N,N-Diethyl-4-[(E)-(pyridin-3-yl)diazen-yl]aniline.

The mol-ecule of the title compound, C15H18N4, adopts a trans conformation with respect to the diazo N=N bond. The dihedral angle between the benzene and pyridine rings in the mol-ecule is 8.03 (5)°. In the crystal, a weak C-H⋯π inter-action arranges the mol-ecules into a corrugated ribbon, with an anti-parallel orientation of neighboring mol-ecules propagating in the [100] direction.

Related literature

For details of the synthesis, see: Peor et al. (2008 ▶). For nonlinear optical properties of stilbene derivatives, see: Forrest et al. (1996 ▶). For the comparision of nonlinear optical properties of stilbene and diazo derivatives, see: Chemla & Zyss (1987 ▶); Morley (1995 ▶). For second-harmonic generation in the P212121 space group, see: Rivera et al. (2006 ▶). For the distribution of endocyclic angles in pyridine derivatives, see: Draguta et al. (2012 ▶).

Experimental

Crystal data

C15H18N4

M = 254.33

Orthorhombic,

a = 7.4332 (7) Å

b = 9.1093 (8) Å

c = 20.1946 (19) Å

V = 1367.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.977, T max = 0.985

16318 measured reflections

4195 independent reflections

4012 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.113

S = 1.00

4195 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019545/cv5422sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019545/cv5422Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813019545/cv5422Isup3.cml

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

C15H18N4	F(000) = 544
Mr = 254.33	Dx = 1.235 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8453 reflections
a = 7.4332 (7) Å	θ = 4.5–30.6°
b = 9.1093 (8) Å	µ = 0.08 mm−1
c = 20.1946 (19) Å	T = 100 K
V = 1367.4 (2) Å3	Plate, red
Z = 4	0.30 × 0.25 × 0.20 mm

Bruker APEXII CCD diffractometer	4195 independent reflections
Radiation source: fine-focus sealed tube	4012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 30.7°, θmin = 4.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.977, Tmax = 0.985	k = −13→13
16318 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.050P)2 + 0.7002P] where P = (Fo2 + 2Fc2)/3
4195 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.62 e Å−3
0 restraints	Δρmin = −0.30 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
N4	0.00601 (15)	0.19116 (12)	0.62882 (5)	0.0171 (2)
C9	0.00202 (16)	0.29808 (13)	0.58137 (6)	0.0156 (2)
C4	0.02116 (18)	0.83461 (14)	0.38104 (7)	0.0203 (2)
C8	−0.10014 (18)	0.27948 (14)	0.52266 (6)	0.0188 (2)
H8	−0.1662	0.1914	0.5161	0.023*
C10	0.09862 (17)	0.43213 (14)	0.58851 (6)	0.0190 (2)
H10	0.1695	0.4479	0.6270	0.023*
N3	−0.03161 (16)	0.61944 (13)	0.42929 (6)	0.0214 (2)
C7	−0.10486 (19)	0.38750 (15)	0.47499 (7)	0.0214 (2)
H7	−0.1736	0.3720	0.4360	0.026*
N2	0.04908 (15)	0.73981 (13)	0.43644 (6)	0.0216 (2)
N1	−0.12281 (17)	0.90062 (14)	0.27805 (6)	0.0252 (2)
C6	−0.01126 (18)	0.51897 (14)	0.48261 (7)	0.0202 (2)
C15	−0.03051 (19)	−0.06308 (14)	0.58509 (7)	0.0232 (3)
H15A	−0.0141	−0.0317	0.5391	0.035*
H15B	−0.1116	−0.1479	0.5865	0.035*
H15C	0.0862	−0.0904	0.6040	0.035*
C14	−0.11139 (17)	0.06233 (14)	0.62505 (6)	0.0182 (2)
H14A	−0.2272	0.0915	0.6047	0.022*
H14B	−0.1369	0.0272	0.6705	0.022*
C3	0.1248 (2)	0.96131 (17)	0.37904 (8)	0.0271 (3)
H3	0.2076	0.9829	0.4135	0.032*
C11	0.09094 (18)	0.54000 (14)	0.54022 (7)	0.0202 (2)
H11	0.1555	0.6290	0.5462	0.024*
C1	−0.0180 (2)	1.02026 (16)	0.27692 (7)	0.0263 (3)
H1	−0.0288	1.0849	0.2402	0.032*
C5	−0.10281 (19)	0.81021 (15)	0.32994 (7)	0.0217 (2)
H5	−0.1766	0.7252	0.3322	0.026*
C12	0.13549 (18)	0.19273 (15)	0.68329 (6)	0.0201 (2)
H12A	0.2440	0.2474	0.6692	0.024*
H12B	0.1724	0.0906	0.6931	0.024*
C2	0.1047 (2)	1.05542 (16)	0.32577 (8)	0.0292 (3)
H2	0.1741	1.1427	0.3229	0.035*
C13	0.0618 (2)	0.2623 (2)	0.74616 (7)	0.0303 (3)
H13A	0.0375	0.3666	0.7382	0.045*
H13B	0.1504	0.2525	0.7818	0.045*
H13C	−0.0500	0.2128	0.7590	0.045*

