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

In the title compound, C(18)H(17)ClN(2)O(2)·C(3)H(6)O, the 4H-pyran ring is nearly planar [maximum deviation = -0.108 (1) Å] and the cyclo-hexene ring is puckered [puckering parameters Q(T) = 0.4596 (17) Å, θ = 55.9 (2)° and ϕ = 226.5 (3)°]. The 4H-pyran ring is approximately perpendicular to the benzene ring [dihedral angle = 84.35 (7)°] and is almost coplanar with the mean plane of the cyclo-hexene ring [dihedral angle = 8.64 (7)°]. In the crystal, inversion-related main mol-ecules are linked into dimers by pairs of N-H⋯N hydrogen bonds, generating an R(2) (2)(12) graph-set motif. These dimers are further connected by N-H⋯O and C-H⋯N hydrogen bonds, forming a layer structure extending parallel to the (011) plane. In addition, the mol-ecules within the layers inter-act with each other via C-H⋯π inter-actions.

Related literature

For the synthesis of chromene compounds, see: Coujon et al. (2002 ▶). For the bioactivity of chromene compounds see: Kaye & Nocanda (2002 ▶). For similar structures, see: Hu et al. (2012 ▶); Mohamed et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C18H17ClN2O2·C3H6O

M = 386.86

Triclinic,

a = 8.1707 (2) Å

b = 9.4386 (2) Å

c = 13.5192 (4) Å

α = 84.446 (1)°

β = 82.546 (2)°

γ = 78.625 (1)°

V = 1010.76 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.28 × 0.25 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.942, T max = 0.952

16320 measured reflections

4769 independent reflections

3390 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.126

S = 1.04

4769 reflections

248 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.34 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: 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/S1600536812024142/xu5550sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024142/xu5550Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812024142/xu5550Isup3.cml

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

C18H17ClN2O2·C3H6O	Z = 2
Mr = 386.86	F(000) = 408
Triclinic, P1	Dx = 1.271 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1707 (2) Å	Cell parameters from 430 reflections
b = 9.4386 (2) Å	θ = 2.2–21°
c = 13.5192 (4) Å	µ = 0.21 mm−1
α = 84.446 (1)°	T = 296 K
β = 82.546 (2)°	Prism, colourless
γ = 78.625 (1)°	0.28 × 0.25 × 0.23 mm
V = 1010.76 (4) Å3

Bruker Kappa APEXII CCD diffractometer	4769 independent reflections
Radiation source: fine-focus sealed tube	3390 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 0.81 pixels mm-1	θmax = 27.9°, θmin = 1.5°
ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
Tmin = 0.942, Tmax = 0.952	l = −17→17
16320 measured reflections

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) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0552P)2 + 0.2106P] where P = (Fo2 + 2Fc2)/3
4769 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.34 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	1.23217 (8)	−0.04097 (7)	0.07282 (5)	0.0908 (3)
O1	0.49042 (12)	0.48205 (10)	0.35120 (8)	0.0400 (3)
O2	1.05221 (14)	0.51811 (13)	0.37189 (11)	0.0565 (5)
N1	0.67987 (18)	0.01830 (15)	0.51140 (12)	0.0536 (5)
N2	0.36160 (16)	0.29958 (14)	0.40904 (11)	0.0480 (5)
C1	0.92881 (17)	0.24000 (15)	0.30888 (11)	0.0342 (4)
C2	1.05201 (19)	0.12327 (17)	0.33381 (14)	0.0460 (5)
C3	1.1449 (2)	0.03660 (19)	0.26177 (16)	0.0555 (6)
C4	1.1148 (2)	0.06724 (19)	0.16419 (15)	0.0531 (6)
C5	0.9934 (2)	0.18223 (19)	0.13653 (14)	0.0513 (6)
C6	0.9008 (2)	0.26753 (17)	0.20960 (12)	0.0430 (5)
C7	0.82134 (17)	0.32702 (15)	0.39096 (11)	0.0337 (4)
C8	0.65888 (18)	0.27155 (15)	0.42120 (11)	0.0335 (4)
C9	0.50856 (18)	0.34425 (15)	0.39607 (11)	0.0342 (4)
C10	0.62537 (18)	0.55179 (15)	0.33926 (11)	0.0334 (4)
C11	0.77873 (17)	0.48648 (15)	0.36014 (11)	0.0326 (4)
C12	0.66848 (18)	0.13136 (16)	0.47074 (12)	0.0380 (4)
C13	0.90997 (19)	0.57350 (16)	0.35344 (12)	0.0388 (5)
C14	0.8623 (2)	0.73361 (17)	0.32758 (14)	0.0463 (5)
C15	0.7272 (2)	0.77363 (16)	0.25591 (12)	0.0409 (5)
C16	0.57651 (18)	0.70488 (15)	0.30076 (12)	0.0387 (5)
C17	0.6697 (2)	0.93797 (18)	0.24419 (17)	0.0592 (7)
C18	0.7976 (2)	0.7186 (2)	0.15339 (14)	0.0564 (6)
O3	0.5451 (2)	0.50051 (18)	0.11608 (13)	0.0843 (7)
C19	0.4295 (3)	0.4388 (2)	0.11692 (15)	0.0603 (7)
C20	0.4577 (4)	0.2802 (3)	0.1159 (2)	0.0995 (13)
C21	0.2546 (3)	0.5175 (3)	0.1176 (3)	0.1166 (13)
H2	1.07260	0.10280	0.40020	0.0550*
H2A	0.35510	0.21450	0.43660	0.0580*
H2B	0.27340	0.35580	0.38990	0.0580*
H3	1.22690	−0.04170	0.27950	0.0670*
H5	0.97400	0.20230	0.06990	0.0620*
H6	0.81800	0.34500	0.19150	0.0520*
H7	0.88370	0.31470	0.44940	0.0410*
H14A	0.96180	0.76980	0.29740	0.0560*
H14B	0.82190	0.78160	0.38870	0.0560*
H16A	0.51530	0.76070	0.35500	0.0460*
H16B	0.50160	0.70960	0.25000	0.0460*
H17A	0.76440	0.98270	0.22010	0.0890*
H17B	0.62060	0.97280	0.30780	0.0890*
H17C	0.58780	0.96160	0.19740	0.0890*
H18A	0.71240	0.74390	0.10870	0.0850*
H18B	0.83210	0.61510	0.16000	0.0850*
H18C	0.89240	0.76210	0.12710	0.0850*
H20A	0.41990	0.25490	0.05680	0.1490*
H20B	0.39630	0.24090	0.17400	0.1490*
H20C	0.57550	0.24120	0.11620	0.1490*
H21A	0.25020	0.61800	0.12620	0.1750*
H21B	0.18550	0.47730	0.17170	0.1750*
H21C	0.21410	0.50840	0.05540	0.1750*

	U11	U22	U33	U12	U13	U23
Cl1	0.0881 (4)	0.0749 (4)	0.1017 (5)	−0.0010 (3)	0.0216 (3)	−0.0411 (3)
O1	0.0293 (5)	0.0326 (5)	0.0566 (7)	−0.0079 (4)	−0.0069 (5)	0.0111 (5)
O2	0.0351 (6)	0.0490 (7)	0.0871 (10)	−0.0102 (5)	−0.0169 (6)	0.0050 (6)
N1	0.0469 (8)	0.0429 (8)	0.0700 (10)	−0.0113 (6)	−0.0163 (7)	0.0197 (7)
N2	0.0314 (7)	0.0391 (7)	0.0715 (10)	−0.0099 (6)	−0.0074 (6)	0.0151 (7)
C1	0.0271 (7)	0.0287 (7)	0.0468 (9)	−0.0067 (6)	−0.0050 (6)	0.0019 (6)
C2	0.0354 (8)	0.0405 (9)	0.0591 (11)	−0.0009 (7)	−0.0090 (7)	0.0036 (8)
C3	0.0384 (9)	0.0392 (9)	0.0830 (14)	0.0046 (7)	−0.0040 (9)	−0.0041 (9)
C4	0.0451 (10)	0.0430 (9)	0.0698 (13)	−0.0097 (8)	0.0099 (8)	−0.0169 (8)
C5	0.0579 (11)	0.0464 (10)	0.0500 (10)	−0.0122 (8)	−0.0019 (8)	−0.0055 (8)
C6	0.0431 (9)	0.0350 (8)	0.0497 (10)	−0.0035 (7)	−0.0075 (7)	−0.0016 (7)
C7	0.0304 (7)	0.0318 (7)	0.0395 (8)	−0.0065 (6)	−0.0093 (6)	0.0036 (6)
C8	0.0330 (7)	0.0294 (7)	0.0371 (8)	−0.0063 (6)	−0.0038 (6)	0.0036 (6)
C9	0.0344 (7)	0.0308 (7)	0.0365 (8)	−0.0083 (6)	−0.0020 (6)	0.0037 (6)
C10	0.0323 (7)	0.0291 (7)	0.0384 (8)	−0.0078 (6)	−0.0012 (6)	−0.0006 (6)
C11	0.0306 (7)	0.0287 (7)	0.0383 (8)	−0.0060 (6)	−0.0031 (6)	−0.0011 (6)
C12	0.0315 (7)	0.0387 (8)	0.0430 (8)	−0.0066 (6)	−0.0072 (6)	0.0050 (7)
C13	0.0363 (8)	0.0367 (8)	0.0443 (9)	−0.0093 (6)	−0.0050 (6)	−0.0024 (6)
C14	0.0442 (9)	0.0355 (8)	0.0619 (11)	−0.0141 (7)	−0.0079 (8)	−0.0013 (7)
C15	0.0423 (8)	0.0298 (8)	0.0508 (9)	−0.0108 (6)	−0.0030 (7)	0.0019 (7)
C16	0.0360 (8)	0.0286 (7)	0.0488 (9)	−0.0032 (6)	−0.0022 (7)	0.0016 (6)
C17	0.0613 (11)	0.0318 (9)	0.0848 (14)	−0.0125 (8)	−0.0127 (10)	0.0085 (9)
C18	0.0596 (11)	0.0564 (11)	0.0512 (11)	−0.0167 (9)	0.0037 (8)	0.0048 (8)
O3	0.0928 (12)	0.0868 (11)	0.0863 (12)	−0.0419 (10)	−0.0209 (9)	−0.0046 (9)
C19	0.0682 (13)	0.0644 (12)	0.0506 (11)	−0.0211 (10)	−0.0033 (9)	−0.0024 (9)
C20	0.109 (2)	0.0637 (15)	0.132 (3)	−0.0259 (15)	−0.0305 (18)	0.0047 (15)
C21	0.0753 (18)	0.115 (2)	0.140 (3)	0.0068 (16)	0.0197 (17)	−0.006 (2)

Cl1—C4	1.743 (2)	C15—C17	1.528 (2)
O1—C9	1.3697 (17)	C15—C18	1.529 (2)
O1—C10	1.3765 (18)	C2—H2	0.9300
O2—C13	1.223 (2)	C3—H3	0.9300
O3—C19	1.202 (3)	C5—H5	0.9300
N1—C12	1.145 (2)	C6—H6	0.9300
N2—C9	1.335 (2)	C7—H7	0.9800
N2—H2B	0.8600	C14—H14B	0.9700
N2—H2A	0.8600	C14—H14A	0.9700
C1—C2	1.385 (2)	C16—H16A	0.9700
C1—C6	1.382 (2)	C16—H16B	0.9700
C1—C7	1.522 (2)	C17—H17B	0.9600
C2—C3	1.383 (3)	C17—H17C	0.9600
C3—C4	1.366 (3)	C17—H17A	0.9600
C4—C5	1.377 (2)	C18—H18B	0.9600
C5—C6	1.384 (2)	C18—H18C	0.9600
C7—C11	1.507 (2)	C18—H18A	0.9600
C7—C8	1.515 (2)	C19—C20	1.470 (3)
C8—C9	1.351 (2)	C19—C21	1.474 (4)
C8—C12	1.417 (2)	C20—H20A	0.9600
C10—C11	1.335 (2)	C20—H20B	0.9600
C10—C16	1.483 (2)	C20—H20C	0.9600
C11—C13	1.463 (2)	C21—H21A	0.9600
C13—C14	1.503 (2)	C21—H21B	0.9600
C14—C15	1.530 (2)	C21—H21C	0.9600
C15—C16	1.533 (2)
C9—O1—C10	118.92 (11)	C4—C5—H5	121.00
C9—N2—H2B	120.00	C6—C5—H5	121.00
H2A—N2—H2B	120.00	C1—C6—H6	119.00
C9—N2—H2A	120.00	C5—C6—H6	119.00
C6—C1—C7	122.04 (13)	C1—C7—H7	108.00
C2—C1—C6	118.08 (14)	C8—C7—H7	108.00
C2—C1—C7	119.74 (14)	C11—C7—H7	108.00
C1—C2—C3	121.22 (17)	C13—C14—H14A	109.00
C2—C3—C4	119.25 (16)	C13—C14—H14B	109.00
Cl1—C4—C3	119.52 (14)	C15—C14—H14A	109.00
C3—C4—C5	121.21 (17)	C15—C14—H14B	109.00
Cl1—C4—C5	119.27 (15)	H14A—C14—H14B	108.00
C4—C5—C6	118.86 (17)	C10—C16—H16A	109.00
C1—C6—C5	121.37 (15)	C10—C16—H16B	109.00
C1—C7—C11	112.80 (12)	C15—C16—H16A	109.00
C1—C7—C8	110.40 (12)	C15—C16—H16B	109.00
C8—C7—C11	108.40 (12)	H16A—C16—H16B	108.00
C7—C8—C9	123.08 (13)	C15—C17—H17A	109.00
C7—C8—C12	117.87 (13)	C15—C17—H17B	109.00
C9—C8—C12	118.83 (14)	C15—C17—H17C	109.00
N2—C9—C8	128.24 (14)	H17A—C17—H17B	109.00
O1—C9—N2	110.31 (12)	H17A—C17—H17C	110.00
O1—C9—C8	121.45 (13)	H17B—C17—H17C	109.00
O1—C10—C11	122.99 (13)	C15—C18—H18A	109.00
O1—C10—C16	111.12 (12)	C15—C18—H18B	109.00
C11—C10—C16	125.89 (14)	C15—C18—H18C	109.00
C10—C11—C13	118.65 (13)	H18A—C18—H18B	109.00
C7—C11—C10	122.53 (13)	H18A—C18—H18C	109.00
C7—C11—C13	118.81 (12)	H18B—C18—H18C	110.00
N1—C12—C8	178.38 (17)	O3—C19—C20	120.9 (2)
O2—C13—C11	120.84 (14)	O3—C19—C21	122.05 (19)
O2—C13—C14	121.28 (14)	C20—C19—C21	117.0 (2)
C11—C13—C14	117.84 (13)	C19—C20—H20A	109.00
C13—C14—C15	113.74 (13)	C19—C20—H20B	110.00
C16—C15—C17	108.70 (13)	C19—C20—H20C	109.00
C16—C15—C18	110.90 (13)	H20A—C20—H20B	109.00
C17—C15—C18	108.98 (15)	H20A—C20—H20C	109.00
C14—C15—C18	109.79 (14)	H20B—C20—H20C	109.00
C14—C15—C16	108.05 (13)	C19—C21—H21A	109.00
C14—C15—C17	110.41 (13)	C19—C21—H21B	109.00
C10—C16—C15	113.11 (12)	C19—C21—H21C	109.00
C1—C2—H2	119.00	H21A—C21—H21B	109.00
C3—C2—H2	119.00	H21A—C21—H21C	110.00
C2—C3—H3	120.00	H21B—C21—H21C	109.00
C4—C3—H3	120.00
C9—O1—C10—C16	−173.19 (12)	C8—C7—C11—C10	−15.79 (19)
C10—O1—C9—N2	174.51 (12)	C8—C7—C11—C13	163.79 (13)
C10—O1—C9—C8	−5.5 (2)	C7—C8—C9—N2	172.17 (15)
C9—O1—C10—C11	7.0 (2)	C12—C8—C9—O1	177.72 (13)
C7—C1—C2—C3	176.02 (14)	C12—C8—C9—N2	−2.3 (2)
C2—C1—C6—C5	−0.5 (2)	C7—C8—C9—O1	−7.8 (2)
C7—C1—C6—C5	−176.29 (15)	O1—C10—C11—C7	5.0 (2)
C6—C1—C2—C3	0.1 (2)	O1—C10—C11—C13	−174.58 (13)
C2—C1—C7—C8	−94.69 (16)	C16—C10—C11—C7	−174.80 (14)
C2—C1—C7—C11	143.88 (14)	C16—C10—C11—C13	5.6 (2)
C6—C1—C7—C8	81.04 (17)	O1—C10—C16—C15	−162.22 (12)
C6—C1—C7—C11	−40.39 (19)	C11—C10—C16—C15	17.6 (2)
C1—C2—C3—C4	0.3 (3)	C7—C11—C13—O2	0.4 (2)
C2—C3—C4—Cl1	179.66 (13)	C7—C11—C13—C14	−176.99 (14)
C2—C3—C4—C5	−0.3 (3)	C10—C11—C13—O2	−180.00 (17)
Cl1—C4—C5—C6	180.00 (15)	C10—C11—C13—C14	2.6 (2)
C3—C4—C5—C6	−0.1 (3)	O2—C13—C14—C15	148.89 (16)
C4—C5—C6—C1	0.5 (3)	C11—C13—C14—C15	−33.7 (2)
C1—C7—C8—C12	67.77 (17)	C13—C14—C15—C16	53.89 (18)
C11—C7—C8—C9	17.28 (19)	C13—C14—C15—C17	172.65 (15)
C11—C7—C8—C12	−168.22 (13)	C13—C14—C15—C18	−67.18 (18)
C1—C7—C11—C10	106.77 (16)	C14—C15—C16—C10	−45.43 (17)
C1—C7—C8—C9	−106.73 (16)	C17—C15—C16—C10	−165.27 (14)
C1—C7—C11—C13	−73.65 (17)	C18—C15—C16—C10	74.94 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.30	3.1552 (19)	171
N2—H2B···O2ii	0.86	2.15	2.9949 (18)	167
C2—H2···N1iii	0.93	2.51	3.234 (2)	135
C6—H6···Cg1	0.93	2.76	3.0785 (17)	101
C17—H17A···Cg2iv	0.96	2.93	3.8221 (18)	155

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the O1/C7–C11 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.30	3.1552 (19)	171
N2—H2B⋯O2ii	0.86	2.15	2.9949 (18)	167
C2—H2⋯N1iii	0.93	2.51	3.234 (2)	135
C17—H17A⋯Cg2iv	0.96	2.93	3.8221 (18)	155

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