2-Amino-4-(4-chloro-phen-yl)-5-oxo-5,6,7,8-tetra-hydro-4H-chromene-3-carbonitrile.

In the title moleclue, C(16)H(13)ClN(2)O(2), the cyclo-hexene ring is in a sofa conformation. The pyran ring is essentialy planar [maximum deviation = 0.038 (2) Å] and forms a dihedral angle of 89.68 (10)° with the benzene ring. In the crystal, mol-ecules are linked by pairs of N-H⋯N hydrogen bonds, forming inversion dimers with R(2) (2)(12) ring motifs. These dimers are further linked by N-H⋯O hydrogen bonds into chains along [110]. Weak C-H⋯O hydrogen bonds are also present.

Related literature

For pharmaceutical background to 2-amino-5-oxo-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile derivatives, see: Gao et al. (2001 ▶); Xu et al. (2011 ▶); Luan et al. (2011 ▶); Wang & Zhu, (2007 ▶); O’Callaghan et al. (1995 ▶). For similar structures, see: Tu et al. (2001 ▶); Qiao et al. (2011 ▶); Kong et al. (2011 ▶); Hu et al. (2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For geometric analysis, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

C16H13ClN2O2

M = 300.73

Monoclinic,

a = 13.753 (4) Å

b = 11.077 (3) Å

c = 19.370 (6) Å

β = 107.856 (5)°

V = 2808.7 (14) Å3

Z = 8

Mo Kα radiation

μ = 0.28 mm−1

T = 150 K

0.43 × 0.27 × 0.07 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.914, T max = 0.981

10643 measured reflections

2755 independent reflections

2124 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.122

S = 1.02

2755 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812015838/lh5452sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015838/lh5452Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812015838/lh5452Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H13ClN2O2	F(000) = 1248
Mr = 300.73	Dx = 1.422 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 833 reflections
a = 13.753 (4) Å	θ = 2.2–28.2°
b = 11.077 (3) Å	µ = 0.28 mm−1
c = 19.370 (6) Å	T = 150 K
β = 107.856 (5)°	Plate, colourless
V = 2808.7 (14) Å3	0.43 × 0.27 × 0.07 mm
Z = 8

Bruker APEX 2000 CCD area-detector diffractometer	2755 independent reflections
Radiation source: fine-focus sealed tube	2124 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
phi and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.914, Tmax = 0.981	k = −13→13
10643 measured reflections	l = −23→23

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/3
2755 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Cl1	0.12556 (5)	0.07141 (5)	0.22343 (4)	0.0510 (2)
O1	−0.04515 (11)	0.45923 (13)	0.41373 (8)	0.0395 (5)
O2	0.20240 (10)	0.74455 (12)	0.39806 (8)	0.0320 (4)
N1	0.37218 (13)	0.72339 (15)	0.44001 (9)	0.0347 (6)
N2	0.41870 (14)	0.40760 (17)	0.49094 (11)	0.0440 (7)
C1	0.13012 (15)	0.19541 (19)	0.28039 (12)	0.0337 (7)
C2	0.12955 (16)	0.17534 (19)	0.35014 (13)	0.0374 (7)
C3	0.13788 (15)	0.27229 (18)	0.39614 (12)	0.0332 (7)
C4	0.14684 (14)	0.38895 (17)	0.37333 (11)	0.0274 (6)
C5	0.14494 (16)	0.40667 (18)	0.30168 (11)	0.0348 (7)
C6	0.13673 (16)	0.3107 (2)	0.25501 (12)	0.0378 (7)
C7	0.16120 (14)	0.49363 (17)	0.42613 (11)	0.0270 (6)
C8	0.08175 (14)	0.59034 (17)	0.40049 (10)	0.0274 (6)
C9	−0.02395 (15)	0.55980 (18)	0.39594 (11)	0.0311 (7)
C10	−0.10332 (17)	0.6565 (2)	0.37309 (14)	0.0470 (8)
C11	−0.07795 (17)	0.7496 (2)	0.32396 (14)	0.0465 (8)
C12	0.02871 (15)	0.80147 (18)	0.35920 (12)	0.0360 (7)
C13	0.10411 (15)	0.70407 (18)	0.38660 (11)	0.0286 (6)
C14	0.28249 (15)	0.66677 (18)	0.42763 (10)	0.0285 (6)
C15	0.26669 (14)	0.54985 (17)	0.44117 (11)	0.0271 (6)
C16	0.35154 (15)	0.47326 (19)	0.46903 (11)	0.0304 (7)
H1A	0.42960	0.68370	0.45910	0.0420*
H1B	0.37370	0.80030	0.42910	0.0420*
H2	0.12350	0.09570	0.36650	0.0450*
H3	0.13750	0.25880	0.44450	0.0400*
H5	0.14940	0.48630	0.28470	0.0420*
H6	0.13560	0.32360	0.20630	0.0450*
H7	0.15570	0.46120	0.47300	0.0320*
H10A	−0.11020	0.69730	0.41680	0.0560*
H10B	−0.16990	0.61890	0.34740	0.0560*
H11A	−0.12890	0.81560	0.31430	0.0560*
H11B	−0.08110	0.71180	0.27700	0.0560*
H12A	0.04920	0.85040	0.32320	0.0430*
H12B	0.02750	0.85500	0.39980	0.0430*

	U11	U22	U33	U12	U13	U23
Cl1	0.0542 (4)	0.0358 (4)	0.0625 (4)	0.0042 (3)	0.0171 (3)	−0.0181 (3)
O1	0.0357 (8)	0.0312 (9)	0.0545 (10)	−0.0086 (7)	0.0182 (7)	0.0011 (7)
O2	0.0301 (8)	0.0212 (7)	0.0432 (8)	−0.0032 (6)	0.0090 (6)	0.0040 (6)
N1	0.0288 (9)	0.0249 (9)	0.0471 (11)	−0.0069 (7)	0.0070 (8)	0.0050 (8)
N2	0.0314 (10)	0.0353 (11)	0.0633 (13)	−0.0011 (8)	0.0116 (9)	0.0139 (10)
C1	0.0238 (10)	0.0288 (12)	0.0460 (13)	0.0027 (9)	0.0071 (9)	−0.0091 (10)
C2	0.0363 (12)	0.0224 (11)	0.0545 (14)	−0.0011 (9)	0.0155 (10)	0.0015 (10)
C3	0.0345 (12)	0.0275 (11)	0.0383 (12)	−0.0036 (9)	0.0120 (9)	0.0030 (9)
C4	0.0224 (10)	0.0224 (10)	0.0366 (11)	−0.0036 (8)	0.0078 (8)	0.0000 (8)
C5	0.0405 (12)	0.0240 (11)	0.0390 (12)	−0.0003 (9)	0.0111 (10)	0.0028 (9)
C6	0.0410 (12)	0.0350 (13)	0.0359 (12)	0.0044 (10)	0.0095 (10)	−0.0001 (10)
C7	0.0279 (10)	0.0222 (10)	0.0309 (11)	−0.0038 (8)	0.0091 (8)	0.0027 (8)
C8	0.0268 (10)	0.0234 (11)	0.0319 (11)	−0.0009 (8)	0.0089 (8)	−0.0005 (8)
C9	0.0303 (11)	0.0285 (12)	0.0344 (11)	−0.0032 (9)	0.0099 (9)	−0.0045 (9)
C10	0.0290 (12)	0.0374 (13)	0.0759 (18)	0.0014 (10)	0.0182 (11)	0.0005 (12)
C11	0.0323 (13)	0.0334 (13)	0.0691 (17)	0.0046 (10)	0.0085 (12)	0.0082 (12)
C12	0.0365 (12)	0.0261 (11)	0.0441 (13)	0.0016 (9)	0.0104 (10)	0.0042 (10)
C13	0.0282 (11)	0.0261 (11)	0.0316 (11)	−0.0014 (9)	0.0095 (8)	−0.0025 (9)
C14	0.0278 (11)	0.0277 (11)	0.0287 (11)	−0.0018 (8)	0.0066 (8)	−0.0004 (8)
C15	0.0256 (10)	0.0230 (10)	0.0311 (11)	−0.0035 (8)	0.0064 (8)	0.0008 (8)
C16	0.0273 (11)	0.0262 (11)	0.0356 (12)	−0.0077 (9)	0.0067 (9)	0.0032 (9)

Cl1—C1	1.751 (2)	C8—C13	1.343 (3)
O1—C9	1.227 (3)	C9—C10	1.496 (3)
O2—C13	1.376 (3)	C10—C11	1.515 (3)
O2—C14	1.377 (3)	C11—C12	1.528 (3)
N1—C14	1.338 (3)	C12—C13	1.478 (3)
N2—C16	1.150 (3)	C14—C15	1.352 (3)
N1—H1B	0.8800	C15—C16	1.410 (3)
N1—H1A	0.8800	C2—H2	0.9500
C1—C6	1.381 (3)	C3—H3	0.9500
C1—C2	1.372 (3)	C5—H5	0.9500
C2—C3	1.378 (3)	C6—H6	0.9500
C3—C4	1.383 (3)	C7—H7	1.0000
C4—C7	1.518 (3)	C10—H10A	0.9900
C4—C5	1.394 (3)	C10—H10B	0.9900
C5—C6	1.378 (3)	C11—H11A	0.9900
C7—C8	1.502 (3)	C11—H11B	0.9900
C7—C15	1.523 (3)	C12—H12A	0.9900
C8—C9	1.469 (3)	C12—H12B	0.9900
C13—O2—C14	118.95 (15)	O2—C14—C15	121.62 (19)
H1A—N1—H1B	120.00	C7—C15—C14	123.71 (18)
C14—N1—H1A	120.00	C7—C15—C16	117.10 (17)
C14—N1—H1B	120.00	C14—C15—C16	119.17 (19)
Cl1—C1—C2	118.92 (16)	N2—C16—C15	177.8 (2)
C2—C1—C6	121.4 (2)	C1—C2—H2	120.00
Cl1—C1—C6	119.64 (17)	C3—C2—H2	120.00
C1—C2—C3	119.1 (2)	C2—C3—H3	119.00
C2—C3—C4	121.3 (2)	C4—C3—H3	119.00
C3—C4—C7	120.28 (18)	C4—C5—H5	119.00
C3—C4—C5	118.24 (18)	C6—C5—H5	119.00
C5—C4—C7	121.46 (17)	C1—C6—H6	121.00
C4—C5—C6	121.16 (19)	C5—C6—H6	121.00
C1—C6—C5	118.8 (2)	C4—C7—H7	108.00
C8—C7—C15	109.00 (16)	C8—C7—H7	108.00
C4—C7—C8	113.00 (17)	C15—C7—H7	108.00
C4—C7—C15	111.14 (16)	C9—C10—H10A	109.00
C7—C8—C9	117.51 (17)	C9—C10—H10B	109.00
C7—C8—C13	123.17 (19)	C11—C10—H10A	109.00
C9—C8—C13	119.15 (18)	C11—C10—H10B	109.00
O1—C9—C8	120.54 (19)	H10A—C10—H10B	108.00
C8—C9—C10	118.15 (18)	C10—C11—H11A	110.00
O1—C9—C10	121.2 (2)	C10—C11—H11B	110.00
C9—C10—C11	112.7 (2)	C12—C11—H11A	109.00
C10—C11—C12	110.5 (2)	C12—C11—H11B	110.00
C11—C12—C13	110.97 (17)	H11A—C11—H11B	108.00
O2—C13—C8	123.17 (18)	C11—C12—H12A	109.00
O2—C13—C12	111.50 (17)	C11—C12—H12B	109.00
C8—C13—C12	125.3 (2)	C13—C12—H12A	109.00
N1—C14—C15	127.46 (19)	C13—C12—H12B	109.00
O2—C14—N1	110.92 (17)	H12A—C12—H12B	108.00
C13—O2—C14—N1	−175.33 (16)	C4—C7—C8—C13	−117.7 (2)
C13—O2—C14—C15	4.4 (3)	C15—C7—C8—C9	−168.89 (17)
C14—O2—C13—C8	−2.4 (3)	C15—C7—C8—C13	6.4 (3)
C14—O2—C13—C12	176.27 (17)	C8—C7—C15—C16	177.19 (17)
Cl1—C1—C2—C3	177.03 (18)	C13—C8—C9—C10	2.3 (3)
Cl1—C1—C6—C5	−177.07 (18)	C7—C8—C13—C12	178.03 (19)
C2—C1—C6—C5	1.3 (3)	C9—C8—C13—O2	171.79 (18)
C6—C1—C2—C3	−1.4 (3)	C7—C8—C13—O2	−3.5 (3)
C1—C2—C3—C4	−0.1 (3)	C7—C8—C9—O1	1.2 (3)
C2—C3—C4—C7	−177.0 (2)	C7—C8—C9—C10	177.81 (18)
C2—C3—C4—C5	1.4 (3)	C13—C8—C9—O1	−174.36 (19)
C3—C4—C7—C15	112.8 (2)	C9—C8—C13—C12	−6.7 (3)
C3—C4—C7—C8	−124.3 (2)	O1—C9—C10—C11	−154.9 (2)
C3—C4—C5—C6	−1.5 (3)	C8—C9—C10—C11	28.4 (3)
C5—C4—C7—C8	57.4 (3)	C9—C10—C11—C12	−53.7 (3)
C5—C4—C7—C15	−65.5 (2)	C10—C11—C12—C13	48.8 (2)
C7—C4—C5—C6	176.9 (2)	C11—C12—C13—O2	161.65 (18)
C4—C5—C6—C1	0.1 (3)	C11—C12—C13—C8	−19.7 (3)
C4—C7—C15—C14	120.7 (2)	O2—C14—C15—C7	−0.6 (3)
C4—C7—C15—C16	−57.6 (2)	O2—C14—C15—C16	177.71 (18)
C8—C7—C15—C14	−4.5 (3)	N1—C14—C15—C7	179.11 (19)
C4—C7—C8—C9	67.0 (2)	N1—C14—C15—C16	−2.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.88	2.25	3.132 (3)	177
N1—H1B···O1ii	0.88	2.15	2.955 (2)	151
C3—H3···N2iii	0.95	2.48	3.226 (3)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.88	2.25	3.132 (3)	177
N1—H1B⋯O1ii	0.88	2.15	2.955 (2)	151
C3—H3⋯N2iii	0.95	2.48	3.226 (3)	135

Symmetry codes: (i) ; (ii) ; (iii) .