3-[4-(Dimethyl­amino)benzyl­ideneamino]benzonitrile

Xu, H.-J.; Tan, Q.-Y.; Cui, L.-J.; Qian, K.

doi:10.1107/S1600536809011568

organic compounds

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Volume 65| Part 5| May 2009| Page o945

doi:10.1107/S1600536809011568

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3-[4-(Dimethylamino)benzylideneamino]benzonitrile

Hai-Jun Xu,^a ^* Qin-Ying Tan,^a Li-Jing Cui ^a and Kun Qian ^b

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, and ^bJiangXi University of Traditional Medicine, Nanchang 330047, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 19 March 2009; accepted 29 March 2009; online 2 April 2009)

The molecule of the title Schiff base, C₁₆H₁₅N₃, is non-planar and displays a trans configuration with respect to the C=N double bond. The two benzene rings make a dihedral angle of 49.24 (3)°.

Related literature

For general background on Schiff base coordination complexes, see: Garnovskii et al. (1993 ). For a related structure, see: Gong & Xu (2008 )

Experimental

Crystal data

C₁₆H₁₅N₃
M_r = 249.31
Monoclinic, P 2₁ /c
a = 6.0924 (6) Å
b = 29.127 (3) Å
c = 7.3768 (7) Å
β = 92.924 (1)°
V = 1307.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.961, T_max = 1.000 (expected range = 0.947–0.985)
7018 measured reflections
2559 independent reflections
2241 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.110
S = 1.05
2559 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011568/dn2436sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011568/dn2436Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have attracted great attention and been extensively investigated in terms of their crystallography and coordination chemistry (Garnovskii et al., 1993). As a continuation of our studies on Schiff-base compounds, we here report the synthesis and crystal structure of the title compound (I).

The molecule displays a trans configuration with respect to the C=N double bond (Fig. 1). The values of the C—C, C=C, C—N and C=N bond distances in (I) are similar to the corresponding bond lengths in 4-(2-Hydroxybenzylideneamino)benzonitrile(Gong & Xu, 2008). The molecule is nonplanar and the dihedral angle between the planes of the two benzene rings is 49.24 (0.03) °.

Related literature top

For general background on Schiff base coordination complexes, see: Garnovskii et al. (1993). For related bond-length data, see: Gong & Xu (2008)

Experimental top

All chemicals were obtained from commercial sources and directly used without further purification. 3-aminobenzonitrile (1.18 g, 10 mmol) and 4-(dimethylamino)benzaldehyde (1.49 g, 10 mmol) were dissolved in ethanol (20 ml). The mixture was heated to reflux for 6 h, then cooled to room temperature overnight and large amounts of a yellow precipitate were formed. Yellow crystals were obtained by recrystallization from ethanol(yield:2.04,82%). ¹H-NMR(CDCl₃, 300 MHz): δ3.10 (s, 6 H), 6.73–6.76(d, 2 H), 7.45–7.50 (m, 4 H), 7.84–7.87 (d, 2 H), 8.27 (s, 1 H). Esi-MS: calcd for C₁₆H₁₅N₃ m/z 249.31, found 250.18[M+1]. For the X-ray diffraction analysis, suitable single crystals of compound (I) were obtained after two weeks by slow evaporation from an ethanol solution.

Computing details top

Data collection: SMART(Bruker, 2000); cell refinement: SAINT(Bruker, 2000); data reduction: SAINT(Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

3-[4-(Dimethylamino)benzylideneamino]benzonitrile top

Crystal data top

C₁₆H₁₅N₃	F(000) = 528
M_r = 249.31	D_x = 1.267 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2559 reflections
a = 6.0924 (6) Å	θ = 2.8–26.0°
b = 29.127 (3) Å	µ = 0.08 mm⁻¹
c = 7.3768 (7) Å	T = 293 K
β = 92.924 (1)°	Block, yellow
V = 1307.3 (2) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2559 independent reflections
Radiation source: fine-focus sealed tube	2241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −7→7
T_min = 0.961, T_max = 1.000	k = −35→25
7018 measured reflections	l = −9→8

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0596P)² + 0.1755P] where P = (F_o² + 2F_c²)/3
2559 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₅N₃	V = 1307.3 (2) Å³
M_r = 249.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0924 (6) Å	µ = 0.08 mm⁻¹
b = 29.127 (3) Å	T = 293 K
c = 7.3768 (7) Å	0.30 × 0.20 × 0.20 mm
β = 92.924 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2559 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2241 reflections with I > 2σ(I)
T_min = 0.961, T_max = 1.000	R_int = 0.064
7018 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
2559 reflections	Δρ_min = −0.25 e Å⁻³
174 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.61108 (15)	0.27979 (3)	0.59956 (13)	0.0190 (2)
N2	0.28428 (16)	0.47022 (3)	0.70360 (14)	0.0263 (3)
N3	0.14557 (15)	0.08098 (3)	0.61116 (13)	0.0189 (2)
C1	0.65373 (17)	0.32723 (4)	0.58571 (14)	0.0171 (2)
C2	0.50894 (17)	0.36071 (4)	0.64200 (14)	0.0169 (2)
H2A	0.3790	0.3523	0.6941	0.020*
C3	0.56051 (17)	0.40708 (4)	0.61955 (14)	0.0175 (3)
C4	0.75672 (18)	0.42049 (4)	0.54437 (14)	0.0190 (3)
H4A	0.7889	0.4514	0.5285	0.023*
C5	0.90207 (18)	0.38678 (4)	0.49403 (15)	0.0207 (3)
H5A	1.0341	0.3951	0.4452	0.025*
C6	0.85265 (17)	0.34081 (4)	0.51572 (15)	0.0197 (3)
H6A	0.9532	0.3186	0.4833	0.024*
C7	0.40682 (18)	0.44200 (4)	0.66975 (15)	0.0198 (3)
C8	0.42252 (17)	0.26531 (4)	0.53867 (14)	0.0174 (3)
H8A	0.3245	0.2863	0.4847	0.021*
C9	0.35526 (17)	0.21769 (4)	0.55017 (14)	0.0171 (3)
C10	0.14627 (17)	0.20363 (4)	0.48467 (15)	0.0188 (3)
H10A	0.0515	0.2251	0.4298	0.023*
C11	0.07713 (17)	0.15861 (4)	0.49941 (15)	0.0187 (3)
H11A	−0.0617	0.1502	0.4526	0.022*
C12	0.21502 (17)	0.12527 (4)	0.58471 (14)	0.0162 (2)
C13	0.42785 (17)	0.13953 (4)	0.64815 (14)	0.0176 (3)
H13A	0.5238	0.1182	0.7028	0.021*
C14	0.49460 (17)	0.18430 (4)	0.63022 (14)	0.0175 (2)
H14A	0.6355	0.1926	0.6722	0.021*
C15	0.30017 (19)	0.04552 (4)	0.67163 (16)	0.0229 (3)
H15A	0.3783	0.0553	0.7812	0.034*
H15B	0.4027	0.0401	0.5793	0.034*
H15C	0.2218	0.0177	0.6943	0.034*
C16	−0.06638 (18)	0.06583 (4)	0.53393 (16)	0.0222 (3)
H16A	−0.1766	0.0881	0.5599	0.033*
H16B	−0.1035	0.0368	0.5860	0.033*
H16C	−0.0590	0.0626	0.4049	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0189 (5)	0.0166 (5)	0.0216 (5)	0.0000 (4)	0.0009 (4)	0.0003 (4)
N2	0.0295 (5)	0.0194 (5)	0.0304 (6)	−0.0017 (4)	0.0058 (4)	−0.0035 (4)
N3	0.0188 (5)	0.0154 (5)	0.0224 (5)	−0.0007 (4)	0.0011 (4)	0.0008 (4)
C1	0.0179 (5)	0.0166 (5)	0.0162 (5)	−0.0016 (4)	−0.0034 (4)	0.0017 (4)
C2	0.0150 (5)	0.0187 (6)	0.0170 (5)	−0.0024 (4)	0.0005 (4)	0.0002 (4)
C3	0.0190 (5)	0.0182 (6)	0.0151 (5)	−0.0014 (4)	−0.0010 (4)	−0.0016 (4)
C4	0.0211 (5)	0.0184 (6)	0.0172 (5)	−0.0060 (4)	−0.0022 (4)	0.0005 (4)
C5	0.0161 (5)	0.0262 (6)	0.0196 (6)	−0.0049 (5)	0.0002 (4)	0.0005 (5)
C6	0.0149 (5)	0.0231 (6)	0.0209 (5)	0.0023 (4)	−0.0010 (4)	−0.0014 (4)
C7	0.0225 (6)	0.0170 (6)	0.0199 (5)	−0.0056 (5)	0.0009 (4)	−0.0009 (4)
C8	0.0165 (5)	0.0171 (6)	0.0187 (5)	0.0033 (4)	0.0027 (4)	0.0015 (4)
C9	0.0171 (5)	0.0170 (5)	0.0174 (6)	0.0012 (4)	0.0039 (4)	0.0001 (4)
C10	0.0164 (5)	0.0180 (6)	0.0221 (6)	0.0042 (4)	0.0013 (4)	0.0018 (4)
C11	0.0147 (5)	0.0196 (6)	0.0219 (6)	−0.0004 (4)	0.0014 (4)	−0.0001 (4)
C12	0.0181 (5)	0.0162 (5)	0.0148 (5)	0.0015 (4)	0.0046 (4)	−0.0003 (4)
C13	0.0186 (5)	0.0176 (5)	0.0167 (5)	0.0041 (4)	0.0013 (4)	0.0013 (4)
C14	0.0162 (5)	0.0189 (5)	0.0175 (5)	0.0008 (4)	0.0012 (4)	−0.0007 (4)
C15	0.0292 (6)	0.0158 (6)	0.0233 (6)	0.0000 (5)	−0.0039 (5)	0.0009 (4)
C16	0.0198 (6)	0.0184 (6)	0.0285 (6)	−0.0020 (4)	0.0035 (5)	−0.0007 (5)

Geometric parameters (Å, º) top

N1—C8	1.2833 (14)	C8—H8A	0.9300
N1—C1	1.4105 (14)	C9—C10	1.3998 (15)
N2—C7	1.1466 (15)	C9—C14	1.4013 (15)
N3—C12	1.3746 (14)	C10—C11	1.3834 (16)
N3—C15	1.4526 (14)	C10—H10A	0.9300
N3—C16	1.4531 (14)	C11—C12	1.4109 (15)
C1—C2	1.3924 (15)	C11—H11A	0.9300
C1—C6	1.3984 (15)	C12—C13	1.4181 (15)
C2—C3	1.3986 (15)	C13—C14	1.3743 (15)
C2—H2A	0.9300	C13—H13A	0.9300
C3—C4	1.3988 (15)	C14—H14A	0.9300
C3—C7	1.4434 (16)	C15—H15A	0.9600
C4—C5	1.3854 (16)	C15—H15B	0.9600
C4—H4A	0.9300	C15—H15C	0.9600
C5—C6	1.3836 (16)	C16—H16A	0.9600
C5—H5A	0.9300	C16—H16B	0.9600
C6—H6A	0.9300	C16—H16C	0.9600
C8—C9	1.4501 (15)

C8—N1—C1	117.49 (9)	C14—C9—C8	121.43 (10)
C12—N3—C15	120.76 (9)	C11—C10—C9	121.69 (10)
C12—N3—C16	120.20 (9)	C11—C10—H10A	119.2
C15—N3—C16	116.99 (9)	C9—C10—H10A	119.2
C2—C1—C6	119.09 (10)	C10—C11—C12	120.71 (10)
C2—C1—N1	122.86 (10)	C10—C11—H11A	119.6
C6—C1—N1	118.04 (10)	C12—C11—H11A	119.6
C1—C2—C3	119.44 (10)	N3—C12—C11	121.91 (9)
C1—C2—H2A	120.3	N3—C12—C13	120.73 (10)
C3—C2—H2A	120.3	C11—C12—C13	117.33 (10)
C2—C3—C4	121.21 (10)	C14—C13—C12	121.08 (10)
C2—C3—C7	119.83 (10)	C14—C13—H13A	119.5
C4—C3—C7	118.94 (10)	C12—C13—H13A	119.5
C5—C4—C3	118.64 (10)	C13—C14—C9	121.54 (10)
C5—C4—H4A	120.7	C13—C14—H14A	119.2
C3—C4—H4A	120.7	C9—C14—H14A	119.2
C6—C5—C4	120.59 (10)	N3—C15—H15A	109.5
C6—C5—H5A	119.7	N3—C15—H15B	109.5
C4—C5—H5A	119.7	H15A—C15—H15B	109.5
C5—C6—C1	120.95 (10)	N3—C15—H15C	109.5
C5—C6—H6A	119.5	H15A—C15—H15C	109.5
C1—C6—H6A	119.5	H15B—C15—H15C	109.5
N2—C7—C3	177.67 (13)	N3—C16—H16A	109.5
N1—C8—C9	123.00 (10)	N3—C16—H16B	109.5
N1—C8—H8A	118.5	H16A—C16—H16B	109.5
C9—C8—H8A	118.5	N3—C16—H16C	109.5
C10—C9—C14	117.61 (10)	H16A—C16—H16C	109.5
C10—C9—C8	120.95 (10)	H16B—C16—H16C	109.5

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃
M_r	249.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.0924 (6), 29.127 (3), 7.3768 (7)
β (°)	92.924 (1)
V (Å³)	1307.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.961, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7018, 2559, 2241
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.05
No. of reflections	2559
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25

Computer programs: SMART(Bruker, 2000), SAINT(Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (2000). SMART. and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Garnovskii, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem. Rev. 126, 1–69. CrossRef CAS Web of Science Google Scholar
Gong, X.-X. & Xu, H.-J. (2008). Acta Cryst. E64, o1188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar