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Adiponitrile, C6H8N2, is a key intermediate in the synthesis of the polyamide Nylon 66 and is produced industrially on a large scale. We have determined the crystal and molecular structure of adiponitrile by single-crystal X-ray analysis at 100 K, a suitable crystal (m.p. 275 K) having been grown from the melt at low temperature. The compound crystallizes in the monoclinic space group P21/c with Z = 2. In the crystal structure, the molecule adopts an exact Ci-symmetric gauche–anti–gauche conformation of the C—C—C—C skeleton about an inversion centre. The molecules are densely packed, with short intermolecular contacts between the α-H and nitrile N atoms.
Supporting information
CCDC reference: 1579139
Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: enCIFer (Allen et al., 2004).
Crystal data top
C6H8N2 | Dx = 1.153 Mg m−3 |
Mr = 108.14 | Melting point: 275 K |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 4.5031 (11) Å | Cell parameters from 2360 reflections |
b = 6.5860 (16) Å | θ = 4.2–71.6° |
c = 10.572 (3) Å | µ = 0.57 mm−1 |
β = 96.540 (6)° | T = 100 K |
V = 311.51 (13) Å3 | Cylinder, colourless |
Z = 2 | 1.60 × 0.50 × 0.50 mm |
F(000) = 116 | |
Data collection top
Bruker X8 Proteum diffractometer | 604 independent reflections |
Radiation source: rotating-anode X-ray tube | 593 reflections with I > 2σ(I) |
Montel graded multilayer optics monochromator | Rint = 0.042 |
Detector resolution: 66.67 pixels mm-1 | θmax = 72.0°, θmin = 7.9° |
φ and ω scans | h = −5→5 |
Absorption correction: gaussian (SADABS; Bruker, 2012) | k = −7→8 |
Tmin = 0.597, Tmax = 0.783 | l = −12→12 |
4525 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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0706P)2 + 0.0851P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
604 reflections | Δρmax = 0.19 e Å−3 |
38 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL2017 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: dual | Extinction coefficient: 0.20 (3) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.1132 (3) | 0.62026 (19) | 0.19625 (11) | 0.0365 (5) | |
C1 | 0.2346 (3) | 0.6812 (2) | 0.28969 (12) | 0.0299 (5) | |
C2 | 0.3942 (3) | 0.7541 (2) | 0.40971 (12) | 0.0315 (5) | |
H2A | 0.247075 | 0.802155 | 0.465812 | 0.038* | |
H2B | 0.521409 | 0.870968 | 0.391941 | 0.038* | |
C3 | 0.5900 (3) | 0.5893 (2) | 0.47906 (11) | 0.0292 (5) | |
H3A | 0.733603 | 0.539156 | 0.422013 | 0.035* | |
H3B | 0.706337 | 0.649791 | 0.554887 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0440 (8) | 0.0359 (8) | 0.0285 (7) | 0.0028 (5) | −0.0002 (5) | 0.0020 (4) |
C1 | 0.0328 (7) | 0.0290 (8) | 0.0280 (7) | 0.0017 (5) | 0.0043 (5) | 0.0044 (5) |
C2 | 0.0373 (8) | 0.0297 (8) | 0.0270 (7) | −0.0027 (5) | 0.0014 (5) | 0.0002 (5) |
C3 | 0.0282 (7) | 0.0336 (8) | 0.0253 (7) | −0.0041 (5) | 0.0004 (5) | 0.0010 (5) |
Geometric parameters (Å, º) top
N1—C1 | 1.1458 (17) | C2—H2B | 0.9900 |
C1—C2 | 1.4662 (18) | C3—C3i | 1.523 (2) |
C2—C3 | 1.5316 (18) | C3—H3A | 0.9900 |
C2—H2A | 0.9900 | C3—H3B | 0.9900 |
| | | |
N1—C1—C2 | 178.49 (14) | C3i—C3—C2 | 112.98 (13) |
C1—C2—C3 | 112.39 (11) | C3i—C3—H3A | 109.0 |
C1—C2—H2A | 109.1 | C2—C3—H3A | 109.0 |
C3—C2—H2A | 109.1 | C3i—C3—H3B | 109.0 |
C1—C2—H2B | 109.1 | C2—C3—H3B | 109.0 |
C3—C2—H2B | 109.1 | H3A—C3—H3B | 107.8 |
H2A—C2—H2B | 107.9 | | |
| | | |
C1—C2—C3—C3i | −63.88 (17) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···N1ii | 0.99 | 2.63 | 3.5123 (18) | 149 |
C2—H2B···N1iii | 0.99 | 2.57 | 3.5436 (19) | 167 |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
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