Ethyl 6-amino-5-cyano-2,4-bis-(4-methyl-phen-yl)-4H-pyran-3-carboxyl-ate.

In the title compound, C(23)H(22)N(2)O(3), the pyran ring adopts a twisted boat conformation. The tolyl rings and carboxyl-ate group are attached to the pyran ring with torsion angles of -77.1 (2), 59.5 (3) and 17.8 (3)°, respectively. The ethyl group is disordered over two orientations with a site-occupancy ratio of 0.508 (5):0.492 (5). In the crystal, mol-ecules are linked by N-H⋯N and N-H⋯O hydrogen bonds, generating a chain running the a axis. Weak C-H⋯O, C-H⋯N and C-H⋯π inter-actions are also observed.

Related literature

For the use of related compounds in organic synthesis, see: Liang et al. (2009 ▶). For the synthesis, see: Vasuki & Kumaravel (2008 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶). For related structures, see: Athimoolam et al. (2007 ▶); Kannan et al. (2010 ▶).

Experimental

Crystal data

C23H22N2O3

M = 374.43

Triclinic,

a = 8.3485 (2) Å

b = 11.4057 (3) Å

c = 11.6689 (3) Å

α = 72.902 (2)°

β = 72.690 (2)°

γ = 89.182 (2)°

V = 1010.64 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.981, T max = 0.984

18989 measured reflections

3554 independent reflections

2971 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.192

S = 1.04

3554 reflections

243 parameters

7 restraints

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035592/ng5024sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035592/ng5024Isup2.hkl

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

C23H22N2O3	Z = 2
Mr = 374.43	F(000) = 396
Triclinic, P1	Dx = 1.230 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3485 (2) Å	Cell parameters from 9717 reflections
b = 11.4057 (3) Å	θ = 2.2–32°
c = 11.6689 (3) Å	µ = 0.08 mm−1
α = 72.902 (2)°	T = 293 K
β = 72.690 (2)°	Rectangular, colourless
γ = 89.182 (2)°	0.30 × 0.20 × 0.20 mm
V = 1010.64 (4) Å3

Bruker Kappa APEXII CCD diffractometer	3554 independent reflections
Radiation source: fine-focus sealed tube	2971 reflections with I > 2σ(I)
graphite	Rint = 0.022
Detector resolution: 0 pixels mm-1	θmax = 25.0°, θmin = 1.9°
ω and φ scan	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→13
Tmin = 0.981, Tmax = 0.984	l = −13→13
18989 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066	H-atom parameters constrained
wR(F2) = 0.192	w = 1/[σ2(Fo2) + (0.0869P)2 + 0.7661P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.025
3554 reflections	Δρmax = 0.56 e Å−3
243 parameters	Δρmin = −0.58 e Å−3
7 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

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	Occ. (<1)
C1	0.4425 (5)	0.8123 (3)	0.3388 (4)	0.0986 (13)
H1A	0.3452	0.7959	0.4120	0.148*
H1B	0.4206	0.8739	0.2701	0.148*
H1C	0.5369	0.8412	0.3568	0.148*
C2	0.4816 (3)	0.69499 (14)	0.30303 (19)	0.0648 (8)
C3	0.4067 (2)	0.58140 (17)	0.38598 (15)	0.0720 (9)
H3	0.3282	0.5769	0.4631	0.086*
C4	0.4491 (2)	0.47452 (13)	0.35366 (15)	0.0618 (7)
H4	0.3990	0.3985	0.4092	0.074*
C5	0.5664 (2)	0.48123 (12)	0.23840 (15)	0.0473 (6)
C6	0.6414 (2)	0.59482 (15)	0.15545 (14)	0.0718 (9)
H6	0.7199	0.5993	0.0783	0.086*
C7	0.5990 (3)	0.70170 (12)	0.18776 (18)	0.0803 (10)
H7	0.6491	0.7777	0.1323	0.096*
C8	0.6149 (3)	0.3670 (2)	0.2054 (2)	0.0449 (5)
C9	0.4918 (3)	0.2162 (2)	0.1459 (2)	0.0466 (6)
C10	0.6432 (3)	0.1734 (2)	0.1069 (2)	0.0472 (6)
C11	0.7915 (3)	0.2049 (2)	0.1436 (2)	0.0453 (6)
H11	0.8914	0.2207	0.0695	0.054*
C12	0.7648 (3)	0.3221 (2)	0.1804 (2)	0.0453 (6)
C13	0.9216 (3)	0.3763 (2)	0.1813 (2)	0.0532 (6)
O2A	0.8984 (11)	0.4720 (4)	0.2391 (6)	0.0562 (13)	0.492 (5)
C14A	1.0588 (11)	0.5280 (9)	0.2238 (9)	0.072 (2)	0.492 (5)
H14A	1.1208	0.5657	0.1357	0.086*	0.492 (5)
H14B	1.1262	0.4692	0.2634	0.086*	0.492 (5)
C15A	1.0050 (13)	0.6246 (9)	0.2921 (12)	0.122 (3)	0.492 (5)
H15A	0.9331	0.6782	0.2539	0.184*	0.492 (5)
H15B	1.1029	0.6719	0.2862	0.184*	0.492 (5)
H15C	0.9453	0.5844	0.3791	0.184*	0.492 (5)
O2B	0.8938 (10)	0.4347 (5)	0.2773 (4)	0.0562 (13)	0.508 (5)
C14B	1.0311 (12)	0.5012 (7)	0.2866 (8)	0.072 (2)	0.508 (5)
H14C	1.1260	0.4507	0.2828	0.086*	0.508 (5)
H14D	0.9984	0.5159	0.3679	0.086*	0.508 (5)
C15B	1.0869 (14)	0.6244 (7)	0.1830 (9)	0.122 (3)	0.508 (5)
H15D	1.1080	0.6118	0.1022	0.184*	0.508 (5)
H15E	1.1879	0.6592	0.1877	0.184*	0.508 (5)
H15F	0.9997	0.6796	0.1941	0.184*	0.508 (5)
C16	0.6647 (3)	0.0898 (2)	0.0364 (3)	0.0536 (6)
C17	0.82337 (19)	0.09928 (12)	0.24806 (13)	0.0442 (5)
C18	0.95357 (19)	0.02588 (15)	0.21696 (12)	0.0555 (6)
H18	1.0204	0.0420	0.1337	0.067*
C19	0.9840 (2)	−0.07159 (15)	0.31037 (16)	0.0649 (7)
H19	1.0711	−0.1207	0.2896	0.078*
C20	0.8841 (2)	−0.09565 (14)	0.43487 (14)	0.0596 (7)
C21	0.7539 (2)	−0.02225 (16)	0.46597 (11)	0.0626 (7)
H21	0.6871	−0.0383	0.5493	0.075*
C22	0.72354 (18)	0.07522 (15)	0.37256 (15)	0.0568 (7)
H22	0.6364	0.1243	0.3934	0.068*
C23	0.9202 (5)	−0.1997 (3)	0.5378 (3)	0.0826 (10)
H23A	0.9932	−0.1682	0.5736	0.124*
H23B	0.9736	−0.2618	0.5026	0.124*
H23C	0.8165	−0.2349	0.6023	0.124*
N1	0.6900 (3)	0.0234 (3)	−0.0223 (3)	0.0743 (8)
N2	0.3450 (3)	0.1811 (2)	0.1388 (2)	0.0598 (6)
H2A	0.3389	0.1238	0.1058	0.072*
H2B	0.2560	0.2157	0.1672	0.072*
O1	0.4731 (2)	0.30688 (16)	0.20301 (18)	0.0545 (5)
O3	1.0577 (2)	0.35407 (19)	0.1320 (2)	0.0723 (6)

	U11	U22	U33	U12	U13	U23
C1	0.112 (3)	0.087 (2)	0.135 (3)	0.041 (2)	−0.050 (3)	−0.079 (3)
C2	0.0700 (18)	0.0665 (18)	0.086 (2)	0.0278 (14)	−0.0392 (16)	−0.0500 (16)
C3	0.0619 (17)	0.088 (2)	0.081 (2)	0.0153 (15)	−0.0124 (15)	−0.0570 (19)
C4	0.0554 (16)	0.0655 (17)	0.0693 (17)	0.0027 (13)	−0.0092 (13)	−0.0376 (14)
C5	0.0441 (12)	0.0527 (14)	0.0593 (14)	0.0138 (10)	−0.0217 (11)	−0.0324 (12)
C6	0.093 (2)	0.0535 (16)	0.0626 (17)	0.0186 (15)	−0.0089 (16)	−0.0245 (14)
C7	0.110 (3)	0.0493 (16)	0.080 (2)	0.0200 (16)	−0.0216 (19)	−0.0258 (15)
C8	0.0424 (12)	0.0490 (13)	0.0520 (13)	0.0063 (10)	−0.0163 (10)	−0.0264 (11)
C9	0.0454 (13)	0.0517 (13)	0.0560 (14)	0.0103 (10)	−0.0202 (11)	−0.0318 (11)
C10	0.0441 (13)	0.0514 (13)	0.0591 (14)	0.0115 (10)	−0.0191 (11)	−0.0329 (12)
C11	0.0371 (12)	0.0496 (13)	0.0564 (14)	0.0096 (10)	−0.0132 (10)	−0.0281 (11)
C12	0.0429 (13)	0.0448 (12)	0.0553 (14)	0.0074 (10)	−0.0161 (10)	−0.0249 (11)
C13	0.0471 (14)	0.0437 (13)	0.0726 (17)	0.0051 (10)	−0.0212 (12)	−0.0204 (12)
O2A	0.0596 (13)	0.029 (3)	0.092 (3)	0.007 (2)	−0.037 (3)	−0.022 (3)
C14A	0.067 (3)	0.061 (4)	0.100 (6)	−0.011 (3)	−0.031 (5)	−0.035 (5)
C15A	0.127 (7)	0.093 (4)	0.177 (8)	−0.009 (4)	−0.073 (6)	−0.058 (6)
O2B	0.0596 (13)	0.029 (3)	0.092 (3)	0.007 (2)	−0.037 (3)	−0.022 (3)
C14B	0.067 (3)	0.061 (4)	0.100 (6)	−0.011 (3)	−0.031 (5)	−0.035 (5)
C15B	0.127 (7)	0.093 (4)	0.177 (8)	−0.009 (4)	−0.073 (6)	−0.058 (6)
C16	0.0396 (13)	0.0638 (15)	0.0714 (17)	0.0123 (11)	−0.0192 (12)	−0.0396 (14)
C17	0.0354 (11)	0.0472 (12)	0.0590 (14)	0.0056 (9)	−0.0157 (10)	−0.0283 (11)
C18	0.0460 (14)	0.0573 (15)	0.0624 (16)	0.0134 (11)	−0.0101 (12)	−0.0238 (13)
C19	0.0545 (16)	0.0587 (16)	0.079 (2)	0.0183 (13)	−0.0179 (14)	−0.0213 (14)
C20	0.0549 (15)	0.0535 (15)	0.0720 (18)	−0.0024 (12)	−0.0233 (13)	−0.0170 (13)
C21	0.0607 (17)	0.0669 (17)	0.0587 (16)	0.0007 (13)	−0.0117 (13)	−0.0233 (14)
C22	0.0497 (14)	0.0629 (16)	0.0636 (16)	0.0121 (12)	−0.0136 (12)	−0.0318 (13)
C23	0.083 (2)	0.0685 (19)	0.089 (2)	−0.0005 (16)	−0.0342 (19)	−0.0051 (17)
N1	0.0520 (13)	0.0912 (18)	0.108 (2)	0.0174 (12)	−0.0227 (13)	−0.0750 (17)
N2	0.0434 (11)	0.0730 (15)	0.0879 (16)	0.0170 (10)	−0.0276 (11)	−0.0542 (13)
O1	0.0403 (9)	0.0644 (11)	0.0780 (12)	0.0137 (8)	−0.0196 (8)	−0.0489 (10)
O3	0.0395 (10)	0.0768 (13)	0.1065 (16)	0.0053 (9)	−0.0157 (10)	−0.0432 (12)

C1—C2	1.518 (3)	C14A—C15A	1.5295 (10)
C1—H1A	0.9600	C14A—H14A	0.9700
C1—H1B	0.9600	C14A—H14B	0.9700
C1—H1C	0.9600	C15A—H15A	0.9600
C2—C3	1.3900	C15A—H15B	0.9600
C2—C7	1.3900	C15A—H15C	0.9600
C3—C4	1.3900	O2B—C14B	1.4309 (10)
C3—H3	0.9300	C14B—C15B	1.5295 (10)
C4—C5	1.3900	C14B—H14C	0.9700
C4—H4	0.9300	C14B—H14D	0.9700
C5—C6	1.3900	C15B—H15D	0.9600
C5—C8	1.482 (2)	C15B—H15E	0.9600
C6—C7	1.3900	C15B—H15F	0.9600
C6—H6	0.9300	C16—N1	1.140 (3)
C7—H7	0.9300	C17—C18	1.3900
C8—C12	1.329 (3)	C17—C22	1.3900
C8—O1	1.388 (3)	C18—C19	1.3900
C9—N2	1.328 (3)	C18—H18	0.9300
C9—C10	1.347 (3)	C19—C20	1.3900
C9—O1	1.371 (3)	C19—H19	0.9300
C10—C16	1.410 (3)	C20—C21	1.3900
C10—C11	1.505 (3)	C20—C23	1.520 (3)
C11—C12	1.514 (3)	C21—C22	1.3900
C11—C17	1.525 (3)	C21—H21	0.9300
C11—H11	0.9800	C22—H22	0.9300
C12—C13	1.460 (3)	C23—H23A	0.9600
C13—O3	1.172 (3)	C23—H23B	0.9600
C13—O2A	1.4256 (10)	C23—H23C	0.9600
C13—O2B	1.4261 (10)	N2—H2A	0.8600
O2A—C14A	1.4309 (10)	N2—H2B	0.8600
C2—C1—H1A	109.5	O2A—C14A—C15A	100.8 (5)
C2—C1—H1B	109.5	O2A—C14A—H14A	111.6
H1A—C1—H1B	109.5	C15A—C14A—H14A	111.6
C2—C1—H1C	109.5	O2A—C14A—H14B	111.6
H1A—C1—H1C	109.5	C15A—C14A—H14B	111.6
H1B—C1—H1C	109.5	H14A—C14A—H14B	109.4
C3—C2—C7	120.0	C13—O2B—C14B	119.8 (6)
C3—C2—C1	120.8 (2)	O2B—C14B—C15B	113.5 (6)
C7—C2—C1	119.1 (2)	O2B—C14B—H14C	108.9
C4—C3—C2	120.0	C15B—C14B—H14C	108.8
C4—C3—H3	120.0	O2B—C14B—H14D	108.9
C2—C3—H3	120.0	C15B—C14B—H14D	108.9
C3—C4—C5	120.0	H14C—C14B—H14D	107.7
C3—C4—H4	120.0	C14B—C15B—H15D	109.5
C5—C4—H4	120.0	C14B—C15B—H15E	109.5
C6—C5—C4	120.0	H15D—C15B—H15E	109.5
C6—C5—C8	120.01 (14)	C14B—C15B—H15F	109.5
C4—C5—C8	119.97 (14)	H15D—C15B—H15F	109.5
C5—C6—C7	120.0	H15E—C15B—H15F	109.5
C5—C6—H6	120.0	N1—C16—C10	176.8 (3)
C7—C6—H6	120.0	C18—C17—C22	120.0
C6—C7—C2	120.0	C18—C17—C11	118.98 (12)
C6—C7—H7	120.0	C22—C17—C11	121.02 (12)
C2—C7—H7	120.0	C17—C18—C19	120.0
C12—C8—O1	121.7 (2)	C17—C18—H18	120.0
C12—C8—C5	129.4 (2)	C19—C18—H18	120.0
O1—C8—C5	108.85 (17)	C20—C19—C18	120.0
N2—C9—C10	128.6 (2)	C20—C19—H19	120.0
N2—C9—O1	110.53 (19)	C18—C19—H19	120.0
C10—C9—O1	120.9 (2)	C19—C20—C21	120.0
C9—C10—C16	120.4 (2)	C19—C20—C23	120.16 (18)
C9—C10—C11	122.1 (2)	C21—C20—C23	119.81 (18)
C16—C10—C11	117.4 (2)	C20—C21—C22	120.0
C10—C11—C12	109.30 (18)	C20—C21—H21	120.0
C10—C11—C17	111.98 (19)	C22—C21—H21	120.0
C12—C11—C17	111.80 (18)	C21—C22—C17	120.0
C10—C11—H11	107.9	C21—C22—H22	120.0
C12—C11—H11	107.9	C17—C22—H22	120.0
C17—C11—H11	107.9	C20—C23—H23A	109.5
C8—C12—C13	126.6 (2)	C20—C23—H23B	109.5
C8—C12—C11	121.9 (2)	H23A—C23—H23B	109.5
C13—C12—C11	111.49 (18)	C20—C23—H23C	109.5
O3—C13—O2A	120.1 (4)	H23A—C23—H23C	109.5
O3—C13—O2B	120.3 (4)	H23B—C23—H23C	109.5
O2A—C13—O2B	20.6 (4)	C9—N2—H2A	120.0
O3—C13—C12	125.93 (19)	C9—N2—H2B	120.0
O2A—C13—C12	113.7 (4)	H2A—N2—H2B	120.0
O2B—C13—C12	111.8 (4)	C9—O1—C8	119.48 (17)
C13—O2A—C14A	109.7 (5)
C7—C2—C3—C4	0.0	C8—C12—C13—O2A	13.2 (5)
C1—C2—C3—C4	−177.4 (2)	C11—C12—C13—O2A	−168.1 (3)
C2—C3—C4—C5	0.0	C8—C12—C13—O2B	35.5 (4)
C3—C4—C5—C6	0.0	C11—C12—C13—O2B	−145.8 (3)
C3—C4—C5—C8	178.43 (18)	O3—C13—O2A—C14A	0.6 (7)
C4—C5—C6—C7	0.0	O2B—C13—O2A—C14A	97.0 (19)
C8—C5—C6—C7	−178.43 (18)	C12—C13—O2A—C14A	−174.0 (5)
C5—C6—C7—C2	0.0	C13—O2A—C14A—C15A	−179.6 (8)
C3—C2—C7—C6	0.0	O3—C13—O2B—C14B	20.1 (7)
C1—C2—C7—C6	177.5 (2)	O2A—C13—O2B—C14B	−75.7 (19)
C6—C5—C8—C12	59.5 (3)	C12—C13—O2B—C14B	−175.3 (5)
C4—C5—C8—C12	−118.9 (3)	C13—O2B—C14B—C15B	73.4 (11)
C6—C5—C8—O1	−120.33 (18)	C9—C10—C16—N1	163 (6)
C4—C5—C8—O1	61.2 (2)	C11—C10—C16—N1	−21 (6)
N2—C9—C10—C16	7.7 (5)	C10—C11—C17—C18	102.33 (18)
O1—C9—C10—C16	−173.2 (2)	C12—C11—C17—C18	−134.63 (16)
N2—C9—C10—C11	−167.9 (3)	C10—C11—C17—C22	−77.07 (19)
O1—C9—C10—C11	11.2 (4)	C12—C11—C17—C22	46.0 (2)
C9—C10—C11—C12	−22.1 (3)	C22—C17—C18—C19	0.0
C16—C10—C11—C12	162.2 (2)	C11—C17—C18—C19	−179.41 (16)
C9—C10—C11—C17	102.4 (3)	C17—C18—C19—C20	0.0
C16—C10—C11—C17	−73.3 (3)	C18—C19—C20—C21	0.0
O1—C8—C12—C13	−179.3 (2)	C18—C19—C20—C23	−178.2 (2)
C5—C8—C12—C13	0.8 (4)	C19—C20—C21—C22	0.0
O1—C8—C12—C11	2.1 (4)	C23—C20—C21—C22	178.2 (2)
C5—C8—C12—C11	−177.8 (2)	C20—C21—C22—C17	0.0
C10—C11—C12—C8	15.4 (3)	C18—C17—C22—C21	0.0
C17—C11—C12—C8	−109.1 (3)	C11—C17—C22—C21	179.39 (16)
C10—C11—C12—C13	−163.4 (2)	N2—C9—O1—C8	−171.9 (2)
C17—C11—C12—C13	72.1 (2)	C10—C9—O1—C8	8.8 (4)
C8—C12—C13—O3	−160.9 (3)	C12—C8—O1—C9	−15.7 (4)
C11—C12—C13—O3	17.8 (4)	C5—C8—O1—C9	164.2 (2)

Cg is the centroid of the C17–C22 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.22	3.081 (3)	177
N2—H2B···O3ii	0.86	2.31	3.088 (3)	150
C6—H6···O3iii	0.93	2.51	3.432 (2)	171
C18—H18···N1iv	0.93	2.60	3.318 (3)	135
C23—H23A···Cgv	0.92	2.85	3.770 (4)	160

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.22	3.081 (3)	177
N2—H2B⋯O3ii	0.86	2.31	3.088 (3)	150
C6—H6⋯O3iii	0.93	2.51	3.432 (2)	171
C18—H18⋯N1iv	0.93	2.60	3.318 (3)	135
C23—H23A⋯Cgv	0.92	2.85	3.770 (4)	160

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