2-Amino-4-(4-chloro­phen­yl)-5,6,7,8,9,10-hexa­hydro­benzo[8]annulene-1,3-dicarbonitrile

Rajni Swamy, V.; Srinivasan, N.; Ranjith Kumar, R.; Krishnakumar, R.V.

doi:10.1107/S1600536812034861

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2692

doi:10.1107/S1600536812034861

Open

access

2-Amino-4-(4-chlorophenyl)-5,6,7,8,9,10-hexahydrobenzo[8]annulene-1,3-dicarbonitrile

V. Rajni Swamy,^a N. Srinivasan,^a R. Ranjith Kumar ^b and R.V. Krishnakumar ^a ^*

^aDepartment of Physics, Thiagarajar College, Madurai 625 009, India, and ^bSchool of Chemistry, Madurai Kamaraj University, Madurai 625 021, India
^*Correspondence e-mail: mailtorvkk@yahoo.co.in

(Received 24 July 2012; accepted 7 August 2012; online 11 August 2012)

In the title compound, C₂₀H₁₈ClN₃, the cyclooctene ring exhibits conformational disorder of two methylene groups with a site-occupation factor of 0.859 (6) for the major occupied site. In the crystal, molecules are connected into inversion dimers via pairs of weak N—H⋯N hydrogen bonds, forming an R₂²(12) graph-set motif. These dimers are further connected via weak N—H⋯Cl interactions into chains running along [011]. There are also C—H⋯N interactions present in the crystal.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For puckering parameters, see: Cremer & Pople (1975 ) For conformational analysis of rings, see: Allen et al. (1996 ); Evans & Boeyens (1988 , 1989 ); Hendrickson (1967 ).

Experimental

Crystal data

C₂₀H₁₈ClN₃
M_r = 335.82
Orthorhombic, P b c a
a = 11.3835 (9) Å
b = 16.9840 (13) Å
c = 18.4766 (14) Å
V = 3572.2 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 K
0.28 × 0.13 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.966, T_max = 0.978
39132 measured reflections
4279 independent reflections
3440 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.137
S = 1.04
4279 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯N3ⁱ	0.86	2.44	3.1636 (18)	142
C11′—H11C⋯N2ⁱⁱ	0.97	2.57	3.319 (16)	135
N1—H1A⋯Cl1ⁱⁱⁱ	0.86	2.87	3.6628 (16)	153
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLUTON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812034861/bt5985sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034861/bt5985Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812034861/bt5985Isup3.cml

checkCIF report

Comment top

Hendrickson (1967) performed energy-minimumization calculations to first establish ten types of conformers for cyclooctanes viz. crown (CR), chair-chair (CC), twist-chair-chair (TCC), boat (B), saddle, also known as twist-boat (TB), boat-boat (BB), boat-chair (BC), twist-boat-chair (TBC), chair (C), and twist-chair (TC). In the title compound, the torsion angle about the diene (C3\═C4) designated \t~1~ [C14—C4—C3—C9 = 3.39] shows that cyclooctene is a cis-conformer (Allen et al., 1996).

The cyclooctene ring exhibits conformational disorder (Fig.1) that may be described as a flip-flop between twist-boat-chair (TBC) and boat-chair (BC) modes (Table 1) with the major and minor component at a ratio of about 86:14. The minor component accounts for the BC mode and seems to have induced by a C—H···N hydrogen bond which connects glide-related molecules into a chain along the b axis. This chain is linked to its inverse through N—H···N hydrogen-bonds lead to a double chain generated through characteristic R²₂(12) graph-set motifs (Bernstein et al., 1995) across alternating centres of inversion (Fig. 2). These double chains, characterized by the primary interactions observed among molecules in the lattice, may be regaraded as the fundamental one-dimensional building units of a two-dimensional layer which extends parallel to the bc-plane through N—H···N hydrogen bonds.

The Cl atoms lie almost on the b-glide plane and close to the intersections of the a- and b- glide planes. A significant non-covalent N···Cl contact of 3.261 (2) Å and a weak N—H···Cl bond is also observed (Table 2)

Related literature top

For hydrogen-bond motifs, see: Bernstein et al. (1995). For puckering parameters, see: Cremer & Pople (1975) For conformational analysis of rings, see: Allen et al. (1996); Evans & Boeyens (1988, 1989); Hendrickson (1967).

Experimental top

Piperidine (2ml) was added to a mixture of 3-(4-chlorophenyl)-2-cyanoacrylamide (1 mmol) , malanonitrile (1 mmol) and cyclooctanone (1 mmol) in ethanol (5ml) and heated to reflux for three hours. The reaction mixture was poured to ice. The resulting solid formed was filtered and dissolved in hot methanol. Slow evaporation of the solvent for two days resulted in crystals suitable for X-ray diffraction.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLUTON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and conformational disorder. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Chain linked to its inverse through N—H···N hydrogen-bonds leading to a double chain generated through characteristic R²₂(12) graph-set motifs across alternating centres of inversion. Non-participating H-atoms are omitted for clarity.

2-Amino-4-(4-chlorophenyl)-5,6,7,8,9,10-hexahydrobenzo[8]annulene-1,3- dicarbonitrile top

Crystal data top

C₂₀H₁₈ClN₃	F(000) = 1408
M_r = 335.82	D_x = 1.249 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3440 reflections
a = 11.3835 (9) Å	θ = 1.1–28.0°
b = 16.9840 (13) Å	µ = 0.22 mm⁻¹
c = 18.4766 (14) Å	T = 298 K
V = 3572.2 (5) Å³	Prismatic, brown
Z = 8	0.28 × 0.13 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4279 independent reflections
Radiation source: fine-focus sealed tube	3440 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and ϕ scan	θ_max = 28.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.966, T_max = 0.978	k = −22→22
39132 measured reflections	l = −24→24

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0739P)² + 0.6829P] where P = (F_o² + 2F_c²)/3
4279 reflections	(Δ/σ)_max < 0.001
226 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₀H₁₈ClN₃	V = 3572.2 (5) Å³
M_r = 335.82	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.3835 (9) Å	µ = 0.22 mm⁻¹
b = 16.9840 (13) Å	T = 298 K
c = 18.4766 (14) Å	0.28 × 0.13 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4279 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3440 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.978	R_int = 0.025
39132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
4279 reflections	Δρ_min = −0.23 e Å⁻³
226 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.19472 (4)	0.24645 (3)	0.44965 (3)	0.0821 (2)
N1	0.34007 (13)	0.06894 (9)	0.89983 (6)	0.0652 (4)
H1A	0.2861	0.1042	0.9030	0.078*
H1B	0.3651	0.0457	0.9382	0.078*
N2	0.17382 (14)	0.18467 (10)	0.78542 (8)	0.0701 (4)
N3	0.54892 (13)	−0.07229 (9)	0.94323 (7)	0.0629 (4)
C1	0.38568 (12)	0.04983 (8)	0.83396 (7)	0.0450 (3)
C2	0.47395 (12)	−0.00739 (8)	0.82566 (7)	0.0440 (3)
C3	0.52167 (12)	−0.02742 (8)	0.75804 (7)	0.0461 (3)
C4	0.48105 (13)	0.01088 (8)	0.69542 (7)	0.0470 (3)
C5	0.39315 (12)	0.06796 (8)	0.70218 (6)	0.0427 (3)
C6	0.34465 (12)	0.08622 (8)	0.77001 (7)	0.0427 (3)
C7	0.25038 (13)	0.14201 (9)	0.77660 (7)	0.0498 (3)
C8	0.51593 (13)	−0.04515 (8)	0.89042 (7)	0.0492 (3)
C9	0.61406 (14)	−0.09109 (10)	0.75523 (9)	0.0608 (4)
H9A	0.6580	−0.0904	0.8002	0.073*
H9B	0.6685	−0.0792	0.7164	0.073*
C10	0.5646 (2)	−0.17414 (11)	0.74346 (11)	0.0802 (6)
H10A	0.6238	−0.2118	0.7585	0.096*	0.859 (6)
H10B	0.4974	−0.1808	0.7751	0.096*	0.859 (6)
H10C	0.5390	−0.1952	0.7896	0.096*	0.141 (6)
H10D	0.6268	−0.2079	0.7253	0.096*	0.141 (6)
C11	0.5268 (3)	−0.19477 (15)	0.66680 (16)	0.0894 (10)	0.859 (6)
H11A	0.5101	−0.2507	0.6649	0.107*	0.859 (6)
H11B	0.5922	−0.1847	0.6345	0.107*	0.859 (6)
C12	0.4193 (3)	−0.15018 (16)	0.63835 (17)	0.0921 (10)	0.859 (6)
H12A	0.3745	−0.1307	0.6793	0.111*	0.859 (6)
H12B	0.3697	−0.1868	0.6121	0.111*	0.859 (6)
C11'	0.4529 (16)	−0.1765 (10)	0.6860 (9)	0.075 (5)*	0.141 (6)
H11C	0.4152	−0.2277	0.6865	0.091*	0.141 (6)
H11D	0.3952	−0.1366	0.6982	0.091*	0.141 (6)
C12'	0.5065 (15)	−0.1601 (8)	0.6134 (8)	0.074 (5)*	0.141 (6)
H12C	0.4884	−0.2021	0.5796	0.089*	0.141 (6)
H12D	0.5912	−0.1551	0.6173	0.089*	0.141 (6)
C13	0.4493 (3)	−0.07954 (14)	0.58781 (11)	0.0994 (8)
H13A	0.4904	−0.0998	0.5457	0.119*	0.859 (6)
H13B	0.3762	−0.0566	0.5710	0.119*	0.859 (6)
H13C	0.4501	−0.0758	0.5354	0.119*	0.141 (6)
H13D	0.3687	−0.0758	0.6044	0.119*	0.141 (6)
C14	0.52427 (17)	−0.01371 (11)	0.62142 (9)	0.0691 (5)
H14A	0.6049	−0.0317	0.6254	0.083*
H14B	0.5234	0.0317	0.5895	0.083*
C15	0.34630 (12)	0.11211 (8)	0.63809 (7)	0.0431 (3)
C16	0.40500 (12)	0.17620 (8)	0.60985 (8)	0.0505 (3)
H16	0.4763	0.1915	0.6300	0.061*
C17	0.35930 (14)	0.21823 (10)	0.55193 (8)	0.0575 (4)
H17	0.3995	0.2613	0.5332	0.069*
C18	0.25412 (13)	0.19528 (9)	0.52285 (7)	0.0522 (3)
C19	0.19350 (18)	0.13276 (14)	0.55030 (11)	0.0832 (7)
H19	0.1219	0.1179	0.5303	0.100*
C20	0.23989 (17)	0.09176 (12)	0.60831 (10)	0.0832 (7)
H20	0.1982	0.0496	0.6276	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0710 (3)	0.1072 (4)	0.0681 (3)	0.0029 (2)	−0.0157 (2)	0.0413 (3)
N1	0.0756 (9)	0.0852 (9)	0.0350 (6)	0.0228 (7)	−0.0014 (6)	0.0009 (6)
N2	0.0683 (9)	0.0782 (10)	0.0640 (8)	0.0204 (8)	−0.0023 (7)	−0.0035 (7)
N3	0.0694 (8)	0.0719 (9)	0.0475 (7)	0.0057 (7)	−0.0065 (6)	0.0127 (6)
C1	0.0487 (7)	0.0516 (7)	0.0347 (6)	−0.0036 (6)	−0.0036 (5)	0.0009 (5)
C2	0.0457 (7)	0.0481 (7)	0.0382 (6)	−0.0039 (5)	−0.0052 (5)	0.0055 (5)
C3	0.0436 (7)	0.0508 (7)	0.0440 (7)	−0.0019 (6)	−0.0002 (5)	0.0038 (6)
C4	0.0492 (7)	0.0527 (7)	0.0391 (7)	−0.0009 (6)	0.0036 (5)	0.0040 (5)
C5	0.0455 (7)	0.0465 (7)	0.0361 (6)	−0.0072 (5)	−0.0036 (5)	0.0041 (5)
C6	0.0456 (6)	0.0451 (6)	0.0373 (6)	−0.0020 (5)	−0.0037 (5)	0.0014 (5)
C7	0.0538 (8)	0.0557 (8)	0.0399 (6)	0.0014 (6)	−0.0042 (6)	0.0004 (6)
C8	0.0503 (7)	0.0544 (8)	0.0429 (7)	−0.0025 (6)	−0.0036 (6)	0.0048 (6)
C9	0.0554 (8)	0.0723 (10)	0.0548 (8)	0.0153 (7)	0.0037 (7)	0.0072 (7)
C10	0.1036 (15)	0.0614 (10)	0.0755 (12)	0.0234 (10)	0.0093 (11)	0.0056 (9)
C11	0.109 (2)	0.0646 (13)	0.095 (2)	0.0137 (13)	0.0081 (16)	−0.0173 (13)
C12	0.097 (2)	0.0822 (16)	0.097 (2)	0.0004 (14)	−0.0155 (15)	−0.0334 (15)
C13	0.148 (2)	0.0973 (15)	0.0526 (10)	0.0276 (15)	−0.0169 (12)	−0.0201 (10)
C14	0.0842 (12)	0.0787 (11)	0.0443 (8)	0.0213 (9)	0.0168 (8)	0.0104 (7)
C15	0.0464 (7)	0.0482 (7)	0.0346 (6)	−0.0049 (5)	−0.0037 (5)	0.0034 (5)
C16	0.0462 (7)	0.0537 (7)	0.0516 (8)	−0.0076 (6)	−0.0084 (6)	0.0088 (6)
C17	0.0566 (8)	0.0567 (8)	0.0592 (9)	−0.0085 (7)	−0.0052 (7)	0.0196 (7)
C18	0.0509 (7)	0.0648 (9)	0.0409 (6)	0.0041 (6)	−0.0043 (6)	0.0129 (6)
C19	0.0713 (11)	0.1031 (14)	0.0752 (12)	−0.0364 (10)	−0.0367 (9)	0.0351 (11)
C20	0.0785 (12)	0.0942 (13)	0.0770 (12)	−0.0470 (10)	−0.0343 (10)	0.0429 (10)

Geometric parameters (Å, º) top

Cl1—C18	1.7441 (14)	C11—H11B	0.9700
N1—C1	1.3624 (17)	C12—C13	1.559 (4)
N1—H1A	0.8597	C12—H12A	0.9700
N1—H1B	0.8603	C12—H12B	0.9700
N2—C7	1.145 (2)	C11'—C12'	1.50 (2)
N3—C8	1.1427 (18)	C11'—H11C	0.9700
C1—C2	1.4063 (19)	C11'—H11D	0.9700
C1—C6	1.4130 (17)	C12'—C13	1.588 (15)
C2—C3	1.4042 (19)	C12'—H12C	0.9700
C2—C8	1.4391 (18)	C12'—H12D	0.9700
C3—C4	1.4056 (18)	C13—C14	1.537 (3)
C3—C9	1.509 (2)	C13—H13A	0.9700
C4—C5	1.399 (2)	C13—H13B	0.9700
C4—C14	1.512 (2)	C13—H13C	0.9700
C5—C6	1.4042 (18)	C13—H13D	0.9700
C5—C15	1.4996 (17)	C14—H14A	0.9700
C6—C7	1.437 (2)	C14—H14B	0.9700
C9—C10	1.534 (3)	C15—C20	1.375 (2)
C9—H9A	0.9700	C15—C16	1.3797 (19)
C9—H9B	0.9700	C16—C17	1.388 (2)
C10—C11	1.521 (3)	C16—H16	0.9300
C10—C11'	1.656 (17)	C17—C18	1.369 (2)
C10—H10A	0.9700	C17—H17	0.9300
C10—H10B	0.9700	C18—C19	1.364 (2)
C10—H10C	0.9700	C19—C20	1.383 (2)
C10—H10D	0.9700	C19—H19	0.9300
C11—C12	1.532 (5)	C20—H20	0.9300
C11—H11A	0.9700

C1—N1—H1A	120.0	C13—C12—H12B	108.7
C1—N1—H1B	120.1	H12A—C12—H12B	107.6
H1A—N1—H1B	120.0	C12'—C11'—C10	104.9 (12)
N1—C1—C2	122.30 (12)	C12'—C11'—H11C	110.8
N1—C1—C6	121.13 (13)	C10—C11'—H11C	110.8
C2—C1—C6	116.57 (12)	C12'—C11'—H11D	110.8
C3—C2—C1	122.74 (12)	C10—C11'—H11D	110.8
C3—C2—C8	120.22 (12)	H11C—C11'—H11D	108.8
C1—C2—C8	117.03 (12)	C11'—C12'—C13	105.0 (12)
C2—C3—C4	119.54 (12)	C11'—C12'—H12C	110.7
C2—C3—C9	118.28 (12)	C13—C12'—H12C	110.7
C4—C3—C9	122.17 (13)	C11'—C12'—H12D	110.7
C5—C4—C3	118.86 (12)	C13—C12'—H12D	110.7
C5—C4—C14	120.33 (12)	H12C—C12'—H12D	108.8
C3—C4—C14	120.63 (13)	C14—C13—C12	116.08 (17)
C4—C5—C6	120.93 (11)	C14—C13—C12'	106.2 (6)
C4—C5—C15	122.04 (11)	C12—C13—C12'	41.2 (6)
C6—C5—C15	117.03 (12)	C14—C13—H13A	108.3
C5—C6—C1	121.32 (12)	C12—C13—H13A	108.3
C5—C6—C7	121.00 (11)	C12'—C13—H13A	74.7
C1—C6—C7	117.67 (12)	C14—C13—H13B	108.3
N2—C7—C6	176.28 (16)	C12—C13—H13B	108.3
N3—C8—C2	177.25 (16)	C12'—C13—H13B	142.5
C3—C9—C10	114.08 (14)	H13A—C13—H13B	107.4
C3—C9—H9A	108.7	C14—C13—H13C	110.5
C10—C9—H9A	108.7	C12—C13—H13C	130.6
C3—C9—H9B	108.7	C12'—C13—H13C	110.5
C10—C9—H9B	108.7	H13A—C13—H13C	38.7
H9A—C9—H9B	107.6	H13B—C13—H13C	70.2
C11—C10—C9	116.58 (18)	C14—C13—H13D	110.5
C11—C10—C11'	35.0 (6)	C12—C13—H13D	69.7
C9—C10—C11'	113.2 (6)	C12'—C13—H13D	110.5
C11—C10—H10A	108.1	H13A—C13—H13D	137.1
C9—C10—H10A	108.1	H13B—C13—H13D	42.6
C11'—C10—H10A	134.5	H13C—C13—H13D	108.7
C11—C10—H10B	108.1	C4—C14—C13	112.68 (16)
C9—C10—H10B	108.1	C4—C14—H14A	109.1
C11'—C10—H10B	77.2	C13—C14—H14A	109.1
H10A—C10—H10B	107.3	C4—C14—H14B	109.1
C11—C10—H10C	130.5	C13—C14—H14B	109.1
C9—C10—H10C	108.9	H14A—C14—H14B	107.8
C11'—C10—H10C	108.9	C20—C15—C16	118.28 (13)
H10A—C10—H10C	73.3	C20—C15—C5	120.25 (12)
H10B—C10—H10C	35.8	C16—C15—C5	121.39 (11)
C11—C10—H10D	75.5	C15—C16—C17	121.06 (13)
C9—C10—H10D	108.9	C15—C16—H16	119.5
C11'—C10—H10D	108.9	C17—C16—H16	119.5
H10A—C10—H10D	37.1	C18—C17—C16	118.95 (13)
H10B—C10—H10D	135.6	C18—C17—H17	120.5
H10C—C10—H10D	107.7	C16—C17—H17	120.5
C10—C11—C12	115.6 (2)	C19—C18—C17	121.21 (13)
C10—C11—H11A	108.4	C19—C18—Cl1	118.69 (12)
C12—C11—H11A	108.4	C17—C18—Cl1	120.10 (12)
C10—C11—H11B	108.4	C18—C19—C20	119.13 (15)
C12—C11—H11B	108.4	C18—C19—H19	120.4
H11A—C11—H11B	107.4	C20—C19—H19	120.4
C11—C12—C13	114.2 (3)	C15—C20—C19	121.34 (15)
C11—C12—H12A	108.7	C15—C20—H20	119.3
C13—C12—H12A	108.7	C19—C20—H20	119.3
C11—C12—H12B	108.7

N1—C1—C2—C3	−179.89 (14)	C3—C9—C10—C11	77.1 (2)
C6—C1—C2—C3	1.1 (2)	C9—C10—C11—C12	−67.7 (3)
N1—C1—C2—C8	−0.6 (2)	C10—C11—C12—C13	99.9 (3)
C6—C1—C2—C8	−179.67 (12)	C11—C12—C13—C14	−60.5 (3)
C1—C2—C3—C4	0.3 (2)	C12—C13—C14—C4	−46.5 (3)
C8—C2—C3—C4	−178.99 (13)	C3—C4—C14—C13	88.71 (19)
C1—C2—C3—C9	−178.57 (13)	C3—C9—C10—C11'	38.5 (7)
C8—C2—C3—C9	2.2 (2)	C9—C10—C11'—C12'	70.7 (12)
C2—C3—C4—C5	−0.4 (2)	C10—C11'—C12'—C13	−116.6 (11)
C9—C3—C4—C5	178.44 (13)	C11'—C12'—C13—C14	85.5 (10)
C2—C3—C4—C14	−175.42 (14)	C12'—C13—C14—C4	−89.6 (6)
C3—C4—C5—C6	−0.9 (2)	C11'—C10—C11—C12	25.4 (10)
C14—C4—C5—C6	174.16 (14)	C11—C10—C11'—C12'	−33.0 (8)
C3—C4—C5—C15	179.21 (12)	C11—C12—C13—C12'	24.5 (8)
C14—C4—C5—C15	−5.7 (2)	C11'—C12'—C13—C12	−25.8 (8)
C4—C5—C6—C1	2.3 (2)	C5—C4—C14—C13	−86.27 (19)
C15—C5—C6—C1	−177.79 (11)	C4—C5—C15—C20	102.07 (19)
C4—C5—C6—C7	−176.91 (13)	C6—C5—C15—C20	−77.81 (19)
C15—C5—C6—C7	2.97 (19)	C4—C5—C15—C16	−81.27 (18)
N1—C1—C6—C5	178.61 (14)	C6—C5—C15—C16	98.85 (16)
C2—C1—C6—C5	−2.33 (19)	C20—C15—C16—C17	−1.3 (2)
N1—C1—C6—C7	−2.1 (2)	C5—C15—C16—C17	−178.01 (14)
C2—C1—C6—C7	176.94 (12)	C15—C16—C17—C18	0.1 (2)
C5—C6—C7—N2	159 (3)	C16—C17—C18—C19	0.7 (3)
C1—C6—C7—N2	−20 (3)	C16—C17—C18—Cl1	−179.58 (13)
C3—C2—C8—N3	141 (3)	C17—C18—C19—C20	−0.4 (3)
C1—C2—C8—N3	−38 (3)	Cl1—C18—C19—C20	179.96 (18)
C2—C3—C9—C10	90.97 (18)	C16—C15—C20—C19	1.7 (3)
C9—C3—C4—C14	3.4 (2)	C5—C15—C20—C19	178.4 (2)
C4—C3—C9—C10	−87.84 (18)	C18—C19—C20—C15	−0.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N3ⁱ	0.86	2.44	3.1636 (18)	142
C11′—H11C···N2ⁱⁱ	0.97	2.57	3.319 (16)	135
N1—H1A···Cl1ⁱⁱⁱ	0.86	2.87	3.6628 (16)	153

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1/2, y−1/2, z; (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈ClN₃
M_r	335.82
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	11.3835 (9), 16.9840 (13), 18.4766 (14)
V (Å³)	3572.2 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.28 × 0.13 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.966, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	39132, 4279, 3440
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.137, 1.04
No. of reflections	4279
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLUTON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N3ⁱ	0.86	2.44	3.1636 (18)	141.9
C11'—H11C···N2ⁱⁱ	0.97	2.57	3.319 (16)	134.6
N1—H1A···Cl1ⁱⁱⁱ	0.86	2.87	3.6628 (16)	153.3

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1/2, y−1/2, z; (iii) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank Dr B. Sridhar for help with the data collection and Dr K. Ravikumar for useful discussions on the structural significance.

References

Allen, F. H., Howard, J. A. K. & Pitchford, N. A. (1996). Acta Cryst. B52, 882–891. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Evans, D. G. & Boeyens, J. C. A. (1988). Acta Cryst. B44, 663–671. CrossRef CAS Web of Science IUCr Journals Google Scholar
Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hendrickson, J. B. (1967). J. Am. Chem. Soc. 89, 7036–7043. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2692

doi:10.1107/S1600536812034861

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Amino-4-(4-chloro­phen­yl)-5,6,7,8,9,10-hexa­hydro­benzo[8]annulene-1,3-dicarbo­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Amino-4-(4-chlorophenyl)-5,6,7,8,9,10-hexahydrobenzo[8]annulene-1,3-dicarbonitrile