Crystal structure of 2-amino-4-phenyl-4H-benzo[h]chromene-3-carbo-nitrile.

In the title compound, C20H14N2O, the plane of the phenyl ring is almost normal to that of the naphthalene ring system, forming a dihedral angle of 83.15 (8)°. The 4H-pyran ring fused with the naphthalene ring system has a flattened boat conformation. In the crystal, mol-ecules are linked by pairs of N-H⋯N hydrogen bonds, forming inversion dimers with an R 2 (2)(12) ring motif. The dimers are connected by C-H⋯π inter-actions, forming supra-molecular chains along [010].

Related literature

For synthesis of chromene-containing compounds, see: Elagamey et al. (1988 ▸); El-Maghraby (2014 ▸). For industrial applications of amino­chromenes, see: Ellis (1977 ▸); Hafez et al. (1987 ▸). For various biological activities of fused chromenes, see: Hiramoto et al. (1997 ▸); Bianchi & Tava (1987 ▸); Eiden & Denk (1991 ▸); Smith et al. (1998 ▸); Taylor et al. (1998 ▸). For the crystal structure of the isomer of the title compound, 3-amino-1-phenyl-1H-benzo[f]chromene-2-carbo­nitrile, see: Akkurt et al. (2013 ▸).

Experimental

Crystal data

C20H14N2O

M = 298.33

Monoclinic,

a = 9.1662 (1) Å

b = 5.7246 (1) Å

c = 13.9177 (2) Å

β = 90.153 (1)°

V = 730.30 (2) Å3

Z = 2

Cu Kα radiation

μ = 0.67 mm−1

T = 100 K

0.28 × 0.13 × 0.10 mm

Data collection

Rigaku AFC11 diffractometer

Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▸) T min = 0.883, T max = 1.000

5778 measured reflections

2201 independent reflections

2184 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.093

S = 1.09

2201 reflections

216 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack x determined using 775 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)

Absolute structure parameter: 0.2 (3)

Data collection: CrystalClearSM Expert (Rigaku, 2012 ▸); cell refinement: CrystalClearSM Expert; data reduction: CrystalClearSM Expert; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011536/tk5369sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011536/tk5369Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015011536/tk5369Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015011536/tk5369fig1.tif

View of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015011536/tk5369fig2.tif

View of the dimers formed by N—H⋯O hydrogen bonds.

CCDC reference: 1406770

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H14N2O	F(000) = 312
Mr = 298.33	Dx = 1.357 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 5573 reflections
a = 9.1662 (1) Å	θ = 6.3–66.6°
b = 5.7246 (1) Å	µ = 0.67 mm−1
c = 13.9177 (2) Å	T = 100 K
β = 90.153 (1)°	Block, brown
V = 730.30 (2) Å3	0.28 × 0.13 × 0.10 mm
Z = 2

Rigaku AFC11 diffractometer	2201 independent reflections
Radiation source: Rotating Anode	2184 reflections with I > 2σ(I)
Detector resolution: 22.2222 pixels mm-1	Rint = 0.029
profile data from ω–scans	θmax = 66.7°, θmin = 4.8°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	h = −10→10
Tmin = 0.883, Tmax = 1.000	k = −6→6
5778 measured reflections	l = −16→16

