Crystal structure of 3-amino-1-(4-meth-oxy-phen-yl)-1H-benzo[f]chromene-2-carbo-nitrile.

In the title compound, C21H16N2O2, the meth-oxy-benzene ring is almost perpendicular to the mean plane of the naphthalene ring system, making a dihedral angle of 83.62 (5)°. The 4H-pyran ring fused with the naphthalene ring system is almost planar [maximum deviation = 0.033 (1) Å]. In the crystal, mol-ecules are linked into inversion dimers by pairs of N-H⋯N hydrogen bonds. N-H⋯O hydrogen bonds connect the dimers, forming a helical supra-molecular chain along the a-axis direction. The crystal packing also features C-H⋯π inter-actions.

Related literature

For the biological inter­est of benzochromene derivatives, see: Gourdeau et al. (2004 ▸); Sangani et al. (2012 ▸); Cheng et al. (2003 ▸); Kamal et al. (2012 ▸); Denish et al. (2012 ▸); Nitin et al.. (2012 ▸); Bhat et al. (2008 ▸). For a similar structure, see: Akkurt et al. (2013 ▸).

Experimental

Crystal data

C21H16N2O2

M = 328.36

Monoclinic,

a = 20.6017 (14) Å

b = 6.1461 (4) Å

c = 25.9689 (16) Å

β = 94.332 (4)°

V = 3278.8 (4) Å3

Z = 8

Cu Kα radiation

μ = 0.70 mm−1

T = 100 K

0.38 × 0.23 × 0.13 mm

Data collection

Rigaku AFC11 diffractometer

Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▸) T min = 0.910, T max = 1.000

12941 measured reflections

2914 independent reflections

2832 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.03

2914 reflections

236 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.23 e Å−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/S2056989015011020/hg5445sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011020/hg5445Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015011020/hg5445Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015011020/hg5445fig1.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/S2056989015011020/hg5445fig2.tif

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

CCDC reference: 1405398

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

C21H16N2O2	F(000) = 1376
Mr = 328.36	Dx = 1.330 Mg m−3
Monoclinic, I2/a	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -I 2ya	Cell parameters from 15816 reflections
a = 20.6017 (14) Å	θ = 2.6–68.3°
b = 6.1461 (4) Å	µ = 0.70 mm−1
c = 25.9689 (16) Å	T = 100 K
β = 94.332 (4)°	Prism, colourless
V = 3278.8 (4) Å3	0.38 × 0.23 × 0.13 mm
Z = 8

Rigaku AFC11 diffractometer	2914 independent reflections
Radiation source: Rotating Anode	2832 reflections with I > 2σ(I)
Detector resolution: 22.2222 pixels mm-1	Rint = 0.037
profile data from ω–scans	θmax = 68.2°, θmin = 3.4°
Absorption correction: multi-scan (CrystalClearSM Expert; Rigaku, 2012)	h = −24→24
Tmin = 0.910, Tmax = 1.000	k = −5→7
12941 measured reflections	l = −31→24

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)] = 0.041	w = 1/[σ2(Fo2) + (0.0752P)2 + 2.3851P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.31 e Å−3
2914 reflections	Δρmin = −0.23 e Å−3
236 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
0 restraints	Extinction coefficient: 0.0014 (2)

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	0.46524 (4)	1.06769 (14)	0.61312 (3)	0.0180 (2)
O2	0.82346 (4)	0.82919 (15)	0.54600 (3)	0.0243 (3)
N1	0.43089 (5)	0.85280 (19)	0.54736 (4)	0.0229 (3)
N2	0.54448 (5)	0.39845 (17)	0.54907 (4)	0.0212 (3)
C1	0.47727 (6)	0.88455 (19)	0.58585 (5)	0.0171 (3)
C2	0.52947 (6)	0.75466 (19)	0.59874 (5)	0.0172 (3)
C3	0.58264 (6)	0.80882 (19)	0.64036 (4)	0.0166 (3)
C4	0.56459 (6)	1.01315 (19)	0.66861 (4)	0.0166 (3)
C5	0.60414 (6)	1.0884 (2)	0.71278 (5)	0.0184 (3)
C6	0.65975 (6)	0.9729 (2)	0.73361 (5)	0.0233 (4)
C7	0.69636 (7)	1.0479 (3)	0.77625 (5)	0.0303 (4)
C8	0.68002 (7)	1.2444 (3)	0.80039 (5)	0.0301 (4)
C9	0.62635 (6)	1.3586 (2)	0.78173 (5)	0.0245 (4)
C10	0.58687 (6)	1.2843 (2)	0.73818 (5)	0.0190 (3)
C11	0.52962 (6)	1.39706 (19)	0.71978 (5)	0.0189 (3)
C12	0.49085 (6)	1.3200 (2)	0.67886 (5)	0.0181 (3)
C13	0.50912 (6)	1.12794 (19)	0.65376 (4)	0.0164 (3)
C14	0.53658 (5)	0.5592 (2)	0.57068 (4)	0.0170 (3)
C15	0.64862 (5)	0.8191 (2)	0.61700 (4)	0.0162 (3)
C16	0.68716 (6)	0.6343 (2)	0.61775 (5)	0.0192 (3)
C17	0.74603 (6)	0.6302 (2)	0.59448 (5)	0.0204 (3)
C18	0.76660 (6)	0.8158 (2)	0.57027 (5)	0.0189 (3)
C19	0.72851 (6)	1.0035 (2)	0.56930 (5)	0.0198 (3)
C20	0.66979 (6)	1.0046 (2)	0.59208 (4)	0.0180 (3)
C21	0.85852 (6)	0.6305 (2)	0.53986 (6)	0.0306 (4)
H1A	0.4404 (8)	0.772 (3)	0.5202 (7)	0.031 (4)*
H1B	0.3976 (8)	0.948 (3)	0.5451 (6)	0.028 (4)*
H3	0.58470	0.68680	0.66590	0.0200*
H6	0.67180	0.84130	0.71770	0.0280*
H7	0.73310	0.96680	0.78970	0.0360*
H8	0.70620	1.29690	0.82940	0.0360*
H9	0.61530	1.49000	0.79820	0.0290*
H11	0.51810	1.52820	0.73620	0.0230*
H12	0.45200	1.39460	0.66740	0.0220*
H16	0.67320	0.50720	0.63450	0.0230*
H17	0.77170	0.50160	0.59520	0.0250*
H19	0.74290	1.13120	0.55290	0.0240*
H20	0.64380	1.13240	0.59070	0.0220*
H21A	0.83040	0.52570	0.52050	0.0460*
H21B	0.87210	0.57030	0.57390	0.0460*
H21C	0.89700	0.65970	0.52100	0.0460*

	U11	U22	U33	U12	U13	U23
O1	0.0168 (4)	0.0180 (4)	0.0191 (4)	0.0025 (3)	0.0012 (3)	−0.0031 (3)
O2	0.0162 (4)	0.0278 (5)	0.0297 (5)	−0.0001 (4)	0.0079 (4)	−0.0048 (4)
N1	0.0184 (5)	0.0256 (6)	0.0243 (6)	0.0045 (4)	−0.0010 (4)	−0.0081 (5)
N2	0.0229 (5)	0.0203 (6)	0.0204 (5)	0.0018 (4)	0.0015 (4)	−0.0013 (4)
C1	0.0171 (6)	0.0171 (6)	0.0176 (6)	−0.0016 (4)	0.0052 (4)	−0.0018 (4)
C2	0.0169 (6)	0.0171 (6)	0.0179 (6)	−0.0010 (5)	0.0039 (4)	−0.0010 (5)
C3	0.0166 (6)	0.0169 (6)	0.0163 (6)	−0.0003 (4)	0.0023 (4)	0.0006 (5)
C4	0.0167 (6)	0.0177 (6)	0.0159 (6)	−0.0012 (5)	0.0055 (4)	0.0013 (5)
C5	0.0188 (6)	0.0204 (6)	0.0165 (6)	−0.0013 (5)	0.0049 (5)	0.0009 (5)
C6	0.0238 (6)	0.0262 (7)	0.0199 (6)	0.0044 (5)	0.0010 (5)	−0.0027 (5)
C7	0.0255 (7)	0.0398 (8)	0.0248 (7)	0.0073 (6)	−0.0039 (5)	−0.0037 (6)
C8	0.0283 (7)	0.0398 (8)	0.0213 (6)	−0.0005 (6)	−0.0041 (5)	−0.0086 (6)
C9	0.0268 (7)	0.0261 (7)	0.0210 (6)	−0.0020 (5)	0.0045 (5)	−0.0057 (5)
C10	0.0209 (6)	0.0199 (6)	0.0170 (6)	−0.0026 (5)	0.0063 (5)	−0.0003 (5)
C11	0.0231 (6)	0.0164 (6)	0.0180 (6)	−0.0017 (5)	0.0078 (5)	−0.0003 (5)
C12	0.0183 (6)	0.0179 (6)	0.0188 (6)	0.0010 (5)	0.0062 (5)	0.0025 (5)
C13	0.0170 (6)	0.0183 (6)	0.0143 (5)	−0.0022 (4)	0.0038 (4)	0.0015 (4)
C14	0.0156 (6)	0.0197 (6)	0.0160 (6)	−0.0003 (4)	0.0024 (4)	0.0019 (5)
C15	0.0149 (6)	0.0189 (6)	0.0146 (5)	−0.0004 (4)	−0.0001 (4)	−0.0024 (4)
C16	0.0199 (6)	0.0165 (6)	0.0213 (6)	0.0000 (5)	0.0015 (5)	0.0007 (5)
C17	0.0178 (6)	0.0194 (6)	0.0240 (6)	0.0046 (5)	0.0008 (5)	−0.0031 (5)
C18	0.0139 (5)	0.0257 (6)	0.0172 (6)	−0.0013 (5)	0.0019 (4)	−0.0053 (5)
C19	0.0213 (6)	0.0181 (6)	0.0203 (6)	−0.0025 (5)	0.0031 (5)	0.0001 (5)
C20	0.0185 (6)	0.0163 (6)	0.0192 (6)	0.0022 (4)	0.0016 (4)	−0.0016 (5)
C21	0.0197 (6)	0.0321 (8)	0.0410 (8)	0.0025 (5)	0.0089 (6)	−0.0137 (6)

O1—C1	1.3625 (15)	C11—C12	1.3650 (18)
O1—C13	1.3871 (14)	C12—C13	1.4132 (17)
O2—C18	1.3740 (15)	C15—C20	1.3970 (17)
O2—C21	1.4338 (15)	C15—C16	1.3851 (17)
N1—C1	1.3438 (16)	C16—C17	1.3955 (18)
N2—C14	1.1538 (16)	C17—C18	1.3843 (18)
C1—C2	1.3607 (17)	C18—C19	1.3944 (17)
N1—H1B	0.900 (17)	C19—C20	1.3862 (17)
N1—H1A	0.896 (18)	C3—H3	1.0000
C2—C14	1.4184 (17)	C6—H6	0.9500
C2—C3	1.5166 (17)	C7—H7	0.9500
C3—C4	1.5149 (16)	C8—H8	0.9500
C3—C15	1.5311 (16)	C9—H9	0.9500
C4—C13	1.3733 (17)	C11—H11	0.9500
C4—C5	1.4326 (17)	C12—H12	0.9500
C5—C10	1.4307 (18)	C16—H16	0.9500
C5—C6	1.4197 (18)	C17—H17	0.9500
C6—C7	1.3716 (19)	C19—H19	0.9500
C7—C8	1.413 (2)	C20—H20	0.9500
C8—C9	1.367 (2)	C21—H21A	0.9800
C9—C10	1.4178 (18)	C21—H21B	0.9800
C10—C11	1.4194 (18)	C21—H21C	0.9800
C1—O1—C13	118.84 (9)	C15—C16—C17	121.65 (11)
C18—O2—C21	117.01 (10)	C16—C17—C18	119.19 (11)
O1—C1—N1	111.07 (10)	O2—C18—C19	116.12 (11)
O1—C1—C2	121.89 (11)	O2—C18—C17	123.96 (11)
N1—C1—C2	127.02 (12)	C17—C18—C19	119.92 (12)
H1A—N1—H1B	121.3 (15)	C18—C19—C20	120.29 (11)
C1—N1—H1A	118.7 (11)	C15—C20—C19	120.45 (11)
C1—N1—H1B	116.7 (11)	C2—C3—H3	107.00
C1—C2—C3	124.15 (11)	C4—C3—H3	107.00
C1—C2—C14	118.75 (11)	C15—C3—H3	107.00
C3—C2—C14	117.06 (10)	C5—C6—H6	119.00
C2—C3—C4	109.67 (10)	C7—C6—H6	119.00
C4—C3—C15	114.55 (10)	C6—C7—H7	120.00
C2—C3—C15	109.98 (9)	C8—C7—H7	120.00
C5—C4—C13	118.03 (10)	C7—C8—H8	120.00
C3—C4—C5	120.65 (10)	C9—C8—H8	120.00
C3—C4—C13	121.29 (10)	C8—C9—H9	119.00
C4—C5—C6	122.51 (11)	C10—C9—H9	119.00
C4—C5—C10	119.65 (11)	C10—C11—H11	119.00
C6—C5—C10	117.83 (11)	C12—C11—H11	119.00
C5—C6—C7	121.22 (12)	C11—C12—H12	120.00
C6—C7—C8	120.70 (13)	C13—C12—H12	120.00
C7—C8—C9	119.67 (13)	C15—C16—H16	119.00
C8—C9—C10	121.15 (12)	C17—C16—H16	119.00
C5—C10—C9	119.42 (11)	C16—C17—H17	120.00
C5—C10—C11	119.01 (11)	C18—C17—H17	120.00
C9—C10—C11	121.56 (11)	C18—C19—H19	120.00
C10—C11—C12	121.01 (11)	C20—C19—H19	120.00
C11—C12—C13	119.23 (11)	C15—C20—H20	120.00
C4—C13—C12	123.00 (11)	C19—C20—H20	120.00
O1—C13—C12	113.14 (10)	O2—C21—H21A	109.00
O1—C13—C4	123.86 (10)	O2—C21—H21B	109.00
N2—C14—C2	177.37 (12)	O2—C21—H21C	109.00
C3—C15—C16	119.06 (10)	H21A—C21—H21B	109.00
C3—C15—C20	122.33 (10)	H21A—C21—H21C	109.00
C16—C15—C20	118.49 (10)	H21B—C21—H21C	109.00
C13—O1—C1—N1	−178.67 (10)	C5—C4—C13—O1	−177.22 (10)
C13—O1—C1—C2	2.86 (17)	C5—C4—C13—C12	2.37 (18)
C1—O1—C13—C4	−0.19 (16)	C4—C5—C6—C7	−179.38 (13)
C1—O1—C13—C12	−179.81 (10)	C10—C5—C6—C7	−0.91 (19)
C21—O2—C18—C17	8.50 (17)	C4—C5—C10—C9	−179.71 (11)
C21—O2—C18—C19	−171.07 (11)	C4—C5—C10—C11	1.72 (18)
O1—C1—C2—C3	−6.34 (19)	C6—C5—C10—C9	1.78 (18)
O1—C1—C2—C14	175.95 (11)	C6—C5—C10—C11	−176.80 (12)
N1—C1—C2—C3	175.45 (12)	C5—C6—C7—C8	−0.7 (2)
N1—C1—C2—C14	−2.3 (2)	C6—C7—C8—C9	1.4 (2)
C1—C2—C3—C4	6.28 (16)	C7—C8—C9—C10	−0.5 (2)
C1—C2—C3—C15	−120.55 (13)	C8—C9—C10—C5	−1.10 (19)
C14—C2—C3—C4	−175.97 (10)	C8—C9—C10—C11	177.44 (13)
C14—C2—C3—C15	57.20 (14)	C5—C10—C11—C12	0.73 (19)
C2—C3—C4—C5	174.52 (11)	C9—C10—C11—C12	−177.82 (12)
C2—C3—C4—C13	−3.53 (15)	C10—C11—C12—C13	−1.63 (19)
C15—C3—C4—C5	−61.27 (14)	C11—C12—C13—O1	179.67 (11)
C15—C3—C4—C13	120.68 (12)	C11—C12—C13—C4	0.03 (19)
C2—C3—C15—C16	−93.24 (12)	C3—C15—C16—C17	176.32 (11)
C2—C3—C15—C20	82.78 (13)	C20—C15—C16—C17	0.14 (18)
C4—C3—C15—C16	142.72 (11)	C3—C15—C20—C19	−176.89 (10)
C4—C3—C15—C20	−41.26 (14)	C16—C15—C20—C19	−0.85 (17)
C3—C4—C5—C6	−2.87 (18)	C15—C16—C17—C18	0.34 (19)
C3—C4—C5—C10	178.69 (11)	C16—C17—C18—O2	−179.67 (11)
C13—C4—C5—C6	175.25 (12)	C16—C17—C18—C19	−0.12 (19)
C13—C4—C5—C10	−3.20 (17)	O2—C18—C19—C20	179.00 (11)
C3—C4—C13—O1	0.88 (17)	C17—C18—C19—C20	−0.59 (19)
C3—C4—C13—C12	−179.53 (11)	C18—C19—C20—C15	1.08 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.896 (18)	2.125 (18)	3.0174 (15)	173.8 (16)
N1—H1B···O2ii	0.900 (17)	2.053 (17)	2.9509 (14)	175.5 (14)
C11—H11···Cg2iii	0.95	2.56	3.3913 (14)	147

Table 1

Hydrogen-bond geometry (, )

Cg2 is the centroid of the C4/C5/C10C13 ring.

DHA	DH	HA	D A	DHA
N1H1AN2i	0.896(18)	2.125(18)	3.0174(15)	173.8(16)
N1H1BO2ii	0.900(17)	2.053(17)	2.9509(14)	175.5(14)
C11H11Cg2iii	0.95	2.56	3.3913(14)	147

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