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

In the crystal structure of the title compound, C(19)H(20)N(2)O(3)·C(3)H(6)O, mol-ecules are linked into inversion dimers with an R(2) (2)(12) motif by pairs of N-H⋯N hydrogen bonds. These dimers are further connected into chains running along the a axis by N-H⋯O hydrogen bonds. C-H⋯N and C-H⋯π inter-actions also feature in the packing. The cyclohexene ring adopts nearly an envelope conformation [puckering parameters are Q(T) = 0.456 (2) Å, θ = 54.6 (3)° and ϕ = 225.2 (3)°].

Related literature

For pharmacological properties of 4H-chromene and fused 4H-chromene derivatives, see: Kemnitzer et al. (2007 ▶, 2008 ▶); Abd-El-Aziz et al. (2004 ▶, 2007 ▶); Sabry et al. (2011 ▶); Gourdeau et al. (2004 ▶); Mahdavi et al. (2011 ▶); Brühlmann et al. (2001 ▶). For a related structure, see: Mohamed et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C19H20N2O3·C3H6O

M = 382.45

Triclinic,

a = 8.2037 (4) Å

b = 9.5319 (4) Å

c = 13.8390 (7) Å

α = 77.743 (2)°

β = 87.307 (3)°

γ = 80.672 (2)°

V = 1043.43 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 296 K

0.28 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.978, T max = 0.983

16752 measured reflections

4917 independent reflections

3284 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.182

S = 1.04

4917 reflections

246 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.50 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/S160053681202781X/bt5943sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202781X/bt5943Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681202781X/bt5943Isup3.cml

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

C19H20N2O3·C3H6O	Z = 2
Mr = 382.45	F(000) = 408
Triclinic, P1	Dx = 1.217 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2037 (4) Å	Cell parameters from 360 reflections
b = 9.5319 (4) Å	θ = 21.3–3.4°
c = 13.8390 (7) Å	µ = 0.08 mm−1
α = 77.743 (2)°	T = 296 K
β = 87.307 (3)°	Prism, white
γ = 80.672 (2)°	0.28 × 0.22 × 0.20 mm
V = 1043.43 (9) Å3

Bruker Kappa APEXII CCD diffractometer	4917 independent reflections
Radiation source: fine-focus sealed tube	3284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 0.81 pixels mm-1	θmax = 28.0°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→9
Tmin = 0.978, Tmax = 0.983	l = −18→18
16752 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0878P)2 + 0.2431P] where P = (Fo2 + 2Fc2)/3
4917 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 0.59 e Å−3
1 restraint	Δρmin = −0.50 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
O1	0.4032 (2)	0.66247 (19)	0.08006 (13)	0.0802 (7)
O2	1.02042 (14)	0.08753 (13)	0.35411 (10)	0.0488 (4)
O3	0.45650 (17)	0.03885 (16)	0.37857 (13)	0.0629 (6)
N1	0.8196 (2)	0.4700 (2)	0.51973 (16)	0.0656 (7)
N2	1.14500 (19)	0.24295 (18)	0.41136 (14)	0.0563 (6)
C1	0.6070 (2)	0.33700 (18)	0.31182 (14)	0.0399 (5)
C2	0.6619 (2)	0.3463 (2)	0.21430 (15)	0.0483 (6)
C3	0.5919 (3)	0.4548 (2)	0.13983 (16)	0.0543 (7)
C4	0.4642 (3)	0.5588 (2)	0.16012 (16)	0.0532 (7)
C5	0.4076 (2)	0.5523 (2)	0.25594 (17)	0.0549 (7)
C6	0.4797 (2)	0.4416 (2)	0.33068 (15)	0.0473 (6)
C7	0.2741 (4)	0.7714 (3)	0.0945 (2)	0.0952 (11)
C8	0.6896 (2)	0.22102 (18)	0.39559 (14)	0.0389 (5)
C9	0.8474 (2)	0.26366 (19)	0.42629 (14)	0.0437 (4)
C10	0.9993 (2)	0.20384 (19)	0.39964 (14)	0.0419 (5)
C11	0.8333 (2)	0.37739 (19)	0.47771 (14)	0.0437 (4)
C12	0.8867 (2)	0.02105 (18)	0.34609 (14)	0.0408 (5)
C13	0.7325 (2)	0.07535 (18)	0.36796 (13)	0.0403 (5)
C14	0.5994 (2)	−0.00856 (19)	0.36226 (15)	0.0455 (6)
C15	0.6483 (2)	−0.1573 (2)	0.33914 (17)	0.0538 (7)
C16	0.7957 (3)	−0.1685 (2)	0.26744 (17)	0.0570 (5)
C17	0.9388 (2)	−0.11592 (19)	0.30923 (16)	0.0475 (6)
C18	0.8500 (3)	−0.3269 (2)	0.2591 (2)	0.0702 (9)
C19	0.7493 (3)	−0.0761 (2)	0.16615 (17)	0.0570 (5)
O4	0.0402 (4)	0.1650 (4)	0.0951 (3)	0.1652 (16)
C20	0.1432 (4)	0.2327 (4)	0.1086 (2)	0.0875 (11)
C21	0.3163 (5)	0.1707 (5)	0.1206 (4)	0.149 (2)
C22	0.1030 (5)	0.3830 (4)	0.1273 (4)	0.142 (2)
H2	0.74790	0.27740	0.19950	0.0580*
H2A	1.14960	0.31490	0.43900	0.0680*
H2B	1.23420	0.19620	0.39120	0.0680*
H3	0.63040	0.45860	0.07520	0.0650*
H5	0.32180	0.62150	0.27050	0.0660*
H6	0.44110	0.43780	0.39530	0.0570*
H7A	0.18230	0.72780	0.12580	0.1420*
H7B	0.24060	0.83210	0.03180	0.1420*
H7C	0.31060	0.82910	0.13580	0.1420*
H8	0.61350	0.21200	0.45250	0.0470*
H15A	0.55440	−0.18350	0.31090	0.0650*
H15B	0.67530	−0.22710	0.40040	0.0650*
H17A	0.98780	−0.19130	0.36310	0.0570*
H17B	1.02270	−0.10000	0.25810	0.0570*
H18A	0.75920	−0.36330	0.23680	0.1050*
H18B	0.88460	−0.38430	0.32260	0.1050*
H18C	0.94030	−0.33260	0.21270	0.1050*
H19A	0.71430	0.02300	0.17170	0.0850*
H19B	0.66090	−0.11140	0.14030	0.0850*
H19C	0.84340	−0.08150	0.12240	0.0850*
H21A	0.35150	0.17590	0.18470	0.2240*
H21B	0.38070	0.22410	0.07060	0.2240*
H21C	0.33130	0.07090	0.11440	0.2240*
H22A	0.15880	0.44750	0.07910	0.2140*
H22B	0.13850	0.38360	0.19230	0.2140*
H22C	−0.01410	0.41450	0.12260	0.2140*

	U11	U22	U33	U12	U13	U23
O1	0.0853 (12)	0.0744 (11)	0.0695 (11)	0.0109 (9)	−0.0079 (9)	−0.0055 (9)
O2	0.0325 (6)	0.0517 (7)	0.0730 (9)	−0.0094 (5)	0.0028 (6)	−0.0355 (7)
O3	0.0363 (7)	0.0646 (9)	0.0955 (12)	−0.0134 (6)	0.0069 (7)	−0.0313 (8)
N1	0.0476 (10)	0.0739 (12)	0.0915 (14)	−0.0128 (9)	0.0111 (9)	−0.0534 (11)
N2	0.0338 (8)	0.0609 (10)	0.0875 (13)	−0.0101 (7)	−0.0002 (8)	−0.0433 (9)
C1	0.0310 (8)	0.0410 (9)	0.0535 (11)	−0.0093 (7)	0.0008 (7)	−0.0203 (8)
C2	0.0443 (10)	0.0474 (10)	0.0576 (12)	−0.0066 (8)	0.0043 (9)	−0.0224 (9)
C3	0.0581 (12)	0.0571 (11)	0.0512 (12)	−0.0099 (10)	0.0041 (10)	−0.0193 (9)
C4	0.0499 (11)	0.0530 (11)	0.0580 (13)	−0.0082 (9)	−0.0084 (10)	−0.0128 (9)
C5	0.0408 (10)	0.0538 (11)	0.0708 (14)	0.0020 (8)	−0.0011 (9)	−0.0216 (10)
C6	0.0367 (9)	0.0521 (10)	0.0557 (12)	−0.0056 (8)	0.0043 (8)	−0.0189 (9)
C7	0.093 (2)	0.0738 (17)	0.101 (2)	0.0192 (15)	−0.0154 (17)	−0.0002 (15)
C8	0.0314 (8)	0.0416 (9)	0.0480 (10)	−0.0077 (7)	0.0039 (7)	−0.0184 (7)
C9	0.0351 (7)	0.0473 (7)	0.0538 (8)	−0.0064 (5)	0.0003 (6)	−0.0222 (6)
C10	0.0381 (9)	0.0428 (9)	0.0505 (10)	−0.0070 (7)	−0.0030 (8)	−0.0214 (8)
C11	0.0351 (7)	0.0473 (7)	0.0538 (8)	−0.0064 (5)	0.0003 (6)	−0.0222 (6)
C12	0.0355 (9)	0.0407 (9)	0.0504 (10)	−0.0082 (7)	−0.0015 (8)	−0.0172 (8)
C13	0.0350 (9)	0.0401 (9)	0.0484 (10)	−0.0073 (7)	−0.0005 (7)	−0.0142 (7)
C14	0.0388 (10)	0.0458 (9)	0.0553 (11)	−0.0118 (8)	0.0007 (8)	−0.0145 (8)
C15	0.0479 (11)	0.0469 (10)	0.0738 (14)	−0.0187 (8)	0.0022 (10)	−0.0208 (9)
C16	0.0577 (9)	0.0558 (8)	0.0649 (9)	−0.0136 (7)	−0.0035 (7)	−0.0248 (7)
C17	0.0408 (10)	0.0410 (9)	0.0656 (13)	−0.0045 (7)	−0.0014 (9)	−0.0233 (9)
C18	0.0664 (14)	0.0530 (12)	0.1049 (19)	−0.0192 (10)	0.0059 (13)	−0.0410 (13)
C19	0.0577 (9)	0.0558 (8)	0.0649 (9)	−0.0136 (7)	−0.0035 (7)	−0.0248 (7)
O4	0.118 (2)	0.219 (3)	0.206 (3)	−0.089 (2)	0.007 (2)	−0.104 (3)
C20	0.0769 (19)	0.110 (2)	0.090 (2)	−0.0446 (17)	0.0029 (15)	−0.0312 (17)
C21	0.092 (3)	0.125 (3)	0.237 (6)	−0.014 (2)	−0.018 (3)	−0.049 (4)
C22	0.115 (3)	0.115 (3)	0.199 (5)	−0.032 (2)	0.019 (3)	−0.031 (3)

O1—C4	1.372 (3)	C16—C18	1.531 (3)
O1—C7	1.397 (4)	C2—H2	0.9300
O2—C10	1.371 (2)	C3—H3	0.9300
O2—C12	1.373 (2)	C5—H5	0.9300
O3—C14	1.215 (2)	C6—H6	0.9300
O4—C20	1.187 (5)	C7—H7B	0.9600
N1—C11	1.144 (3)	C7—H7C	0.9600
N2—C10	1.335 (2)	C7—H7A	0.9600
N2—H2B	0.8600	C8—H8	0.9800
N2—H2A	0.8600	C15—H15B	0.9700
C1—C2	1.392 (3)	C15—H15A	0.9700
C1—C8	1.521 (3)	C17—H17A	0.9700
C1—C6	1.379 (3)	C17—H17B	0.9700
C2—C3	1.368 (3)	C18—H18B	0.9600
C3—C4	1.383 (3)	C18—H18C	0.9600
C4—C5	1.376 (3)	C18—H18A	0.9600
C5—C6	1.387 (3)	C19—H19B	0.9600
C8—C9	1.522 (2)	C19—H19C	0.9600
C8—C13	1.501 (2)	C19—H19A	0.9600
C9—C10	1.353 (2)	C20—C21	1.450 (5)
C9—C11	1.405 (3)	C20—C22	1.492 (5)
C12—C13	1.333 (2)	C21—H21A	0.9600
C12—C17	1.493 (3)	C21—H21B	0.9600
C13—C14	1.468 (2)	C21—H21C	0.9600
C14—C15	1.507 (3)	C22—H22A	0.9600
C15—C16	1.533 (3)	C22—H22B	0.9600
C16—C19	1.518 (3)	C22—H22C	0.9600
C16—C17	1.530 (3)
C4—O1—C7	119.00 (19)	C1—C6—H6	119.00
C10—O2—C12	118.71 (13)	C5—C6—H6	119.00
C10—N2—H2B	120.00	O1—C7—H7A	109.00
H2A—N2—H2B	120.00	O1—C7—H7B	109.00
C10—N2—H2A	120.00	O1—C7—H7C	110.00
C6—C1—C8	120.86 (17)	H7A—C7—H7B	109.00
C2—C1—C6	117.49 (17)	H7A—C7—H7C	110.00
C2—C1—C8	121.58 (16)	H7B—C7—H7C	109.00
C1—C2—C3	121.33 (18)	C1—C8—H8	108.00
C2—C3—C4	120.4 (2)	C9—C8—H8	108.00
O1—C4—C3	115.55 (19)	C13—C8—H8	109.00
C3—C4—C5	119.50 (19)	C14—C15—H15A	109.00
O1—C4—C5	124.96 (19)	C14—C15—H15B	109.00
C4—C5—C6	119.47 (18)	C16—C15—H15A	109.00
C1—C6—C5	121.83 (18)	C16—C15—H15B	109.00
C1—C8—C13	112.40 (15)	H15A—C15—H15B	108.00
C1—C8—C9	110.68 (14)	C12—C17—H17A	109.00
C9—C8—C13	108.21 (14)	C12—C17—H17B	109.00
C8—C9—C10	122.50 (16)	C16—C17—H17A	109.00
C8—C9—C11	118.28 (15)	C16—C17—H17B	109.00
C10—C9—C11	119.04 (16)	H17A—C17—H17B	108.00
N2—C10—C9	128.41 (18)	C16—C18—H18A	109.00
O2—C10—N2	110.29 (15)	C16—C18—H18B	110.00
O2—C10—C9	121.30 (15)	C16—C18—H18C	110.00
N1—C11—C9	179.09 (19)	H18A—C18—H18B	109.00
O2—C12—C13	123.20 (16)	H18A—C18—H18C	109.00
O2—C12—C17	110.77 (14)	H18B—C18—H18C	109.00
C13—C12—C17	126.03 (16)	C16—C19—H19A	109.00
C12—C13—C14	118.86 (16)	C16—C19—H19B	109.00
C8—C13—C14	118.84 (15)	C16—C19—H19C	109.00
C8—C13—C12	122.28 (15)	H19A—C19—H19B	109.00
O3—C14—C13	121.03 (17)	H19A—C19—H19C	109.00
O3—C14—C15	121.68 (16)	H19B—C19—H19C	109.00
C13—C14—C15	117.26 (15)	O4—C20—C21	122.9 (4)
C14—C15—C16	113.98 (16)	O4—C20—C22	122.7 (4)
C17—C16—C18	108.51 (18)	C21—C20—C22	114.0 (3)
C17—C16—C19	110.37 (18)	C20—C21—H21A	109.00
C18—C16—C19	109.63 (19)	C20—C21—H21B	109.00
C15—C16—C19	110.12 (19)	C20—C21—H21C	109.00
C15—C16—C17	108.13 (17)	H21A—C21—H21B	109.00
C15—C16—C18	110.05 (18)	H21A—C21—H21C	109.00
C12—C17—C16	112.99 (15)	H21B—C21—H21C	109.00
C1—C2—H2	119.00	C20—C22—H22A	109.00
C3—C2—H2	119.00	C20—C22—H22B	109.00
C2—C3—H3	120.00	C20—C22—H22C	109.00
C4—C3—H3	120.00	H22A—C22—H22B	109.00
C4—C5—H5	120.00	H22A—C22—H22C	110.00
C6—C5—H5	120.00	H22B—C22—H22C	109.00
C7—O1—C4—C3	−180.0 (2)	C1—C8—C13—C14	−74.3 (2)
C7—O1—C4—C5	0.2 (3)	C9—C8—C13—C12	−18.5 (2)
C12—O2—C10—N2	172.48 (16)	C9—C8—C13—C14	163.20 (16)
C12—O2—C10—C9	−7.6 (3)	C8—C9—C10—O2	−8.6 (3)
C10—O2—C12—C13	9.5 (3)	C8—C9—C10—N2	171.34 (19)
C10—O2—C12—C17	−171.11 (16)	C11—C9—C10—O2	176.45 (17)
C6—C1—C2—C3	−0.2 (3)	C11—C9—C10—N2	−3.6 (3)
C8—C1—C2—C3	−177.04 (18)	O2—C12—C13—C8	5.1 (3)
C2—C1—C6—C5	0.2 (3)	O2—C12—C13—C14	−176.54 (17)
C8—C1—C6—C5	177.02 (16)	C17—C12—C13—C8	−174.16 (18)
C2—C1—C8—C9	79.6 (2)	C17—C12—C13—C14	4.2 (3)
C2—C1—C8—C13	−41.5 (2)	O2—C12—C17—C16	−161.46 (16)
C6—C1—C8—C9	−97.08 (19)	C13—C12—C17—C16	17.9 (3)
C6—C1—C8—C13	141.80 (17)	C8—C13—C14—O3	0.7 (3)
C1—C2—C3—C4	0.2 (3)	C8—C13—C14—C15	−177.12 (17)
C2—C3—C4—O1	−180.0 (2)	C12—C13—C14—O3	−177.70 (19)
C2—C3—C4—C5	−0.1 (3)	C12—C13—C14—C15	4.5 (3)
O1—C4—C5—C6	179.9 (2)	O3—C14—C15—C16	147.2 (2)
C3—C4—C5—C6	0.1 (3)	C13—C14—C15—C16	−35.0 (3)
C4—C5—C6—C1	−0.1 (3)	C14—C15—C16—C17	54.3 (2)
C1—C8—C9—C10	−103.3 (2)	C14—C15—C16—C18	172.66 (18)
C1—C8—C9—C11	71.7 (2)	C14—C15—C16—C19	−66.4 (2)
C13—C8—C9—C10	20.3 (2)	C15—C16—C17—C12	−45.0 (2)
C13—C8—C9—C11	−164.75 (16)	C18—C16—C17—C12	−164.36 (18)
C1—C8—C13—C12	104.1 (2)	C19—C16—C17—C12	75.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.30	3.142 (3)	168
N2—H2B···O3ii	0.86	2.19	3.029 (2)	165
C6—H6···N1iii	0.93	2.51	3.258 (3)	137
C18—H18A···Cg2iv	0.96	2.77	3.677 (2)	158

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the O2/C8–C10/C12/C13) 4H-pyran ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.30	3.142 (3)	168
N2—H2B⋯O3ii	0.86	2.19	3.029 (2)	165
C6—H6⋯N1iii	0.93	2.51	3.258 (3)	137
C18—H18A⋯Cg2iv	0.96	2.77	3.677 (2)	158

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