1-(4-Chloro­phen­yl)-2-(1,3-diazepan-2-yl­idene)ethanone

Zhang, X.-W.; Xia, J.-H.; Xu, Z.-H.; Wang, L.-B.; Yu, C.-Y.

doi:10.1107/S1600536813013858

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o971

doi:10.1107/S1600536813013858

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1-(4-Chlorophenyl)-2-(1,3-diazepan-2-ylidene)ethanone

Xiao-Wei Zhang,^a Jian-Hui Xia,^a Zhao-Hui Xu,^a Li-Ben Wang ^b and Chu-Yi Yu ^b ^*

^aCollege of Chemistry and Chemical Engineering, Jiang Xi Normal University, Nanchang, Jiang Xi 330022, People's Republic of China, and ^bBeijing National Laboratory for Molecular Science (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China
^*Correspondence e-mail: yucy@iccas.ac.cn

(Received 16 March 2013; accepted 20 May 2013; online 25 May 2013)

In the title compound, C₁₃H₁₅ClN₂O, there are two crystallographically independent but conformationally similar (E)-molecules in the asymmetric unit [dihedral angles between the phenyl ring and a common planar fragment of the 1,3-diazepane moiety = 47.34 (16) and 48.00 (16)°]. The seven-membered ring system adopts a chair conformation in both molecules. In the crystal, N—H⋯O hydrogen bonds lead to chains extending along the b-axis direction.

Related literature

Heterocyclic ketene aminals are a useful synthon for the synthesis of fused heterocycles, see: Huang & Wang (1994 ). For their bioactivity and potential applications as pesticides and in medicine, see: Kondo et al. (1990 ); Jordan et al. (2002 ). For the synthesis, see: Huang & Liu (1989 ). For a similar structure, see: Yu et al. (2006 ).

Experimental

Crystal data

C₁₃H₁₅ClN₂O
M_r = 250.72
Triclinic, $[P \overline 1]$
a = 10.779 (4) Å
b = 10.815 (3) Å
c = 12.158 (4) Å
α = 96.091 (4)°
β = 110.710 (4)°
γ = 101.244 (4)°
V = 1276.4 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.25 × 0.15 × 0.14 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.606, T_max = 1.000
11344 measured reflections
5780 independent reflections
4854 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.162
S = 1.12
5780 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.88	2.07	2.834 (3)	145
N3—H3⋯O1ⁱ	0.88	2.09	2.878 (3)	149
Symmetry code: (i) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813013858/zs2253sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813013858/zs2253Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813013858/zs2253Isup3.cml

checkCIF report

Comment top

Heterocyclic ketene aminals are viewed as a useful synthon for the synthesis of fused heterocycles (Huang & Wang, 1994). Also, some of these compounds display certain bioactivities and show potential for applications in the fields of pesticides and medicine, e.g. as antimicrobial reagents (Kondo et al., 1990) and anti-anxiety reagents (Jordan et al., 2002). In the title compound, C₁₃H₁₅ClN₂O, there are two crystallographically independent but similar (E)-molecules in the asymmetric unit (Fig. 1), with the dihedral angle between the phenyl ring and the ethylenic moiety [(C8–C13) and N1, N2, C5, C6 in molecule 1 and (C21–C26) and (N3, N4, C18, C19) in molecule 2] being 47.34 (16) and 48.00 (16)°, respectively. Intramolecular interactions (N1—H···O1 in molecule 1 and N4—H···O2 in molecule 2) (Table 1) stabilize the conformations. The seven-membered ring adopts a stable chair conformation. In the crystal, intermolecular N—H···O hydrogen-bonding interactions (Table 1) give one-dimensional chains which extend down b (Fig. 2).

Related literature top

Heterocyclic ketene aminals are a useful synthon for the synthesis of fused heterocycles, see: Huang & Wang (1994). For their bioactivity and potential applications as pesticides and in medicine, see: Kondo et al. (1990); Jordan et al. (2002). For the synthesis, see: Huang & Liu (1989). For a similar structure, see: Yu et al. (2006).

