Ethyl 2,6-bis-(4-chloro-phen-yl)-1-iso-cyano-4-oxo-cyclo-hexa-necarboxyl-ate.

In the title compound, C22H19Cl2NO3, the central six-membered ring is in a twist-boat conformation. The two aryl groups are in equatorial positions, trans to each other and with a dihedral angle of 77.50 (2)° between them. One of the least hindered -CH2- groups and one of the aryl-substituted C atoms, with its axial H atom, are in the flagpole positions. The eth-oxy-carbonyl group is in an equatorial position and is cis to the second aryl group. In the crystal, molecules are linked via weak C-H⋯O hydrogen bonds, forming chains along [010].

Related literature

For the synthesis, see: Zhang et al. (2010 ▶); Tan et al. (2009 ▶). For related structures, see: Rowland & Gill (1988 ▶); Aleman et al. (2009 ▶); Wu et al. (2011 ▶); Li et al. (2011 ▶). For other [5 + 1] annulation reactions, see: Bi et al. (2005 ▶); Zhao et al. (2006 ▶); Fu et al. (2009 ▶); Xu et al. (2012 ▶).

Experimental

Crystal data

C22H19Cl2NO3

M = 416.28

Monoclinic,

a = 21.6980 (17) Å

b = 11.0770 (19) Å

c = 17.515 (3) Å

β = 104.535 (2)°

V = 4075.0 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.34 mm−1

T = 293 K

0.21 × 0.19 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.932, T max = 0.951

9983 measured reflections

3602 independent reflections

2584 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.117

S = 1.01

3602 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablock(s) I. DOI: 10.1107/S160053681401383X/lr2127sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401383X/lr2127Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401383X/lr2127Isup3.cml

CCDC reference: 1008201

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H19Cl2NO3	F(000) = 1728
Mr = 416.28	Dx = 1.357 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 106 reflections
a = 21.6980 (17) Å	θ = 1.3–26.0°
b = 11.0770 (19) Å	µ = 0.34 mm−1
c = 17.515 (3) Å	T = 293 K
β = 104.535 (2)°	BLOCK, colorless
V = 4075.0 (10) Å3	0.21 × 0.19 × 0.15 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	3602 independent reflections
Radiation source: fine-focus sealed tube	2584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
Tmin = 0.932, Tmax = 0.951	k = −13→13
9983 measured reflections	l = −20→9

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0514P)2 + 2.7869P] where P = (Fo2 + 2Fc2)/3
3602 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl2	−0.01505 (3)	0.07074 (6)	0.62309 (5)	0.0780 (2)
Cl1	0.59500 (4)	0.06816 (9)	0.99930 (6)	0.1128 (4)
O2	0.30900 (7)	0.21848 (13)	0.84990 (9)	0.0528 (4)
C12	0.18929 (9)	0.19357 (17)	0.66846 (12)	0.0443 (5)
C18	0.30971 (9)	0.15687 (17)	0.72324 (12)	0.0435 (5)
N1	0.30407 (9)	0.04712 (16)	0.67773 (12)	0.0524 (5)
C11	0.25594 (9)	0.24575 (18)	0.68262 (12)	0.0424 (5)
H11	0.2578	0.3129	0.7196	0.051*
C4	0.42949 (9)	0.17517 (19)	0.79764 (14)	0.0492 (5)
O1	0.28944 (9)	0.02289 (15)	0.82275 (11)	0.0759 (5)
C7	0.37764 (9)	0.21213 (18)	0.72628 (13)	0.0477 (5)
H7	0.3901	0.1767	0.6811	0.057*
C19	0.30148 (9)	0.12206 (19)	0.80460 (13)	0.0475 (5)
C9	0.33050 (11)	0.3749 (2)	0.63092 (15)	0.0552 (6)
C17	0.15361 (10)	0.2176 (2)	0.72194 (14)	0.0561 (6)
H17	0.1719	0.2608	0.7676	0.067*
O3	0.34259 (9)	0.45029 (17)	0.58723 (12)	0.0832 (6)
C14	0.09922 (11)	0.0868 (2)	0.58857 (14)	0.0567 (6)
H14	0.0811	0.0413	0.5440	0.068*
C10	0.27117 (10)	0.2997 (2)	0.60953 (13)	0.0517 (5)
H10A	0.2767	0.2352	0.5744	0.062*
H10B	0.2358	0.3494	0.5818	0.062*
C15	0.06450 (10)	0.1152 (2)	0.64196 (15)	0.0551 (6)
C8	0.37399 (10)	0.34828 (19)	0.71039 (14)	0.0542 (6)
H8A	0.3584	0.3888	0.7509	0.065*
H8B	0.4162	0.3791	0.7125	0.065*
C13	0.16142 (10)	0.12688 (19)	0.60210 (13)	0.0526 (6)
H13	0.1849	0.1086	0.5659	0.063*
C20	0.30188 (13)	0.2027 (3)	0.93036 (14)	0.0705 (7)
H20A	0.2595	0.2272	0.9327	0.085*
H20B	0.3074	0.1183	0.9452	0.085*
C16	0.09146 (11)	0.1789 (2)	0.70886 (16)	0.0646 (7)
H16	0.0680	0.1961	0.7453	0.078*
C3	0.46190 (11)	0.2575 (2)	0.85150 (16)	0.0690 (7)
H3	0.4496	0.3381	0.8459	0.083*
C5	0.44867 (12)	0.0562 (2)	0.80921 (17)	0.0694 (7)
H5	0.4275	−0.0025	0.7744	0.083*
C1	0.53022 (11)	0.1084 (3)	0.92278 (17)	0.0717 (7)
C6	0.49881 (14)	0.0224 (3)	0.87177 (19)	0.0829 (9)
H6	0.5109	−0.0582	0.8789	0.099*
C22	0.30053 (14)	−0.0380 (2)	0.63980 (18)	0.0765 (8)
C2	0.51188 (12)	0.2252 (3)	0.91352 (18)	0.0793 (8)
H2	0.5329	0.2834	0.9489	0.095*
C21	0.34862 (18)	0.2745 (3)	0.98441 (18)	0.1104 (12)
H21A	0.3437	0.2640	1.0370	0.166*
H21B	0.3428	0.3581	0.9698	0.166*
H21C	0.3905	0.2493	0.9825	0.166*

	U11	U22	U33	U12	U13	U23
Cl2	0.0464 (3)	0.0811 (5)	0.1010 (6)	−0.0096 (3)	0.0083 (3)	−0.0033 (4)
Cl1	0.0699 (5)	0.1466 (8)	0.1075 (7)	0.0144 (5)	−0.0045 (4)	0.0360 (6)
O2	0.0637 (9)	0.0523 (9)	0.0461 (9)	−0.0020 (7)	0.0207 (7)	0.0016 (7)
C12	0.0474 (11)	0.0384 (10)	0.0454 (12)	0.0012 (9)	0.0087 (10)	0.0009 (9)
C18	0.0492 (11)	0.0345 (10)	0.0487 (13)	−0.0035 (8)	0.0159 (10)	−0.0030 (9)
N1	0.0580 (11)	0.0386 (10)	0.0609 (12)	−0.0003 (8)	0.0153 (9)	−0.0051 (9)
C11	0.0472 (11)	0.0377 (10)	0.0428 (12)	−0.0030 (8)	0.0122 (9)	−0.0017 (9)
C4	0.0417 (11)	0.0520 (12)	0.0586 (14)	−0.0016 (9)	0.0216 (10)	0.0030 (11)
O1	0.1060 (14)	0.0511 (10)	0.0770 (13)	−0.0162 (9)	0.0350 (11)	0.0125 (9)
C7	0.0480 (12)	0.0463 (12)	0.0534 (13)	−0.0034 (9)	0.0210 (10)	−0.0009 (10)
C19	0.0430 (11)	0.0458 (12)	0.0543 (14)	−0.0024 (9)	0.0136 (10)	0.0049 (11)
C9	0.0647 (14)	0.0492 (12)	0.0582 (15)	−0.0031 (11)	0.0275 (12)	0.0072 (12)
C17	0.0511 (13)	0.0594 (14)	0.0583 (15)	−0.0059 (10)	0.0147 (11)	−0.0144 (12)
O3	0.0888 (13)	0.0857 (13)	0.0778 (13)	−0.0170 (10)	0.0257 (11)	0.0318 (11)
C14	0.0580 (14)	0.0522 (13)	0.0528 (14)	−0.0055 (10)	0.0009 (11)	−0.0060 (11)
C10	0.0611 (13)	0.0484 (12)	0.0456 (13)	0.0006 (10)	0.0133 (11)	0.0013 (10)
C15	0.0456 (12)	0.0486 (12)	0.0674 (16)	−0.0023 (10)	0.0076 (11)	0.0037 (12)
C8	0.0538 (12)	0.0498 (13)	0.0609 (15)	−0.0114 (10)	0.0179 (11)	0.0043 (11)
C13	0.0548 (13)	0.0538 (13)	0.0491 (14)	−0.0020 (10)	0.0130 (11)	−0.0039 (11)
C20	0.0799 (17)	0.0865 (19)	0.0499 (15)	0.0054 (14)	0.0254 (14)	0.0099 (14)
C16	0.0535 (13)	0.0734 (16)	0.0714 (17)	−0.0050 (12)	0.0240 (13)	−0.0131 (14)
C3	0.0583 (14)	0.0608 (15)	0.0810 (19)	0.0014 (12)	0.0046 (14)	−0.0045 (14)
C5	0.0659 (15)	0.0577 (15)	0.0817 (19)	0.0030 (12)	0.0130 (14)	0.0013 (14)
C1	0.0472 (13)	0.095 (2)	0.0732 (18)	0.0015 (13)	0.0148 (13)	0.0141 (16)
C6	0.0760 (18)	0.0686 (17)	0.102 (2)	0.0186 (15)	0.0177 (17)	0.0211 (17)
C22	0.0902 (19)	0.0528 (15)	0.083 (2)	0.0022 (14)	0.0155 (16)	−0.0109 (15)
C2	0.0608 (16)	0.087 (2)	0.080 (2)	−0.0032 (14)	−0.0005 (15)	−0.0080 (16)
C21	0.143 (3)	0.130 (3)	0.0617 (19)	−0.051 (2)	0.033 (2)	−0.021 (2)

Cl2—C15	1.745 (2)	C14—C15	1.377 (3)
Cl1—C1	1.739 (3)	C14—C13	1.383 (3)
O2—C19	1.316 (3)	C14—H14	0.9300
O2—C20	1.466 (3)	C10—H10A	0.9700
C12—C13	1.382 (3)	C10—H10B	0.9700
C12—C17	1.383 (3)	C15—C16	1.367 (3)
C12—C11	1.519 (3)	C8—H8A	0.9700
C18—N1	1.442 (3)	C8—H8B	0.9700
C18—C19	1.529 (3)	C13—H13	0.9300
C18—C11	1.556 (3)	C20—C21	1.441 (4)
C18—C7	1.584 (3)	C20—H20A	0.9700
N1—C22	1.144 (3)	C20—H20B	0.9700
C11—C10	1.523 (3)	C16—H16	0.9300
C11—H11	0.9800	C3—C2	1.376 (4)
C4—C3	1.373 (3)	C3—H3	0.9300
C4—C5	1.382 (3)	C5—C6	1.388 (4)
C4—C7	1.513 (3)	C5—H5	0.9300
O1—C19	1.191 (3)	C1—C2	1.352 (4)
C7—C8	1.532 (3)	C1—C6	1.365 (4)
C7—H7	0.9800	C6—H6	0.9300
C9—O3	1.205 (3)	C2—H2	0.9300
C9—C10	1.500 (3)	C21—H21A	0.9600
C9—C8	1.502 (3)	C21—H21B	0.9600
C17—C16	1.378 (3)	C21—H21C	0.9600
C17—H17	0.9300
C19—O2—C20	117.11 (18)	H10A—C10—H10B	108.0
C13—C12—C17	118.1 (2)	C16—C15—C14	120.7 (2)
C13—C12—C11	122.58 (19)	C16—C15—Cl2	119.88 (19)
C17—C12—C11	119.21 (19)	C14—C15—Cl2	119.39 (18)
N1—C18—C19	106.80 (16)	C9—C8—C7	110.72 (19)
N1—C18—C11	109.33 (17)	C9—C8—H8A	109.5
C19—C18—C11	109.64 (16)	C7—C8—H8A	109.5
N1—C18—C7	107.07 (16)	C9—C8—H8B	109.5
C19—C18—C7	113.03 (17)	C7—C8—H8B	109.5
C11—C18—C7	110.82 (15)	H8A—C8—H8B	108.1
C22—N1—C18	177.6 (2)	C12—C13—C14	121.2 (2)
C12—C11—C10	114.26 (17)	C12—C13—H13	119.4
C12—C11—C18	114.07 (16)	C14—C13—H13	119.4
C10—C11—C18	109.69 (16)	C21—C20—O2	109.8 (2)
C12—C11—H11	106.0	C21—C20—H20A	109.7
C10—C11—H11	106.0	O2—C20—H20A	109.7
C18—C11—H11	106.0	C21—C20—H20B	109.7
C3—C4—C5	116.7 (2)	O2—C20—H20B	109.7
C3—C4—C7	122.3 (2)	H20A—C20—H20B	108.2
C5—C4—C7	120.9 (2)	C15—C16—C17	119.6 (2)
C4—C7—C8	114.22 (18)	C15—C16—H16	120.2
C4—C7—C18	114.57 (17)	C17—C16—H16	120.2
C8—C7—C18	111.65 (16)	C4—C3—C2	122.4 (3)
C4—C7—H7	105.1	C4—C3—H3	118.8
C8—C7—H7	105.1	C2—C3—H3	118.8
C18—C7—H7	105.1	C4—C5—C6	121.4 (3)
O1—C19—O2	126.2 (2)	C4—C5—H5	119.3
O1—C19—C18	124.5 (2)	C6—C5—H5	119.3
O2—C19—C18	109.36 (17)	C2—C1—C6	120.4 (3)
O3—C9—C10	122.4 (2)	C2—C1—Cl1	119.6 (2)
O3—C9—C8	122.6 (2)	C6—C1—Cl1	120.0 (2)
C10—C9—C8	114.99 (18)	C1—C6—C5	119.5 (3)
C16—C17—C12	121.2 (2)	C1—C6—H6	120.2
C16—C17—H17	119.4	C5—C6—H6	120.2
C12—C17—H17	119.4	C1—C2—C3	119.6 (3)
C15—C14—C13	119.1 (2)	C1—C2—H2	120.2
C15—C14—H14	120.4	C3—C2—H2	120.2
C13—C14—H14	120.4	C20—C21—H21A	109.5
C9—C10—C11	111.22 (18)	C20—C21—H21B	109.5
C9—C10—H10A	109.4	H21A—C21—H21B	109.5
C11—C10—H10A	109.4	C20—C21—H21C	109.5
C9—C10—H10B	109.4	H21A—C21—H21C	109.5
C11—C10—H10B	109.4	H21B—C21—H21C	109.5
C19—C18—N1—C22	−164 (6)	C7—C18—C19—O2	59.8 (2)
C11—C18—N1—C22	78 (6)	C13—C12—C17—C16	−1.5 (3)
C7—C18—N1—C22	−43 (6)	C11—C12—C17—C16	175.7 (2)
C13—C12—C11—C10	41.3 (3)	O3—C9—C10—C11	−160.1 (2)
C17—C12—C11—C10	−135.7 (2)	C8—C9—C10—C11	20.6 (3)
C13—C12—C11—C18	−86.0 (2)	C12—C11—C10—C9	166.34 (18)
C17—C12—C11—C18	96.9 (2)	C18—C11—C10—C9	−64.1 (2)
N1—C18—C11—C12	55.2 (2)	C13—C14—C15—C16	−2.0 (4)
C19—C18—C11—C12	−61.5 (2)	C13—C14—C15—Cl2	177.18 (17)
C7—C18—C11—C12	173.01 (17)	O3—C9—C8—C7	−139.3 (2)
N1—C18—C11—C10	−74.4 (2)	C10—C9—C8—C7	40.1 (3)
C19—C18—C11—C10	168.84 (17)	C4—C7—C8—C9	169.06 (18)
C7—C18—C11—C10	43.4 (2)	C18—C7—C8—C9	−58.9 (2)
C3—C4—C7—C8	11.8 (3)	C17—C12—C13—C14	1.1 (3)
C5—C4—C7—C8	−164.7 (2)	C11—C12—C13—C14	−176.0 (2)
C3—C4—C7—C18	−118.7 (2)	C15—C14—C13—C12	0.7 (3)
C5—C4—C7—C18	64.7 (3)	C19—O2—C20—C21	140.9 (3)
N1—C18—C7—C4	−93.2 (2)	C14—C15—C16—C17	1.6 (4)
C19—C18—C7—C4	24.1 (2)	Cl2—C15—C16—C17	−177.61 (19)
C11—C18—C7—C4	147.63 (18)	C12—C17—C16—C15	0.2 (4)
N1—C18—C7—C8	134.96 (19)	C5—C4—C3—C2	1.1 (4)
C19—C18—C7—C8	−107.7 (2)	C7—C4—C3—C2	−175.6 (2)
C11—C18—C7—C8	15.8 (2)	C3—C4—C5—C6	−0.8 (4)
C20—O2—C19—O1	−0.1 (3)	C7—C4—C5—C6	176.0 (2)
C20—O2—C19—C18	179.17 (17)	C2—C1—C6—C5	1.3 (4)
N1—C18—C19—O1	−3.5 (3)	Cl1—C1—C6—C5	−177.6 (2)
C11—C18—C19—O1	114.8 (2)	C4—C5—C6—C1	−0.4 (4)
C7—C18—C19—O1	−121.0 (2)	C6—C1—C2—C3	−1.0 (4)
N1—C18—C19—O2	177.26 (16)	Cl1—C1—C2—C3	178.0 (2)
C11—C18—C19—O2	−64.4 (2)	C4—C3—C2—C1	−0.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1i	0.98	2.57	3.218 (3)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1i	0.98	2.57	3.218 (3)	123

Symmetry code: (i) .