4-(4-Cyano­benzoyl­meth­yl)benzonitrile

Wang, W.; Zhao, H.

doi:10.1107/S1600536808015079

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1148

doi:10.1107/S1600536808015079

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4-(4-Cyanobenzoylmethyl)benzonitrile

Wenxiang Wang ^a and Hong Zhao ^a ^*

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

(Received 1 May 2008; accepted 19 May 2008; online 24 May 2008)

In the title compound, C₁₆H₁₀N₂O, the dihedral angle formed by the benzene rings is 84.99 (7)°. The crystal structure is stabilized by intermolecular C—H⋯N and C—H⋯O hydrogen-bond interactions, forming chains running parallel to the b axis.

Related literature

For related literature, see: Arıcı et al. (2004 ); Radl et al. (2000 ); Bernstein et al. (1995 ); Zhao (2008 ).

Experimental

Crystal data

C₁₆H₁₀N₂O
M_r = 246.26
Triclinic, $[P \overline 1]$
a = 7.5217 (15) Å
b = 7.9759 (16) Å
c = 10.881 (2) Å
α = 96.78 (3)°
β = 93.34 (3)°
γ = 102.10 (3)°
V = 631.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.20 × 0.20 × 0.16 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.964, T_max = 0.988
6576 measured reflections
2898 independent reflections
1943 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.157
S = 1.04
2898 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.93	2.62	3.486 (3)	154
C12—H12⋯O1ⁱⁱ	0.93	2.42	3.268 (2)	152
Symmetry codes: (i) -x, -y+2, -z; (ii) x, y-1, z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015079/rz2215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015079/rz2215Isup2.hkl

checkCIF report

Comment top

Benzonitriles and their derivatives are important starting materials in the synthesis of some heterocyclic molecules (Radl et al., 2000; Arıcı et al., 2004). As part of our ongoing study on benzonitrile derivatives (Zhao, 2008), the crystal structure of one such derivatives is reported here.

The molecular structure of the title compound (Fig. 1) shows normal bond lengths and angles. The C≡N triple bond and C=O double bond lengths are 1.142 (2) and and 1.193 (2) Å, respectively. The benzene ring are oriented nearly perpendicular to each other, the dihedral angle they form being 84.99 (7)°. In the crystal structure, centrosymmetrically-related molecules are linked into dimeric units by intermolecular C—H···N hydrogen bonds (Table 1) forming ten-membered rings of graph-set R²₂(10) (Berstein et al., 1995). These dimers are further connected by intermolecular C—H···O hydrogen interactions to form chains running parallel to the b axis.

Related literature top

For related literature, see: Arıcı et al. (2004); Radl et al. (2000); Bernstein et al. (1995); Zhao (2008).

Experimental top

To a solution of sodium cyanide (2 g) in water (18 ml) was added 4-formylbenzonitrile (2.62 g). The mixture was stirred for 15 min at room temperature, then a saturated sodium hydrosulfite solution (15 ml) was added dropwise. The resulting mixture was stirred at 293K until a yellow solid was obtained. The solid was filtered and recrystallized from a mixture of methanol (18 ml) and DMF (6 ml), to give crystals of the title compound suitable for X-ray diffraction analysis on slow evaporation of the solvents.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level

4-(4-Cyanobenzoylmethyl)benzonitrile top

Crystal data top

C₁₆H₁₀N₂O	Z = 2
M_r = 246.26	F(000) = 256
Triclinic, P1	D_x = 1.295 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5217 (15) Å	Cell parameters from 2232 reflections
b = 7.9759 (16) Å	θ = 3.0–27.4°
c = 10.881 (2) Å	µ = 0.08 mm⁻¹
α = 96.78 (3)°	T = 293 K
β = 93.34 (3)°	Block, yellow
γ = 102.10 (3)°	0.20 × 0.20 × 0.16 mm
V = 631.5 (2) Å³

Data collection top

Rigaku Mercury2 diffractometer	2898 independent reflections
Radiation source: fine-focus sealed tube	1943 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −10→10
T_min = 0.964, T_max = 0.988	l = −14→14
6576 measured reflections

Refinement top

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)] = 0.059	H-atom parameters constrained
wR(F²) = 0.157	w = 1/[σ²(F_o²) + (0.0717P)² + 0.1009P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
2898 reflections	Δρ_max = 0.25 e Å⁻³
173 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.168 (18)

Crystal data top

C₁₆H₁₀N₂O	γ = 102.10 (3)°
M_r = 246.26	V = 631.5 (2) Å³
Triclinic, P1	Z = 2
a = 7.5217 (15) Å	Mo Kα radiation
b = 7.9759 (16) Å	µ = 0.08 mm⁻¹
c = 10.881 (2) Å	T = 293 K
α = 96.78 (3)°	0.20 × 0.20 × 0.16 mm
β = 93.34 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2898 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1943 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.988	R_int = 0.028
6576 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
2898 reflections	Δρ_min = −0.21 e Å⁻³
173 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
C1	0.1774 (2)	0.4661 (2)	0.18751 (15)	0.0468 (4)
C2	0.0347 (3)	0.5506 (2)	0.18255 (17)	0.0546 (5)
H2	−0.0715	0.5081	0.2189	0.066*
C3	0.0475 (3)	0.6970 (2)	0.12455 (17)	0.0532 (5)
H3	−0.0493	0.7528	0.1218	0.064*
C4	0.2055 (2)	0.7599 (2)	0.07065 (15)	0.0468 (4)
C5	0.3487 (3)	0.6762 (2)	0.07410 (17)	0.0550 (5)
H5	0.4545	0.7181	0.0371	0.066*
C6	0.3339 (3)	0.5301 (2)	0.13273 (17)	0.0550 (5)
H6	0.4306	0.4742	0.1353	0.066*
C7	0.2217 (3)	0.9131 (2)	0.00999 (17)	0.0558 (5)
C8	0.2389 (2)	0.2017 (2)	0.46012 (15)	0.0457 (4)
C9	0.2979 (3)	0.2430 (2)	0.58529 (16)	0.0580 (5)
H9	0.3178	0.3571	0.6226	0.070*
C10	0.3274 (3)	0.1162 (2)	0.65476 (17)	0.0599 (5)
H10	0.3668	0.1447	0.7387	0.072*
C11	0.2980 (2)	−0.0536 (2)	0.59929 (16)	0.0476 (4)
C12	0.2369 (2)	−0.0974 (2)	0.47534 (17)	0.0521 (5)
H12	0.2158	−0.2118	0.4384	0.062*
C13	0.2074 (3)	0.0309 (2)	0.40669 (16)	0.0508 (5)
H13	0.1656	0.0018	0.3232	0.061*
C14	0.3367 (3)	−0.1839 (2)	0.67244 (18)	0.0560 (5)
C15	0.2138 (3)	0.3455 (2)	0.38867 (17)	0.0589 (5)
N1	0.2355 (3)	1.0349 (2)	−0.03745 (18)	0.0757 (5)
N2	0.3690 (3)	−0.2834 (2)	0.73238 (17)	0.0742 (6)
O1	0.2335 (4)	0.48933 (19)	0.44054 (14)	0.1312 (10)
C16	0.1648 (3)	0.3057 (2)	0.25106 (16)	0.0529 (5)
H16A	0.0413	0.2365	0.2358	0.063*
H16B	0.2458	0.2374	0.2147	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0585 (11)	0.0387 (8)	0.0433 (9)	0.0106 (8)	−0.0022 (8)	0.0092 (7)
C2	0.0563 (11)	0.0512 (10)	0.0595 (11)	0.0119 (9)	0.0080 (9)	0.0189 (9)
C3	0.0581 (11)	0.0491 (10)	0.0585 (11)	0.0204 (8)	0.0042 (9)	0.0166 (8)
C4	0.0600 (11)	0.0400 (8)	0.0405 (8)	0.0105 (8)	−0.0016 (8)	0.0090 (7)
C5	0.0575 (11)	0.0531 (10)	0.0572 (11)	0.0126 (9)	0.0064 (9)	0.0171 (9)
C6	0.0573 (11)	0.0531 (10)	0.0592 (11)	0.0196 (9)	0.0014 (9)	0.0142 (9)
C7	0.0694 (13)	0.0504 (10)	0.0516 (10)	0.0168 (9)	0.0060 (9)	0.0153 (8)
C8	0.0579 (10)	0.0367 (8)	0.0456 (9)	0.0140 (7)	0.0060 (8)	0.0104 (7)
C9	0.0864 (14)	0.0370 (9)	0.0500 (10)	0.0134 (9)	0.0019 (10)	0.0055 (8)
C10	0.0798 (14)	0.0507 (10)	0.0478 (10)	0.0099 (10)	−0.0036 (9)	0.0133 (8)
C11	0.0474 (9)	0.0431 (9)	0.0569 (10)	0.0109 (7)	0.0092 (8)	0.0212 (8)
C12	0.0656 (12)	0.0330 (8)	0.0596 (11)	0.0121 (8)	0.0076 (9)	0.0106 (8)
C13	0.0668 (11)	0.0378 (9)	0.0486 (10)	0.0132 (8)	0.0022 (8)	0.0073 (7)
C14	0.0566 (11)	0.0512 (10)	0.0661 (12)	0.0144 (9)	0.0103 (9)	0.0243 (9)
C15	0.0930 (15)	0.0367 (9)	0.0514 (10)	0.0225 (9)	0.0028 (10)	0.0108 (8)
N1	0.0880 (13)	0.0672 (11)	0.0853 (13)	0.0269 (10)	0.0212 (10)	0.0399 (10)
N2	0.0837 (13)	0.0672 (11)	0.0843 (13)	0.0263 (10)	0.0116 (10)	0.0410 (10)
O1	0.296 (3)	0.0429 (8)	0.0603 (10)	0.0630 (13)	−0.0189 (13)	0.0018 (7)
C16	0.0680 (12)	0.0387 (9)	0.0527 (10)	0.0126 (8)	−0.0010 (9)	0.0108 (8)

Geometric parameters (Å, º) top

C1—C6	1.380 (3)	C8—C15	1.496 (2)
C1—C2	1.383 (2)	C9—C10	1.377 (2)
C1—C16	1.513 (2)	C9—H9	0.9300
C2—C3	1.381 (2)	C10—C11	1.384 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.381 (3)	C11—C12	1.379 (2)
C3—H3	0.9300	C11—C14	1.446 (2)
C4—C5	1.382 (3)	C12—C13	1.382 (2)
C4—C7	1.442 (2)	C12—H12	0.9300
C5—C6	1.381 (2)	C13—H13	0.9300
C5—H5	0.9300	C14—N2	1.140 (2)
C6—H6	0.9300	C15—O1	1.193 (2)
C7—N1	1.142 (2)	C15—C16	1.501 (3)
C8—C13	1.383 (2)	C16—H16A	0.9700
C8—C9	1.387 (2)	C16—H16B	0.9700

C6—C1—C2	118.89 (15)	C8—C9—H9	119.7
C6—C1—C16	119.65 (16)	C9—C10—C11	119.80 (17)
C2—C1—C16	121.46 (16)	C9—C10—H10	120.1
C3—C2—C1	121.07 (17)	C11—C10—H10	120.1
C3—C2—H2	119.5	C12—C11—C10	120.45 (15)
C1—C2—H2	119.5	C12—C11—C14	120.50 (16)
C2—C3—C4	119.32 (17)	C10—C11—C14	119.03 (17)
C2—C3—H3	120.3	C11—C12—C13	119.21 (16)
C4—C3—H3	120.3	C11—C12—H12	120.4
C3—C4—C5	120.28 (15)	C13—C12—H12	120.4
C3—C4—C7	120.13 (16)	C12—C13—C8	121.10 (17)
C5—C4—C7	119.59 (16)	C12—C13—H13	119.5
C6—C5—C4	119.70 (17)	C8—C13—H13	119.5
C6—C5—H5	120.2	N2—C14—C11	178.3 (2)
C4—C5—H5	120.2	O1—C15—C8	120.30 (17)
C1—C6—C5	120.74 (17)	O1—C15—C16	120.78 (16)
C1—C6—H6	119.6	C8—C15—C16	118.92 (15)
C5—C6—H6	119.6	C15—C16—C1	113.15 (14)
N1—C7—C4	179.5 (2)	C15—C16—H16A	108.9
C13—C8—C9	118.91 (15)	C1—C16—H16A	108.9
C13—C8—C15	122.97 (16)	C15—C16—H16B	108.9
C9—C8—C15	118.12 (15)	C1—C16—H16B	108.9
C10—C9—C8	120.52 (16)	H16A—C16—H16B	107.8
C10—C9—H9	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93	2.62	3.486 (3)	154
C12—H12···O1ⁱⁱ	0.93	2.42	3.268 (2)	152

Symmetry codes: (i) −x, −y+2, −z; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀N₂O
M_r	246.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5217 (15), 7.9759 (16), 10.881 (2)
α, β, γ (°)	96.78 (3), 93.34 (3), 102.10 (3)
V (Å³)	631.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.964, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6576, 2898, 1943
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.157, 1.04
No. of reflections	2898
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93	2.62	3.486 (3)	154
C12—H12···O1ⁱⁱ	0.93	2.42	3.268 (2)	152

Symmetry codes: (i) −x, −y+2, −z; (ii) x, y−1, z.

Acknowledgements

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

References

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