6-(4-Amino-phen-yl)-4-(4-eth-oxy-phen-yl)-2-meth-oxy-nicotinonitrile.

In the title mol-ecule, C(21)H(19)N(3)O(2), the central pyridine ring makes dihedral angles of 14.46 (9) and 34.67 (8)° with the 4-amino- and 4-eth-oxy-substituted benzene rings, respectively. The eth-oxy group is essentially coplanar with the attached benzene ring [C-O-C-C torsion angle = 178.70 (16)°] as is the meth-oxy group with the pyridine ring [C-O-C-N torsion angle = -3.0 (3)°]. In the crystal, mol-ecules are linked by N-H⋯N hydrogen bonds into chains along [201]. Weak C-H⋯O hydrogen bonds and C-H⋯π inter-actions are also present.

Related literature

The title nicotinonitrile derivative is a cyclized product of a chalcone and a malononitrile in the present of sodium methoxide. For the synthesis and applications of substituted pyridines and nicotinonitrile derivatives, see: Al-Jaber et al. (2012 ▶); Brandt et al. (2010 ▶); El-Sayed et al. (2011 ▶); Goda et al. (2004 ▶); Ji et al. (2007 ▶); Kamal et al. (2007 ▶); Kim et al. (2005 ▶); Kolev et al. (2005 ▶); Koner et al. (2012 ▶); Zhou et al. (2006 ▶). For a related structure, see: Chantrapromma et al. (2010 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C21H19N3O2

M = 345.39

Monoclinic,

a = 5.3924 (2) Å

b = 16.5111 (5) Å

c = 20.1415 (6) Å

β = 91.315 (2)°

V = 1792.82 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.54 × 0.25 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.956, T max = 0.982

17814 measured reflections

5216 independent reflections

3013 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.159

S = 1.04

5216 reflections

245 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036276/lh5514sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036276/lh5514Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812036276/lh5514Isup3.cml

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

C21H19N3O2	F(000) = 728
Mr = 345.39	Dx = 1.280 Mg m−3
Monoclinic, P21/c	Melting point = 477–478 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.3924 (2) Å	Cell parameters from 5216 reflections
b = 16.5111 (5) Å	θ = 2.0–30.0°
c = 20.1415 (6) Å	µ = 0.08 mm−1
β = 91.315 (2)°	T = 298 K
V = 1792.82 (10) Å3	Block, pale-brown
Z = 4	0.54 × 0.25 × 0.22 mm

Bruker APEXII CCD area-detector diffractometer	5216 independent reflections
Radiation source: sealed tube	3013 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
Tmin = 0.956, Tmax = 0.982	k = −23→23
17814 measured reflections	l = −28→28

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0647P)2 + 0.3033P] where P = (Fo2 + 2Fc2)/3
5216 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

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	0.3134 (2)	0.38320 (7)	0.14470 (6)	0.0637 (3)
O2	1.3927 (3)	0.09389 (7)	0.37553 (7)	0.0737 (4)
N1	1.3663 (3)	0.21531 (8)	0.43089 (6)	0.0543 (3)
N2	1.0455 (4)	0.08668 (10)	0.23879 (9)	0.0858 (6)
N3	1.6313 (5)	0.48378 (15)	0.64781 (10)	0.0987 (7)
C1	1.5687 (4)	0.32043 (10)	0.52550 (9)	0.0654 (5)
H1A	1.6556	0.2743	0.5133	0.078*
C2	1.6575 (4)	0.36652 (11)	0.57804 (9)	0.0675 (5)
H2A	1.8018	0.3506	0.6006	0.081*
C3	1.5363 (4)	0.43554 (12)	0.59760 (9)	0.0663 (5)
C4	1.3212 (5)	0.45547 (16)	0.56331 (12)	0.1042 (9)
H4A	1.2332	0.5012	0.5759	0.125*
C5	1.2329 (4)	0.40959 (14)	0.51089 (11)	0.0874 (7)
H5A	1.0877	0.4254	0.4887	0.105*
C6	1.3538 (3)	0.34094 (10)	0.49045 (8)	0.0514 (4)
C7	1.2622 (3)	0.28980 (9)	0.43520 (8)	0.0501 (4)
C8	1.0805 (3)	0.31513 (10)	0.38963 (8)	0.0540 (4)
H8A	1.0110	0.3663	0.3941	0.065*
C9	1.0004 (3)	0.26572 (9)	0.33750 (7)	0.0485 (4)
C10	1.1104 (3)	0.18863 (9)	0.33383 (8)	0.0509 (4)
C11	1.2909 (3)	0.16807 (9)	0.38214 (8)	0.0537 (4)
C12	0.8139 (3)	0.29470 (9)	0.28753 (7)	0.0484 (4)
C13	0.8087 (3)	0.37611 (10)	0.26827 (8)	0.0547 (4)
H13A	0.9214	0.4122	0.2876	0.066*
C14	0.6399 (3)	0.40372 (10)	0.22128 (8)	0.0564 (4)
H14A	0.6392	0.4581	0.2093	0.068*
C15	0.4699 (3)	0.35068 (10)	0.19151 (8)	0.0511 (4)
C16	0.4713 (3)	0.27011 (10)	0.21019 (8)	0.0544 (4)
H16A	0.3585	0.2341	0.1908	0.065*
C17	0.6410 (3)	0.24309 (10)	0.25784 (8)	0.0534 (4)
H17A	0.6391	0.1889	0.2703	0.064*
C18	0.1324 (3)	0.33169 (12)	0.11351 (9)	0.0643 (5)
H18A	0.0257	0.3082	0.1465	0.077*
H18B	0.2131	0.2881	0.0900	0.077*
C19	−0.0167 (4)	0.38315 (14)	0.06586 (11)	0.0864 (7)
H19A	−0.1479	0.3513	0.0461	0.130*
H19B	0.0887	0.4030	0.0317	0.130*
H19C	−0.0865	0.4281	0.0893	0.130*
C20	1.0686 (3)	0.13264 (10)	0.28075 (9)	0.0608 (5)
C21	1.5900 (4)	0.07236 (12)	0.42137 (11)	0.0818 (7)
H21A	1.6516	0.0196	0.4105	0.123*
H21B	1.5285	0.0719	0.4657	0.123*
H21C	1.7217	0.1112	0.4185	0.123*
H2N3	1.747 (5)	0.4641 (15)	0.6750 (13)	0.101 (8)*
H1N3	1.536 (5)	0.5205 (19)	0.6634 (15)	0.129 (11)*

	U11	U22	U33	U12	U13	U23
O1	0.0660 (7)	0.0607 (7)	0.0629 (8)	−0.0029 (6)	−0.0309 (6)	0.0055 (6)
O2	0.0944 (9)	0.0481 (6)	0.0765 (9)	0.0129 (6)	−0.0432 (8)	−0.0048 (6)
N1	0.0654 (8)	0.0489 (7)	0.0478 (7)	−0.0002 (6)	−0.0171 (6)	0.0033 (6)
N2	0.1065 (14)	0.0644 (10)	0.0843 (12)	0.0134 (9)	−0.0443 (11)	−0.0191 (9)
N3	0.1089 (16)	0.1055 (16)	0.0794 (13)	0.0313 (13)	−0.0496 (12)	−0.0399 (12)
C1	0.0775 (12)	0.0515 (9)	0.0655 (11)	0.0122 (8)	−0.0303 (9)	−0.0019 (8)
C2	0.0783 (12)	0.0623 (10)	0.0603 (11)	0.0073 (9)	−0.0347 (9)	0.0019 (8)
C3	0.0720 (11)	0.0775 (12)	0.0485 (10)	0.0090 (9)	−0.0192 (9)	−0.0112 (8)
C4	0.0993 (16)	0.1191 (19)	0.0918 (16)	0.0551 (14)	−0.0506 (13)	−0.0563 (15)
C5	0.0796 (13)	0.1055 (16)	0.0750 (14)	0.0393 (12)	−0.0402 (11)	−0.0366 (12)
C6	0.0576 (9)	0.0548 (9)	0.0411 (8)	0.0016 (7)	−0.0128 (7)	0.0017 (7)
C7	0.0555 (9)	0.0513 (8)	0.0431 (8)	−0.0004 (7)	−0.0106 (7)	0.0030 (6)
C8	0.0626 (10)	0.0513 (8)	0.0472 (9)	0.0068 (7)	−0.0148 (7)	−0.0027 (7)
C9	0.0510 (8)	0.0499 (8)	0.0439 (8)	−0.0027 (7)	−0.0108 (7)	0.0037 (6)
C10	0.0586 (9)	0.0466 (8)	0.0468 (8)	−0.0045 (7)	−0.0156 (7)	0.0023 (6)
C11	0.0651 (10)	0.0436 (8)	0.0516 (9)	0.0004 (7)	−0.0162 (8)	0.0048 (7)
C12	0.0505 (8)	0.0499 (8)	0.0442 (8)	0.0006 (7)	−0.0123 (7)	−0.0004 (6)
C13	0.0628 (10)	0.0474 (8)	0.0530 (9)	−0.0030 (7)	−0.0209 (8)	−0.0033 (7)
C14	0.0675 (10)	0.0444 (8)	0.0562 (10)	0.0000 (7)	−0.0212 (8)	0.0020 (7)
C15	0.0523 (8)	0.0531 (8)	0.0471 (9)	0.0016 (7)	−0.0146 (7)	0.0007 (7)
C16	0.0503 (9)	0.0545 (9)	0.0576 (10)	−0.0071 (7)	−0.0172 (7)	0.0012 (7)
C17	0.0543 (9)	0.0487 (8)	0.0568 (9)	−0.0036 (7)	−0.0122 (7)	0.0068 (7)
C18	0.0598 (10)	0.0711 (11)	0.0608 (11)	−0.0038 (8)	−0.0226 (8)	−0.0032 (8)
C19	0.0809 (14)	0.0989 (16)	0.0775 (14)	−0.0139 (12)	−0.0418 (11)	0.0149 (12)
C20	0.0703 (11)	0.0479 (8)	0.0630 (11)	0.0020 (8)	−0.0256 (9)	−0.0007 (8)
C21	0.0986 (15)	0.0603 (11)	0.0843 (14)	0.0193 (10)	−0.0444 (12)	−0.0005 (10)

O1—C15	1.3612 (17)	C9—C10	1.407 (2)
O1—C18	1.4291 (19)	C9—C12	1.485 (2)
O2—C11	1.3502 (19)	C10—C11	1.402 (2)
O2—C21	1.437 (2)	C10—C20	1.427 (2)
N1—C11	1.3114 (19)	C12—C17	1.388 (2)
N1—C7	1.356 (2)	C12—C13	1.399 (2)
N2—C20	1.141 (2)	C13—C14	1.376 (2)
N3—C3	1.377 (2)	C13—H13A	0.9300
N3—H2N3	0.88 (3)	C14—C15	1.393 (2)
N3—H1N3	0.86 (3)	C14—H14A	0.9300
C1—C2	1.380 (2)	C15—C16	1.382 (2)
C1—C6	1.385 (2)	C16—C17	1.385 (2)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.376 (3)	C17—H17A	0.9300
C2—H2A	0.9300	C18—C19	1.501 (3)
C3—C4	1.376 (3)	C18—H18A	0.9700
C4—C5	1.375 (3)	C18—H18B	0.9700
C4—H4A	0.9300	C19—H19A	0.9600
C5—C6	1.375 (3)	C19—H19B	0.9600
C5—H5A	0.9300	C19—H19C	0.9600
C6—C7	1.473 (2)	C21—H21A	0.9600
C7—C8	1.391 (2)	C21—H21B	0.9600
C8—C9	1.391 (2)	C21—H21C	0.9600
C8—H8A	0.9300
C15—O1—C18	118.42 (13)	O2—C11—C10	115.38 (14)
C11—O2—C21	117.24 (13)	C17—C12—C13	117.46 (14)
C11—N1—C7	117.77 (13)	C17—C12—C9	122.12 (14)
C3—N3—H2N3	119.3 (17)	C13—C12—C9	120.42 (13)
C3—N3—H1N3	117 (2)	C14—C13—C12	121.20 (14)
H2N3—N3—H1N3	117 (3)	C14—C13—H13A	119.4
C2—C1—C6	121.82 (17)	C12—C13—H13A	119.4
C2—C1—H1A	119.1	C13—C14—C15	120.40 (15)
C6—C1—H1A	119.1	C13—C14—H14A	119.8
C3—C2—C1	121.18 (16)	C15—C14—H14A	119.8
C3—C2—H2A	119.4	O1—C15—C16	124.59 (14)
C1—C2—H2A	119.4	O1—C15—C14	116.19 (14)
C2—C3—C4	117.04 (17)	C16—C15—C14	119.22 (14)
C2—C3—N3	121.22 (18)	C15—C16—C17	119.88 (14)
C4—C3—N3	121.7 (2)	C15—C16—H16A	120.1
C5—C4—C3	121.77 (19)	C17—C16—H16A	120.1
C5—C4—H4A	119.1	C16—C17—C12	121.83 (15)
C3—C4—H4A	119.1	C16—C17—H17A	119.1
C6—C5—C4	121.70 (17)	C12—C17—H17A	119.1
C6—C5—H5A	119.1	O1—C18—C19	107.14 (15)
C4—C5—H5A	119.1	O1—C18—H18A	110.3
C5—C6—C1	116.47 (15)	C19—C18—H18A	110.3
C5—C6—C7	123.06 (15)	O1—C18—H18B	110.3
C1—C6—C7	120.46 (15)	C19—C18—H18B	110.3
N1—C7—C8	121.12 (14)	H18A—C18—H18B	108.5
N1—C7—C6	115.86 (13)	C18—C19—H19A	109.5
C8—C7—C6	123.02 (14)	C18—C19—H19B	109.5
C9—C8—C7	121.57 (15)	H19A—C19—H19B	109.5
C9—C8—H8A	119.2	C18—C19—H19C	109.5
C7—C8—H8A	119.2	H19A—C19—H19C	109.5
C8—C9—C10	116.51 (13)	H19B—C19—H19C	109.5
C8—C9—C12	121.09 (14)	N2—C20—C10	177.0 (2)
C10—C9—C12	122.38 (13)	O2—C21—H21A	109.5
C11—C10—C9	118.00 (14)	O2—C21—H21B	109.5
C11—C10—C20	117.27 (14)	H21A—C21—H21B	109.5
C9—C10—C20	124.46 (13)	O2—C21—H21C	109.5
N1—C11—O2	119.58 (13)	H21A—C21—H21C	109.5
N1—C11—C10	125.03 (15)	H21B—C21—H21C	109.5
C6—C1—C2—C3	−0.5 (3)	C7—N1—C11—C10	0.1 (3)
C1—C2—C3—C4	1.2 (3)	C21—O2—C11—N1	−3.0 (3)
C1—C2—C3—N3	−176.7 (2)	C21—O2—C11—C10	176.03 (17)
C2—C3—C4—C5	−1.3 (4)	C9—C10—C11—N1	0.0 (3)
N3—C3—C4—C5	176.6 (3)	C20—C10—C11—N1	174.15 (17)
C3—C4—C5—C6	0.7 (5)	C9—C10—C11—O2	−179.00 (15)
C4—C5—C6—C1	0.1 (4)	C20—C10—C11—O2	−4.8 (2)
C4—C5—C6—C7	179.0 (2)	C8—C9—C12—C17	−146.49 (17)
C2—C1—C6—C5	−0.2 (3)	C10—C9—C12—C17	35.4 (2)
C2—C1—C6—C7	−179.14 (17)	C8—C9—C12—C13	34.1 (2)
C11—N1—C7—C8	0.3 (2)	C10—C9—C12—C13	−144.01 (17)
C11—N1—C7—C6	−179.60 (15)	C17—C12—C13—C14	−0.5 (3)
C5—C6—C7—N1	−165.10 (19)	C9—C12—C13—C14	178.94 (16)
C1—C6—C7—N1	13.8 (2)	C12—C13—C14—C15	−0.2 (3)
C5—C6—C7—C8	15.0 (3)	C18—O1—C15—C16	1.8 (3)
C1—C6—C7—C8	−166.12 (17)	C18—O1—C15—C14	−178.89 (15)
N1—C7—C8—C9	−0.8 (3)	C13—C14—C15—O1	−178.79 (16)
C6—C7—C8—C9	179.16 (16)	C13—C14—C15—C16	0.6 (3)
C7—C8—C9—C10	0.8 (2)	O1—C15—C16—C17	179.15 (16)
C7—C8—C9—C12	−177.43 (15)	C14—C15—C16—C17	−0.2 (3)
C8—C9—C10—C11	−0.4 (2)	C15—C16—C17—C12	−0.6 (3)
C12—C9—C10—C11	177.79 (15)	C13—C12—C17—C16	1.0 (3)
C8—C9—C10—C20	−174.09 (17)	C9—C12—C17—C16	−178.51 (16)
C12—C9—C10—C20	4.1 (3)	C15—O1—C18—C19	178.70 (16)
C7—N1—C11—O2	178.99 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N2i	0.88 (3)	2.20 (3)	3.084 (3)	177 (2)
C21—H21A···O1ii	0.96	2.52	3.439 (2)	160
C18—H18A···Cgiii	0.96	2.84	3.7135 (18)	151

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C12–C17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯N2i	0.88 (3)	2.20 (3)	3.084 (3)	177 (2)
C21—H21A⋯O1ii	0.96	2.52	3.439 (2)	160
C18—H18A⋯Cg iii	0.96	2.84	3.7135 (18)	151

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