2-Amino-7,7-dimethyl-5-oxo-4-(p-tol-yl)-5,6,7,8-tetra-hydro-4H-chromene-3-carbonitrile.

In the title mol-ecule, C(19)H(20)N(2)O(2), the cyclo-hexene ring adopts a sofa conformation, while the pyran ring adopts a flattened boat conformation. In the crystal, mol-ecules are linked by N-H⋯N and N-H⋯O hydrogen bonds, forming a two-dimensional network parallel to (010).

Related literature

For background to compounds containing the 4H-pyran unit, see: Brahmachari (2010 ▶); Hatakeyama et al. (1988 ▶). For the biological activity of compounds containing a tetra­hydro­benzo[b]pyran ring system, see: Andreani & Lapi (1960 ▶); Bonsignore et al. (1993 ▶); Brahmachari (2011 ▶); Konkoy et al. (2001 ▶). For 2-amino-4H-pyrans as photoactive materials, see: Armetso et al. (1989 ▶). For the synthesis of related compounds, see: Jin et al. (2004 ▶); Balalaie et al. (2007 ▶). For related structures, see: Tu et al. (2001 ▶); Wang (2011 ▶). For ring conformations, see: Duax et al. (1975 ▶).

Experimental

Crystal data

C19H20N2O2

M = 308.37

Monoclinic,

a = 9.4622 (3) Å

b = 16.8820 (5) Å

c = 10.8301 (4) Å

β = 111.842 (4)°

V = 1605.82 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.862, T max = 1.000

18449 measured reflections

3149 independent reflections

2428 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.115

S = 1.05

3149 reflections

219 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812033570/lh5503sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033570/lh5503Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812033570/lh5503Isup3.cml

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

C19H20N2O2	F(000) = 656
Mr = 308.37	Dx = 1.276 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7806 reflections
a = 9.4622 (3) Å	θ = 3.6–29.1°
b = 16.8820 (5) Å	µ = 0.08 mm−1
c = 10.8301 (4) Å	T = 293 K
β = 111.842 (4)°	Block, white
V = 1605.82 (9) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3149 independent reflections
Radiation source: fine-focus sealed tube	2428 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.6°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −20→20
Tmin = 0.862, Tmax = 1.000	l = −13→13
18449 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0501P)2 + 0.4013P] where P = (Fo2 + 2Fc2)/3
3149 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Experimental. Absorption correction: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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	0.62616 (12)	0.12747 (6)	0.06792 (11)	0.0370 (3)
C1'	0.87094 (17)	0.17332 (9)	0.42111 (15)	0.0324 (4)
C2'	1.00784 (18)	0.14575 (11)	0.41998 (17)	0.0433 (4)
H2'	1.0343	0.1568	0.3472	0.052*
C3'	1.1067 (2)	0.10204 (11)	0.52474 (19)	0.0498 (5)
H3'	1.1978	0.0842	0.5206	0.060*
C4'	1.0732 (2)	0.08433 (10)	0.63476 (17)	0.0442 (4)
C5'	0.9371 (2)	0.11238 (11)	0.63673 (18)	0.0504 (5)
H5'	0.9118	0.1018	0.7103	0.060*
C6'	0.8370 (2)	0.15591 (11)	0.53232 (17)	0.0456 (4)
H6'	0.7459	0.1737	0.5367	0.055*
C7'	1.1810 (2)	0.03593 (13)	0.7475 (2)	0.0645 (6)
H7'1	1.1854	−0.0172	0.7175	0.097*
H7'2	1.1456	0.0350	0.8199	0.097*
H7'3	1.2807	0.0592	0.7770	0.097*
C2	0.74563 (17)	0.17699 (9)	0.07890 (15)	0.0324 (4)
C3	0.80680 (17)	0.22511 (9)	0.18489 (15)	0.0325 (4)
C4	0.75981 (17)	0.22126 (9)	0.30428 (15)	0.0325 (4)
H4	0.7564	0.2755	0.3353	0.039*
O5	0.53082 (14)	0.26138 (8)	0.40897 (12)	0.0488 (3)
C5	0.49500 (18)	0.21056 (10)	0.32139 (16)	0.0372 (4)
C6	0.33944 (19)	0.17324 (11)	0.27258 (19)	0.0455 (4)
H6A	0.2688	0.2083	0.2076	0.055*
H6B	0.3062	0.1686	0.3469	0.055*
C7	0.33113 (18)	0.09159 (10)	0.20960 (17)	0.0386 (4)
C8	0.39789 (18)	0.09955 (11)	0.10153 (17)	0.0406 (4)
H8A	0.4110	0.0472	0.0705	0.049*
H8B	0.3267	0.1284	0.0267	0.049*
C9	0.54697 (16)	0.14144 (9)	0.14978 (15)	0.0321 (4)
C10	0.60023 (17)	0.18777 (9)	0.25695 (15)	0.0312 (4)
C11	0.4198 (2)	0.03164 (12)	0.3151 (2)	0.0568 (5)
H11A	0.5238	0.0486	0.3562	0.085*
H11B	0.4164	−0.0192	0.2743	0.085*
H11C	0.3752	0.0277	0.3813	0.085*
C12	0.1651 (2)	0.06452 (13)	0.1450 (2)	0.0579 (5)
H12A	0.1612	0.0141	0.1030	0.087*
H12B	0.1084	0.1027	0.0797	0.087*
H12C	0.1218	0.0598	0.2120	0.087*
N13	0.78732 (18)	0.16693 (10)	−0.02573 (15)	0.0432 (4)
C14	0.92224 (19)	0.27927 (10)	0.18699 (16)	0.0396 (4)
N15	1.01708 (19)	0.32308 (10)	0.19332 (17)	0.0578 (5)
H131	0.864 (2)	0.1956 (12)	−0.0300 (19)	0.055 (6)*
H132	0.716 (2)	0.1541 (12)	−0.101 (2)	0.059 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0355 (6)	0.0427 (6)	0.0391 (6)	−0.0084 (5)	0.0212 (5)	−0.0064 (5)
C1'	0.0317 (8)	0.0332 (8)	0.0311 (8)	−0.0050 (6)	0.0102 (6)	−0.0051 (6)
C2'	0.0344 (9)	0.0567 (11)	0.0404 (9)	0.0021 (8)	0.0159 (7)	0.0041 (8)
C3'	0.0340 (9)	0.0609 (12)	0.0502 (11)	0.0054 (8)	0.0108 (8)	0.0035 (9)
C4'	0.0430 (10)	0.0388 (10)	0.0396 (10)	−0.0060 (8)	0.0024 (8)	−0.0022 (7)
C5'	0.0597 (12)	0.0567 (12)	0.0361 (9)	−0.0019 (9)	0.0194 (9)	0.0032 (8)
C6'	0.0459 (10)	0.0552 (11)	0.0400 (10)	0.0052 (8)	0.0210 (8)	0.0014 (8)
C7'	0.0638 (13)	0.0584 (13)	0.0519 (12)	0.0001 (10)	−0.0010 (10)	0.0096 (10)
C2	0.0269 (7)	0.0373 (9)	0.0351 (8)	−0.0002 (6)	0.0139 (6)	0.0059 (7)
C3	0.0289 (8)	0.0349 (9)	0.0345 (8)	−0.0019 (6)	0.0127 (6)	0.0044 (6)
C4	0.0311 (8)	0.0311 (8)	0.0366 (8)	−0.0005 (6)	0.0141 (7)	−0.0034 (6)
O5	0.0463 (7)	0.0556 (8)	0.0513 (7)	0.0043 (6)	0.0260 (6)	−0.0126 (6)
C5	0.0367 (9)	0.0374 (9)	0.0412 (9)	0.0067 (7)	0.0188 (7)	0.0033 (7)
C6	0.0359 (9)	0.0487 (11)	0.0608 (11)	0.0036 (8)	0.0284 (8)	−0.0003 (8)
C7	0.0317 (8)	0.0417 (10)	0.0482 (10)	−0.0005 (7)	0.0215 (7)	0.0046 (7)
C8	0.0322 (8)	0.0479 (10)	0.0422 (9)	−0.0069 (7)	0.0146 (7)	−0.0028 (7)
C9	0.0289 (8)	0.0362 (9)	0.0343 (8)	0.0034 (6)	0.0156 (7)	0.0046 (7)
C10	0.0290 (8)	0.0327 (8)	0.0345 (8)	0.0027 (6)	0.0147 (6)	0.0018 (6)
C11	0.0588 (12)	0.0526 (12)	0.0643 (13)	0.0024 (9)	0.0290 (10)	0.0162 (10)
C12	0.0373 (10)	0.0653 (13)	0.0772 (14)	−0.0096 (9)	0.0283 (10)	−0.0017 (11)
N13	0.0352 (8)	0.0630 (10)	0.0359 (8)	−0.0091 (7)	0.0184 (7)	0.0004 (7)
C14	0.0355 (9)	0.0425 (10)	0.0399 (9)	−0.0034 (8)	0.0132 (7)	0.0035 (7)
N15	0.0501 (9)	0.0570 (10)	0.0648 (11)	−0.0187 (8)	0.0198 (8)	0.0028 (8)

O1—C2	1.3751 (18)	O5—C5	1.229 (2)
O1—C9	1.3774 (18)	C5—C10	1.464 (2)
C1'—C2'	1.381 (2)	C5—C6	1.505 (2)
C1'—C6'	1.389 (2)	C6—C7	1.527 (2)
C1'—C4	1.540 (2)	C6—H6A	0.9700
C2'—C3'	1.384 (2)	C6—H6B	0.9700
C2'—H2'	0.9300	C7—C11	1.523 (2)
C3'—C4'	1.375 (3)	C7—C8	1.529 (2)
C3'—H3'	0.9300	C7—C12	1.532 (2)
C4'—C5'	1.380 (3)	C8—C9	1.488 (2)
C4'—C7'	1.508 (2)	C8—H8A	0.9700
C5'—C6'	1.385 (3)	C8—H8B	0.9700
C5'—H5'	0.9300	C9—C10	1.333 (2)
C6'—H6'	0.9300	C11—H11A	0.9600
C7'—H7'1	0.9600	C11—H11B	0.9600
C7'—H7'2	0.9600	C11—H11C	0.9600
C7'—H7'3	0.9600	C12—H12A	0.9600
C2—N13	1.342 (2)	C12—H12B	0.9600
C2—C3	1.348 (2)	C12—H12C	0.9600
C3—C14	1.418 (2)	N13—H131	0.88 (2)
C3—C4	1.517 (2)	N13—H132	0.87 (2)
C4—C10	1.512 (2)	C14—N15	1.145 (2)
C4—H4	0.9800
C2—O1—C9	117.83 (12)	C5—C6—C7	114.58 (13)
C2'—C1'—C6'	117.19 (15)	C5—C6—H6A	108.6
C2'—C1'—C4	121.74 (14)	C7—C6—H6A	108.6
C6'—C1'—C4	121.08 (14)	C5—C6—H6B	108.6
C1'—C2'—C3'	121.49 (17)	C7—C6—H6B	108.6
C1'—C2'—H2'	119.3	H6A—C6—H6B	107.6
C3'—C2'—H2'	119.3	C11—C7—C6	110.02 (15)
C4'—C3'—C2'	121.53 (17)	C11—C7—C8	111.30 (14)
C4'—C3'—H3'	119.2	C6—C7—C8	107.18 (14)
C2'—C3'—H3'	119.2	C11—C7—C12	109.22 (15)
C3'—C4'—C5'	117.14 (16)	C6—C7—C12	110.29 (14)
C3'—C4'—C7'	120.99 (18)	C8—C7—C12	108.80 (15)
C5'—C4'—C7'	121.87 (18)	C9—C8—C7	112.37 (14)
C4'—C5'—C6'	121.89 (17)	C9—C8—H8A	109.1
C4'—C5'—H5'	119.1	C7—C8—H8A	109.1
C6'—C5'—H5'	119.1	C9—C8—H8B	109.1
C5'—C6'—C1'	120.77 (17)	C7—C8—H8B	109.1
C5'—C6'—H6'	119.6	H8A—C8—H8B	107.9
C1'—C6'—H6'	119.6	C10—C9—O1	122.74 (14)
C4'—C7'—H7'1	109.5	C10—C9—C8	125.90 (14)
C4'—C7'—H7'2	109.5	O1—C9—C8	111.36 (13)
H7'1—C7'—H7'2	109.5	C9—C10—C5	117.73 (14)
C4'—C7'—H7'3	109.5	C9—C10—C4	121.39 (14)
H7'1—C7'—H7'3	109.5	C5—C10—C4	120.70 (14)
H7'2—C7'—H7'3	109.5	C7—C11—H11A	109.5
N13—C2—C3	128.83 (15)	C7—C11—H11B	109.5
N13—C2—O1	109.91 (14)	H11A—C11—H11B	109.5
C3—C2—O1	121.24 (14)	C7—C11—H11C	109.5
C2—C3—C14	119.09 (15)	H11A—C11—H11C	109.5
C2—C3—C4	122.04 (13)	H11B—C11—H11C	109.5
C14—C3—C4	118.83 (14)	C7—C12—H12A	109.5
C10—C4—C3	107.42 (12)	C7—C12—H12B	109.5
C10—C4—C1'	111.87 (12)	H12A—C12—H12B	109.5
C3—C4—C1'	113.31 (13)	C7—C12—H12C	109.5
C10—C4—H4	108.0	H12A—C12—H12C	109.5
C3—C4—H4	108.0	H12B—C12—H12C	109.5
C1'—C4—H4	108.0	C2—N13—H131	118.5 (13)
O5—C5—C10	120.66 (15)	C2—N13—H132	116.8 (14)
O5—C5—C6	121.07 (15)	H131—N13—H132	116.9 (19)
C10—C5—C6	118.19 (15)	N15—C14—C3	177.67 (18)
C6'—C1'—C2'—C3'	0.5 (3)	C10—C5—C6—C7	26.8 (2)
C4—C1'—C2'—C3'	−179.38 (16)	C5—C6—C7—C11	67.88 (19)
C1'—C2'—C3'—C4'	−0.2 (3)	C5—C6—C7—C8	−53.27 (19)
C2'—C3'—C4'—C5'	−0.4 (3)	C5—C6—C7—C12	−171.57 (15)
C2'—C3'—C4'—C7'	179.35 (17)	C11—C7—C8—C9	−71.62 (19)
C3'—C4'—C5'—C6'	0.6 (3)	C6—C7—C8—C9	48.72 (18)
C7'—C4'—C5'—C6'	−179.09 (18)	C12—C7—C8—C9	167.98 (15)
C4'—C5'—C6'—C1'	−0.3 (3)	C2—O1—C9—C10	−15.5 (2)
C2'—C1'—C6'—C5'	−0.2 (3)	C2—O1—C9—C8	163.73 (13)
C4—C1'—C6'—C5'	179.64 (15)	C7—C8—C9—C10	−19.0 (2)
C9—O1—C2—N13	−166.15 (13)	C7—C8—C9—O1	161.72 (13)
C9—O1—C2—C3	15.4 (2)	O1—C9—C10—C5	168.43 (13)
N13—C2—C3—C14	6.5 (3)	C8—C9—C10—C5	−10.7 (2)
O1—C2—C3—C14	−175.37 (14)	O1—C9—C10—C4	−6.7 (2)
N13—C2—C3—C4	−171.42 (16)	C8—C9—C10—C4	174.14 (15)
O1—C2—C3—C4	6.7 (2)	O5—C5—C10—C9	−170.15 (15)
C2—C3—C4—C10	−25.3 (2)	C6—C5—C10—C9	6.7 (2)
C14—C3—C4—C10	156.78 (14)	O5—C5—C10—C4	5.0 (2)
C2—C3—C4—C1'	98.75 (17)	C6—C5—C10—C4	−178.09 (14)
C14—C3—C4—C1'	−79.14 (18)	C3—C4—C10—C9	25.20 (19)
C2'—C1'—C4—C10	129.01 (16)	C1'—C4—C10—C9	−99.76 (17)
C6'—C1'—C4—C10	−50.87 (19)	C3—C4—C10—C5	−149.80 (14)
C2'—C1'—C4—C3	7.4 (2)	C1'—C4—C10—C5	85.24 (17)
C6'—C1'—C4—C3	−172.49 (15)	C2—C3—C14—N15	−157 (5)
O5—C5—C6—C7	−156.36 (16)	C4—C3—C14—N15	20 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H131···O5i	0.89 (2)	2.06 (2)	2.913 (2)	161 (2)
N13—H132···N15ii	0.87 (2)	2.35 (2)	3.168 (2)	156 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H131⋯O5i	0.89 (2)	2.06 (2)	2.913 (2)	161 (2)
N13—H132⋯N15ii	0.87 (2)	2.35 (2)	3.168 (2)	156 (2)

Symmetry codes: (i) ; (ii) .