	U11	U22	U33	U12	U13	U23
N4	0.0193 (5)	0.0161 (4)	0.0160 (4)	−0.0027 (4)	−0.0034 (4)	0.0008 (4)
C9	0.0150 (5)	0.0145 (5)	0.0173 (5)	0.0002 (4)	0.0011 (4)	−0.0009 (4)
C4	0.0194 (6)	0.0191 (5)	0.0224 (6)	0.0049 (5)	0.0038 (5)	0.0017 (4)
C8	0.0185 (5)	0.0175 (5)	0.0205 (5)	−0.0005 (4)	−0.0030 (5)	0.0011 (4)
C10	0.0178 (5)	0.0164 (5)	0.0228 (5)	−0.0006 (5)	−0.0006 (5)	−0.0031 (4)
N3	0.0187 (5)	0.0212 (5)	0.0241 (5)	−0.0001 (4)	−0.0010 (4)	−0.0014 (4)
C7	0.0207 (6)	0.0224 (6)	0.0211 (5)	0.0028 (5)	−0.0025 (5)	0.0023 (5)
N2	0.0196 (5)	0.0210 (5)	0.0241 (5)	0.0008 (4)	−0.0007 (4)	−0.0009 (4)
N1	0.0250 (6)	0.0263 (6)	0.0241 (5)	−0.0002 (5)	−0.0011 (5)	0.0021 (5)
C6	0.0187 (6)	0.0176 (5)	0.0242 (6)	0.0022 (5)	0.0026 (5)	0.0028 (4)
C15	0.0217 (6)	0.0174 (5)	0.0305 (6)	−0.0012 (5)	−0.0006 (5)	−0.0037 (5)
C14	0.0181 (5)	0.0157 (5)	0.0208 (5)	−0.0028 (4)	−0.0003 (4)	0.0016 (4)
C3	0.0237 (6)	0.0271 (7)	0.0305 (7)	−0.0012 (6)	−0.0042 (6)	0.0011 (6)
C11	0.0188 (6)	0.0156 (5)	0.0262 (6)	−0.0004 (5)	0.0021 (5)	−0.0004 (4)
C1	0.0253 (6)	0.0242 (6)	0.0295 (7)	0.0016 (5)	0.0042 (6)	0.0097 (5)
C5	0.0217 (6)	0.0169 (5)	0.0266 (6)	−0.0001 (5)	0.0020 (5)	0.0004 (5)
C12	0.0209 (6)	0.0220 (6)	0.0174 (5)	−0.0008 (5)	−0.0050 (4)	0.0003 (4)
C2	0.0240 (6)	0.0221 (6)	0.0414 (8)	−0.0046 (5)	0.0011 (6)	0.0038 (6)
C13	0.0338 (8)	0.0389 (8)	0.0183 (6)	−0.0062 (7)	−0.0009 (5)	−0.0064 (6)

N4—C9	1.3665 (15)	C15—C14	1.5224 (18)
N4—C14	1.4645 (16)	C15—H15A	0.9800
N4—C12	1.4616 (16)	C15—H15B	0.9800
C9—C8	1.4182 (17)	C15—H15C	0.9800
C9—C10	1.4239 (17)	C14—H14A	0.9900
C4—C3	1.388 (2)	C14—H14B	0.9900
C4—C5	1.4012 (19)	C3—C2	1.384 (2)
C4—N2	1.4285 (17)	C3—H3	0.9500
C8—C7	1.3770 (18)	C11—H11	0.9500
C8—H8	0.9500	C1—C2	1.381 (2)
C10—C11	1.3856 (18)	C1—H1	0.9500
C10—H10	0.9500	C5—H5	0.9500
N3—N2	1.2581 (16)	C12—C13	1.5212 (19)
N3—C6	1.4213 (17)	C12—H12A	0.9900
C7—C6	1.3936 (19)	C12—H12B	0.9900
C7—H7	0.9500	C2—H2	0.9500
N1—C1	1.3398 (19)	C13—H13A	0.9800
N1—C5	1.3411 (18)	C13—H13B	0.9800
C6—C11	1.4027 (19)	C13—H13C	0.9800
C9—N4—C14	121.45 (10)	C15—C14—H14A	108.9
C9—N4—C12	122.34 (11)	N4—C14—H14B	108.9
C14—N4—C12	116.06 (10)	C15—C14—H14B	108.9
N4—C9—C8	120.84 (11)	H14A—C14—H14B	107.8
N4—C9—C10	121.95 (11)	C4—C3—C2	118.55 (14)
C8—C9—C10	117.20 (11)	C4—C3—H3	120.7
C3—C4—C5	118.38 (12)	C2—C3—H3	120.7
C3—C4—N2	116.42 (12)	C10—C11—C6	120.61 (12)
C5—C4—N2	125.20 (12)	C10—C11—H11	119.7
C7—C8—C9	120.85 (12)	C6—C11—H11	119.7
C7—C8—H8	119.6	N1—C1—C2	124.08 (13)
C9—C8—H8	119.6	N1—C1—H1	118.0
C11—C10—C9	121.08 (12)	C2—C1—H1	118.0
C11—C10—H10	119.5	N1—C5—C4	123.43 (13)
C9—C10—H10	119.5	N1—C5—H5	118.3
N2—N3—C6	115.05 (11)	C4—C5—H5	118.3
C8—C7—C6	121.61 (12)	N4—C12—C13	113.27 (12)
C8—C7—H7	119.2	N4—C12—H12A	108.9
C6—C7—H7	119.2	C13—C12—H12A	108.9
N3—N2—C4	111.57 (11)	N4—C12—H12B	108.9
C1—N1—C5	116.64 (13)	C13—C12—H12B	108.9
C7—C6—C11	118.64 (12)	H12A—C12—H12B	107.7
C7—C6—N3	114.62 (12)	C1—C2—C3	118.88 (14)
C11—C6—N3	126.74 (12)	C1—C2—H2	120.6
C14—C15—H15A	109.5	C3—C2—H2	120.6
C14—C15—H15B	109.5	C12—C13—H13A	109.5
H15A—C15—H15B	109.5	C12—C13—H13B	109.5
C14—C15—H15C	109.5	H13A—C13—H13B	109.5
H15A—C15—H15C	109.5	C12—C13—H13C	109.5
H15B—C15—H15C	109.5	H13A—C13—H13C	109.5
N4—C14—C15	113.18 (11)	H13B—C13—H13C	109.5
N4—C14—H14A	108.9
C14—N4—C9—C8	−7.75 (18)	C9—N4—C14—C15	87.55 (14)
C12—N4—C9—C8	167.67 (12)	C12—N4—C14—C15	−88.15 (14)
C14—N4—C9—C10	172.05 (11)	C5—C4—C3—C2	−1.9 (2)
C12—N4—C9—C10	−12.53 (18)	N2—C4—C3—C2	178.95 (13)
N4—C9—C8—C7	179.69 (12)	C9—C10—C11—C6	−0.63 (19)
C10—C9—C8—C7	−0.12 (18)	C7—C6—C11—C10	0.04 (19)
N4—C9—C10—C11	−179.14 (12)	N3—C6—C11—C10	179.91 (12)
C8—C9—C10—C11	0.66 (18)	C5—N1—C1—C2	−1.0 (2)
C9—C8—C7—C6	−0.5 (2)	C1—N1—C5—C4	−0.7 (2)
C6—N3—N2—C4	−179.69 (11)	C3—C4—C5—N1	2.1 (2)
C3—C4—N2—N3	−170.84 (12)	N2—C4—C5—N1	−178.75 (13)
C5—C4—N2—N3	10.04 (18)	C9—N4—C12—C13	95.10 (15)
C8—C7—C6—C11	0.5 (2)	C14—N4—C12—C13	−89.25 (14)
C8—C7—C6—N3	−179.38 (12)	N1—C1—C2—C3	1.2 (2)
N2—N3—C6—C7	178.43 (12)	C4—C3—C2—C1	0.3 (2)
N2—N3—C6—C11	−1.45 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cgi	0.95	2.60	3.483 (2)	158

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of C6–C11 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg i	0.95	2.60	3.483 (2)	158

Symmetry code: (i) .