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

In the title nicotinonitrile derivative, C(18)H(15)N(3)OS, the central pyridyl ring makes dihedral angles of 25.22 (10) and 24.80 (16)° with the 4-amino-phenyl and thio-phene rings, respectively. The thio-phene ring is disordered over two orientations by rotation around the C(thio-phene)-C(pyridine) bond; the occupancies are 0.858 (2) and 0.142 (2). The eth-oxy group is slightly twisted from the attached pyridyl ring [C-O-C-C torsion angle = 171.13 (16)°]. In the crystal structure, mol-ecules are linked by N-H⋯N hydrogen bonds into chains along [010]. These chains are stacked along the a axis. C-H⋯π weak inter-actions involving the thio-phene ring are observed.

Related literature

For reference bond-length data, see: Allen et al. (1987 ▶). For the synthesis and applications of nicotinonitrile derivatives, see: Amr & Abdulla (2006 ▶); Borgna et al. (1993 ▶); Fun et al. (2009 ▶); Goda et al. (2004 ▶); Kamal et al. (2007 ▶); Malinka et al. (1998 ▶). For related structures, see: Chantrapromma et al. (2009 ▶, 2010 ▶); Fun et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C18H15N3OS

M = 321.38

Orthorhombic,

a = 7.0751 (12) Å

b = 20.843 (4) Å

c = 20.983 (4) Å

V = 3094.3 (9) Å3

Z = 8

Mo Kα radiation

μ = 0.22 mm−1

T = 100 K

0.35 × 0.11 × 0.04 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.928, T max = 0.992

34805 measured reflections

3045 independent reflections

2188 reflections with I > 2σ(I)

R int = 0.092

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.085

S = 1.05

3045 reflections

233 parameters

88 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablocks global, I. DOI: 10.1107/S160053681002369X/wn2394sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002369X/wn2394Isup2.hkl

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

C18H15N3OS	Dx = 1.380 Mg m−3
Mr = 321.38	Melting point = 470–471 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3045 reflections
a = 7.0751 (12) Å	θ = 1.9–26.0°
b = 20.843 (4) Å	µ = 0.22 mm−1
c = 20.983 (4) Å	T = 100 K
V = 3094.3 (9) Å3	Plate, yellow
Z = 8	0.35 × 0.11 × 0.04 mm
F(000) = 1344

Bruker APEXII DUO CCD area-detector diffractometer	3045 independent reflections
Radiation source: sealed tube	2188 reflections with I > 2σ(I)
graphite	Rint = 0.092
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.928, Tmax = 0.992	k = −25→24
34805 measured reflections	l = −25→25

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0278P)2 + 1.8001P] where P = (Fo2 + 2Fc2)/3
3045 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.21 e Å−3
88 restraints	Δρmin = −0.32 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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)
O1	0.56053 (19)	0.37231 (6)	0.25979 (6)	0.0190 (3)
N1	0.5847 (2)	0.26630 (7)	0.22980 (7)	0.0163 (4)
N2	0.6671 (3)	0.01670 (9)	0.05279 (9)	0.0245 (4)
N3	0.5866 (2)	0.39328 (8)	0.41791 (8)	0.0245 (4)
C4	0.6016 (3)	0.21000 (9)	0.42677 (9)	0.0167 (4)
S1	0.68410 (11)	0.13404 (3)	0.44617 (3)	0.01858 (19)	0.8583 (19)
C1	0.6115 (5)	0.14171 (15)	0.52389 (16)	0.0192 (7)	0.8583 (19)
H1A	0.6270	0.1101	0.5547	0.023*	0.8583 (19)
C2	0.5284 (8)	0.1996 (2)	0.53499 (16)	0.0168 (8)	0.8583 (19)
H2A	0.4807	0.2124	0.5743	0.020*	0.8583 (19)
C3	0.5240 (8)	0.2374 (2)	0.4797 (2)	0.0231 (10)	0.8583 (19)
H3A	0.4718	0.2783	0.4791	0.028*	0.8583 (19)
S1X	0.5077 (14)	0.2515 (4)	0.4850 (4)	0.0200 (18)*	0.1417 (19)
C1X	0.560 (5)	0.1904 (12)	0.5376 (10)	0.021 (8)*	0.1417 (19)
H1XA	0.5349	0.1919	0.5810	0.025*	0.1417 (19)
C2X	0.643 (3)	0.1399 (10)	0.5079 (8)	0.012 (5)*	0.1417 (19)
H2XA	0.6719	0.1011	0.5274	0.014*	0.1417 (19)
C3X	0.679 (3)	0.1544 (8)	0.4425 (9)	0.0231 (10)	0.14
H3XA	0.7470	0.1284	0.4149	0.028*	0.1417 (19)
C5	0.6017 (3)	0.23136 (9)	0.36009 (9)	0.0163 (4)
C6	0.6082 (3)	0.18612 (9)	0.31136 (9)	0.0176 (4)
H6A	0.6197	0.1429	0.3217	0.021*
C7	0.5978 (3)	0.20381 (9)	0.24772 (9)	0.0164 (4)
C8	0.6032 (3)	0.15594 (9)	0.19636 (9)	0.0158 (4)
C9	0.5488 (3)	0.09205 (9)	0.20666 (9)	0.0203 (4)
H9A	0.5016	0.0800	0.2463	0.024*
C10	0.5641 (3)	0.04666 (9)	0.15893 (9)	0.0201 (4)
H10A	0.5253	0.0047	0.1666	0.024*
C11	0.6372 (3)	0.06310 (9)	0.09920 (9)	0.0178 (4)
C12	0.6864 (3)	0.12704 (9)	0.08808 (9)	0.0181 (4)
H12A	0.7319	0.1392	0.0483	0.022*
C13	0.6680 (3)	0.17231 (9)	0.13553 (9)	0.0171 (4)
H13A	0.6995	0.2147	0.1269	0.021*
C14	0.5779 (3)	0.30963 (9)	0.27536 (9)	0.0168 (4)
C15	0.5874 (3)	0.29610 (9)	0.34132 (9)	0.0163 (4)
C16	0.5537 (3)	0.38737 (9)	0.19226 (9)	0.0197 (4)
H16A	0.4594	0.3611	0.1712	0.024*
H16B	0.6754	0.3791	0.1727	0.024*
C17	0.5035 (3)	0.45707 (9)	0.18628 (10)	0.0248 (5)
H17A	0.5012	0.4689	0.1421	0.037*
H17B	0.5961	0.4825	0.2082	0.037*
H17C	0.3813	0.4644	0.2047	0.037*
C18	0.5861 (3)	0.34927 (9)	0.38470 (9)	0.0181 (4)
H1N2	0.586 (3)	−0.0177 (12)	0.0555 (11)	0.039 (7)*
H2N2	0.678 (3)	0.0308 (10)	0.0137 (11)	0.029 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0293 (7)	0.0135 (7)	0.0143 (7)	0.0002 (6)	0.0006 (6)	0.0000 (6)
N1	0.0175 (8)	0.0123 (9)	0.0191 (9)	−0.0004 (7)	0.0020 (7)	−0.0014 (7)
N2	0.0355 (10)	0.0196 (10)	0.0184 (9)	−0.0040 (8)	−0.0002 (9)	−0.0040 (8)
N3	0.0352 (10)	0.0189 (10)	0.0195 (9)	0.0024 (8)	0.0004 (8)	0.0006 (8)
C4	0.0162 (9)	0.0156 (10)	0.0182 (10)	0.0001 (8)	−0.0005 (8)	0.0003 (8)
S1	0.0220 (3)	0.0159 (4)	0.0179 (3)	0.0049 (3)	0.0012 (2)	0.0032 (3)
C1	0.0239 (16)	0.0225 (16)	0.0113 (15)	0.0003 (12)	0.0022 (13)	0.0024 (13)
C2	0.015 (2)	0.0202 (19)	0.0150 (15)	0.0005 (13)	0.0000 (11)	0.0003 (10)
C3	0.0245 (19)	0.019 (2)	0.025 (2)	−0.0002 (17)	0.0011 (13)	−0.0016 (17)
C3X	0.0245 (19)	0.019 (2)	0.025 (2)	−0.0002 (17)	0.0011 (13)	−0.0016 (17)
C5	0.0132 (9)	0.0181 (10)	0.0177 (10)	0.0004 (8)	0.0000 (8)	0.0014 (8)
C6	0.0178 (9)	0.0123 (10)	0.0227 (11)	0.0007 (8)	0.0019 (8)	0.0005 (8)
C7	0.0136 (9)	0.0154 (10)	0.0202 (10)	−0.0013 (8)	0.0019 (8)	−0.0003 (9)
C8	0.0157 (9)	0.0144 (10)	0.0172 (10)	0.0012 (8)	0.0009 (8)	0.0002 (8)
C9	0.0222 (10)	0.0195 (11)	0.0192 (10)	−0.0001 (9)	0.0026 (8)	0.0016 (9)
C10	0.0247 (10)	0.0138 (10)	0.0217 (11)	−0.0015 (8)	−0.0007 (9)	0.0009 (8)
C11	0.0179 (10)	0.0191 (10)	0.0163 (10)	0.0024 (8)	−0.0038 (8)	−0.0024 (8)
C12	0.0171 (9)	0.0217 (11)	0.0156 (10)	−0.0017 (9)	−0.0013 (8)	0.0029 (8)
C13	0.0161 (9)	0.0160 (10)	0.0193 (10)	−0.0005 (8)	−0.0008 (8)	0.0015 (8)
C14	0.0152 (9)	0.0145 (11)	0.0207 (10)	0.0007 (8)	0.0010 (8)	0.0009 (8)
C15	0.0146 (9)	0.0169 (10)	0.0174 (10)	0.0003 (8)	0.0020 (8)	−0.0015 (8)
C16	0.0265 (10)	0.0186 (11)	0.0141 (10)	−0.0010 (9)	0.0004 (8)	0.0002 (8)
C17	0.0347 (12)	0.0198 (11)	0.0200 (11)	0.0012 (9)	0.0033 (9)	0.0007 (9)
C18	0.0197 (10)	0.0173 (11)	0.0173 (10)	0.0019 (8)	0.0009 (8)	0.0048 (9)

O1—C14	1.352 (2)	C3X—H3XA	0.9300
O1—C16	1.452 (2)	C5—C6	1.392 (3)
N1—C14	1.316 (2)	C5—C15	1.409 (3)
N1—C7	1.359 (2)	C6—C7	1.387 (3)
N2—C11	1.389 (2)	C6—H6A	0.9300
N2—H1N2	0.92 (2)	C7—C8	1.469 (3)
N2—H2N2	0.87 (2)	C8—C13	1.398 (3)
N3—C18	1.152 (2)	C8—C9	1.403 (3)
C4—C3X	1.323 (14)	C9—C10	1.382 (3)
C4—C3	1.364 (5)	C9—H9A	0.9300
C4—C5	1.468 (3)	C10—C11	1.399 (3)
C4—S1X	1.638 (8)	C10—H10A	0.9300
C4—S1	1.736 (2)	C11—C12	1.397 (3)
S1—C1	1.717 (3)	C12—C13	1.378 (3)
C1—C2	1.361 (4)	C12—H12A	0.9300
C1—H1A	0.9300	C13—H13A	0.9300
C2—C3	1.404 (6)	C14—C15	1.414 (3)
C2—H2A	0.9300	C15—C18	1.434 (3)
C3—H3A	0.9300	C16—C17	1.501 (3)
S1X—C1X	1.725 (17)	C16—H16A	0.9700
C1X—C2X	1.355 (16)	C16—H16B	0.9700
C1X—H1XA	0.9300	C17—H17A	0.9600
C2X—C3X	1.427 (17)	C17—H17B	0.9600
C2X—H2XA	0.9300	C17—H17C	0.9600
C14—O1—C16	116.59 (14)	N1—C7—C8	116.73 (17)
C14—N1—C7	117.34 (16)	C6—C7—C8	121.62 (17)
C11—N2—H1N2	113.9 (15)	C13—C8—C9	117.52 (17)
C11—N2—H2N2	116.0 (14)	C13—C8—C7	120.83 (17)
H1N2—N2—H2N2	112 (2)	C9—C8—C7	121.63 (17)
C3X—C4—C3	109.2 (9)	C10—C9—C8	121.11 (18)
C3X—C4—C5	120.2 (8)	C10—C9—H9A	119.4
C3—C4—C5	130.5 (3)	C8—C9—H9A	119.4
C3X—C4—S1X	116.3 (8)	C9—C10—C11	120.71 (18)
C5—C4—S1X	123.5 (3)	C9—C10—H10A	119.6
C3—C4—S1	109.1 (2)	C11—C10—H10A	119.6
C5—C4—S1	119.99 (14)	N2—C11—C12	120.63 (18)
S1X—C4—S1	116.3 (3)	N2—C11—C10	120.94 (18)
C1—S1—C4	92.13 (12)	C12—C11—C10	118.39 (17)
C2—C1—S1	112.0 (3)	C13—C12—C11	120.61 (18)
C2—C1—H1A	124.0	C13—C12—H12A	119.7
S1—C1—H1A	124.0	C11—C12—H12A	119.7
C1—C2—C3	111.5 (3)	C12—C13—C8	121.57 (18)
C1—C2—H2A	124.3	C12—C13—H13A	119.2
C3—C2—H2A	124.3	C8—C13—H13A	119.2
C4—C3—C2	115.4 (4)	N1—C14—O1	119.39 (17)
C4—C3—H3A	122.3	N1—C14—C15	124.92 (17)
C2—C3—H3A	122.3	O1—C14—C15	115.69 (16)
C4—S1X—C1X	90.0 (8)	C5—C15—C14	117.90 (17)
C2X—C1X—S1X	111.9 (15)	C5—C15—C18	124.26 (17)
C2X—C1X—H1XA	124.1	C14—C15—C18	117.83 (17)
S1X—C1X—H1XA	124.1	O1—C16—C17	107.39 (15)
C1X—C2X—C3X	110.7 (16)	O1—C16—H16A	110.2
C1X—C2X—H2XA	124.6	C17—C16—H16A	110.2
C3X—C2X—H2XA	124.6	O1—C16—H16B	110.2
C4—C3X—C2X	110.6 (14)	C17—C16—H16B	110.2
C4—C3X—H3XA	124.7	H16A—C16—H16B	108.5
C2X—C3X—H3XA	124.7	C16—C17—H17A	109.5
C6—C5—C15	116.48 (17)	C16—C17—H17B	109.5
C6—C5—C4	119.64 (17)	H17A—C17—H17B	109.5
C15—C5—C4	123.82 (17)	C16—C17—H17C	109.5
C7—C6—C5	121.69 (18)	H17A—C17—H17C	109.5
C7—C6—H6A	119.2	H17B—C17—H17C	109.5
C5—C6—H6A	119.2	N3—C18—C15	177.8 (2)
N1—C7—C6	121.64 (17)
C3X—C4—S1—C1	93 (10)	C14—N1—C7—C6	−1.5 (3)
C3—C4—S1—C1	0.1 (3)	C14—N1—C7—C8	179.37 (16)
C5—C4—S1—C1	−172.59 (18)	C5—C6—C7—N1	1.4 (3)
S1X—C4—S1—C1	1.6 (4)	C5—C6—C7—C8	−179.56 (17)
C4—S1—C1—C2	−0.2 (3)	N1—C7—C8—C13	25.1 (3)
S1—C1—C2—C3	0.2 (5)	C6—C7—C8—C13	−154.02 (19)
C3X—C4—C3—C2	−5.3 (12)	N1—C7—C8—C9	−156.59 (17)
C5—C4—C3—C2	171.7 (3)	C6—C7—C8—C9	24.3 (3)
S1X—C4—C3—C2	−170 (5)	C13—C8—C9—C10	1.9 (3)
S1—C4—C3—C2	−0.1 (5)	C7—C8—C9—C10	−176.49 (18)
C1—C2—C3—C4	−0.1 (7)	C8—C9—C10—C11	1.0 (3)
C3X—C4—S1X—C1X	−3(2)	C9—C10—C11—N2	174.78 (18)
C3—C4—S1X—C1X	14 (4)	C9—C10—C11—C12	−2.9 (3)
C5—C4—S1X—C1X	176.6 (14)	N2—C11—C12—C13	−175.82 (17)
S1—C4—S1X—C1X	2.6 (15)	C10—C11—C12—C13	1.8 (3)
C4—S1X—C1X—C2X	−2(3)	C11—C12—C13—C8	1.1 (3)
S1X—C1X—C2X—C3X	6(4)	C9—C8—C13—C12	−2.9 (3)
C3—C4—C3X—C2X	4(2)	C7—C8—C13—C12	175.46 (17)
C5—C4—C3X—C2X	−173.0 (13)	C7—N1—C14—O1	−178.52 (15)
S1X—C4—C3X—C2X	6(2)	C7—N1—C14—C15	1.5 (3)
S1—C4—C3X—C2X	−85 (10)	C16—O1—C14—N1	−1.0 (2)
C1X—C2X—C3X—C4	−8(3)	C16—O1—C14—C15	179.01 (16)
C3X—C4—C5—C6	26.4 (13)	C6—C5—C15—C14	0.9 (3)
C3—C4—C5—C6	−150.2 (4)	C4—C5—C15—C14	−176.28 (17)
S1X—C4—C5—C6	−153.1 (5)	C6—C5—C15—C18	−177.58 (17)
S1—C4—C5—C6	20.7 (2)	C4—C5—C15—C18	5.2 (3)
C3X—C4—C5—C15	−156.5 (12)	N1—C14—C15—C5	−1.2 (3)
C3—C4—C5—C15	26.9 (4)	O1—C14—C15—C5	178.77 (16)
S1X—C4—C5—C15	24.1 (5)	N1—C14—C15—C18	177.37 (17)
S1—C4—C5—C15	−162.13 (15)	O1—C14—C15—C18	−2.6 (3)
C15—C5—C6—C7	−1.0 (3)	C14—O1—C16—C17	171.13 (16)
C4—C5—C6—C7	176.29 (17)

Cg1 is the centroid of the major disorder component of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N3i	0.92 (2)	2.29 (2)	3.197 (3)	168.2 (19)
C3—H3A···Cg1ii	0.93	2.93	3.566 (6)	127
C12—H12A···Cg1iii	0.93	2.78	3.430 (3)	128

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the major disorder component of the thio­phene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯N3i	0.92 (2)	2.29 (2)	3.197 (3)	168.2 (19)
C3—H3A⋯Cg1ii	0.93	2.93	3.566 (6)	127
C12—H12A⋯Cg1iii	0.93	2.78	3.430 (3)	128

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