(1E,2E)-1,2-Bis(2,3-dihydro-1H-inden-1-yl­idene)hydrazine

Imhof, W.; Wunderle, J.

doi:10.1107/S160053681203560X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2741

doi:10.1107/S160053681203560X

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(1E,2E)-1,2-Bis(2,3-dihydro-1H-inden-1-ylidene)hydrazine

Wolfgang Imhof ^a ^* and Joachim Wunderle ^b

^aInstitute of Integrated Natural Sciences, Universitαtsstr. 1, 56070 Koblenz, Germany, and ^bInstitute of Inorganic and Analytical Chemistry, Friedrich-Schiller-University Jena, Humboldtstr. 8, 07743 Jena, Germany
^*Correspondence e-mail: Imhof@uni-koblenz.de

(Received 28 June 2012; accepted 13 August 2012; online 23 August 2012)

In the title compound, C₁₈H₁₆N₂, there are two independent half-molecules (A and B) in the asymmetric unit, each molecule being completed by an inversion center situated in the mid-point of the central N—N bond. The molecules themselves therefore are essentially planar with r.m.s. deviations of 0.015 (1) and 0.020 (1) Å, respectively. In the crystal, molecules are connected via C—H⋯π interactions in which only type B molecules are donors, while both A and B molecules act as acceptors. As a result, type B molecules are linked into infinite chains along b, which are interconnected by molecules of type A.

Related literature

For structural and physical properties of indanone-derived azines, see: Choytun et al. (2004 ). For the reactivity of azines towards Fe₂(CO)₉, see: Dönnecke et al. (2004a ,b ); Wu et al. (2006 ).

Experimental

Crystal data

C₁₈H₁₆N₂
M_r = 260.33
Triclinic, $[P \overline 1]$
a = 5.1161 (10) Å
b = 11.877 (2) Å
c = 12.245 (2) Å
α = 109.59 (3)°
β = 99.93 (3)°
γ = 100.47 (3)°
V = 667.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 183 K
0.6 × 0.1 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer
4726 measured reflections
2999 independent reflections
1901 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.114
S = 1.02
2999 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17B⋯Cg1	0.99	2.76	3.687 (3)	157
C16—H16B⋯Cg2ⁱ	0.99	2.79	3.649 (2)	146
Symmetry code: (i) x-1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681203560X/bg2471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681203560X/bg2471Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681203560X/bg2471Isup3.mol

Supporting information file. DOI: 10.1107/S160053681203560X/bg2471Isup4.mol

Supporting information file. DOI: 10.1107/S160053681203560X/bg2471Isup5.cml

checkCIF report

Comment top

In the course of a study concerning the reactivity of azines towards Fe₂(CO)₉ we became interested in the structual properties of several substituted aromatic azine derivatives (Dönnecke et al., 2004a, 2004b). Azines derived from indanone derivatives have been investigated concerning their structural and physical properties due to the fact that some of them exhibit NLO properties (Choytun et al., 2004).

In the asymmetric unit of the crystal structure two independent halves of the molecules of the title compound, C₁₈H₁₆N₂, are observed (fIG. 1). Each fragment is expanded to a complete molecule by crystallographic inversion centers that are situated in the middle of the central N—N bonds of both molecules. The molecules themselves therefore are essentially planar with Rms deviations of 0.015 (1) (molecule A: N1, C1 to C9) and 0.020 (1) (molecule B: N2, C10 to C18) Å, respectively. The central N—N bonds are 1.412 (2) (N1—N1ⁱ) and 1.415 (3) (N2—N2ⁱⁱ) Å (i = -x, 1-y, 2- z; ii = -x, - y, 1- z). The planes of the two molecules form an angle of 5.77 (7)° with respect to each other. In the crystal structure molecules are connected via C—H···π interactions (Cg···Cg distances: 2.76 and 2.79 Å). Molecules B are linked by mutual C—H···π contacts in which the molecules act as hydrogen bond donors and acceptors resulting in infinite chains. These chains are interconnected by molecules A which only act as acceptor sites for C—H···π interactions (Figure 2).

Related literature top

For structural and physical properties of indanone-derived azines, see: Choytun et al. (2004). For the reactivity of azines towards Fe₂(CO)₉, see: Dönnecke et al. (2004a,b); Wu et al. (2006).

Experimental top

2,3-Dihydro-1H-inden-1-one (2 g, 1.8 ml, 15.15 mmol) is dissolved in 30 ml ethanol and mixed with hydrazine hydrate (379 mg, 0.37 ml, 7.58 mmol) in the presence of a catalytic amount of p-toluene sulfonic acid. The resulting orange colored mixture is stirred at room temperature for 3 h. Evaporation of the solvent at room temperature for 3 d leads to the formation of the crystalline title compound (yield: 78%).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Figure 1: Molecular structure of the independent molecules of the title compounds with displacement ellipsoids at the 50% probability level (i = -x, 1-y, 2 - z; ii = -x, - y, 1- z).

Figure 2: Packing diagram of the title compound.

