1,2-Bis[4-(1H-imidazol-1-yl)benzyl­idene]hydrazine

Jin, Y.-B.; Li, J.; Zhang, Y.; Lei, K.-W.

doi:10.1107/S160053681202291X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1949

doi:10.1107/S160053681202291X

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1,2-Bis[4-(1H-imidazol-1-yl)benzylidene]hydrazine

Yue-Bao Jin,^a Jie Li,^a Ying Zhang ^a and Ke-Wei Lei ^a ^*

^aState Key Lab. Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 7 May 2012; accepted 19 May 2012; online 31 May 2012)

The title compound, C₂₀H₁₆N₆, is centrosymmetric with the mid-point of the N—N bond located on an inversion center. The imidazole ring is oriented at a dihedral angle of 28.03 (6)° with respect to the attached benzene ring. In the crystal, molecules are linked via C—H⋯N interactions.

Related literature

For a related compound, see: Chen et al. (2005 ).

Experimental

Crystal data

C₂₀H₁₆N₆
M_r = 340.39
Monoclinic, P 2₁ /n
a = 8.1342 (3) Å
b = 7.8172 (3) Å
c = 13.2191 (6) Å
β = 90.259 (4)°
V = 840.55 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.44 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
4180 measured reflections
1695 independent reflections
1249 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.143
S = 1.13
1695 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N2ⁱ	0.93	2.60	3.453 (2)	153
C6—H6⋯N2ⁱⁱ	0.93	2.59	3.421 (3)	149
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2004 ); 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/S160053681202291X/xu5536sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202291X/xu5536Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202291X/xu5536Isup3.cml

checkCIF report

Comment top

The molecular structure of the title compound is illustrated in Fig. 1. The molecular structures is central symmetry. The bond lengths and bond angles in are within normal ranges. The N3—N3 bond length of 1.423 (3)%A is a slightly smaller than the normal length. The N3—C10 bond length is 1.273 (2)%A. The dihedral angle between the imidazole and benzene rings is 28.03 (6) Å

Related literature top

For a related compound, see: Chen et al. (2005).

Experimental top

Hydrazine monohydrate (20 mmol, 1.08 g) and 4-imidazole benzaldehyde (40 mmol, 6.88 g) were dissolved in ethanol and the solution was refluxed for 2 h. After evaporation, a crude product was recrystallized twice from DMF and methanol to give a pure pale yellow product (Chen et al., 2005). Yield: 85.2%. Calcd. for C₂₀H₂₀N₆: C, 69.75; H, 5.85; N, 24.40; Found: C, 69.88; H, 5.73; N, 24.67%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2004); 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 structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

1,2-Bis[4-(1H-imidazol-1-yl)benzylidene]hydrazine top

Crystal data top

C₂₀H₁₆N₆	F(000) = 356
M_r = 340.39	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7835 reflections
a = 8.1342 (3) Å	θ = 2.9–26.4°
b = 7.8172 (3) Å	µ = 0.09 mm⁻¹
c = 13.2191 (6) Å	T = 293 K
β = 90.259 (4)°	Block, yellow
V = 840.55 (6) Å³	0.44 × 0.20 × 0.15 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1249 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 26.4°, θ_min = 2.9°
Detector resolution: 0 pixels mm^-1	h = −10→8
ω scans	k = −9→9
4180 measured reflections	l = −15→16
1695 independent 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0589P)² + 0.0922P] where P = (F_o² + 2F_c²)/3
1695 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₀H₁₆N₆	V = 840.55 (6) Å³
M_r = 340.39	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1342 (3) Å	µ = 0.09 mm⁻¹
b = 7.8172 (3) Å	T = 293 K
c = 13.2191 (6) Å	0.44 × 0.20 × 0.15 mm
β = 90.259 (4)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1249 reflections with I > 2σ(I)
4180 measured reflections	R_int = 0.022
1695 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	Δρ_max = 0.12 e Å⁻³
1695 reflections	Δρ_min = −0.17 e Å⁻³
118 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	0.03400 (17)	0.26891 (18)	0.65029 (11)	0.0443 (4)
N2	−0.1631 (2)	0.1350 (2)	0.73547 (13)	0.0605 (5)
N3	0.44959 (19)	0.9458 (2)	0.52999 (13)	0.0559 (5)
C1	−0.0938 (2)	0.2826 (2)	0.71607 (15)	0.0529 (5)
H1	−0.1281	0.3856	0.7442	0.063*
C2	−0.0742 (2)	0.0193 (3)	0.67959 (16)	0.0610 (6)
H2	−0.0941	−0.0978	0.6783	0.073*
C3	0.0454 (2)	0.0977 (2)	0.62695 (16)	0.0555 (5)
H3	0.1206	0.0465	0.5836	0.067*
C4	0.1305 (2)	0.4043 (2)	0.61009 (13)	0.0409 (4)
C5	0.1995 (2)	0.3884 (2)	0.51484 (14)	0.0471 (5)
H5	0.1838	0.2888	0.4775	0.057*
C6	0.2917 (2)	0.5209 (2)	0.47552 (15)	0.0497 (5)
H6	0.3385	0.5091	0.4118	0.060*
C7	0.3157 (2)	0.6717 (2)	0.52950 (14)	0.0447 (5)
C8	0.2452 (2)	0.6857 (2)	0.62521 (15)	0.0490 (5)
H8	0.2595	0.7857	0.6623	0.059*
C9	0.1546 (2)	0.5532 (2)	0.66558 (14)	0.0481 (5)
H9	0.1097	0.5635	0.7299	0.058*
C10	0.4159 (2)	0.8068 (2)	0.48435 (16)	0.0516 (5)
H10	0.4567	0.7903	0.4195	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0431 (8)	0.0387 (8)	0.0513 (9)	0.0015 (6)	0.0069 (7)	0.0030 (7)
N2	0.0615 (11)	0.0520 (10)	0.0681 (12)	−0.0074 (8)	0.0195 (9)	0.0048 (8)
N3	0.0572 (10)	0.0453 (9)	0.0653 (11)	−0.0046 (8)	0.0160 (8)	0.0124 (8)
C1	0.0528 (11)	0.0464 (10)	0.0597 (13)	0.0007 (8)	0.0150 (10)	0.0014 (9)
C2	0.0690 (14)	0.0436 (11)	0.0705 (15)	−0.0099 (10)	0.0131 (11)	0.0013 (10)
C3	0.0615 (12)	0.0402 (10)	0.0650 (13)	0.0000 (9)	0.0147 (10)	−0.0029 (9)
C4	0.0393 (9)	0.0370 (9)	0.0465 (11)	0.0018 (7)	0.0028 (8)	0.0040 (7)
C5	0.0493 (11)	0.0424 (10)	0.0497 (11)	0.0009 (8)	0.0063 (9)	−0.0022 (8)
C6	0.0510 (11)	0.0492 (11)	0.0490 (12)	0.0041 (8)	0.0106 (9)	0.0033 (8)
C7	0.0402 (10)	0.0433 (10)	0.0504 (11)	0.0031 (8)	0.0032 (8)	0.0099 (8)
C8	0.0543 (11)	0.0374 (9)	0.0553 (12)	−0.0006 (8)	0.0044 (9)	−0.0001 (8)
C9	0.0554 (12)	0.0434 (10)	0.0455 (11)	−0.0004 (8)	0.0101 (9)	0.0008 (8)
C10	0.0495 (11)	0.0465 (11)	0.0590 (13)	0.0030 (8)	0.0087 (10)	0.0129 (9)

Geometric parameters (Å, º) top

N1—C1	1.362 (2)	C4—C9	1.389 (2)
N1—C3	1.377 (2)	C5—C6	1.382 (2)
N1—C4	1.422 (2)	C5—H5	0.9300
N2—C1	1.311 (2)	C6—C7	1.391 (3)
N2—C2	1.375 (3)	C6—H6	0.9300
N3—C10	1.273 (2)	C7—C8	1.396 (3)
N3—N3ⁱ	1.423 (3)	C7—C10	1.463 (2)
C1—H1	0.9300	C8—C9	1.380 (2)
C2—C3	1.346 (3)	C8—H8	0.9300
C2—H2	0.9300	C9—H9	0.9300
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.386 (2)

C1—N1—C3	105.79 (15)	C6—C5—H5	120.1
C1—N1—C4	127.14 (15)	C4—C5—H5	120.1
C3—N1—C4	127.01 (16)	C5—C6—C7	121.14 (18)
C1—N2—C2	104.24 (17)	C5—C6—H6	119.4
C10—N3—N3ⁱ	111.6 (2)	C7—C6—H6	119.4
N2—C1—N1	112.69 (17)	C6—C7—C8	118.32 (16)
N2—C1—H1	123.7	C6—C7—C10	118.64 (18)
N1—C1—H1	123.7	C8—C7—C10	123.03 (18)
C3—C2—N2	111.20 (18)	C9—C8—C7	120.93 (17)
C3—C2—H2	124.4	C9—C8—H8	119.5
N2—C2—H2	124.4	C7—C8—H8	119.5
C2—C3—N1	106.07 (18)	C8—C9—C4	119.92 (18)
C2—C3—H3	127.0	C8—C9—H9	120.0
N1—C3—H3	127.0	C4—C9—H9	120.0
C5—C4—C9	119.88 (16)	N3—C10—C7	122.85 (19)
C5—C4—N1	119.93 (16)	N3—C10—H10	118.6
C9—C4—N1	120.19 (16)	C7—C10—H10	118.6
C6—C5—C4	119.80 (17)

C2—N2—C1—N1	0.5 (2)	N1—C4—C5—C6	179.29 (15)
C3—N1—C1—N2	−0.2 (2)	C4—C5—C6—C7	−0.6 (3)
C4—N1—C1—N2	177.01 (17)	C5—C6—C7—C8	0.5 (3)
C1—N2—C2—C3	−0.6 (2)	C5—C6—C7—C10	179.37 (16)
N2—C2—C3—N1	0.5 (2)	C6—C7—C8—C9	0.3 (3)
C1—N1—C3—C2	−0.2 (2)	C10—C7—C8—C9	−178.54 (16)
C4—N1—C3—C2	−177.38 (16)	C7—C8—C9—C4	−1.0 (3)
C1—N1—C4—C5	−150.06 (18)	C5—C4—C9—C8	0.9 (3)
C3—N1—C4—C5	26.6 (3)	N1—C4—C9—C8	−178.52 (16)
C1—N1—C4—C9	29.3 (3)	N3ⁱ—N3—C10—C7	179.27 (17)
C3—N1—C4—C9	−154.04 (18)	C6—C7—C10—N3	−177.13 (17)
C9—C4—C5—C6	−0.1 (3)	C8—C7—C10—N3	1.7 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2ⁱⁱ	0.93	2.60	3.453 (2)	153
C6—H6···N2ⁱⁱⁱ	0.93	2.59	3.421 (3)	149

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₆N₆
M_r	340.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.1342 (3), 7.8172 (3), 13.2191 (6)
β (°)	90.259 (4)
V (Å³)	840.55 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.44 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4180, 1695, 1249
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.143, 1.13
No. of reflections	1695
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.17

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2004), 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
C1—H1···N2ⁱ	0.93	2.60	3.453 (2)	153
C6—H6···N2ⁱⁱ	0.93	2.59	3.421 (3)	149

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

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Talent Fund of Ningbo Municipal Natural Science Foundation (No. 2010 A610187) and the Talent Fund of Ningbo University, China (No. Xkl09070).

References

Chen, C. L., Goforth, A. M., Smith, M. D., Su, C. Y. & Loye, H. C. (2005). Inorg. Chem. 44, 8762–8769. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). 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