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.031	w = 1/[σ2(FO2) + (0.0642P)2 + 0.1186P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.14 e Å−3
2201 reflections	Δρmin = −0.15 e Å−3
216 parameters	Absolute structure: Flack x determined using 775 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.2 (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	0.64120 (15)	0.8755 (3)	0.32053 (9)	0.0250 (4)
N1	0.5228 (2)	0.9831 (4)	0.18837 (13)	0.0279 (6)
N2	0.58898 (19)	0.5238 (4)	0.01142 (12)	0.0305 (6)
C1	0.6097 (2)	0.8195 (4)	0.22720 (13)	0.0223 (5)
C2	0.6647 (2)	0.6252 (4)	0.18462 (14)	0.0228 (6)
C3	0.7792 (2)	0.4700 (4)	0.23142 (13)	0.0222 (6)
C4	0.7851 (2)	0.5235 (4)	0.33777 (13)	0.0225 (6)
C5	0.8612 (2)	0.3703 (4)	0.40074 (14)	0.0264 (6)
C6	0.8631 (2)	0.4068 (4)	0.49782 (15)	0.0286 (6)
C7	0.7877 (2)	0.5997 (4)	0.53815 (14)	0.0255 (6)
C8	0.7844 (2)	0.6408 (5)	0.63859 (14)	0.0297 (6)
C9	0.7137 (2)	0.8309 (5)	0.67554 (14)	0.0301 (6)
C10	0.6403 (2)	0.9868 (5)	0.61433 (15)	0.0307 (6)
C11	0.6388 (2)	0.9514 (4)	0.51680 (14)	0.0275 (6)
C12	0.7134 (2)	0.7592 (4)	0.47686 (14)	0.0239 (6)
C13	0.7165 (2)	0.7126 (4)	0.37642 (13)	0.0226 (6)
C14	0.6217 (2)	0.5720 (4)	0.08901 (13)	0.0241 (6)
C15	0.9263 (2)	0.4943 (4)	0.18151 (13)	0.0222 (6)
C16	0.9754 (2)	0.3182 (4)	0.12136 (13)	0.0261 (6)
C17	1.1057 (2)	0.3423 (5)	0.07107 (14)	0.0301 (6)
C18	1.1876 (2)	0.5433 (5)	0.08102 (14)	0.0301 (6)
C19	1.1396 (2)	0.7208 (5)	0.14112 (14)	0.0293 (6)
C20	1.0097 (2)	0.6961 (4)	0.19070 (14)	0.0260 (6)
H1A	0.474 (3)	1.088 (5)	0.2297 (18)	0.034 (7)*
H1B	0.501 (3)	0.971 (6)	0.125 (2)	0.040 (7)*
H3	0.74660	0.30430	0.22390	0.0270*
H5	0.91180	0.24000	0.37480	0.0320*
H6	0.91520	0.30260	0.53850	0.0340*
H8	0.83200	0.53470	0.68080	0.0360*
H9	0.71420	0.85760	0.74290	0.0360*
H10	0.59130	1.11800	0.64070	0.0370*
H11	0.58740	1.05650	0.47620	0.0330*
H16	0.91940	0.17950	0.11430	0.0310*
H17	1.13830	0.22050	0.03000	0.0360*
H18	1.27650	0.56020	0.04680	0.0360*
H19	1.19580	0.85910	0.14820	0.0350*
H20	0.97710	0.81850	0.23150	0.0310*

	U11	U22	U33	U12	U13	U23
O1	0.0306 (8)	0.0258 (8)	0.0186 (6)	0.0031 (7)	−0.0059 (5)	−0.0008 (6)
N1	0.0309 (9)	0.0322 (11)	0.0205 (9)	0.0045 (9)	−0.0056 (7)	−0.0012 (8)
N2	0.0297 (9)	0.0375 (12)	0.0243 (9)	0.0007 (9)	−0.0046 (7)	−0.0041 (8)
C1	0.0219 (9)	0.0273 (11)	0.0178 (8)	−0.0041 (9)	−0.0026 (7)	0.0026 (8)
C2	0.0202 (9)	0.0293 (12)	0.0190 (9)	−0.0025 (9)	−0.0022 (7)	0.0002 (8)
C3	0.0226 (9)	0.0205 (10)	0.0236 (10)	−0.0015 (9)	−0.0021 (7)	−0.0009 (8)
C4	0.0191 (9)	0.0272 (12)	0.0213 (9)	−0.0039 (8)	−0.0007 (7)	0.0010 (8)
C5	0.0249 (9)	0.0270 (12)	0.0272 (10)	0.0003 (10)	0.0001 (7)	0.0025 (9)
C6	0.0276 (10)	0.0325 (13)	0.0256 (10)	−0.0010 (10)	−0.0044 (8)	0.0074 (9)
C7	0.0220 (9)	0.0321 (12)	0.0223 (9)	−0.0050 (9)	−0.0013 (7)	0.0029 (9)
C8	0.0259 (10)	0.0414 (14)	0.0219 (9)	−0.0058 (10)	−0.0031 (8)	0.0058 (9)
C9	0.0275 (10)	0.0427 (14)	0.0200 (9)	−0.0106 (11)	0.0002 (7)	−0.0028 (10)
C10	0.0296 (10)	0.0356 (13)	0.0268 (10)	−0.0044 (11)	0.0024 (8)	−0.0060 (9)
C11	0.0280 (10)	0.0298 (12)	0.0246 (10)	−0.0018 (10)	−0.0018 (8)	−0.0021 (9)
C12	0.0202 (9)	0.0301 (12)	0.0214 (9)	−0.0064 (9)	−0.0012 (7)	0.0006 (8)
C13	0.0214 (9)	0.0251 (11)	0.0213 (9)	−0.0029 (9)	−0.0031 (7)	0.0036 (8)
C14	0.0226 (9)	0.0263 (11)	0.0235 (10)	−0.0010 (9)	0.0001 (7)	0.0003 (9)
C15	0.0227 (10)	0.0265 (11)	0.0173 (8)	0.0004 (9)	−0.0025 (7)	0.0029 (8)
C16	0.0301 (10)	0.0250 (12)	0.0231 (9)	0.0024 (10)	−0.0032 (7)	−0.0016 (8)
C17	0.0319 (11)	0.0346 (13)	0.0238 (9)	0.0069 (10)	0.0008 (7)	−0.0020 (10)
C18	0.0245 (10)	0.0429 (14)	0.0230 (9)	0.0041 (10)	0.0002 (7)	0.0067 (9)
C19	0.0264 (10)	0.0328 (12)	0.0286 (10)	−0.0040 (10)	−0.0030 (8)	0.0056 (9)
C20	0.0274 (10)	0.0263 (12)	0.0244 (10)	0.0001 (10)	−0.0001 (8)	−0.0024 (9)

