2,2′-o-Phenyl­enediacetonitrile

Li, Y.; Hua, G.; Slawin, A.M.Z.; Woollins, J.D.

doi:10.1107/S1600536809041506

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2757

https://doi.org/10.1107/S1600536809041506

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2,2′-o-Phenylenediacetonitrile

Yang Li,^a Guoxiong Hua,^a Alexandra M. Z Slawin ^a and J. Derek Woollins ^a ^*

^aDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
^*Correspondence e-mail: jdw3@st-and.ac.uk

(Received 17 September 2009; accepted 11 October 2009; online 17 October 2009)

In the title compound, NCCH₂C₆H₄CH₂CN, the bond lengths and angles are within normal ranges. The benzene ring makes dihedral angles of 4.94 (8) and 77.04 (8)° with the C—C—C—N mean planes. Weak non-conventional C—H⋯N hydrogen bonds are effective in the stabilization of the crystal structure. The weak C—H⋯N contacts form antiparallel chains running in the a + c direction, and ring systems with two N-atom acceptors and four H-atom donors.

Related literature

For reactions of Woollins' Reagent see: Gray et al. (2005 ); Hua et al. (2006 , 2009 ); Hua & Woollins (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₈N₂
M_r = 156.18
Monoclinic, P 2₁ /n
a = 8.3882 (18) Å
b = 8.1605 (15) Å
c = 11.993 (2) Å
β = 101.890 (6)°
V = 803.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 93 K
0.30 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004 ) T_min = 0.977, T_max = 0.988
5271 measured reflections
1660 independent reflections
1330 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.133
S = 1.09
1660 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.28 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
C9—H9A⋯N1ⁱ	0.99	2.57	3.5605 (18)	176
C9—H9B⋯N1ⁱⁱ	0.99	2.56	3.5210 (17)	165
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2004); 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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041506/si2203sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041506/si2203Isup2.hkl

checkCIF report

Comment top

Recently, we have continued our studies exploring the reactivity of Woollins reagent towards different organic substituents (Gray et al. 2005, Hua et al. 2006 and 2009; Hua & Woollins 2009). Thereby 2,2'-(1,2-phenylene)diacetonitrile represents one of the starting materials. Single crystals of 2,5-dihydroxybenzaldehyde for X-ray crystallographic analysis were obtained by recrystallization from dichloromethane-hexane solution.

The bond lengths (Allen et al., 1987) and angles are within normal ranges.The benzene ring makes the dihedral angles of 4.94 (8) and 77.04 (8)° with the mean planes of C1—C7—C8—N1 and C2—C9—C10—N2 respectively. The antiparallel chains running in a+c direction are generated through the weak C—H···N contacts, glide plane and inversinon symmetry operations[see Fig. 2 and Table 1]. Inversion symmetry forms also C—H···N ring systems consisting of two N acceptors and four H atom donors,where the centroid-centroid distance between the inversion-related benzene ring planes is 3.6809 (10) Å, the perpendicular plane to plane distance is 3.364 Å, and the slippage between the planes is 1.495 Å.

Related literature top

For reactions of Woollins' Reagent see: Gray et al. (2005); Hua et al. (2006, 2009); Hua & Woollins (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

Commercially available 2,2'-(1,2-phenylene)diacetonitrile was recrystallized from dichloromethane-hexane.

Structure description top

For reactions of Woollins' Reagent see: Gray et al. (2005); Hua et al. (2006, 2009); Hua & Woollins (2009). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View along the b direction of the crystal packing of the title compound with non-conventional hydrogen bonding shown as dashed lines.

2,2'-o-Phenylenediacetonitrile top

Crystal data top

C₁₀H₈N₂	F(000) = 328
M_r = 156.18	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3882 (18) Å	Cell parameters from 2633 reflections
b = 8.1605 (15) Å	θ = 2.7–28.3°
c = 11.993 (2) Å	µ = 0.08 mm⁻¹
β = 101.890 (6)°	T = 93 K
V = 803.4 (3) Å³	Block, colorless
Z = 4	0.30 × 0.25 × 0.15 mm

Data collection top

Rigaku Mercury CCD diffractometer	1660 independent reflections
Radiation source: rotating anode	1330 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.031
Detector resolution: 0.83 pixels mm^-1	θ_max = 28.7°, θ_min = 2.7°
ω scans	h = −11→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004)	k = −9→10
T_min = 0.977, T_max = 0.988	l = −13→15
5271 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0698P)² + 0.0077P] where P = (F_o² + 2F_c²)/3
1660 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₈N₂	V = 803.4 (3) Å³
M_r = 156.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3882 (18) Å	µ = 0.08 mm⁻¹
b = 8.1605 (15) Å	T = 93 K
c = 11.993 (2) Å	0.30 × 0.25 × 0.15 mm
β = 101.890 (6)°

Data collection top

Rigaku Mercury CCD diffractometer	1660 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004)	1330 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.988	R_int = 0.031
5271 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.09	Δρ_max = 0.28 e Å⁻³
1660 reflections	Δρ_min = −0.21 e Å⁻³
109 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	0.77845 (13)	0.05887 (16)	0.95174 (10)	0.0215 (3)
C2	0.72184 (13)	0.13136 (16)	1.04228 (10)	0.0218 (3)
C7	0.83384 (14)	0.16768 (16)	0.86390 (10)	0.0257 (3)
H7A	0.7404	0.2350	0.8253	0.031*
H7B	0.9191	0.2433	0.9038	0.031*
C3	0.66532 (15)	0.03264 (16)	1.12009 (11)	0.0250 (3)
H3	0.6273	0.0817	1.1816	0.030*
C8	0.89813 (14)	0.07728 (16)	0.77779 (10)	0.0252 (3)
N1	0.94789 (13)	0.00673 (14)	0.70957 (10)	0.0313 (3)
C10	0.88145 (15)	0.38338 (15)	1.10361 (10)	0.0248 (4)
C9	0.71906 (14)	0.31597 (16)	1.05579 (11)	0.0249 (3)
H9A	0.6768	0.3666	0.9805	0.030*
H9B	0.6438	0.3448	1.1064	0.030*
C5	0.71958 (14)	−0.20835 (16)	1.02028 (11)	0.0278 (4)
H5	0.7192	−0.3242	1.0126	0.033*
C6	0.77646 (14)	−0.11076 (16)	0.94203 (11)	0.0248 (4)
H6	0.8146	−0.1607	0.8809	0.030*
N2	1.00792 (13)	0.43446 (14)	1.14226 (9)	0.0318 (3)
C4	0.66348 (14)	−0.13701 (17)	1.10929 (11)	0.0271 (3)
H4	0.6239	−0.2034	1.1628	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0169 (6)	0.0226 (7)	0.0238 (7)	0.0002 (4)	0.0009 (5)	0.0007 (5)
C2	0.0176 (6)	0.0247 (7)	0.0221 (7)	0.0023 (5)	0.0013 (5)	−0.0002 (5)
C7	0.0267 (7)	0.0232 (7)	0.0274 (7)	0.0013 (5)	0.0062 (5)	0.0001 (6)
C3	0.0207 (7)	0.0311 (8)	0.0220 (7)	−0.0002 (5)	0.0019 (5)	−0.0002 (6)
C8	0.0217 (7)	0.0285 (7)	0.0252 (7)	−0.0031 (5)	0.0043 (5)	0.0008 (6)
N1	0.0292 (7)	0.0337 (8)	0.0319 (7)	−0.0012 (5)	0.0085 (5)	−0.0019 (5)
C10	0.0321 (7)	0.0198 (7)	0.0243 (7)	0.0044 (5)	0.0097 (6)	−0.0012 (5)
C9	0.0256 (7)	0.0240 (8)	0.0250 (7)	0.0021 (5)	0.0049 (5)	−0.0018 (6)
C5	0.0257 (7)	0.0210 (7)	0.0342 (8)	−0.0006 (5)	0.0007 (6)	0.0018 (6)
C6	0.0241 (7)	0.0235 (8)	0.0263 (7)	0.0027 (5)	0.0040 (5)	−0.0023 (6)
N2	0.0325 (7)	0.0272 (7)	0.0359 (7)	−0.0019 (5)	0.0071 (5)	−0.0044 (5)
C4	0.0234 (7)	0.0314 (8)	0.0253 (7)	−0.0034 (5)	0.0022 (5)	0.0054 (6)

Geometric parameters (Å, º) top

C1—C6	1.3890 (19)	C8—N1	1.1471 (15)
C1—C2	1.4025 (16)	C10—N2	1.1452 (15)
C1—C7	1.5218 (18)	C10—C9	1.4714 (17)
C2—C3	1.3882 (18)	C9—H9A	0.9900
C2—C9	1.5159 (18)	C9—H9B	0.9900
C7—C8	1.4599 (17)	C5—C4	1.3809 (18)
C7—H7A	0.9900	C5—C6	1.3882 (17)
C7—H7B	0.9900	C5—H5	0.9500
C3—C4	1.390 (2)	C6—H6	0.9500
C3—H3	0.9500	C4—H4	0.9500

C6—C1—C2	119.02 (11)	N2—C10—C9	178.97 (14)
C6—C1—C7	121.58 (11)	C10—C9—C2	112.32 (10)
C2—C1—C7	119.36 (12)	C10—C9—H9A	109.1
C3—C2—C1	119.52 (13)	C2—C9—H9A	109.1
C3—C2—C9	119.34 (11)	C10—C9—H9B	109.1
C1—C2—C9	121.14 (11)	C2—C9—H9B	109.1
C8—C7—C1	113.88 (11)	H9A—C9—H9B	107.9
C8—C7—H7A	108.8	C4—C5—C6	120.00 (12)
C1—C7—H7A	108.8	C4—C5—H5	120.0
C8—C7—H7B	108.8	C6—C5—H5	120.0
C1—C7—H7B	108.8	C1—C6—C5	121.00 (11)
H7A—C7—H7B	107.7	C1—C6—H6	119.5
C2—C3—C4	120.94 (12)	C5—C6—H6	119.5
C2—C3—H3	119.5	C5—C4—C3	119.53 (12)
C4—C3—H3	119.5	C5—C4—H4	120.2
N1—C8—C7	179.54 (14)	C3—C4—H4	120.2

C6—C1—C2—C3	0.04 (16)	C3—C2—C9—C10	103.33 (13)
C7—C1—C2—C3	177.52 (11)	C1—C2—C9—C10	−77.54 (13)
C6—C1—C2—C9	−179.09 (11)	C2—C1—C6—C5	0.00 (17)
C7—C1—C2—C9	−1.61 (15)	C7—C1—C6—C5	−177.43 (10)
C6—C1—C7—C8	−5.75 (16)	C4—C5—C6—C1	0.15 (18)
C2—C1—C7—C8	176.84 (10)	C6—C5—C4—C3	−0.34 (18)
C1—C2—C3—C4	−0.23 (17)	C2—C3—C4—C5	0.38 (18)
C9—C2—C3—C4	178.91 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N1ⁱ	0.99	2.57	3.5605 (18)	176
C9—H9B···N1ⁱⁱ	0.99	2.56	3.5210 (17)	165

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂
M_r	156.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	93
a, b, c (Å)	8.3882 (18), 8.1605 (15), 11.993 (2)
β (°)	101.890 (6)
V (Å³)	803.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2004)
T_min, T_max	0.977, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5271, 1660, 1330
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.133, 1.09
No. of reflections	1660
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.21

Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N1ⁱ	0.99	2.57	3.5605 (18)	176.2
C9—H9B···N1ⁱⁱ	0.99	2.56	3.5210 (17)	164.6

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1/2, −y+1/2, z+1/2.

Acknowledgements

The authors are grateful to the University of St Andrews and the Engineering and Physical Science Research Council (EPRSC, UK) for financial support.

References

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