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

In the title compound, C22H19Br2NO3, the central oxo-cyclo-hexane ring is in a twist-boat conformation; all the substituents (one eth-oxy-carbonyl and two aryl groups) are located in equatorial orientations. One of the -CH2- groups and the opposite -CH- group bearing a bromo-benzene substituent form the flagpoles of the twist-boat. The dihedral angle between the aromatic rings is 76.4 (4)°. In the crystal, weak C-H⋯O inter-actions link the mol-ecules into C(5) chains propagating in the [010] direction. A short Br⋯O contact of 3.254 (4) Å is observed.

Related literature

For further details of the synthesis, see: Tan et al. (2009 ▶); Zhang et al. (2010 ▶). For more [5 + 1] annulation reactions, see: Bi et al. (2005 ▶); Dong et al. (2005 ▶); Hu et al. (2008 ▶); Zhao et al. (2006 ▶); Fu et al. (2009 ▶); Xu et al. (2012 ▶).

Experimental

Crystal data

C22H19Br2NO3

M = 505.20

Monoclinic,

a = 21.9920 (17) Å

b = 11.0750 (19) Å

c = 17.648 (3) Å

β = 103.560 (2)°

V = 4178.6 (11) Å3

Z = 8

Mo Kα radiation

μ = 3.90 mm−1

T = 293 K

0.17 × 0.16 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.557, T max = 0.631

10763 measured reflections

3904 independent reflections

2578 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.113

S = 1.03

3904 reflections

253 parameters

H-atom parameters constrained

Δρmax = 1.11 e Å−3

Δρmin = −0.92 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/S160053681401530X/hb7238sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401530X/hb7238Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401530X/hb7238Isup3.cml

CCDC reference: 1011009

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

C22H19Br2NO3	F(000) = 2016
Mr = 505.20	Dx = 1.606 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 78 reflections
a = 21.9920 (17) Å	θ = 1.3–26.0°
b = 11.0750 (19) Å	µ = 3.90 mm−1
c = 17.648 (3) Å	T = 293 K
β = 103.560 (2)°	BLOCK, colorless
V = 4178.6 (11) Å3	0.17 × 0.16 × 0.13 mm
Z = 8

Bruker SMART APEXII CCD diffractometer	3904 independent reflections
Radiation source: fine-focus sealed tube	2578 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 25.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −26→25
Tmin = 0.557, Tmax = 0.631	k = −13→13
10763 measured reflections	l = −21→18

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0466P)2 + 7.9699P] where P = (Fo2 + 2Fc2)/3
3904 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 1.11 e Å−3
0 restraints	Δρmin = −0.92 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
Br2	−0.01743 (2)	0.57808 (4)	0.12001 (3)	0.06681 (18)
Br1	0.59543 (3)	0.56713 (6)	0.49860 (4)	0.0979 (2)
O2	0.30729 (12)	0.7231 (2)	0.34697 (15)	0.0512 (7)
C17	0.19183 (17)	0.6993 (3)	0.1672 (2)	0.0406 (9)
C11	0.25738 (17)	0.7509 (3)	0.1820 (2)	0.0401 (8)
H11	0.2588	0.8177	0.2188	0.048*
N1	0.30420 (15)	0.5508 (3)	0.1772 (2)	0.0505 (8)
C10	0.27366 (18)	0.8048 (4)	0.1094 (2)	0.0468 (9)
H10A	0.2798	0.7402	0.0749	0.056*
H10B	0.2392	0.8544	0.0818	0.056*
C12	0.30963 (17)	0.6605 (3)	0.2217 (2)	0.0409 (9)
O3	0.28934 (16)	0.5274 (3)	0.32118 (18)	0.0754 (10)
C13	0.30092 (17)	0.6265 (4)	0.3028 (2)	0.0453 (9)
C9	0.33168 (19)	0.8799 (4)	0.1308 (2)	0.0523 (10)
C7	0.37673 (17)	0.7151 (3)	0.2243 (2)	0.0443 (9)
H7	0.3893	0.6799	0.1794	0.053*
O1	0.34440 (16)	0.9555 (3)	0.08779 (19)	0.0795 (10)
C18	0.16493 (18)	0.6331 (4)	0.1019 (2)	0.0495 (10)
H18	0.1885	0.6140	0.0661	0.059*
C22	0.15553 (18)	0.7240 (4)	0.2200 (2)	0.0521 (10)
H22	0.1731	0.7666	0.2653	0.062*
C4	0.42738 (17)	0.6782 (4)	0.2946 (2)	0.0470 (9)
C5	0.4465 (2)	0.5596 (4)	0.3050 (3)	0.0652 (12)
H5	0.4261	0.5013	0.2703	0.078*
C1	0.5261 (2)	0.6100 (5)	0.4171 (3)	0.0622 (12)
C19	0.10326 (19)	0.5942 (4)	0.0883 (2)	0.0512 (10)
H19	0.0859	0.5486	0.0443	0.061*
C20	0.06841 (17)	0.6234 (3)	0.1403 (2)	0.0475 (9)
C14	0.2992 (2)	0.7071 (5)	0.4265 (2)	0.0679 (13)
H14A	0.2574	0.7320	0.4290	0.082*
H14B	0.3043	0.6226	0.4411	0.082*
C8	0.37386 (18)	0.8521 (4)	0.2093 (2)	0.0518 (10)
H8A	0.3582	0.8925	0.2497	0.062*
H8B	0.4156	0.8824	0.2112	0.062*
C21	0.09395 (19)	0.6872 (4)	0.2070 (3)	0.0584 (11)
H21	0.0702	0.7052	0.2428	0.070*
C2	0.5071 (2)	0.7263 (5)	0.4093 (3)	0.0709 (13)
H2	0.5272	0.7839	0.4448	0.085*
C3	0.4580 (2)	0.7598 (4)	0.3488 (3)	0.0653 (12)
H3	0.4453	0.8401	0.3446	0.078*
C16	0.3003 (3)	0.4647 (5)	0.1399 (3)	0.0748 (14)
C6	0.4956 (2)	0.5251 (5)	0.3664 (3)	0.0748 (14)
H6	0.5076	0.4445	0.3727	0.090*
C15	0.3453 (3)	0.7792 (6)	0.4799 (3)	0.109 (2)
H15A	0.3401	0.7688	0.5320	0.163*
H15B	0.3398	0.8628	0.4655	0.163*
H15C	0.3866	0.7537	0.4775	0.163*

	U11	U22	U33	U12	U13	U23
Br2	0.0384 (2)	0.0767 (3)	0.0818 (3)	−0.0098 (2)	0.0069 (2)	−0.0024 (3)
Br1	0.0605 (4)	0.1272 (5)	0.0961 (4)	0.0137 (3)	−0.0018 (3)	0.0346 (4)
O2	0.0579 (18)	0.0531 (17)	0.0452 (16)	−0.0035 (13)	0.0171 (13)	0.0031 (13)
C17	0.038 (2)	0.041 (2)	0.042 (2)	−0.0016 (16)	0.0067 (16)	−0.0005 (17)
C11	0.040 (2)	0.036 (2)	0.044 (2)	−0.0041 (16)	0.0086 (16)	−0.0025 (16)
N1	0.048 (2)	0.0387 (19)	0.064 (2)	0.0000 (15)	0.0124 (16)	−0.0055 (17)
C10	0.045 (2)	0.049 (2)	0.046 (2)	−0.0029 (18)	0.0093 (18)	0.0037 (18)
C12	0.039 (2)	0.036 (2)	0.049 (2)	−0.0044 (16)	0.0121 (17)	−0.0028 (17)
O3	0.105 (3)	0.0497 (19)	0.079 (2)	−0.0167 (18)	0.037 (2)	0.0120 (16)
C13	0.036 (2)	0.047 (2)	0.054 (2)	−0.0041 (17)	0.0122 (18)	0.004 (2)
C9	0.056 (3)	0.048 (2)	0.057 (3)	−0.006 (2)	0.021 (2)	0.006 (2)
C7	0.039 (2)	0.045 (2)	0.052 (2)	−0.0061 (17)	0.0164 (18)	−0.0018 (18)
O1	0.076 (2)	0.087 (2)	0.073 (2)	−0.0251 (19)	0.0141 (17)	0.0293 (19)
C18	0.046 (2)	0.055 (2)	0.049 (2)	−0.0012 (19)	0.0135 (19)	−0.002 (2)
C22	0.046 (2)	0.056 (3)	0.054 (2)	−0.0102 (19)	0.0110 (19)	−0.015 (2)
C4	0.037 (2)	0.050 (2)	0.059 (3)	−0.0004 (18)	0.0198 (19)	0.005 (2)
C5	0.064 (3)	0.055 (3)	0.075 (3)	−0.002 (2)	0.012 (2)	−0.001 (2)
C1	0.038 (2)	0.080 (3)	0.068 (3)	0.002 (2)	0.012 (2)	0.014 (3)
C19	0.046 (2)	0.053 (2)	0.050 (2)	−0.0054 (19)	0.0004 (19)	−0.0075 (19)
C20	0.036 (2)	0.047 (2)	0.057 (3)	−0.0054 (17)	0.0056 (18)	0.0036 (19)
C14	0.070 (3)	0.086 (3)	0.050 (3)	0.005 (3)	0.019 (2)	0.010 (2)
C8	0.044 (2)	0.051 (2)	0.060 (3)	−0.0136 (19)	0.0130 (19)	0.003 (2)
C21	0.044 (2)	0.072 (3)	0.063 (3)	−0.008 (2)	0.021 (2)	−0.010 (2)
C2	0.049 (3)	0.076 (3)	0.078 (3)	−0.005 (2)	−0.004 (2)	−0.007 (3)
C3	0.052 (3)	0.057 (3)	0.079 (3)	0.004 (2)	0.000 (2)	−0.001 (2)
C16	0.079 (4)	0.055 (3)	0.088 (4)	0.002 (3)	0.015 (3)	−0.008 (3)
C6	0.067 (3)	0.062 (3)	0.094 (4)	0.018 (3)	0.015 (3)	0.017 (3)
C15	0.137 (6)	0.129 (5)	0.063 (3)	−0.042 (5)	0.028 (4)	−0.023 (3)

Br2—C20	1.904 (4)	C22—C21	1.381 (5)
Br1—C1	1.896 (4)	C22—H22	0.9300
O2—C13	1.312 (5)	C4—C3	1.373 (6)
O2—C14	1.466 (5)	C4—C5	1.378 (6)
C17—C18	1.378 (5)	C5—C6	1.392 (7)
C17—C22	1.388 (5)	C5—H5	0.9300
C17—C11	1.515 (5)	C1—C2	1.351 (7)
C11—C10	1.530 (5)	C1—C6	1.361 (7)
C11—C12	1.560 (5)	C19—C20	1.365 (5)
C11—H11	0.9800	C19—H19	0.9300
N1—C16	1.150 (5)	C20—C21	1.375 (5)
N1—C12	1.437 (5)	C14—C15	1.451 (7)
C10—C9	1.495 (5)	C14—H14A	0.9700
C10—H10A	0.9700	C14—H14B	0.9700
C10—H10B	0.9700	C8—H8A	0.9700
C12—C13	1.534 (5)	C8—H8B	0.9700
C12—C7	1.585 (5)	C21—H21	0.9300
O3—C13	1.190 (5)	C2—C3	1.380 (6)
C9—O1	1.206 (4)	C2—H2	0.9300
C9—C8	1.507 (6)	C3—H3	0.9300
C7—C4	1.516 (5)	C6—H6	0.9300
C7—C8	1.539 (5)	C15—H15A	0.9600
C7—H7	0.9800	C15—H15B	0.9600
C18—C19	1.389 (5)	C15—H15C	0.9600
C18—H18	0.9300
C13—O2—C14	116.8 (3)	C5—C4—C7	120.6 (4)
C18—C17—C22	117.7 (3)	C4—C5—C6	121.5 (5)
C18—C17—C11	123.3 (3)	C4—C5—H5	119.2
C22—C17—C11	118.9 (3)	C6—C5—H5	119.2
C17—C11—C10	113.7 (3)	C2—C1—C6	120.0 (4)
C17—C11—C12	114.0 (3)	C2—C1—Br1	119.3 (4)
C10—C11—C12	109.5 (3)	C6—C1—Br1	120.6 (4)
C17—C11—H11	106.3	C20—C19—C18	119.4 (4)
C10—C11—H11	106.3	C20—C19—H19	120.3
C12—C11—H11	106.3	C18—C19—H19	120.3
C16—N1—C12	178.1 (4)	C19—C20—C21	121.1 (4)
C9—C10—C11	111.1 (3)	C19—C20—Br2	119.9 (3)
C9—C10—H10A	109.4	C21—C20—Br2	119.0 (3)
C11—C10—H10A	109.4	C15—C14—O2	109.4 (4)
C9—C10—H10B	109.4	C15—C14—H14A	109.8
C11—C10—H10B	109.4	O2—C14—H14A	109.8
H10A—C10—H10B	108.0	C15—C14—H14B	109.8
N1—C12—C13	106.9 (3)	O2—C14—H14B	109.8
N1—C12—C11	109.8 (3)	H14A—C14—H14B	108.2
C13—C12—C11	109.6 (3)	C9—C8—C7	110.5 (3)
N1—C12—C7	107.2 (3)	C9—C8—H8A	109.5
C13—C12—C7	112.7 (3)	C7—C8—H8A	109.5
C11—C12—C7	110.6 (3)	C9—C8—H8B	109.5
O3—C13—O2	126.2 (4)	C7—C8—H8B	109.5
O3—C13—C12	124.2 (4)	H8A—C8—H8B	108.1
O2—C13—C12	109.6 (3)	C20—C21—C22	118.8 (4)
O1—C9—C10	122.5 (4)	C20—C21—H21	120.6
O1—C9—C8	122.4 (4)	C22—C21—H21	120.6
C10—C9—C8	115.0 (3)	C1—C2—C3	120.1 (5)
C4—C7—C8	113.6 (3)	C1—C2—H2	119.9
C4—C7—C12	114.9 (3)	C3—C2—H2	119.9
C8—C7—C12	111.8 (3)	C4—C3—C2	122.0 (4)
C4—C7—H7	105.2	C4—C3—H3	119.0
C8—C7—H7	105.2	C2—C3—H3	119.0
C12—C7—H7	105.2	C1—C6—C5	119.6 (5)
C17—C18—C19	121.3 (4)	C1—C6—H6	120.2
C17—C18—H18	119.4	C5—C6—H6	120.2
C19—C18—H18	119.4	C14—C15—H15A	109.5
C21—C22—C17	121.8 (4)	C14—C15—H15B	109.5
C21—C22—H22	119.1	H15A—C15—H15B	109.5
C17—C22—H22	119.1	C14—C15—H15C	109.5
C3—C4—C5	116.7 (4)	H15A—C15—H15C	109.5
C3—C4—C7	122.6 (4)	H15B—C15—H15C	109.5
C18—C17—C11—C10	41.2 (5)	C11—C12—C7—C8	16.0 (4)
C22—C17—C11—C10	−135.7 (4)	C22—C17—C18—C19	1.2 (6)
C18—C17—C11—C12	−85.3 (4)	C11—C17—C18—C19	−175.8 (4)
C22—C17—C11—C12	97.8 (4)	C18—C17—C22—C21	−1.9 (6)
C17—C11—C10—C9	166.2 (3)	C11—C17—C22—C21	175.2 (4)
C12—C11—C10—C9	−65.0 (4)	C8—C7—C4—C3	13.6 (5)
C16—N1—C12—C13	−174 (100)	C12—C7—C4—C3	−116.9 (4)
C16—N1—C12—C11	67 (14)	C8—C7—C4—C5	−163.9 (4)
C16—N1—C12—C7	−53 (14)	C12—C7—C4—C5	65.7 (5)
C17—C11—C12—N1	54.1 (4)	C3—C4—C5—C6	−1.7 (7)
C10—C11—C12—N1	−74.6 (4)	C7—C4—C5—C6	175.9 (4)
C17—C11—C12—C13	−63.0 (4)	C17—C18—C19—C20	0.8 (6)
C10—C11—C12—C13	168.3 (3)	C18—C19—C20—C21	−2.2 (6)
C17—C11—C12—C7	172.1 (3)	C18—C19—C20—Br2	176.7 (3)
C10—C11—C12—C7	43.5 (4)	C13—O2—C14—C15	140.1 (5)
C14—O2—C13—O3	−0.2 (6)	O1—C9—C8—C7	−139.2 (4)
C14—O2—C13—C12	178.9 (3)	C10—C9—C8—C7	39.5 (5)
N1—C12—C13—O3	−2.8 (5)	C4—C7—C8—C9	168.9 (3)
C11—C12—C13—O3	116.1 (4)	C12—C7—C8—C9	−59.1 (4)
C7—C12—C13—O3	−120.3 (4)	C19—C20—C21—C22	1.5 (6)
N1—C12—C13—O2	178.1 (3)	Br2—C20—C21—C22	−177.4 (3)
C11—C12—C13—O2	−62.9 (4)	C17—C22—C21—C20	0.6 (7)
C7—C12—C13—O2	60.6 (4)	C6—C1—C2—C3	−1.7 (8)
C11—C10—C9—O1	−159.9 (4)	Br1—C1—C2—C3	177.9 (4)
C11—C10—C9—C8	21.4 (5)	C5—C4—C3—C2	2.4 (7)
N1—C12—C7—C4	−93.0 (4)	C7—C4—C3—C2	−175.2 (4)
C13—C12—C7—C4	24.3 (4)	C1—C2—C3—C4	−0.7 (8)
C11—C12—C7—C4	147.3 (3)	C2—C1—C6—C5	2.4 (7)
N1—C12—C7—C8	135.7 (3)	Br1—C1—C6—C5	−177.3 (4)
C13—C12—C7—C8	−107.0 (4)	C4—C5—C6—C1	−0.6 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O3i	0.98	2.58	3.226 (5)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O3i	0.98	2.58	3.226 (5)	123

Symmetry code: (i) .