O1—C1	1.368 (2)	C11—C12	1.410 (3)
O1—C13	1.396 (3)	C12—C13	1.424 (3)
N1—C1	1.342 (3)	C15—C20	1.391 (3)
N2—C14	1.154 (3)	C15—C16	1.386 (3)
C1—C2	1.358 (3)	C16—C17	1.393 (3)
N1—H1B	0.91 (3)	C17—C18	1.381 (4)
N1—H1A	0.95 (3)	C18—C19	1.388 (3)
C2—C14	1.420 (3)	C19—C20	1.385 (3)
C2—C3	1.520 (3)	C3—H3	1.0000
C3—C4	1.512 (3)	C5—H5	0.9500
C3—C15	1.525 (3)	C6—H6	0.9500
C4—C13	1.363 (3)	C8—H8	0.9500
C4—C5	1.422 (3)	C9—H9	0.9500
C5—C6	1.367 (3)	C10—H10	0.9500
C6—C7	1.419 (3)	C11—H11	0.9500
C7—C12	1.422 (3)	C16—H16	0.9500
C7—C8	1.418 (3)	C17—H17	0.9500
C8—C9	1.368 (4)	C18—H18	0.9500
C9—C10	1.404 (3)	C19—H19	0.9500
C10—C11	1.373 (3)	C20—H20	0.9500
C1—O1—C13	118.39 (17)	C3—C15—C20	121.36 (18)
O1—C1—N1	110.02 (18)	C16—C15—C20	118.70 (17)
O1—C1—C2	121.91 (18)	C15—C16—C17	120.8 (2)
N1—C1—C2	128.06 (18)	C16—C17—C18	119.9 (2)
C1—N1—H1B	118 (2)	C17—C18—C19	119.82 (18)
H1A—N1—H1B	123 (3)	C18—C19—C20	120.0 (2)
C1—N1—H1A	118.7 (16)	C15—C20—C19	120.8 (2)
C1—C2—C3	123.25 (17)	C2—C3—H3	108.00
C1—C2—C14	118.83 (19)	C4—C3—H3	108.00
C3—C2—C14	117.76 (18)	C15—C3—H3	108.00
C2—C3—C15	111.21 (16)	C4—C5—H5	119.00
C4—C3—C15	113.46 (15)	C6—C5—H5	119.00
C2—C3—C4	108.89 (17)	C5—C6—H6	120.00
C3—C4—C13	122.12 (18)	C7—C6—H6	120.00
C3—C4—C5	119.65 (19)	C7—C8—H8	120.00
C5—C4—C13	118.21 (17)	C9—C8—H8	120.00
C4—C5—C6	121.3 (2)	C8—C9—H9	120.00
C5—C6—C7	120.32 (19)	C10—C9—H9	120.00
C8—C7—C12	118.3 (2)	C9—C10—H10	120.00
C6—C7—C8	122.1 (2)	C11—C10—H10	120.00
C6—C7—C12	119.69 (18)	C10—C11—H11	120.00
C7—C8—C9	120.9 (2)	C12—C11—H11	120.00
C8—C9—C10	120.29 (19)	C15—C16—H16	120.00
C9—C10—C11	120.6 (2)	C17—C16—H16	120.00
C10—C11—C12	120.1 (2)	C16—C17—H17	120.00
C11—C12—C13	122.97 (19)	C18—C17—H17	120.00
C7—C12—C11	119.76 (18)	C17—C18—H18	120.00
C7—C12—C13	117.26 (19)	C19—C18—H18	120.00
O1—C13—C12	114.26 (18)	C18—C19—H19	120.00
O1—C13—C4	122.59 (16)	C20—C19—H19	120.00
C4—C13—C12	123.14 (19)	C15—C20—H20	120.00
N2—C14—C2	178.3 (2)	C19—C20—H20	120.00
C3—C15—C16	119.85 (19)
C13—O1—C1—N1	172.70 (17)	C4—C5—C6—C7	0.3 (3)
C13—O1—C1—C2	−8.3 (3)	C5—C6—C7—C8	178.6 (2)
C1—O1—C13—C4	13.6 (3)	C5—C6—C7—C12	−1.8 (3)
C1—O1—C13—C12	−165.44 (17)	C6—C7—C8—C9	178.5 (2)
O1—C1—C2—C3	−7.7 (3)	C12—C7—C8—C9	−1.1 (3)
O1—C1—C2—C14	176.97 (18)	C6—C7—C12—C11	−179.80 (18)
N1—C1—C2—C3	171.1 (2)	C6—C7—C12—C13	1.3 (3)
N1—C1—C2—C14	−4.2 (3)	C8—C7—C12—C11	−0.2 (3)
C1—C2—C3—C4	16.6 (3)	C8—C7—C12—C13	−179.15 (19)
C1—C2—C3—C15	−109.1 (2)	C7—C8—C9—C10	1.3 (3)
C14—C2—C3—C4	−168.01 (18)	C8—C9—C10—C11	−0.2 (3)
C14—C2—C3—C15	66.3 (2)	C9—C10—C11—C12	−1.1 (3)
C2—C3—C4—C5	167.12 (18)	C10—C11—C12—C7	1.3 (3)
C2—C3—C4—C13	−11.3 (3)	C10—C11—C12—C13	−179.9 (2)
C15—C3—C4—C5	−68.5 (3)	C7—C12—C13—O1	179.84 (17)
C15—C3—C4—C13	113.1 (2)	C7—C12—C13—C4	0.8 (3)
C2—C3—C15—C16	−105.1 (2)	C11—C12—C13—O1	0.9 (3)
C2—C3—C15—C20	71.3 (2)	C11—C12—C13—C4	−178.1 (2)
C4—C3—C15—C16	131.7 (2)	C3—C15—C16—C17	176.54 (18)
C4—C3—C15—C20	−51.9 (3)	C20—C15—C16—C17	0.1 (3)
C3—C4—C5—C6	−176.86 (18)	C3—C15—C20—C19	−176.69 (18)
C13—C4—C5—C6	1.6 (3)	C16—C15—C20—C19	−0.3 (3)
C3—C4—C13—O1	−2.7 (3)	C15—C16—C17—C18	0.1 (3)
C3—C4—C13—C12	176.26 (18)	C16—C17—C18—C19	−0.1 (3)
C5—C4—C13—O1	178.81 (18)	C17—C18—C19—C20	−0.2 (3)
C5—C4—C13—C12	−2.2 (3)	C18—C19—C20—C15	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2i	0.91 (3)	2.09 (3)	2.970 (2)	163 (3)
C9—H9···Cg1ii	0.95	2.88	3.574 (2)	131

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the C15C20 phenyl ring.

DHA	DH	HA	D A	DHA
N1H1BN2i	0.91(3)	2.09(3)	2.970(2)	163(3)
C9H9Cg1ii	0.95	2.88	3.574(2)	131

Symmetry codes: (i) ; (ii) .