2,2′-(Piperazine-1,4-di­yl)diacetonitrile

Gao, W.; Yang, J.; Wang, X.-L.; Zhou, N.; Wu, X.-F.

doi:10.1107/S1600536812021733

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1798

doi:10.1107/S1600536812021733

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2,2′-(Piperazine-1,4-diyl)diacetonitrile

Wei Gao,^a ^* Jing Yang,^a Xin-Ling Wang,^a Ning Zhou ^a and Xue-Fen Wu ^a

^aSchool of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: xiaojun801115@163.com

(Received 11 May 2012; accepted 14 May 2012; online 19 May 2012)

The complete molecule of the title compound, C₈H₁₂N₄, is generated by a crystallographic inversion centre. The piperazine ring adopts a chair conformation with the N-bonded substituents in equatorial positions. In the crystal, molecules are linked by C—H⋯N_c (c = cyanide) hydrogen bonds.

Related literature

For related structures, see: Ma et al. (2007 ); Liu & Liu (2011 ); Luo & Weng (2011 ).

Experimental

Crystal data

C₈H₁₂N₄
M_r = 164.22
Monoclinic, P 2₁ /c
a = 6.3452 (13) Å
b = 6.6731 (13) Å
c = 11.077 (2) Å
β = 95.61 (3)°
V = 466.78 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.985, T_max = 0.992
3739 measured reflections
1076 independent reflections
835 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.150
S = 1.05
1076 reflections
55 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N2ⁱ	0.97	2.57	3.427 (2)	147
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021733/hb6795sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021733/hb6795Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021733/hb6795Isup3.cml

checkCIF report

Related literature top

For related structures, see: Ma et al. (2007); Liu & Liu (2011); Luo & Weng (2011).

Experimental top

Piperazine (25 mmol) and triethylamine (50 mmol), dissolved in 20 ml 95% of ethanol, was added dropwise to the stirred solution of chloroacetonitrile (50 mmol) at reflux. The mixture was stirred for 8 h at reflux. The mixture was stirred overnight at room temperature, evaporated in vacuum and the residue was purified by recrystallization from ethanol to give the title compound. Colourless blocks were grown from dichloromethane/ethanol solution.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing for (I).

2,2'-(Piperazine-1,4-diyl)diacetonitrile top

Crystal data top

C₈H₁₂N₄	F(000) = 176
M_r = 164.22	D_x = 1.168 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3452 (13) Å	Cell parameters from 1156 reflections
b = 6.6731 (13) Å	θ = 3.1–27.8°
c = 11.077 (2) Å	µ = 0.08 mm⁻¹
β = 95.61 (3)°	T = 293 K
V = 466.78 (16) Å³	Block, colorless
Z = 2	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn CCD diffractometer	1076 independent reflections
Radiation source: rotating anode	835 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.032
ω scans	θ_max = 27.9°, θ_min = 6.4°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −8→5
T_min = 0.985, T_max = 0.992	k = −8→8
3739 measured reflections	l = −14→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0937P)² + 0.0176P] where P = (F_o² + 2F_c²)/3
1076 reflections	(Δ/σ)_max < 0.001
55 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₈H₁₂N₄	V = 466.78 (16) Å³
M_r = 164.22	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3452 (13) Å	µ = 0.08 mm⁻¹
b = 6.6731 (13) Å	T = 293 K
c = 11.077 (2) Å	0.20 × 0.18 × 0.10 mm
β = 95.61 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	1076 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	835 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.992	R_int = 0.032
3739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.05	Δρ_max = 0.10 e Å⁻³
1076 reflections	Δρ_min = −0.15 e Å⁻³
55 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
N1	0.06045 (14)	0.54542 (14)	0.12377 (8)	0.0464 (4)
N2	0.3536 (2)	0.9796 (2)	0.16532 (15)	0.0904 (6)
C1	−0.21559 (17)	0.52728 (19)	−0.04400 (11)	0.0497 (4)
H1A	−0.2823	0.4143	−0.0078	0.060*
H1B	−0.3249	0.6036	−0.0910	0.060*
C2	−0.10710 (17)	0.65762 (18)	0.05439 (11)	0.0499 (4)
H2A	−0.0474	0.7746	0.0184	0.060*
H2B	−0.2095	0.7030	0.1079	0.060*
C3	0.1569 (2)	0.6568 (2)	0.22683 (12)	0.0584 (4)
H3A	0.2562	0.5701	0.2741	0.070*
H3B	0.0476	0.6945	0.2779	0.070*
C4	0.2700 (2)	0.8402 (2)	0.19376 (13)	0.0647 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0471 (6)	0.0463 (6)	0.0461 (5)	0.0023 (4)	0.0062 (4)	−0.0010 (4)
N2	0.0816 (10)	0.0743 (10)	0.1129 (13)	−0.0215 (7)	−0.0029 (9)	−0.0028 (8)
C1	0.0410 (6)	0.0516 (7)	0.0570 (7)	0.0054 (4)	0.0062 (5)	−0.0018 (5)
C2	0.0465 (6)	0.0479 (7)	0.0561 (7)	0.0087 (4)	0.0092 (5)	−0.0032 (5)
C3	0.0657 (8)	0.0575 (8)	0.0512 (7)	−0.0009 (6)	0.0013 (5)	−0.0049 (5)
C4	0.0592 (8)	0.0618 (9)	0.0707 (9)	−0.0035 (6)	−0.0057 (6)	−0.0112 (7)

