Second monoclinic modification of cyclo­hexane-1,1-dicarbonitrile

Sadikhova, N.D.; Khalilov, A.N.; Gurbanov, A.V.; Brito, I.

doi:10.1107/S1600536811023592

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1801

doi:10.1107/S1600536811023592

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Second monoclinic modification of cyclohexane-1,1-dicarbonitrile

Nurlana D. Sadikhova,^a Ali. N. Khalilov,^a Atash V. Gurbanov ^a and Iván Brito ^b ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and ^bDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 22 May 2011; accepted 16 June 2011; online 25 June 2011)

In the title compound, C₈H₁₀N₂, the cyclohexane ring adopts a chair conformation. he crystal structure of the previously reported monoclinic modification have intramolecular CN⋯CN and C—H⋯N interactions. These types of interaction are not present in this new modification whose crystal structure is built up by van der Waals interactions.

Related literature

For the previously reported monoclinic modification, see: Echeverria et al. (1995 ). For synthetic methods, see: Tsai et al. (2003 ); Suissa et al. (1977 ); Julia & Maumy (1969 ). For puckering parameters see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₈H₁₀N₂
M_r = 134.18
Monoclinic, P 2₁ /n
a = 8.9300 (5) Å
b = 8.3656 (5) Å
c = 9.8725 (6) Å
β = 92.662 (1)°
V = 736.73 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.978, T_max = 0.978
9584 measured reflections
2794 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.03
2794 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023592/ng5170sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023592/ng5170Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811023592/ng5170Isup3.cml

checkCIF report

Comment top

Fig.1 shows the structure of title compound, (I), which is a positional isomer of a previously reported by (Echeverria et al., 1995), (II). The bond distances and the six C—C—C bond angles in (I) are slightly longer than (II). The crystal structure of (II) have intermolecular CN···CN and C—H···N interactions, whereas this kind of interactions are not present in (I). The values of the ring puckering parameters: Q_T = 0.5665 Å, θ =0.72° and ϕ=107.4° (Cremer & Pople, 1975), indicate that the cyclohexane has a chair conformation. The C1—C2 and C1—C6 bond distances are more longer than the other C—C distances in the cyclohexyl ring. The lengthening of these bonds with increasing ring size may be attributed to steric crowding about C1 atom. The cyano groups are essentially collinear with C1 and the N—C—C1 angles is 178.55 (10)° (mean). A σ_h plane passing through the CN groups and the C1 atom which bisects the cyclohexyl ring.

Related literature top

For the reported monoclinic modification, see: Echeverria et al. (1995). For synthetic methods, see: Tsai et al. (2003); Suissa et al. (1977); Julia & Maumy (1969). For puckering parameters see: Cremer & Pople (1975).

Experimental top

A mixture of malonodinitrile (0.1 mol, 6.6 g), 23 gr 1,5-dibromopentane (0.1 mol, 23 g) and 46 gr K₂CO₃ in dry DMSO (50 ml), was stirred for 12 h at 70 °C. After cooling down, the reaction mixture was poured into water and extracted with ether. The organic layer was washed several times with water, dried over Na₂SO₄ and the solvent evaporated. The crude product was purified by vacuum distillation yielding 10.5 gr (87%) of a solid compound which after recrystallization in hexane gave white crystals: mp 65 °C.; ¹H NMR (300 MHz, CDCI₃) δ 1.52 (m, 2H, CH₂), 1.72 (m, 4H, 2CH₂), 2.12 (t, 4H,2CH₂); ¹³CNMR (75 MHz, CDCI₃) δ 22.3, 23.8, 34.7, 41.2, 117.3. Analysis, found, %: C: 71.42, H: 7.78, N: 20.63 (C₈H₁₀N₂); calculated, %: C: 71.61, H: 7.51, N: 20.88

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level.

cyclohexane-1,1-dicarbonitrile top

Crystal data top

C₈H₁₀N₂	F(000) = 288
M_r = 134.18	D_x = 1.210 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2571 reflections
a = 8.9300 (5) Å	θ = 3.0–33.1°
b = 8.3656 (5) Å	µ = 0.08 mm⁻¹
c = 9.8725 (6) Å	T = 100 K
β = 92.662 (1)°	Prism, colourless
V = 736.73 (8) Å³	0.30 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2794 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 33.2°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −13→13
T_min = 0.978, T_max = 0.978	k = −12→12
9584 measured reflections	l = −15→14

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0492P)² + 0.1357P] where P = (F_o² + 2F_c²)/3
2794 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₁₀N₂	V = 736.73 (8) Å³
M_r = 134.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9300 (5) Å	µ = 0.08 mm⁻¹
b = 8.3656 (5) Å	T = 100 K
c = 9.8725 (6) Å	0.30 × 0.30 × 0.30 mm
β = 92.662 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2794 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2236 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.978	R_int = 0.033
9584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
2794 reflections	Δρ_min = −0.21 e Å⁻³
91 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.36573 (9)	−0.12113 (9)	0.57950 (8)	0.02114 (17)
N2	−0.02890 (8)	0.15605 (9)	0.63201 (8)	0.01948 (16)
C1	0.24232 (8)	0.16105 (9)	0.53895 (8)	0.01226 (14)
C2	0.23203 (9)	0.19844 (9)	0.38467 (8)	0.01370 (15)
H2A	0.3327	0.1888	0.3476	0.016*
H2B	0.1652	0.1197	0.3376	0.016*
C3	0.17144 (9)	0.36675 (10)	0.35831 (9)	0.01563 (16)
H3A	0.0672	0.3734	0.3878	0.019*
H3B	0.1701	0.3895	0.2598	0.019*
C4	0.26762 (9)	0.49156 (9)	0.43440 (9)	0.01663 (16)
H4A	0.2237	0.5990	0.4185	0.020*
H4B	0.3697	0.4915	0.3992	0.020*
C5	0.27741 (9)	0.45676 (10)	0.58644 (8)	0.01565 (16)
H5A	0.3437	0.5367	0.6326	0.019*
H5B	0.1765	0.4671	0.6230	0.019*
C6	0.33813 (9)	0.28925 (9)	0.61680 (8)	0.01401 (15)
H6A	0.3367	0.2685	0.7155	0.017*
H6B	0.4433	0.2823	0.5898	0.017*
C7	0.30994 (9)	0.00103 (10)	0.56201 (8)	0.01494 (15)
C8	0.08948 (9)	0.15673 (9)	0.59186 (8)	0.01406 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0225 (3)	0.0166 (3)	0.0245 (4)	0.0026 (3)	0.0035 (3)	0.0023 (3)
N2	0.0181 (3)	0.0193 (3)	0.0213 (4)	−0.0012 (3)	0.0039 (3)	−0.0003 (3)
C1	0.0127 (3)	0.0109 (3)	0.0134 (3)	0.0006 (2)	0.0021 (2)	0.0006 (2)
C2	0.0170 (3)	0.0128 (3)	0.0115 (3)	−0.0012 (3)	0.0017 (3)	−0.0003 (3)
C3	0.0179 (3)	0.0144 (3)	0.0145 (3)	0.0001 (3)	−0.0010 (3)	0.0019 (3)
C4	0.0214 (4)	0.0116 (3)	0.0169 (4)	−0.0007 (3)	0.0006 (3)	0.0011 (3)
C5	0.0188 (3)	0.0124 (3)	0.0157 (4)	0.0003 (3)	0.0003 (3)	−0.0021 (3)
C6	0.0141 (3)	0.0136 (3)	0.0141 (3)	−0.0002 (2)	−0.0007 (3)	−0.0009 (3)
C7	0.0156 (3)	0.0143 (3)	0.0152 (4)	−0.0005 (3)	0.0032 (3)	0.0007 (3)
C8	0.0161 (3)	0.0125 (3)	0.0136 (3)	−0.0002 (3)	0.0009 (3)	0.0004 (3)

Geometric parameters (Å, º) top

N1—C7	1.1465 (11)	C3—H3A	0.9900
N2—C8	1.1462 (11)	C3—H3B	0.9900
C1—C7	1.4818 (11)	C4—C5	1.5275 (12)
C1—C8	1.4843 (11)	C4—H4A	0.9900
C1—C6	1.5530 (11)	C4—H4B	0.9900
C1—C2	1.5535 (11)	C5—C6	1.5272 (11)
C2—C3	1.5265 (11)	C5—H5A	0.9900
C2—H2A	0.9900	C5—H5B	0.9900
C2—H2B	0.9900	C6—H6A	0.9900
C3—C4	1.5272 (11)	C6—H6B	0.9900

C7—C1—C8	107.39 (6)	C3—C4—H4A	109.4
C7—C1—C6	109.67 (6)	C5—C4—H4A	109.4
C8—C1—C6	109.70 (6)	C3—C4—H4B	109.4
C7—C1—C2	109.73 (6)	C5—C4—H4B	109.4
C8—C1—C2	109.66 (6)	H4A—C4—H4B	108.0
C6—C1—C2	110.63 (6)	C6—C5—C4	111.80 (7)
C3—C2—C1	110.93 (6)	C6—C5—H5A	109.3
C3—C2—H2A	109.5	C4—C5—H5A	109.3
C1—C2—H2A	109.5	C6—C5—H5B	109.3
C3—C2—H2B	109.5	C4—C5—H5B	109.3
C1—C2—H2B	109.5	H5A—C5—H5B	107.9
H2A—C2—H2B	108.0	C5—C6—C1	110.74 (6)
C2—C3—C4	111.10 (6)	C5—C6—H6A	109.5
C2—C3—H3A	109.4	C1—C6—H6A	109.5
C4—C3—H3A	109.4	C5—C6—H6B	109.5
C2—C3—H3B	109.4	C1—C6—H6B	109.5
C4—C3—H3B	109.4	H6A—C6—H6B	108.1
H3A—C3—H3B	108.0	N1—C7—C1	178.29 (8)
C3—C4—C5	110.99 (7)	N2—C8—C1	178.83 (8)

C7—C1—C2—C3	−176.59 (6)	C8—C1—C6—C5	−66.44 (8)
C8—C1—C2—C3	65.69 (8)	C2—C1—C6—C5	54.66 (8)
C6—C1—C2—C3	−55.45 (8)	C8—C1—C7—N1	−161 (3)
C1—C2—C3—C4	56.61 (9)	C6—C1—C7—N1	−42 (3)
C2—C3—C4—C5	−56.87 (9)	C2—C1—C7—N1	80 (3)
C3—C4—C5—C6	56.58 (9)	C7—C1—C8—N2	−179 (100)
C4—C5—C6—C1	−55.55 (9)	C6—C1—C8—N2	62 (4)
C7—C1—C6—C5	175.84 (7)	C2—C1—C8—N2	−60 (4)

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂
M_r	134.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.9300 (5), 8.3656 (5), 9.8725 (6)
β (°)	92.662 (1)
V (Å³)	736.73 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.30 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.978, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	9584, 2794, 2236
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.03
No. of reflections	2794
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.21

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

The authors are grateful to Baku State University for supporting this study. IB thanks the Spanish Research Council (CSIC) for the provision of a free-of-charge licence for the Cambridge Structural Database.

References

Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Echeverria, G., Punte, G., Rivero, B. E. & Barón, M. (1995). Acta Cryst. C51, 1020–1023. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Julia, M. & Maumy, M. (1969). Bull. Soc. Chim. Fr. pp. 2415–2427. Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suissa, M. R., Romming, C. & Dale, J. (1977). Chem. Commun. pp. 113–114. Google Scholar
Tsai, T.-Y., Kak-Shan Shia, K.-S. & Liu, H.-J. (2003). Synlett, pp. 97–101. Google Scholar