)	0.99930 (16)	0.0436 (5)
C22	0.8897 (3)	0.9239 (2)	0.96049 (16)	0.0290 (5)
C20	1.5502 (2)	0.3513 (2)	0.24686 (18)	0.0286 (5)
H20A	1.5316	0.4267	0.2785	0.034*
H20B	1.5926	0.3778	0.1682	0.034*
C1	0.4348 (3)	1.3060 (2)	0.63482 (18)	0.0342 (5)
H1A	0.5036	1.3608	0.5891	0.051*
H1B	0.3498	1.3553	0.6880	0.051*
H1C	0.3839	1.2901	0.5902	0.051*
C2	0.4306 (3)	1.0779 (2)	0.76748 (19)	0.0338 (5)
H2A	0.3449	1.1278	0.8200	0.051*
H2B	0.4975	0.9902	0.8053	0.051*
H2C	0.3807	1.0607	0.7231	0.051*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0324 (3)	0.0429 (4)	0.0442 (4)	−0.0126 (3)	−0.0161 (3)	−0.0062 (3)
Cl2	0.0276 (3)	0.0419 (4)	0.0561 (4)	−0.0014 (3)	−0.0205 (3)	−0.0012 (3)
N1	0.0230 (9)	0.0203 (8)	0.0260 (9)	−0.0007 (7)	−0.0093 (7)	−0.0077 (7)
C6	0.0148 (9)	0.0188 (9)	0.0262 (10)	−0.0013 (8)	−0.0050 (8)	−0.0051 (8)
C7	0.0155 (9)	0.0237 (10)	0.0215 (10)	−0.0078 (8)	−0.0010 (8)	−0.0052 (8)
C14	0.0192 (10)	0.0201 (10)	0.0264 (11)	−0.0076 (8)	−0.0039 (8)	−0.0066 (8)
C5	0.0155 (9)	0.0218 (10)	0.0230 (10)	−0.0066 (8)	−0.0007 (8)	−0.0054 (8)
C12	0.0176 (9)	0.0205 (10)	0.0306 (11)	−0.0027 (8)	−0.0090 (8)	−0.0068 (8)
C10	0.0168 (9)	0.0211 (10)	0.0279 (11)	−0.0054 (8)	−0.0036 (8)	−0.0069 (8)
C16	0.0228 (10)	0.0234 (10)	0.0207 (10)	−0.0066 (8)	−0.0051 (8)	−0.0048 (8)
C11	0.0166 (9)	0.0226 (10)	0.0245 (10)	−0.0068 (8)	−0.0030 (8)	−0.0062 (8)
C9	0.0144 (9)	0.0228 (10)	0.0251 (10)	−0.0034 (8)	−0.0035 (8)	−0.0055 (8)
C13	0.0203 (10)	0.0258 (10)	0.0229 (10)	−0.0040 (8)	−0.0089 (8)	−0.0066 (8)
C21	0.0236 (10)	0.0220 (10)	0.0227 (10)	−0.0050 (8)	−0.0049 (8)	−0.0049 (8)
C23	0.0296 (11)	0.0281 (11)	0.0225 (10)	−0.0079 (9)	−0.0051 (9)	−0.0048 (9)
C15	0.0199 (10)	0.0184 (10)	0.0255 (10)	−0.0037 (8)	−0.0084 (8)	0.0002 (8)
C4	0.0214 (10)	0.0216 (10)	0.0242 (10)	−0.0032 (8)	−0.0037 (8)	−0.0072 (8)
C19	0.0236 (10)	0.0188 (10)	0.0275 (10)	−0.0040 (8)	−0.0065 (8)	−0.0064 (8)
N3	0.0463 (12)	0.0337 (11)	0.0319 (10)	−0.0050 (9)	−0.0035 (9)	−0.0153 (9)
C8	0.0226 (10)	0.0261 (10)	0.0257 (10)	−0.0040 (9)	−0.0081 (8)	−0.0076 (8)
C3	0.0169 (9)	0.0238 (10)	0.0255 (10)	−0.0028 (8)	−0.0058 (8)	−0.0047 (8)
C17	0.0270 (10)	0.0221 (10)	0.0248 (10)	−0.0039 (9)	−0.0059 (9)	−0.0060 (8)
C18	0.0338 (12)	0.0320 (11)	0.0313 (11)	−0.0044 (10)	−0.0137 (10)	−0.0105 (9)
N2	0.0468 (12)	0.0374 (11)	0.0357 (11)	0.0032 (10)	−0.0214 (10)	−0.0062 (9)
C22	0.0338 (12)	0.0310 (12)	0.0206 (10)	−0.0080 (10)	−0.0058 (9)	−0.0085 (9)
C20	0.0230 (10)	0.0258 (11)	0.0326 (11)	−0.0032 (9)	−0.0097 (9)	−0.0048 (9)
C1	0.0275 (11)	0.0303 (12)	0.0360 (12)	0.0020 (9)	−0.0116 (10)	−0.0081 (10)
C2	0.0190 (10)	0.0352 (12)	0.0431 (13)	−0.0079 (9)	−0.0035 (9)	−0.0097 (10)