Geometric parameters (Å, º) top

N1—C3	1.4471 (16)	C1—H1B	0.9700
N1—C2	1.4567 (15)	C2—H2A	0.9700
N1—C1ⁱ	1.4680 (14)	C2—H2B	0.9700
N2—C4	1.1305 (19)	C3—C4	1.4824 (19)
C1—N1ⁱ	1.4681 (14)	C3—H3A	0.9700
C1—C2	1.5071 (17)	C3—H3B	0.9700
C1—H1A	0.9700

C3—N1—C2	112.51 (10)	C1—C2—H2A	109.6
C3—N1—C1ⁱ	112.82 (9)	N1—C2—H2B	109.6
C2—N1—C1ⁱ	110.49 (9)	C1—C2—H2B	109.6
N1ⁱ—C1—C2	109.89 (9)	H2A—C2—H2B	108.2
N1ⁱ—C1—H1A	109.7	N1—C3—C4	114.00 (10)
C2—C1—H1A	109.7	N1—C3—H3A	108.8
N1ⁱ—C1—H1B	109.7	C4—C3—H3A	108.8
C2—C1—H1B	109.7	N1—C3—H3B	108.8
H1A—C1—H1B	108.2	C4—C3—H3B	108.8
N1—C2—C1	110.06 (9)	H3A—C3—H3B	107.6
N1—C2—H2A	109.6	N2—C4—C3	178.07 (16)

C3—N1—C2—C1	−174.46 (8)	C2—N1—C3—C4	−64.42 (14)
C1ⁱ—N1—C2—C1	58.45 (13)	C1ⁱ—N1—C3—C4	61.41 (14)
N1ⁱ—C1—C2—N1	−58.10 (13)	N1—C3—C4—N2	13 (5)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N2ⁱⁱ	0.97	2.57	3.427 (2)	147

Symmetry code: (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₄
M_r	164.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.3452 (13), 6.6731 (13), 11.077 (2)
β (°)	95.61 (3)
V (Å³)	466.78 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.985, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	3739, 1076, 835
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.150, 1.05
No. of reflections	1076
No. of parameters	55
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.15

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—H3A···N2ⁱ	0.97	2.57	3.427 (2)	147

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

We gratefully acknowledge financial support from the Doctoral Research Fund of Henan University of Traditional Chinese Medicine.

References

Liu, X.-F. & Liu, X.-H. (2011). Acta Cryst. E67, o202. Web of Science CrossRef IUCr Journals Google Scholar
Luo, L.-J. & Weng, J.-Q. (2011). Acta Cryst. E67, o3094. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, H.-F., Jia, H.-S., Qian, Y., Wen, F. & Chen, B.-L. (2007). Acta Cryst. E63, o311–o312. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc. The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar