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

Abstract

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,

• a = 8.1342 (3) Å

• b = 7.8172 (3) Å

• c = 13.2191 (6) Å

• β = 90.259 (4)°

• V = 840.55 (6) ų

• 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[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202291X/xu5536Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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

Experimental

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%.

Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93 Å) and U_iso(H) values equal to 1.2U_eq(C).

Figures

Fig. 1.

The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C20H16N6	F(000) = 356
Mr = 340.39	Dx = 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

Rigaku R-AXIS RAPID diffractometer	1249 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 26.4°, θmin = 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

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(Fo2) + (0.0589P)2 + 0.0922P] where P = (Fo2 + 2Fc2)/3
1695 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.