Cl1—C18	1.811 (3)	C23—N3	1.146 (3)
Cl2—C20	1.783 (2)	C15—H15A	0.9300
N1—C14	1.382 (3)	C4—C3	1.520 (3)
N1—C19	1.448 (2)	C4—H4A	0.9700
N1—C17	1.453 (2)	C4—H4B	0.9700
C6—C7	1.347 (3)	C19—C20	1.520 (3)
C6—C5	1.432 (3)	C19—H19A	0.9700
C6—H6A	0.9300	C19—H19B	0.9700
C7—C9	1.438 (3)	C8—C3	1.532 (3)
C7—C8	1.503 (3)	C8—H8A	0.9700
C14—C15	1.398 (3)	C8—H8B	0.9700
C14—C13	1.400 (3)	C3—C1	1.523 (3)
C5—C21	1.360 (3)	C3—C2	1.542 (3)
C5—C4	1.499 (3)	C17—C18	1.504 (3)
C12—C13	1.372 (3)	C17—H17A	0.9700
C12—C11	1.391 (3)	C17—H17B	0.9700
C12—H12A	0.9300	C18—H18A	0.9700
C10—C9	1.340 (3)	C18—H18B	0.9700
C10—C11	1.442 (3)	N2—C22	1.135 (3)
C10—H10A	0.9300	C20—H20A	0.9700
C16—C15	1.376 (3)	C20—H20B	0.9700
C16—C11	1.398 (3)	C1—H1A	0.9600
C16—H16A	0.9300	C1—H1B	0.9600
C9—H9A	0.9300	C1—H1C	0.9600
C13—H13	0.9300	C2—H2A	0.9600
C21—C22	1.428 (3)	C2—H2B	0.9600
C21—C23	1.430 (3)	C2—H2C	0.9600

C14—N1—C19	121.33 (16)	C20—C19—H19A	109.3
C14—N1—C17	122.58 (16)	N1—C19—H19B	109.3
C19—N1—C17	115.10 (15)	C20—C19—H19B	109.3
C7—C6—C5	122.55 (17)	H19A—C19—H19B	108.0
C7—C6—H6A	118.7	C7—C8—C3	114.66 (16)
C5—C6—H6A	118.7	C7—C8—H8A	108.6
C6—C7—C9	119.65 (17)	C3—C8—H8A	108.6
C6—C7—C8	119.76 (17)	C7—C8—H8B	108.6
C9—C7—C8	120.58 (16)	C3—C8—H8B	108.6
N1—C14—C15	121.12 (17)	H8A—C8—H8B	107.6
N1—C14—C13	122.14 (17)	C4—C3—C1	108.99 (17)
C15—C14—C13	116.74 (17)	C4—C3—C8	108.14 (16)
C21—C5—C6	121.30 (18)	C1—C3—C8	109.44 (16)
C21—C5—C4	119.90 (17)	C4—C3—C2	109.59 (17)
C6—C5—C4	118.78 (16)	C1—C3—C2	109.60 (17)
C13—C12—C11	122.83 (18)	C8—C3—C2	111.03 (17)
C13—C12—H12A	118.6	N1—C17—C18	112.94 (17)
C11—C12—H12A	118.6	N1—C17—H17A	109.0
C9—C10—C11	128.83 (18)	C18—C17—H17A	109.0
C9—C10—H10A	115.6	N1—C17—H17B	109.0
C11—C10—H10A	115.6	C18—C17—H17B	109.0
C15—C16—C11	121.91 (18)	H17A—C17—H17B	107.8
C15—C16—H16A	119.0	C17—C18—Cl1	112.66 (15)
C11—C16—H16A	119.0	C17—C18—H18A	109.1
C12—C11—C16	115.97 (17)	Cl1—C18—H18A	109.1
C12—C11—C10	118.97 (17)	C17—C18—H18B	109.1
C16—C11—C10	125.06 (17)	Cl1—C18—H18B	109.1
C10—C9—C7	124.63 (18)	H18A—C18—H18B	107.8
C10—C9—H9A	117.7	N2—C22—C21	178.7 (2)
C7—C9—H9A	117.7	C19—C20—Cl2	109.49 (15)
C12—C13—C14	120.96 (17)	C19—C20—H20A	109.8
C12—C13—H13	119.5	Cl2—C20—H20A	109.8
C14—C13—H13	119.5	C19—C20—H20B	109.8
C5—C21—C22	121.90 (18)	Cl2—C20—H20B	109.8
C5—C21—C23	121.02 (18)	H20A—C20—H20B	108.2
C22—C21—C23	117.08 (17)	C3—C1—H1A	109.5
N3—C23—C21	178.5 (2)	C3—C1—H1B	109.5
C16—C15—C14	121.56 (17)	H1A—C1—H1B	109.5
C16—C15—H15A	119.2	C3—C1—H1C	109.5
C14—C15—H15A	119.2	H1A—C1—H1C	109.5
C5—C4—C3	112.19 (16)	H1B—C1—H1C	109.5
C5—C4—H4A	109.2	C3—C2—H2A	109.5
C3—C4—H4A	109.2	C3—C2—H2B	109.5
C5—C4—H4B	109.2	H2A—C2—H2B	109.5
C3—C4—H4B	109.2	C3—C2—H2C	109.5
H4A—C4—H4B	107.9	H2A—C2—H2C	109.5
N1—C19—C20	111.41 (16)	H2B—C2—H2C	109.5
N1—C19—H19A	109.3

C5—C6—C7—C9	179.91 (16)	C6—C5—C21—C23	−179.48 (17)
C5—C6—C7—C8	0.6 (3)	C4—C5—C21—C23	2.4 (3)
C19—N1—C14—C15	−2.1 (3)	C11—C16—C15—C14	−0.8 (3)
C17—N1—C14—C15	−170.09 (17)	N1—C14—C15—C16	179.16 (17)
C19—N1—C14—C13	177.77 (17)	C13—C14—C15—C16	−0.7 (3)
C17—N1—C14—C13	9.8 (3)	C21—C5—C4—C3	−148.39 (18)
C7—C6—C5—C21	176.34 (18)	C6—C5—C4—C3	33.4 (2)
C7—C6—C5—C4	−5.5 (3)	C14—N1—C19—C20	−81.3 (2)
C13—C12—C11—C16	0.1 (3)	C17—N1—C19—C20	87.5 (2)
C13—C12—C11—C10	−179.90 (17)	C6—C7—C8—C3	−24.2 (3)
C15—C16—C11—C12	1.1 (3)	C9—C7—C8—C3	156.51 (17)
C15—C16—C11—C10	−178.87 (18)	C5—C4—C3—C1	−172.37 (16)
C9—C10—C11—C12	−177.25 (19)	C5—C4—C3—C8	−53.5 (2)
C9—C10—C11—C16	2.7 (3)	C5—C4—C3—C2	67.7 (2)
C11—C10—C9—C7	−179.01 (17)	C7—C8—C3—C4	49.7 (2)
C6—C7—C9—C10	−177.52 (18)	C7—C8—C3—C1	168.33 (16)
C8—C7—C9—C10	1.8 (3)	C7—C8—C3—C2	−70.5 (2)
C11—C12—C13—C14	−1.7 (3)	C14—N1—C17—C18	−110.7 (2)
N1—C14—C13—C12	−177.95 (18)	C19—N1—C17—C18	80.6 (2)
C15—C14—C13—C12	1.9 (3)	N1—C17—C18—Cl1	64.6 (2)
C6—C5—C21—C22	−0.2 (3)	N1—C19—C20—Cl2	172.98 (13)
C4—C5—C21—C22	−178.39 (18)

Cg1 is the centroid of the C11–C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18B···Cl1Bⁱ	0.97	2.91	3.822 (2)	158
C4—H4A···Cg1ⁱⁱ	0.97	2.55	3.459 (2)	156

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18B⋯Cl1Bⁱ	0.97	2.91	3.822 (2)	158
C4—H4A⋯Cg1ⁱⁱ	0.97	2.55	3.459 (2)	156

Symmetry codes: (i) ; (ii) .

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. 2-(3-benzoyl-1-pyridinio)-3,4-dioxocyclobutenolate.

Authors: Tsonko Kolev; Denitsa Yancheva; Boris Shivachev; Rosica Petrova; Michael Spiteller
Journal: Acta Crystallogr C Date: 2005-03-11 Impact factor: 1.172

2 in total