2-Amino-4-(4-meth-oxy-phen-yl)-5-oxo-5,6,7,8-tetra-hydro-4H-chromene-3-carbonitrile 1,4-dioxane hemisolvate.

In the crystal structure of the title compound, C(17)H(16)N(2)O(3)·0.5C(4)H(8)O(2), pairs of N-H⋯N hydrogen bonds link mol-ecules into dimers with R(2) (2)(12) motifs, which are connected by N-H⋯O hydrogen bonds, forming a supra-molecular array in the ab plane. The 1,4-dioxane ring, which lies about an inversion center, adopts a chair conformation.

Related literature

For the biological activity of pyran and fused-pyran mol­ecules, see: Bargagna et al. (1992 ▶); Symeonidis et al. (2009 ▶); Narender & Gupta (2009 ▶); Alvey et al. (2009 ▶); Gorlitzer et al. (1984 ▶); Han et al. (2008 ▶); Martinez & Marco (1997 ▶); Smith et al. (1998 ▶); Taylor et al. (1998 ▶). For related structures, see: Gourdeau et al. (2004 ▶); Foroumadi et al. (2007 ▶); Mohamed et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C17H16N2O3·0.5C4H8O2

M = 340.37

Triclinic,

a = 8.0876 (4) Å

b = 9.2013 (4) Å

c = 12.1613 (6) Å

α = 94.376 (2)°

β = 102.827 (1)°

γ = 95.972 (2)°

V = 873.01 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.35 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.973, T max = 0.980

14186 measured reflections

4108 independent reflections

3134 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.194

S = 1.07

4108 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.39 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/S1600536812027729/tk5115sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027729/tk5115Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812027729/tk5115Isup3.cml

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

C17H16N2O3·0.5C4H8O2	Z = 2
Mr = 340.37	F(000) = 360
Triclinic, P1	Dx = 1.295 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0876 (4) Å	Cell parameters from 420 reflections
b = 9.2013 (4) Å	θ = 3.6–22.5°
c = 12.1613 (6) Å	µ = 0.09 mm−1
α = 94.376 (2)°	T = 293 K
β = 102.827 (1)°	Prism, light-yellow
γ = 95.972 (2)°	0.35 × 0.25 × 0.22 mm
V = 873.01 (7) Å3

Bruker Kappa APEXII CCD diffractometer	4108 independent reflections
Radiation source: fine-focus sealed tube	3134 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 0.81 pixels mm-1	θmax = 27.9°, θmin = 1.7°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→8
Tmin = 0.973, Tmax = 0.980	l = −16→15
14186 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) = 0.194	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0997P)2 + 0.273P] where P = (Fo2 + 2Fc2)/3
4108 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.39 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	0.1813 (2)	0.42680 (19)	0.00491 (15)	0.0760 (6)
O2	0.93204 (16)	0.95097 (14)	0.33842 (12)	0.0512 (4)
O3	0.36871 (18)	0.99158 (15)	0.37001 (14)	0.0595 (5)
N1	1.0877 (2)	0.77420 (19)	0.39337 (15)	0.0563 (6)
N2	0.8057 (3)	0.5088 (2)	0.49805 (19)	0.0712 (7)
C1	0.5009 (2)	0.70436 (17)	0.26984 (14)	0.0389 (5)
C2	0.4984 (3)	0.7302 (2)	0.15944 (17)	0.0531 (6)
C3	0.3939 (3)	0.6405 (2)	0.06812 (18)	0.0583 (7)
C4	0.2893 (3)	0.5219 (2)	0.08782 (18)	0.0537 (6)
C5	0.2917 (3)	0.4941 (2)	0.19793 (19)	0.0563 (7)
C6	0.3951 (2)	0.58441 (19)	0.28771 (17)	0.0476 (6)
C7	0.1568 (4)	0.4634 (3)	−0.1082 (2)	0.0809 (9)
C8	0.6180 (2)	0.79962 (17)	0.37058 (14)	0.0387 (5)
C9	0.7912 (2)	0.74660 (18)	0.40311 (14)	0.0405 (5)
C10	0.9333 (2)	0.81758 (19)	0.38054 (14)	0.0420 (5)
C11	0.8019 (2)	0.6148 (2)	0.45477 (17)	0.0487 (6)
C12	0.7895 (2)	1.02140 (18)	0.33096 (14)	0.0422 (5)
C13	0.6429 (2)	0.95783 (18)	0.34927 (14)	0.0403 (5)
C14	0.5022 (2)	1.04491 (19)	0.35100 (15)	0.0461 (6)
C15	0.5308 (3)	1.2042 (2)	0.3328 (2)	0.0634 (8)
C16	0.6528 (3)	1.2323 (2)	0.2563 (2)	0.0660 (8)
C17	0.8203 (3)	1.1737 (2)	0.29963 (18)	0.0537 (6)
O4	0.8992 (4)	0.9746 (4)	1.0758 (2)	0.1475 (16)
C18	0.8279 (5)	0.9756 (5)	0.9615 (4)	0.1243 (19)
C19	0.9322 (6)	1.0707 (6)	0.9113 (4)	0.138 (2)
H1A	1.10620	0.69140	0.41900	0.0680*
H1B	1.16900	0.82900	0.37610	0.0680*
H2	0.56870	0.81000	0.14570	0.0640*
H3	0.39450	0.66020	−0.00570	0.0700*
H5	0.22270	0.41340	0.21170	0.0680*
H6	0.39390	0.56470	0.36140	0.0570*
H7A	0.11860	0.55860	−0.11240	0.1210*
H7B	0.07240	0.39170	−0.15710	0.1210*
H7C	0.26270	0.46480	−0.13150	0.1210*
H8	0.56480	0.79380	0.43530	0.0460*
H15A	0.57660	1.26170	0.40550	0.0760*
H15B	0.42210	1.23650	0.29930	0.0760*
H16A	0.60040	1.18570	0.18050	0.0790*
H16B	0.67420	1.33710	0.25170	0.0790*
H17A	0.88530	1.17380	0.24150	0.0640*
H17B	0.88670	1.23700	0.36540	0.0640*
H18A	0.71550	1.00780	0.95170	0.1500*
H18B	0.81450	0.87690	0.92390	0.1500*
H19A	0.94160	1.17020	0.94680	0.1660*
H19B	0.87970	1.07000	0.83140	0.1660*

	U11	U22	U33	U12	U13	U23
O1	0.0761 (11)	0.0640 (10)	0.0702 (10)	−0.0133 (8)	−0.0058 (8)	−0.0056 (8)
O2	0.0475 (7)	0.0467 (7)	0.0657 (8)	0.0030 (5)	0.0229 (6)	0.0207 (6)
O3	0.0480 (8)	0.0506 (8)	0.0832 (10)	0.0060 (6)	0.0217 (7)	0.0084 (7)
N1	0.0429 (9)	0.0552 (10)	0.0748 (11)	0.0057 (7)	0.0169 (8)	0.0229 (8)
N2	0.0600 (11)	0.0595 (11)	0.1025 (16)	0.0096 (8)	0.0244 (10)	0.0413 (11)
C1	0.0359 (8)	0.0347 (8)	0.0472 (9)	0.0047 (6)	0.0112 (7)	0.0063 (6)
C2	0.0594 (12)	0.0473 (10)	0.0514 (10)	−0.0082 (8)	0.0170 (9)	0.0062 (8)
C3	0.0649 (13)	0.0591 (12)	0.0475 (10)	−0.0043 (10)	0.0117 (9)	0.0042 (9)
C4	0.0487 (11)	0.0441 (10)	0.0612 (12)	0.0022 (8)	0.0016 (9)	−0.0009 (8)
C5	0.0505 (11)	0.0417 (10)	0.0702 (13)	−0.0070 (8)	0.0040 (9)	0.0124 (9)
C6	0.0454 (10)	0.0423 (9)	0.0543 (10)	0.0002 (7)	0.0091 (8)	0.0148 (8)
C7	0.0762 (17)	0.0896 (18)	0.0618 (14)	0.0016 (13)	−0.0056 (12)	−0.0107 (13)
C8	0.0407 (8)	0.0354 (8)	0.0418 (8)	0.0004 (6)	0.0145 (7)	0.0071 (6)
C9	0.0423 (9)	0.0372 (8)	0.0413 (8)	0.0004 (6)	0.0085 (7)	0.0087 (6)
C10	0.0443 (9)	0.0398 (8)	0.0414 (8)	0.0015 (7)	0.0092 (7)	0.0082 (7)
C11	0.0413 (9)	0.0462 (10)	0.0586 (11)	0.0016 (7)	0.0104 (8)	0.0144 (8)
C12	0.0499 (10)	0.0354 (8)	0.0420 (9)	0.0005 (7)	0.0133 (7)	0.0070 (7)
C13	0.0460 (9)	0.0341 (8)	0.0407 (8)	0.0008 (7)	0.0114 (7)	0.0049 (6)
C14	0.0494 (10)	0.0393 (9)	0.0481 (10)	0.0031 (7)	0.0091 (8)	0.0041 (7)
C15	0.0664 (13)	0.0403 (10)	0.0882 (16)	0.0107 (9)	0.0234 (12)	0.0150 (10)
C16	0.0820 (16)	0.0462 (11)	0.0748 (14)	0.0089 (10)	0.0219 (12)	0.0245 (10)
C17	0.0659 (12)	0.0391 (9)	0.0605 (11)	−0.0019 (8)	0.0251 (10)	0.0135 (8)
O4	0.125 (2)	0.236 (4)	0.0879 (17)	0.028 (2)	0.0352 (16)	0.018 (2)
C18	0.105 (3)	0.152 (4)	0.107 (3)	0.002 (3)	0.010 (2)	0.020 (3)
C19	0.114 (3)	0.200 (5)	0.111 (3)	0.038 (3)	0.022 (2)	0.069 (3)

O1—C4	1.364 (3)	C13—C14	1.461 (2)
O1—C7	1.417 (3)	C14—C15	1.501 (3)
O2—C10	1.366 (2)	C15—C16	1.516 (3)
O2—C12	1.369 (2)	C16—C17	1.511 (3)
O3—C14	1.216 (2)	C2—H2	0.9300
O4—C18	1.383 (5)	C3—H3	0.9300
O4—C19i	1.446 (6)	C5—H5	0.9300
N1—C10	1.330 (2)	C6—H6	0.9300
N2—C11	1.143 (3)	C7—H7C	0.9600
N1—H1B	0.8600	C7—H7A	0.9600
N1—H1A	0.8600	C7—H7B	0.9600
C1—C2	1.377 (3)	C8—H8	0.9800
C1—C8	1.521 (2)	C15—H15B	0.9700
C1—C6	1.386 (2)	C15—H15A	0.9700
C2—C3	1.388 (3)	C16—H16A	0.9700
C3—C4	1.379 (3)	C16—H16B	0.9700
C4—C5	1.379 (3)	C17—H17B	0.9700
C5—C6	1.376 (3)	C17—H17A	0.9700
C8—C13	1.499 (2)	C18—C19	1.417 (7)
C8—C9	1.511 (2)	C18—H18A	0.9700
C9—C10	1.354 (2)	C18—H18B	0.9700
C9—C11	1.410 (3)	C19—H19A	0.9700
C12—C13	1.338 (2)	C19—H19B	0.9700
C12—C17	1.491 (3)
C4—O1—C7	117.78 (19)	C2—C3—H3	120.00
C10—O2—C12	118.91 (14)	C6—C5—H5	120.00
C18—O4—C19i	108.6 (3)	C4—C5—H5	120.00
H1A—N1—H1B	120.00	C1—C6—H6	120.00
C10—N1—H1B	120.00	C5—C6—H6	120.00
C10—N1—H1A	120.00	O1—C7—H7A	109.00
C2—C1—C6	117.77 (17)	O1—C7—H7B	109.00
C6—C1—C8	119.84 (15)	H7A—C7—H7B	109.00
C2—C1—C8	122.37 (15)	H7A—C7—H7C	109.00
C1—C2—C3	121.88 (19)	H7B—C7—H7C	110.00
C2—C3—C4	119.41 (19)	O1—C7—H7C	109.00
O1—C4—C5	116.23 (19)	C9—C8—H8	108.00
C3—C4—C5	119.3 (2)	C13—C8—H8	108.00
O1—C4—C3	124.49 (19)	C1—C8—H8	108.00
C4—C5—C6	120.73 (19)	C14—C15—H15B	109.00
C1—C6—C5	120.93 (18)	C16—C15—H15A	109.00
C9—C8—C13	108.63 (14)	C16—C15—H15B	109.00
C1—C8—C13	112.38 (14)	H15A—C15—H15B	108.00
C1—C8—C9	111.95 (13)	C14—C15—H15A	109.00
C8—C9—C10	122.54 (15)	C15—C16—H16B	109.00
C10—C9—C11	119.42 (16)	C17—C16—H16A	109.00
C8—C9—C11	118.00 (14)	C15—C16—H16A	109.00
O2—C10—N1	110.30 (15)	H16A—C16—H16B	108.00
N1—C10—C9	128.22 (17)	C17—C16—H16B	109.00
O2—C10—C9	121.48 (15)	C12—C17—H17A	110.00
N2—C11—C9	177.6 (2)	C12—C17—H17B	110.00
O2—C12—C13	122.91 (15)	C16—C17—H17B	110.00
C13—C12—C17	125.75 (17)	H17A—C17—H17B	108.00
O2—C12—C17	111.34 (16)	C16—C17—H17A	110.00
C8—C13—C14	118.19 (14)	O4—C18—C19	110.9 (4)
C8—C13—C12	122.27 (15)	O4i—C19—C18	110.8 (4)
C12—C13—C14	119.54 (15)	O4—C18—H18A	109.00
C13—C14—C15	117.57 (16)	O4—C18—H18B	109.00
O3—C14—C13	121.28 (16)	C19—C18—H18A	109.00
O3—C14—C15	121.11 (17)	C19—C18—H18B	109.00
C14—C15—C16	112.24 (17)	H18A—C18—H18B	108.00
C15—C16—C17	111.57 (18)	C18—C19—H19A	109.00
C12—C17—C16	110.51 (18)	C18—C19—H19B	109.00
C1—C2—H2	119.00	H19A—C19—H19B	108.00
C3—C2—H2	119.00	O4i—C19—H19A	109.00
C4—C3—H3	120.00	O4i—C19—H19B	110.00
C7—O1—C4—C3	−9.3 (3)	C1—C8—C9—C10	105.99 (18)
C7—O1—C4—C5	171.1 (2)	C1—C8—C9—C11	−71.4 (2)
C10—O2—C12—C17	171.59 (15)	C9—C8—C13—C14	−161.46 (15)
C12—O2—C10—N1	−172.95 (15)	C1—C8—C13—C14	74.12 (19)
C10—O2—C12—C13	−8.8 (2)	C9—C8—C13—C12	17.3 (2)
C12—O2—C10—C9	7.4 (2)	C11—C9—C10—N1	5.4 (3)
C18i—O4i—C19—C18	−58.0 (5)	C8—C9—C10—O2	7.6 (3)
C19i—O4—C18—C19	−58.0 (5)	C8—C9—C10—N1	−172.00 (17)
C8—C1—C2—C3	178.46 (19)	C11—C9—C10—O2	−175.05 (16)
C8—C1—C6—C5	−178.09 (17)	C17—C12—C13—C8	174.55 (17)
C2—C1—C6—C5	0.2 (3)	C17—C12—C13—C14	−6.7 (3)
C2—C1—C8—C9	−87.6 (2)	O2—C12—C17—C16	162.26 (16)
C2—C1—C8—C13	34.9 (2)	C13—C12—C17—C16	−17.3 (3)
C6—C1—C8—C9	90.63 (19)	O2—C12—C13—C14	173.82 (15)
C6—C1—C8—C13	−146.80 (16)	O2—C12—C13—C8	−5.0 (3)
C6—C1—C2—C3	0.2 (3)	C12—C13—C14—O3	−178.26 (18)
C1—C2—C3—C4	0.0 (3)	C8—C13—C14—O3	0.6 (3)
C2—C3—C4—C5	−0.5 (3)	C12—C13—C14—C15	−0.5 (3)
C2—C3—C4—O1	179.8 (2)	C8—C13—C14—C15	178.31 (16)
O1—C4—C5—C6	−179.37 (19)	O3—C14—C15—C16	−151.3 (2)
C3—C4—C5—C6	1.0 (3)	C13—C14—C15—C16	31.0 (3)
C4—C5—C6—C1	−0.8 (3)	C14—C15—C16—C17	−54.6 (2)
C13—C8—C9—C11	163.92 (15)	C15—C16—C17—C12	46.9 (2)
C1—C8—C13—C12	−107.09 (18)	O4—C18—C19—O4i	59.3 (5)
C13—C8—C9—C10	−18.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ii	0.86	2.27	3.123 (3)	171
N1—H1B···O3iii	0.86	2.10	2.945 (2)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	2.27	3.123 (3)	171
N1—H1B⋯O3ii	0.86	2.10	2.945 (2)	167

Symmetry codes: (i) ; (ii) .