2,2′,6,6′-Tetra­ethyl-4,4′-methyl­enedibenzonitrile

Yuan, J.; Zhu, Y.

doi:10.1107/S1600536810020052

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1523

doi:10.1107/S1600536810020052

Open

access

2,2′,6,6′-Tetraethyl-4,4′-methylenedibenzonitrile

Jingjing Yuan ^a ^* and Yanping Zhu ^a

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: jingjingyuan0503@163.com

(Received 9 May 2010; accepted 27 May 2010; online 5 June 2010)

The asymmetric unit of the title compound, C₂₃H₂₆N₂, contains one half-molecule, which is completed by the operation of a crystallographic twofold axis. In the molecule, the two benzene rings form a dihedral angle of 77.09 (7)°.

Related literature

For applications of aromatic nitriles, see: Debasree et al. (2009 ); Lal Dhar et al. (2009 ); Ren et al. (2009 ); Zhou et al. (2009 ). For the preparation of the title compound, see: Donald et al. (1955 ).

Experimental

Crystal data

C₂₃H₂₆N₂
M_r = 330.46
Monoclinic, C 2/c
a = 16.016 (3) Å
b = 9.3218 (19) Å
c = 13.977 (3) Å
β = 115.55 (3)°
V = 1882.6 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 290 K
0.16 × 0.10 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
8636 measured reflections
2055 independent reflections
1405 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.16
2055 reflections
117 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810020052/cv2718sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020052/cv2718Isup2.hkl

checkCIF report

Comment top

Aromatic nitriles are important intermediates in the synthesis of pharmaceuticals, agrochemicals, herbicides, dyes and pigments, and serve as precursors for many useful compounds including benzoic acid derivatives, benzylamines, benzaldehydes, and heterocycles (Debasree et al., 2009; Lal Dhar et al., 2009; Ren et al., 2009; Zhou et al., 2009).

In this paper, we report the synthesis and crystal structure of the title compound (Fig. 1). In the molecule, two benzene rings form a dihedral angle of 77.09 (7)°, and N···N separation is 11.67 (3)Å. The crystal packing doesn't exhibit hydrogen bonds or classical interactions.

Related literature top

For applications of aromatic nitriles, see: Debasree et al. (2009); Lal Dhar et al. (2009); Ren et al. (2009); Zhou et al. (2009). For the preparation of the title compound, see: Donald et al. (1955).

Experimental top

The title compound has been synthesized following the known procedure (Donald et al., 1955). To an ice-bath cooled solution of 4,4'-methylenebis(2,6-diethylaniline) and sodium nitrite in water was added dropwise concentrated hydrogen chloride, keeping the temperature at 0-5^oC for 30 minutes. Then added potassium iodide into the mixed solution, and the white solid bis(3,5-diethyl-4-iodophenyl)methane was obtained. It reacted with cyanocopper in DMF solution at 180^oC for 1 hour, then the title compound was obtained. X-ray quality crystal of the title compound was obtained by slow evaporation from chloroform solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. A view of (I), showing the atom-labelling scheme and 40% probability displacement ellipsoids [symmetry code: (a) -x, y, 1/2-z]. H atoms omitted for clarity.

2,2',6,6'-Tetraethyl-4,4'-methylenedibenzonitrile top

Crystal data top

C₂₃H₂₆N₂	F(000) = 712
M_r = 330.46	D_x = 1.166 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2049 reflections
a = 16.016 (3) Å	θ = 2.2–23.2°
b = 9.3218 (19) Å	µ = 0.07 mm⁻¹
c = 13.977 (3) Å	T = 290 K
β = 115.55 (3)°	Block, colourless
V = 1882.6 (7) Å³	0.16 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1405 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 27.0°, θ_min = 3.2°
phi and ω scans	h = −20→20
8636 measured reflections	k = −11→11
2055 independent reflections	l = −17→17

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0506P)² + 0.6433P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.003
2055 reflections	Δρ_max = 0.24 e Å⁻³
117 parameters	Δρ_min = −0.20 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: 0.0066 (13)

Crystal data top

C₂₃H₂₆N₂	V = 1882.6 (7) Å³
M_r = 330.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.016 (3) Å	µ = 0.07 mm⁻¹
b = 9.3218 (19) Å	T = 290 K
c = 13.977 (3) Å	0.16 × 0.10 × 0.10 mm
β = 115.55 (3)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1405 reflections with I > 2σ(I)
8636 measured reflections	R_int = 0.028
2055 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.16	Δρ_max = 0.24 e Å⁻³
2055 reflections	Δρ_min = −0.20 e Å⁻³
117 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.15377 (8)	0.06614 (13)	0.12294 (10)	0.0215 (3)
C2	0.17923 (8)	0.06280 (13)	0.23286 (10)	0.0214 (3)
C3	0.12805 (8)	0.14471 (13)	0.27126 (10)	0.0217 (3)
H3	0.1444	0.1449	0.3437	0.026*
C4	0.05275 (8)	0.22672 (14)	0.20424 (10)	0.0222 (3)
C5	0.02799 (8)	0.22437 (14)	0.09566 (10)	0.0239 (3)
H5	−0.0233	0.2768	0.0504	0.029*
C6	0.07756 (8)	0.14604 (14)	0.05298 (10)	0.0227 (3)
C7	0.26297 (9)	−0.01923 (15)	0.30817 (10)	0.0254 (3)
H7A	0.2723	−0.1023	0.2721	0.030*
H7B	0.2524	−0.0530	0.3677	0.030*
C8	0.34907 (10)	0.07400 (17)	0.34864 (13)	0.0379 (4)
H8A	0.3615	0.1031	0.2902	0.057*
H8B	0.4008	0.0205	0.3984	0.057*
H8C	0.3394	0.1574	0.3829	0.057*
C9	0.20907 (9)	−0.01286 (15)	0.08264 (10)	0.0251 (3)
C10	0.05135 (9)	0.15086 (15)	−0.06463 (10)	0.0277 (3)
H10A	−0.0150	0.1648	−0.1028	0.033*
H10B	0.0664	0.0595	−0.0865	0.033*
C11	0.10057 (11)	0.26976 (19)	−0.09430 (12)	0.0392 (4)
H11A	0.0849	0.3607	−0.0742	0.059*
H11B	0.0817	0.2684	−0.1695	0.059*
H11C	0.1662	0.2554	−0.0580	0.059*
C12	0.0000	0.3165 (2)	0.2500	0.0265 (4)
H12	0.0432	0.3778	0.3053	0.032*
N1	0.25510 (9)	−0.07416 (14)	0.05233 (10)	0.0370 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0215 (6)	0.0215 (7)	0.0221 (6)	−0.0050 (5)	0.0099 (5)	−0.0016 (5)
C2	0.0203 (6)	0.0210 (7)	0.0229 (6)	−0.0039 (5)	0.0094 (5)	0.0005 (5)
C3	0.0223 (6)	0.0245 (7)	0.0183 (6)	−0.0037 (5)	0.0088 (5)	0.0003 (5)
C4	0.0203 (6)	0.0215 (6)	0.0263 (7)	−0.0048 (5)	0.0113 (5)	−0.0001 (5)
C5	0.0199 (6)	0.0241 (7)	0.0246 (7)	−0.0025 (5)	0.0066 (5)	0.0033 (5)
C6	0.0226 (6)	0.0235 (7)	0.0203 (6)	−0.0075 (5)	0.0077 (5)	0.0002 (5)
C7	0.0275 (7)	0.0270 (7)	0.0212 (7)	0.0034 (6)	0.0101 (6)	0.0026 (5)
C8	0.0263 (7)	0.0374 (9)	0.0385 (9)	0.0013 (6)	0.0031 (6)	0.0020 (7)
C9	0.0283 (7)	0.0266 (7)	0.0201 (6)	−0.0042 (6)	0.0102 (6)	−0.0004 (5)
C10	0.0273 (7)	0.0327 (8)	0.0195 (7)	−0.0039 (6)	0.0066 (6)	0.0002 (6)
C11	0.0393 (8)	0.0505 (10)	0.0266 (8)	−0.0096 (7)	0.0132 (7)	0.0069 (7)
C12	0.0255 (9)	0.0243 (10)	0.0309 (10)	0.000	0.0132 (8)	0.000
N1	0.0443 (7)	0.0378 (7)	0.0333 (7)	0.0020 (6)	0.0209 (6)	−0.0010 (6)

Geometric parameters (Å, º) top

C1—C6	1.4040 (18)	C7—H7B	0.9700
C1—C2	1.4096 (18)	C8—H8A	0.9600
C1—C9	1.4402 (18)	C8—H8B	0.9600
C2—C3	1.3865 (18)	C8—H8C	0.9600
C2—C7	1.5079 (18)	C9—N1	1.1486 (17)
C3—C4	1.3935 (18)	C10—C11	1.5178 (19)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.3935 (18)	C10—H10B	0.9700
C4—C12	1.5129 (16)	C11—H11A	0.9600
C5—C6	1.3885 (19)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600
C6—C10	1.5115 (18)	C12—C4ⁱ	1.5130 (16)
C7—C8	1.5179 (19)	C12—H12	0.9700
C7—H7A	0.9700

C6—C1—C2	121.79 (11)	H7A—C7—H7B	108.0
C6—C1—C9	119.69 (11)	C7—C8—H8A	109.5
C2—C1—C9	118.51 (11)	C7—C8—H8B	109.5
C3—C2—C1	117.92 (11)	H8A—C8—H8B	109.5
C3—C2—C7	120.36 (11)	C7—C8—H8C	109.5
C1—C2—C7	121.61 (11)	H8A—C8—H8C	109.5
C2—C3—C4	121.78 (12)	H8B—C8—H8C	109.5
C2—C3—H3	119.1	N1—C9—C1	178.28 (14)
C4—C3—H3	119.1	C6—C10—C11	112.67 (11)
C5—C4—C3	118.74 (12)	C6—C10—H10A	109.1
C5—C4—C12	121.37 (11)	C11—C10—H10A	109.1
C3—C4—C12	119.89 (10)	C6—C10—H10B	109.1
C6—C5—C4	121.96 (12)	C11—C10—H10B	109.1
C6—C5—H5	119.0	H10A—C10—H10B	107.8
C4—C5—H5	119.0	C10—C11—H11A	109.5
C5—C6—C1	117.78 (11)	C10—C11—H11B	109.5
C5—C6—C10	120.63 (12)	H11A—C11—H11B	109.5
C1—C6—C10	121.57 (12)	C10—C11—H11C	109.5
C2—C7—C8	111.18 (11)	H11A—C11—H11C	109.5
C2—C7—H7A	109.4	H11B—C11—H11C	109.5
C8—C7—H7A	109.4	C4—C12—C4ⁱ	112.85 (15)
C2—C7—H7B	109.4	C4—C12—H12	109.0
C8—C7—H7B	109.4

C6—C1—C2—C3	−1.79 (18)	C4—C5—C6—C10	−177.34 (11)
C9—C1—C2—C3	177.02 (11)	C2—C1—C6—C5	0.88 (18)
C6—C1—C2—C7	−177.97 (11)	C9—C1—C6—C5	−177.92 (11)
C9—C1—C2—C7	0.85 (18)	C2—C1—C6—C10	179.15 (11)
C1—C2—C3—C4	0.93 (18)	C9—C1—C6—C10	0.35 (18)
C7—C2—C3—C4	177.15 (11)	C3—C2—C7—C8	−86.55 (15)
C2—C3—C4—C5	0.80 (18)	C1—C2—C7—C8	89.53 (15)
C2—C3—C4—C12	−178.92 (11)	C5—C6—C10—C11	89.82 (15)
C3—C4—C5—C6	−1.77 (19)	C1—C6—C10—C11	−88.39 (15)
C12—C4—C5—C6	177.94 (12)	C5—C4—C12—C4ⁱ	112.50 (12)
C4—C5—C6—C1	0.94 (18)	C3—C4—C12—C4ⁱ	−67.79 (10)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₆N₂
M_r	330.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	290
a, b, c (Å)	16.016 (3), 9.3218 (19), 13.977 (3)
β (°)	115.55 (3)
V (Å³)	1882.6 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.16 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8636, 2055, 1405
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.16
No. of reflections	2055
No. of parameters	117
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.20

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful to the Central China Normal University for financial support.

References

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Debasree, S., Amit, S. & Brindaban, C. R. (2009). Tetrahedron Lett. 50, 6088–6091. Google Scholar
Donald, L. V., Jonthan, L. H. & Henry, C. W. (1955). J. Org. Chem. 20, 797–802. Google Scholar
Lal Dhar, S. Y., Vishnu, P. S. & Rajesh, P. (2009). Tetrahedron Lett. 50, 5532–5535. Google Scholar
Ren, Y., Wang, W., Zhao, S., Tian, X., Wang, J., Yin, W. & Cheng, L. (2009). Tetrahedron Lett. 50, 4595–4597. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, K. J., Daniele, A., Shoubhik, D. & Matthias, B. (2009). Org. Lett. 11, 2461–2464. Web of Science CrossRef PubMed CAS Google Scholar