Experimental top

The title compound was prepared according to the method of Huang & Liu (1989). m.p. 448–450 K. MS: m/z = 250 (M⁺). IR: 3180 (NH), 1630 (C=O), 1578 cm^-l (C=C). ¹H-NMR: δ = 7.70 (d, 2H), 7.40 (d, 2H), 11.13 (s, lH), 7.10 (s, lH), 5.27 (s, lH), 3.05–3.30 (m, 4H), 1.55–1.72 (m, 4H) p.p.m.. ¹³C-NMR: δ = 179.7, 168.4, 140.2, 133.4, 127.7, 127.4, 79.1, 43.8, 27.6 p.p.m.. Anal. calc. for C₁₃H₁₅ClN₂O: C, 62.27; H, 6.03; N, 11.18. Found C, 62.09; H, 5.94; N, 11.02.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX-2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure and atom numbering scheme for the two independent molecules in the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radius.
	Fig. 2. The packing of the title compound in the unit cell. Dashed lines indicate N—H···O hydrogen bonds and intramolecular N—H···O interactions. For symmetry code (i), see Table 1.

1-(4-Chlorophenyl)-2-(1,3-diazepan-2-ylidene)ethanone top

Crystal data top

C₁₃H₁₅ClN₂O	Z = 4
M_r = 250.72	F(000) = 528
Triclinic, P1	D_x = 1.305 Mg m⁻³
Hall symbol: -P 1	Melting point = 448–450 K
a = 10.779 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.815 (3) Å	Cell parameters from 3768 reflections
c = 12.158 (4) Å	θ = 1.8–27.5°
α = 96.091 (4)°	µ = 0.29 mm⁻¹
β = 110.710 (4)°	T = 173 K
γ = 101.244 (4)°	Block, white
V = 1276.4 (7) Å³	0.25 × 0.15 × 0.14 mm

Data collection top

Rigaku Saturn724+ CCD diffractometer	5780 independent reflections
Radiation source: sealed tube	4854 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −13→13
T_min = 0.606, T_max = 1.000	k = −14→13
11344 measured reflections	l = −15→15

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0466P)² + 1.3126P] where P = (F_o² + 2F_c²)/3
5780 reflections	(Δ/σ)_max < 0.001
307 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₃H₁₅ClN₂O	γ = 101.244 (4)°
M_r = 250.72	V = 1276.4 (7) Å³
Triclinic, P1	Z = 4
a = 10.779 (4) Å	Mo Kα radiation
b = 10.815 (3) Å	µ = 0.29 mm⁻¹
c = 12.158 (4) Å	T = 173 K
α = 96.091 (4)°	0.25 × 0.15 × 0.14 mm
β = 110.710 (4)°

Data collection top

Rigaku Saturn724+ CCD diffractometer	5780 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	4854 reflections with I > 2σ(I)
T_min = 0.606, T_max = 1.000	R_int = 0.048
11344 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.12	Δρ_max = 0.49 e Å⁻³
5780 reflections	Δρ_min = −0.42 e Å⁻³
307 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
Cl1	0.01481 (9)	0.17456 (9)	0.95043 (7)	0.0515 (2)
Cl	0.43184 (9)	0.64786 (9)	0.02814 (7)	0.0516 (2)
O1	0.3033 (2)	0.92241 (17)	0.48282 (17)	0.0311 (4)
O2	0.2480 (2)	0.42103 (17)	0.56002 (18)	0.0335 (5)
N1	0.1989 (2)	0.8486 (2)	0.6444 (2)	0.0305 (5)
H1	0.1868	0.9035	0.5954	0.037*
N2	0.1648 (2)	0.6291 (2)	0.6502 (2)	0.0315 (5)
H2	0.2118	0.5704	0.6555	0.038*
N3	0.3217 (2)	0.1261 (2)	0.3506 (2)	0.0305 (5)
H3	0.3486	0.0677	0.3921	0.037*
N4	0.3187 (2)	0.3421 (2)	0.3784 (2)	0.0304 (5)
H4	0.2633	0.3913	0.3810	0.036*
C1	0.2192 (3)	0.8941 (3)	0.7685 (3)	0.0360 (7)
H1A	0.2364	0.9889	0.7827	0.043*
H1B	0.3023	0.8726	0.8219	0.043*
C2	0.1006 (3)	0.8396 (3)	0.8037 (3)	0.0414 (7)
H2A	0.0144	0.8483	0.7429	0.050*
H2B	0.1138	0.8906	0.8813	0.050*
C3	0.0865 (4)	0.6990 (3)	0.8145 (3)	0.0413 (7)
H3A	0.1724	0.6903	0.8755	0.050*
H3B	0.0117	0.6713	0.8427	0.050*
C4	0.0566 (3)	0.6115 (3)	0.6977 (3)	0.0343 (6)
H4A	0.0362	0.5216	0.7089	0.041*
H4B	−0.0273	0.6239	0.6366	0.041*
C5	0.1976 (3)	0.7281 (2)	0.5993 (2)	0.0275 (6)
C6	0.2322 (3)	0.7060 (2)	0.4985 (2)	0.0268 (5)
H6	0.2198	0.6194	0.4635	0.032*
C7	0.2834 (3)	0.8023 (2)	0.4467 (2)	0.0258 (5)
C8	0.3180 (3)	0.7624 (2)	0.3414 (2)	0.0259 (5)
C9	0.2356 (3)	0.6569 (3)	0.2512 (3)	0.0327 (6)
H9	0.1552	0.6079	0.2564	0.039*
C10	0.2687 (3)	0.6221 (3)	0.1543 (3)	0.0359 (6)
H10	0.2111	0.5508	0.0927	0.043*
C11	0.3869 (3)	0.6927 (3)	0.1485 (2)	0.0337 (6)
C12	0.4705 (3)	0.7977 (3)	0.2366 (3)	0.0365 (7)
H12	0.5520	0.8451	0.2319	0.044*
C13	0.4345 (3)	0.8334 (3)	0.3316 (2)	0.0314 (6)
H13	0.4901	0.9073	0.3908	0.038*
C14	0.3117 (3)	0.1092 (3)	0.2266 (3)	0.0354 (6)
H14A	0.2231	0.1235	0.1755	0.042*
H14B	0.3110	0.0192	0.2005	0.042*
C15	0.4259 (4)	0.1975 (3)	0.2056 (3)	0.0441 (8)
H15A	0.4211	0.1679	0.1239	0.053*
H15B	0.5153	0.1917	0.2634	0.053*
C16	0.4181 (4)	0.3370 (3)	0.2190 (3)	0.0467 (8)
H16A	0.4910	0.3887	0.1993	0.056*
H16B	0.3287	0.3428	0.1612	0.056*
C17	0.4338 (3)	0.3927 (3)	0.3444 (3)	0.0353 (6)
H17A	0.5178	0.3768	0.4022	0.042*
H17B	0.4473	0.4869	0.3519	0.042*
C18	0.2926 (3)	0.2248 (2)	0.4058 (2)	0.0267 (5)
C19	0.2356 (3)	0.2047 (2)	0.4922 (2)	0.0274 (5)
H19	0.2061	0.1188	0.5006	0.033*
C20	0.2198 (3)	0.3026 (2)	0.5660 (2)	0.0266 (5)
C21	0.1675 (3)	0.2680 (2)	0.6605 (2)	0.0258 (5)
C22	0.0618 (3)	0.1599 (3)	0.6392 (2)	0.0299 (6)
H22	0.0222	0.1047	0.5628	0.036*
C23	0.0134 (3)	0.1315 (3)	0.7275 (3)	0.0321 (6)
H23	−0.0601	0.0587	0.7118	0.039*
C24	0.0741 (3)	0.2111 (3)	0.8384 (2)	0.0332 (6)
C25	0.1789 (3)	0.3185 (3)	0.8625 (3)	0.0392 (7)
H25	0.2196	0.3719	0.9398	0.047*
C26	0.2243 (3)	0.3477 (3)	0.7732 (3)	0.0351 (6)
H26	0.2950	0.4229	0.7887	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0604 (5)	0.0674 (6)	0.0365 (4)	0.0123 (4)	0.0303 (4)	0.0159 (4)
Cl	0.0496 (5)	0.0742 (6)	0.0351 (4)	0.0167 (4)	0.0236 (4)	−0.0008 (4)
O1	0.0418 (11)	0.0198 (9)	0.0341 (10)	0.0049 (8)	0.0194 (9)	0.0035 (8)
O2	0.0467 (12)	0.0222 (9)	0.0404 (11)	0.0098 (8)	0.0253 (10)	0.0091 (8)
N1	0.0413 (13)	0.0250 (11)	0.0303 (12)	0.0103 (10)	0.0179 (10)	0.0077 (10)
N2	0.0431 (14)	0.0246 (11)	0.0374 (13)	0.0120 (10)	0.0243 (11)	0.0116 (10)
N3	0.0437 (14)	0.0269 (11)	0.0280 (12)	0.0122 (10)	0.0195 (10)	0.0078 (9)
N4	0.0349 (12)	0.0264 (11)	0.0383 (13)	0.0115 (10)	0.0196 (11)	0.0144 (10)
C1	0.0420 (17)	0.0338 (15)	0.0312 (15)	0.0068 (13)	0.0169 (13)	−0.0027 (12)
C2	0.0494 (19)	0.0418 (17)	0.0387 (17)	0.0122 (14)	0.0251 (15)	0.0019 (14)
C3	0.0521 (19)	0.0480 (18)	0.0365 (16)	0.0151 (15)	0.0293 (15)	0.0124 (14)
C4	0.0371 (15)	0.0328 (15)	0.0395 (16)	0.0073 (12)	0.0215 (13)	0.0120 (13)
C5	0.0281 (13)	0.0233 (12)	0.0318 (14)	0.0061 (10)	0.0129 (11)	0.0036 (11)
C6	0.0343 (14)	0.0194 (12)	0.0286 (13)	0.0064 (10)	0.0149 (11)	0.0022 (10)
C7	0.0257 (12)	0.0226 (12)	0.0274 (13)	0.0047 (10)	0.0090 (10)	0.0049 (10)
C8	0.0308 (14)	0.0217 (12)	0.0269 (13)	0.0063 (10)	0.0128 (11)	0.0062 (10)
C9	0.0355 (15)	0.0280 (14)	0.0337 (15)	0.0016 (11)	0.0163 (12)	0.0035 (12)
C10	0.0408 (16)	0.0325 (15)	0.0298 (14)	0.0049 (12)	0.0130 (12)	−0.0026 (12)
C11	0.0411 (16)	0.0417 (16)	0.0250 (13)	0.0176 (13)	0.0168 (12)	0.0061 (12)
C12	0.0305 (14)	0.0448 (17)	0.0355 (15)	0.0061 (12)	0.0165 (12)	0.0056 (13)
C13	0.0312 (14)	0.0295 (14)	0.0298 (14)	0.0032 (11)	0.0108 (11)	0.0015 (11)
C14	0.0441 (17)	0.0347 (15)	0.0288 (14)	0.0089 (13)	0.0170 (13)	0.0034 (12)
C15	0.055 (2)	0.0457 (18)	0.0421 (18)	0.0109 (15)	0.0318 (16)	0.0065 (15)
C16	0.062 (2)	0.0445 (18)	0.0451 (19)	0.0070 (16)	0.0354 (17)	0.0141 (15)
C17	0.0343 (15)	0.0319 (15)	0.0404 (16)	0.0018 (12)	0.0188 (13)	0.0068 (13)
C18	0.0283 (13)	0.0266 (13)	0.0251 (13)	0.0081 (10)	0.0094 (11)	0.0047 (11)
C19	0.0345 (14)	0.0201 (12)	0.0318 (14)	0.0067 (10)	0.0170 (12)	0.0078 (11)
C20	0.0315 (13)	0.0221 (12)	0.0271 (13)	0.0064 (10)	0.0120 (11)	0.0068 (10)
C21	0.0286 (13)	0.0246 (12)	0.0265 (13)	0.0091 (10)	0.0117 (11)	0.0058 (10)
C22	0.0353 (14)	0.0265 (13)	0.0279 (13)	0.0059 (11)	0.0139 (11)	0.0024 (11)
C23	0.0337 (15)	0.0301 (14)	0.0341 (15)	0.0049 (11)	0.0162 (12)	0.0075 (12)
C24	0.0381 (16)	0.0408 (16)	0.0273 (14)	0.0123 (13)	0.0182 (12)	0.0092 (12)
C25	0.0468 (18)	0.0394 (16)	0.0261 (14)	0.0049 (14)	0.0128 (13)	−0.0013 (12)
C26	0.0405 (16)	0.0288 (14)	0.0302 (15)	−0.0005 (12)	0.0131 (13)	0.0006 (12)

Geometric parameters (Å, º) top

Cl1—C24	1.747 (3)	C9—C10	1.383 (4)
Cl—C11	1.747 (3)	C9—H9	0.9500
O1—C7	1.277 (3)	C10—C11	1.381 (4)
O2—C20	1.273 (3)	C10—H10	0.9500
N1—C5	1.354 (3)	C11—C12	1.382 (4)
N1—C1	1.461 (3)	C12—C13	1.383 (4)
N1—H1	0.8800	C12—H12	0.9500
N2—C5	1.344 (3)	C13—H13	0.9500
N2—C4	1.463 (3)	C14—C15	1.519 (4)
N2—H2	0.8800	C14—H14A	0.9900
N3—C18	1.347 (3)	C14—H14B	0.9900
N3—C14	1.461 (3)	C15—C16	1.522 (5)
N3—H3	0.8800	C15—H15A	0.9900
N4—C18	1.348 (3)	C15—H15B	0.9900
N4—C17	1.468 (3)	C16—C17	1.515 (4)
N4—H4	0.8800	C16—H16A	0.9900
C1—C2	1.520 (4)	C16—H16B	0.9900
C1—H1A	0.9900	C17—H17A	0.9900
C1—H1B	0.9900	C17—H17B	0.9900
C2—C3	1.522 (4)	C18—C19	1.407 (4)
C2—H2A	0.9900	C19—C20	1.390 (4)
C2—H2B	0.9900	C19—H19	0.9500
C3—C4	1.513 (4)	C20—C21	1.499 (4)
C3—H3A	0.9900	C21—C22	1.392 (4)
C3—H3B	0.9900	C21—C26	1.395 (4)
C4—H4A	0.9900	C22—C23	1.387 (4)
C4—H4B	0.9900	C22—H22	0.9500
C5—C6	1.412 (4)	C23—C24	1.377 (4)
C6—C7	1.396 (4)	C23—H23	0.9500
C6—H6	0.9500	C24—C25	1.376 (4)
C7—C8	1.499 (4)	C25—C26	1.381 (4)
C8—C13	1.390 (4)	C25—H25	0.9500
C8—C9	1.394 (4)	C26—H26	0.9500

C5—N1—C1	124.8 (2)	C11—C12—C13	119.4 (3)
C5—N1—H1	117.6	C11—C12—H12	120.3
C1—N1—H1	117.6	C13—C12—H12	120.3
C5—N2—C4	124.8 (2)	C12—C13—C8	120.8 (3)
C5—N2—H2	117.6	C12—C13—H13	119.6
C4—N2—H2	117.6	C8—C13—H13	119.6
C18—N3—C14	124.7 (2)	N3—C14—C15	115.0 (2)
C18—N3—H3	117.7	N3—C14—H14A	108.5
C14—N3—H3	117.7	C15—C14—H14A	108.5
C18—N4—C17	124.0 (2)	N3—C14—H14B	108.5
C18—N4—H4	118.0	C15—C14—H14B	108.5
C17—N4—H4	118.0	H14A—C14—H14B	107.5
N1—C1—C2	115.2 (2)	C14—C15—C16	112.7 (3)
N1—C1—H1A	108.5	C14—C15—H15A	109.1
C2—C1—H1A	108.5	C16—C15—H15A	109.1
N1—C1—H1B	108.5	C14—C15—H15B	109.1
C2—C1—H1B	108.5	C16—C15—H15B	109.1
H1A—C1—H1B	107.5	H15A—C15—H15B	107.8
C1—C2—C3	113.2 (3)	C17—C16—C15	112.6 (3)
C1—C2—H2A	108.9	C17—C16—H16A	109.1
C3—C2—H2A	108.9	C15—C16—H16A	109.1
C1—C2—H2B	108.9	C17—C16—H16B	109.1
C3—C2—H2B	108.9	C15—C16—H16B	109.1
H2A—C2—H2B	107.8	H16A—C16—H16B	107.8
C4—C3—C2	113.0 (2)	N4—C17—C16	115.5 (3)
C4—C3—H3A	109.0	N4—C17—H17A	108.4
C2—C3—H3A	109.0	C16—C17—H17A	108.4
C4—C3—H3B	109.0	N4—C17—H17B	108.4
C2—C3—H3B	109.0	C16—C17—H17B	108.4
H3A—C3—H3B	107.8	H17A—C17—H17B	107.5
N2—C4—C3	116.3 (2)	N3—C18—N4	119.9 (2)
N2—C4—H4A	108.2	N3—C18—C19	119.7 (2)
C3—C4—H4A	108.2	N4—C18—C19	120.4 (2)
N2—C4—H4B	108.2	C20—C19—C18	124.1 (2)
C3—C4—H4B	108.2	C20—C19—H19	117.9
H4A—C4—H4B	107.4	C18—C19—H19	117.9
N2—C5—N1	120.6 (2)	O2—C20—C19	124.6 (2)
N2—C5—C6	119.4 (2)	O2—C20—C21	117.1 (2)
N1—C5—C6	120.0 (2)	C19—C20—C21	118.4 (2)
C7—C6—C5	124.6 (2)	C22—C21—C26	118.6 (2)
C7—C6—H6	117.7	C22—C21—C20	122.2 (2)
C5—C6—H6	117.7	C26—C21—C20	119.2 (2)
O1—C7—C6	124.6 (2)	C23—C22—C21	121.1 (3)
O1—C7—C8	117.5 (2)	C23—C22—H22	119.5
C6—C7—C8	117.9 (2)	C21—C22—H22	119.5
C13—C8—C9	118.4 (2)	C24—C23—C22	118.6 (3)
C13—C8—C7	119.4 (2)	C24—C23—H23	120.7
C9—C8—C7	122.1 (2)	C22—C23—H23	120.7
C10—C9—C8	121.3 (3)	C25—C24—C23	121.8 (3)
C10—C9—H9	119.4	C25—C24—Cl1	119.5 (2)
C8—C9—H9	119.4	C23—C24—Cl1	118.7 (2)
C11—C10—C9	118.9 (3)	C24—C25—C26	119.2 (3)
C11—C10—H10	120.6	C24—C25—H25	120.4
C9—C10—H10	120.6	C26—C25—H25	120.4
C10—C11—C12	121.1 (3)	C25—C26—C21	120.7 (3)
C10—C11—Cl	119.4 (2)	C25—C26—H26	119.6
C12—C11—Cl	119.5 (2)	C21—C26—H26	119.6

C5—N1—C1—C2	−70.7 (4)	C18—N3—C14—C15	75.0 (4)
N1—C1—C2—C3	72.1 (4)	N3—C14—C15—C16	−69.8 (4)
C1—C2—C3—C4	−62.4 (4)	C14—C15—C16—C17	62.4 (4)
C5—N2—C4—C3	−73.6 (4)	C18—N4—C17—C16	74.6 (4)
C2—C3—C4—N2	65.7 (4)	C15—C16—C17—N4	−69.9 (4)
C4—N2—C5—N1	39.6 (4)	C14—N3—C18—N4	−33.7 (4)
C4—N2—C5—C6	−141.0 (3)	C14—N3—C18—C19	146.5 (3)
C1—N1—C5—N2	24.8 (4)	C17—N4—C18—N3	−33.2 (4)
C1—N1—C5—C6	−154.5 (3)	C17—N4—C18—C19	146.6 (3)
N2—C5—C6—C7	−172.1 (3)	N3—C18—C19—C20	170.6 (3)
N1—C5—C6—C7	7.3 (4)	N4—C18—C19—C20	−9.2 (4)
C5—C6—C7—O1	−1.1 (4)	C18—C19—C20—O2	3.9 (4)
C5—C6—C7—C8	178.7 (2)	C18—C19—C20—C21	−175.3 (2)
O1—C7—C8—C13	39.3 (4)	O2—C20—C21—C22	139.5 (3)
C6—C7—C8—C13	−140.5 (3)	C19—C20—C21—C22	−41.2 (4)
O1—C7—C8—C9	−139.7 (3)	O2—C20—C21—C26	−39.2 (4)
C6—C7—C8—C9	40.5 (4)	C19—C20—C21—C26	140.1 (3)
C13—C8—C9—C10	0.5 (4)	C26—C21—C22—C23	0.1 (4)
C7—C8—C9—C10	179.5 (3)	C20—C21—C22—C23	−178.6 (3)
C8—C9—C10—C11	1.0 (4)	C21—C22—C23—C24	−1.4 (4)
C9—C10—C11—C12	−1.0 (5)	C22—C23—C24—C25	1.3 (4)
C9—C10—C11—Cl	178.7 (2)	C22—C23—C24—Cl1	−179.2 (2)
C10—C11—C12—C13	−0.6 (5)	C23—C24—C25—C26	0.3 (5)
Cl—C11—C12—C13	179.8 (2)	Cl1—C24—C25—C26	−179.3 (2)
C11—C12—C13—C8	2.1 (4)	C24—C25—C26—C21	−1.6 (5)
C9—C8—C13—C12	−2.1 (4)	C22—C21—C26—C25	1.5 (4)
C7—C8—C13—C12	178.9 (3)	C20—C21—C26—C25	−179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	2.16	2.704 (3)	119
N2—H2···O2	0.88	2.07	2.834 (3)	145
N3—H3···O1ⁱ	0.88	2.09	2.878 (3)	149
N4—H4···O2	0.88	2.23	2.689 (3)	112
C6—H6···O2	0.95	2.57	3.270 (3)	131
C13—H13···O1ⁱⁱ	0.95	2.47	3.372 (4)	159
C19—H19···O1ⁱ	0.95	2.57	3.274 (3)	132

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅ClN₂O
M_r	250.72
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	10.779 (4), 10.815 (3), 12.158 (4)
α, β, γ (°)	96.091 (4), 110.710 (4), 101.244 (4)
V (Å³)	1276.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.25 × 0.15 × 0.14

Data collection
Diffractometer	Rigaku Saturn724+ CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.606, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11344, 5780, 4854
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.162, 1.12
No. of reflections	5780
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.42

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX-2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.88	2.07	2.834 (3)	145
N3—H3···O1ⁱ	0.88	2.09	2.878 (3)	149

Symmetry code: (i) x, y−1, z.

Acknowledgements

We thank Tongling Liang at the Chinese Academy of Sciences for the X-ray crystallographic determination.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Huang, Z.-T. & Liu, Z.-R. (1989). Synth. Commun. 19, 943–958. CrossRef CAS Web of Science Google Scholar
Huang, Z.-T. & Wang, M.-X. (1994). Heterocycles, 37, 1233–1262. CrossRef CAS Google Scholar
Jordan, A. D., Vaidya, A. H., Rosenthal, D. I., Dubinsky, B., Kordik, C. P., Sanfilippo, P. J., Wu, W.-N. & Reitz, A. B. (2002). Bioorg. Med. Chem. Lett. 12, 2381–2386. Web of Science CrossRef PubMed CAS Google Scholar
Kondo, H., Taguchi, M., Inoue, Y., Sakamoto, F. & Tsukamoto, G. (1990). J. Med. Chem. 33, 2012–2015. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, C.-Y., Yan, S.-J. & Huang, Z.-T. (2006). Acta Cryst. E62, o2655–o2656. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar