6-(4-Bromo-phen-yl)-2-eth-oxy-4-(4-ethoxy-phen-yl)nicotinonitrile.

The mol-ecule of the title nicotinonitrile derivative, C(22)H(19)BrN(2)O(2), is non-planar, the central pyridine ring making dihedral angles of 7.34 (14) and 43.56 (15)° with the 4-bromo-phenyl and 4-ethoxy-phenyl rings, respectively. The eth-oxy group of the 4-ethoxy-phenyl is slightly twisted from the attached benzene ring [C-O-C-C = 174.2 (3)°], whereas the eth-oxy group attached to the pyridine ring is in a (+)syn-clinal conformation [C-O-C-C = 83.0 (3)°]. A weak intra-molecular C-H⋯N inter-action generates an S(5) ring motif. In the crystal structure, the mol-ecules are linked by weak inter-molecular C-H⋯N inter-actions into screw chains along the b axis. These chains stacked along the a axis. π-π inter-actions with centroid-centroid distances of 3.8724 (16) and 3.8727 (16) Å are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the synthesis and applications of nicotinonitrile derivatives, see: Borgna et al. (1993 ▶); Fun et al. (2008 ▶); Goda et al. (2004 ▶); Kamal et al. (2007 ▶); Malinka et al. (1998 ▶). For related structures, see: Chantrapromma et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C22H19BrN2O2

M = 423.29

Orthorhombic,

a = 4.3414 (2) Å

b = 14.7392 (6) Å

c = 29.4409 (13) Å

V = 1883.89 (14) Å3

Z = 4

Mo Kα radiation

μ = 2.20 mm−1

T = 100 K

0.57 × 0.05 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.368, T max = 0.931

18389 measured reflections

5477 independent reflections

4081 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.084

S = 0.99

5477 reflections

246 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.54 e Å−3

Absolute structure: Flack (1983 ▶), 2269 Friedel pairs

Flack parameter: 0.008 (9)

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 datablocks global, I. DOI: 10.1107/S1600536809051861/sj2683sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051861/sj2683Isup2.hkl

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

C22H19BrN2O2	Dx = 1.492 Mg m−3
Mr = 423.29	Melting point = 418–419 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5478 reflections
a = 4.3414 (2) Å	θ = 1.4–30.0°
b = 14.7392 (6) Å	µ = 2.20 mm−1
c = 29.4409 (13) Å	T = 100 K
V = 1883.89 (14) Å3	Needle, colourless
Z = 4	0.57 × 0.05 × 0.03 mm
F(000) = 864

Bruker APEXII CCD area detector diffractometer	5477 independent reflections
Radiation source: sealed tube	4081 reflections with I > 2σ(I)
graphite	Rint = 0.076
φ and ω scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
Tmin = 0.368, Tmax = 0.931	k = −20→20
18389 measured reflections	l = −41→41

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0276P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
5477 reflections	Δρmax = 0.58 e Å−3
246 parameters	Δρmin = −0.54 e Å−3
0 restraints	Absolute structure: Flack (1983), 2269 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.008 (9)

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
Br1	1.58148 (8)	0.282863 (19)	0.048491 (10)	0.02362 (8)
O1	0.4205 (6)	0.74788 (11)	0.14589 (6)	0.0216 (4)
O2	−0.0548 (6)	0.47728 (13)	0.40035 (6)	0.0252 (5)
N2	0.0125 (7)	0.76955 (17)	0.24500 (8)	0.0298 (7)
N1	0.7019 (6)	0.61534 (15)	0.14495 (8)	0.0196 (5)
C1	1.0999 (8)	0.50365 (18)	0.09800 (9)	0.0197 (6)
H1A	1.0551	0.5618	0.0877	0.024*
C2	1.2818 (8)	0.44749 (19)	0.07176 (10)	0.0214 (7)
H2A	1.3606	0.4679	0.0442	0.026*
C3	1.3459 (7)	0.36055 (18)	0.08677 (9)	0.0191 (7)
C4	1.2361 (8)	0.32993 (19)	0.12783 (10)	0.0220 (7)
H4A	1.2821	0.2716	0.1377	0.026*
C5	1.0564 (8)	0.38691 (17)	0.15427 (9)	0.0204 (6)
H5A	0.9838	0.3665	0.1822	0.025*
C6	0.9818 (7)	0.47489 (18)	0.13976 (9)	0.0185 (7)
C7	0.7817 (7)	0.53544 (18)	0.16580 (10)	0.0178 (6)
C8	0.6704 (7)	0.51430 (19)	0.20904 (10)	0.0195 (7)
H8A	0.7262	0.4597	0.2226	0.023*
C9	0.4766 (7)	0.57403 (18)	0.23214 (9)	0.0170 (6)
C10	0.3912 (8)	0.65388 (18)	0.20974 (9)	0.0189 (6)
C11	0.5132 (7)	0.67004 (18)	0.16607 (9)	0.0186 (7)
C12	0.3562 (8)	0.55145 (19)	0.27789 (9)	0.0189 (7)
C13	0.2478 (8)	0.46338 (18)	0.28616 (10)	0.0197 (7)
H13A	0.2680	0.4192	0.2638	0.024*
C14	0.1114 (9)	0.44126 (18)	0.32705 (9)	0.0200 (7)
H14A	0.0369	0.3829	0.3318	0.024*
C15	0.0855 (9)	0.50606 (18)	0.36103 (9)	0.0199 (6)
C16	0.1977 (8)	0.5937 (2)	0.35411 (10)	0.0230 (7)
H16A	0.1834	0.6371	0.3769	0.028*
C17	0.3314 (7)	0.61494 (19)	0.31246 (10)	0.0222 (7)
H17A	0.4061	0.6733	0.3077	0.027*
C18	0.5818 (8)	0.7761 (2)	0.10480 (8)	0.0230 (6)
H18A	0.7994	0.7626	0.1081	0.028*
H18B	0.5605	0.8412	0.1012	0.028*
C19	0.4616 (8)	0.7296 (2)	0.06258 (9)	0.0284 (7)
H19A	0.5543	0.7564	0.0362	0.043*
H19B	0.2420	0.7366	0.0610	0.043*
H19C	0.5123	0.6662	0.0637	0.043*
C20	−0.1371 (8)	0.5444 (2)	0.43323 (10)	0.0243 (8)
H20A	−0.2638	0.5911	0.4195	0.029*
H20B	0.0460	0.5726	0.4458	0.029*
C21	−0.3148 (8)	0.4952 (2)	0.46998 (11)	0.0306 (8)
H21A	−0.3648	0.5368	0.4939	0.046*
H21B	−0.1911	0.4467	0.4819	0.046*
H21C	−0.5011	0.4707	0.4574	0.046*
C22	0.1818 (7)	0.7186 (2)	0.22906 (9)	0.0210 (6)

	U11	U22	U33	U12	U13	U23
Br1	0.02481 (15)	0.02126 (12)	0.02480 (13)	0.00135 (15)	−0.00071 (16)	−0.00381 (13)
O1	0.0280 (11)	0.0181 (9)	0.0186 (9)	0.0039 (10)	0.0014 (12)	0.0043 (7)
O2	0.0376 (14)	0.0207 (9)	0.0173 (9)	0.0022 (11)	0.0044 (11)	−0.0004 (8)
N2	0.040 (2)	0.0236 (13)	0.0260 (12)	0.0087 (13)	−0.0018 (12)	0.0006 (10)
N1	0.0204 (14)	0.0189 (11)	0.0195 (12)	−0.0008 (11)	−0.0024 (11)	0.0008 (9)
C1	0.0211 (16)	0.0187 (12)	0.0192 (13)	0.0005 (15)	−0.0017 (15)	0.0004 (10)
C2	0.0186 (16)	0.0227 (15)	0.0229 (15)	−0.0008 (14)	−0.0008 (14)	0.0022 (12)
C3	0.0169 (18)	0.0196 (13)	0.0209 (14)	−0.0009 (12)	−0.0019 (13)	−0.0023 (11)
C4	0.0259 (18)	0.0154 (13)	0.0246 (16)	0.0012 (13)	−0.0041 (15)	0.0017 (11)
C5	0.0233 (17)	0.0196 (13)	0.0184 (13)	0.0003 (15)	−0.0004 (15)	0.0035 (10)
C6	0.0169 (18)	0.0186 (13)	0.0199 (14)	−0.0010 (12)	−0.0061 (13)	0.0020 (11)
C7	0.0172 (16)	0.0152 (13)	0.0210 (15)	−0.0022 (12)	−0.0055 (13)	0.0014 (11)
C8	0.0186 (19)	0.0190 (14)	0.0208 (15)	0.0006 (13)	−0.0027 (13)	0.0010 (12)
C9	0.0161 (17)	0.0181 (12)	0.0167 (13)	−0.0037 (12)	−0.0049 (12)	0.0021 (10)
C10	0.0219 (16)	0.0165 (12)	0.0182 (13)	0.0004 (14)	−0.0045 (14)	−0.0016 (10)
C11	0.0203 (19)	0.0141 (12)	0.0213 (13)	−0.0008 (12)	−0.0040 (12)	0.0016 (10)
C12	0.023 (2)	0.0186 (13)	0.0157 (14)	−0.0007 (13)	−0.0018 (13)	0.0008 (10)
C13	0.0243 (17)	0.0159 (13)	0.0191 (15)	0.0034 (13)	−0.0033 (14)	−0.0017 (11)
C14	0.0243 (18)	0.0157 (13)	0.0199 (14)	0.0017 (14)	−0.0019 (15)	0.0015 (10)
C15	0.0240 (16)	0.0215 (13)	0.0140 (13)	0.0030 (16)	0.0007 (15)	0.0007 (10)
C16	0.0288 (19)	0.0214 (14)	0.0188 (15)	0.0010 (14)	−0.0027 (15)	−0.0025 (12)
C17	0.0260 (19)	0.0169 (13)	0.0237 (15)	−0.0011 (13)	−0.0053 (14)	0.0001 (11)
C18	0.0266 (15)	0.0221 (13)	0.0204 (13)	−0.0010 (18)	0.0012 (15)	0.0036 (11)
C19	0.0302 (19)	0.0321 (16)	0.0230 (13)	0.0023 (17)	0.0012 (14)	0.0030 (12)
C20	0.029 (2)	0.0276 (15)	0.0165 (13)	0.0029 (15)	0.0022 (14)	−0.0077 (11)
C21	0.033 (2)	0.0360 (18)	0.0228 (16)	−0.0011 (17)	0.0033 (15)	−0.0058 (14)
C22	0.0264 (17)	0.0196 (12)	0.0171 (13)	−0.0023 (16)	−0.0042 (12)	0.0026 (13)

Br1—C3	1.905 (3)	C10—C11	1.411 (4)
O1—C11	1.353 (3)	C10—C22	1.435 (4)
O1—C18	1.458 (3)	C12—C17	1.387 (4)
O2—C15	1.375 (3)	C12—C13	1.402 (4)
O2—C20	1.429 (3)	C13—C14	1.380 (4)
N2—C22	1.151 (4)	C13—H13A	0.9300
N1—C11	1.307 (4)	C14—C15	1.388 (4)
N1—C7	1.372 (3)	C14—H14A	0.9300
C1—C2	1.380 (4)	C15—C16	1.395 (4)
C1—C6	1.398 (4)	C16—C17	1.392 (4)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.384 (4)	C17—H17A	0.9300
C2—H2A	0.9300	C18—C19	1.512 (4)
C3—C4	1.376 (4)	C18—H18A	0.9700
C4—C5	1.386 (4)	C18—H18B	0.9700
C4—H4A	0.9300	C19—H19A	0.9600
C5—C6	1.403 (4)	C19—H19B	0.9600
C5—H5A	0.9300	C19—H19C	0.9600
C6—C7	1.462 (4)	C20—C21	1.514 (4)
C7—C8	1.397 (4)	C20—H20A	0.9700
C8—C9	1.395 (4)	C20—H20B	0.9700
C8—H8A	0.9300	C21—H21A	0.9600
C9—C10	1.399 (4)	C21—H21B	0.9600
C9—C12	1.483 (4)	C21—H21C	0.9600
C11—O1—C18	117.6 (2)	C14—C13—H13A	119.5
C15—O2—C20	117.9 (2)	C12—C13—H13A	119.5
C11—N1—C7	118.4 (3)	C13—C14—C15	120.1 (3)
C2—C1—C6	121.4 (3)	C13—C14—H14A	120.0
C2—C1—H1A	119.3	C15—C14—H14A	120.0
C6—C1—H1A	119.3	O2—C15—C14	115.5 (2)
C1—C2—C3	119.4 (3)	O2—C15—C16	124.3 (2)
C1—C2—H2A	120.3	C14—C15—C16	120.2 (3)
C3—C2—H2A	120.3	C17—C16—C15	118.8 (3)
C4—C3—C2	121.0 (3)	C17—C16—H16A	120.6
C4—C3—Br1	120.6 (2)	C15—C16—H16A	120.6
C2—C3—Br1	118.4 (2)	C12—C17—C16	121.8 (3)
C3—C4—C5	119.3 (3)	C12—C17—H17A	119.1
C3—C4—H4A	120.3	C16—C17—H17A	119.1
C5—C4—H4A	120.3	O1—C18—C19	112.8 (3)
C4—C5—C6	121.3 (3)	O1—C18—H18A	109.0
C4—C5—H5A	119.4	C19—C18—H18A	109.0
C6—C5—H5A	119.4	O1—C18—H18B	109.0
C1—C6—C5	117.6 (3)	C19—C18—H18B	109.0
C1—C6—C7	119.6 (2)	H18A—C18—H18B	107.8
C5—C6—C7	122.8 (3)	C18—C19—H19A	109.5
N1—C7—C8	120.8 (3)	C18—C19—H19B	109.5
N1—C7—C6	116.1 (3)	H19A—C19—H19B	109.5
C8—C7—C6	123.2 (2)	C18—C19—H19C	109.5
C9—C8—C7	120.8 (3)	H19A—C19—H19C	109.5
C9—C8—H8A	119.6	H19B—C19—H19C	109.5
C7—C8—H8A	119.6	O2—C20—C21	106.2 (2)
C8—C9—C10	117.5 (3)	O2—C20—H20A	110.5
C8—C9—C12	120.9 (3)	C21—C20—H20A	110.5
C10—C9—C12	121.6 (3)	O2—C20—H20B	110.5
C9—C10—C11	118.2 (3)	C21—C20—H20B	110.5
C9—C10—C22	122.7 (3)	H20A—C20—H20B	108.7
C11—C10—C22	119.1 (2)	C20—C21—H21A	109.5
N1—C11—O1	120.1 (2)	C20—C21—H21B	109.5
N1—C11—C10	124.4 (3)	H21A—C21—H21B	109.5
O1—C11—C10	115.6 (2)	C20—C21—H21C	109.5
C17—C12—C13	118.1 (3)	H21A—C21—H21C	109.5
C17—C12—C9	122.9 (2)	H21B—C21—H21C	109.5
C13—C12—C9	118.9 (2)	N2—C22—C10	179.0 (3)
C14—C13—C12	120.9 (3)
C6—C1—C2—C3	0.8 (5)	C7—N1—C11—C10	1.9 (4)
C1—C2—C3—C4	−1.3 (5)	C18—O1—C11—N1	−11.6 (4)
C1—C2—C3—Br1	177.1 (2)	C18—O1—C11—C10	168.9 (3)
C2—C3—C4—C5	0.6 (5)	C9—C10—C11—N1	−0.1 (5)
Br1—C3—C4—C5	−177.8 (2)	C22—C10—C11—N1	−179.0 (3)
C3—C4—C5—C6	0.6 (5)	C9—C10—C11—O1	179.4 (3)
C2—C1—C6—C5	0.4 (5)	C22—C10—C11—O1	0.5 (4)
C2—C1—C6—C7	−178.0 (3)	C8—C9—C12—C17	140.0 (3)
C4—C5—C6—C1	−1.1 (5)	C10—C9—C12—C17	−42.6 (5)
C4—C5—C6—C7	177.2 (3)	C8—C9—C12—C13	−43.3 (4)
C11—N1—C7—C8	−1.7 (4)	C10—C9—C12—C13	134.0 (3)
C11—N1—C7—C6	177.2 (3)	C17—C12—C13—C14	2.0 (5)
C1—C6—C7—N1	5.4 (4)	C9—C12—C13—C14	−174.8 (3)
C5—C6—C7—N1	−173.0 (3)	C12—C13—C14—C15	−1.3 (5)
C1—C6—C7—C8	−175.7 (3)	C20—O2—C15—C14	−169.1 (3)
C5—C6—C7—C8	5.9 (5)	C20—O2—C15—C16	10.8 (5)
N1—C7—C8—C9	−0.3 (4)	C13—C14—C15—O2	179.8 (3)
C6—C7—C8—C9	−179.1 (3)	C13—C14—C15—C16	−0.2 (5)
C7—C8—C9—C10	2.0 (4)	O2—C15—C16—C17	−179.1 (3)
C7—C8—C9—C12	179.5 (3)	C14—C15—C16—C17	0.9 (5)
C8—C9—C10—C11	−1.9 (4)	C13—C12—C17—C16	−1.3 (5)
C12—C9—C10—C11	−179.3 (3)	C9—C12—C17—C16	175.4 (3)
C8—C9—C10—C22	177.0 (3)	C15—C16—C17—C12	−0.1 (5)
C12—C9—C10—C22	−0.4 (5)	C11—O1—C18—C19	83.0 (3)
C7—N1—C11—O1	−177.6 (3)	C15—O2—C20—C21	174.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1	0.93	2.41	2.758 (4)	102
C5—H5A···N2i	0.93	2.58	3.446 (4)	156
C13—H13A···N2ii	0.93	2.53	3.206 (4)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N1	0.93	2.41	2.758 (4)	102
C5—H5A⋯N2i	0.93	2.58	3.446 (4)	156
C13—H13A⋯N2ii	0.93	2.53	3.206 (4)	130

Symmetry codes: (i) ; (ii) .