(1E,2E)-1,2-Bis(2,3-dihydro-1H-inden-1-ylidene)hydrazine top

Crystal data top

C₁₈H₁₆N₂	Z = 2
M_r = 260.33	F(000) = 276
Triclinic, P1	D_x = 1.296 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1161 (10) Å	Cell parameters from 4726 reflections
b = 11.877 (2) Å	θ = 1.8–27.5°
c = 12.245 (2) Å	µ = 0.08 mm⁻¹
α = 109.59 (3)°	T = 183 K
β = 99.93 (3)°	Quader, yellow
γ = 100.47 (3)°	0.6 × 0.1 × 0.1 mm
V = 667.1 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	1901 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
phi–scan, ω–scan	h = −6→6
4726 measured reflections	k = −14→15
2999 independent reflections	l = −15→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.050P)²] where P = (F_o² + 2F_c²)/3
2999 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₈H₁₆N₂	γ = 100.47 (3)°
M_r = 260.33	V = 667.1 (2) Å³
Triclinic, P1	Z = 2
a = 5.1161 (10) Å	Mo Kα radiation
b = 11.877 (2) Å	µ = 0.08 mm⁻¹
c = 12.245 (2) Å	T = 183 K
α = 109.59 (3)°	0.6 × 0.1 × 0.1 mm
β = 99.93 (3)°

Data collection top

Nonius KappaCCD diffractometer	1901 reflections with I > 2σ(I)
4726 measured reflections	R_int = 0.037
2999 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
2999 reflections	Δρ_min = −0.19 e Å⁻³
181 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	0.0535 (2)	0.51077 (11)	0.95393 (11)	0.0280 (3)
C1	0.3116 (3)	0.50842 (14)	0.74721 (14)	0.0304 (4)
H1	0.2287	0.5754	0.7683	0.036*
C2	0.4487 (3)	0.49064 (14)	0.65753 (14)	0.0338 (4)
H2	0.4614	0.5461	0.6168	0.041*
N2	0.0565 (3)	−0.00657 (12)	0.45007 (11)	0.0319 (3)
C3	0.5684 (3)	0.39184 (14)	0.62645 (14)	0.0326 (4)
H3	0.6627	0.3807	0.5648	0.039*
C4	0.5518 (3)	0.30961 (14)	0.68430 (14)	0.0309 (4)
H4	0.6330	0.2421	0.6624	0.037*
C5	0.4150 (3)	0.32704 (13)	0.77458 (13)	0.0243 (4)
C6	0.2971 (3)	0.42640 (13)	0.80617 (13)	0.0238 (3)
C7	0.1704 (3)	0.42645 (13)	0.90464 (13)	0.0237 (3)
C8	0.2091 (3)	0.31658 (13)	0.93521 (14)	0.0276 (4)
H8B	0.0291	0.2597	0.9222	0.033*
H8A	0.3110	0.3439	1.0199	0.033*
C9	0.3745 (3)	0.25193 (13)	0.85068 (14)	0.0291 (4)
H9B	0.5534	0.2519	0.8969	0.035*
H9A	0.2712	0.1654	0.8005	0.035*
C10	0.1242 (3)	0.20212 (14)	0.17948 (13)	0.0314 (4)
H10	0.0774	0.2678	0.1594	0.038*
C11	0.2587 (3)	0.12604 (15)	0.11147 (15)	0.0365 (4)
H11	0.3040	0.1397	0.0441	0.044*
C12	0.3292 (3)	0.02931 (15)	0.13998 (14)	0.0356 (4)
H12	0.4231	−0.0217	0.0924	0.043*
C13	0.2633 (3)	0.00749 (14)	0.23669 (14)	0.0302 (4)
H13	0.3104	−0.0583	0.2565	0.036*
C14	0.1258 (3)	0.08405 (13)	0.30495 (13)	0.0250 (3)
C15	0.0581 (3)	0.18161 (13)	0.27746 (13)	0.0259 (4)
C16	−0.0860 (3)	0.25116 (13)	0.36545 (14)	0.0302 (4)
H16B	−0.2718	0.2490	0.3237	0.036*
H16A	0.0203	0.3385	0.4089	0.036*
C17	−0.1032 (3)	0.18309 (14)	0.45227 (14)	0.0289 (4)
H17B	−0.0041	0.2396	0.5352	0.035*
H17A	−0.2971	0.1508	0.4506	0.035*
C18	0.0289 (3)	0.07840 (13)	0.40943 (13)	0.0250 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0332 (7)	0.0306 (7)	0.0251 (7)	0.0124 (6)	0.0151 (6)	0.0108 (6)
C1	0.0360 (9)	0.0302 (9)	0.0310 (9)	0.0135 (7)	0.0142 (7)	0.0136 (7)
C2	0.0429 (10)	0.0356 (9)	0.0322 (9)	0.0135 (8)	0.0172 (8)	0.0190 (8)
N2	0.0459 (8)	0.0310 (7)	0.0301 (8)	0.0157 (6)	0.0198 (6)	0.0174 (6)
C3	0.0365 (9)	0.0392 (9)	0.0297 (9)	0.0143 (7)	0.0183 (8)	0.0150 (8)
C4	0.0328 (9)	0.0349 (9)	0.0317 (9)	0.0171 (7)	0.0162 (7)	0.0126 (8)
C5	0.0221 (7)	0.0268 (8)	0.0242 (8)	0.0068 (6)	0.0072 (7)	0.0091 (7)
C6	0.0251 (8)	0.0236 (7)	0.0223 (8)	0.0061 (6)	0.0079 (6)	0.0073 (6)
C7	0.0223 (7)	0.0238 (8)	0.0233 (8)	0.0059 (6)	0.0063 (6)	0.0066 (6)
C8	0.0298 (8)	0.0270 (8)	0.0289 (9)	0.0080 (7)	0.0120 (7)	0.0115 (7)
C9	0.0311 (8)	0.0280 (8)	0.0325 (9)	0.0116 (7)	0.0123 (7)	0.0125 (7)
C10	0.0423 (9)	0.0325 (9)	0.0300 (9)	0.0151 (7)	0.0142 (8)	0.0195 (8)
C11	0.0509 (10)	0.0400 (9)	0.0322 (9)	0.0170 (8)	0.0226 (8)	0.0219 (8)
C12	0.0476 (10)	0.0350 (9)	0.0333 (10)	0.0187 (8)	0.0227 (8)	0.0141 (8)
C13	0.0377 (9)	0.0265 (8)	0.0310 (9)	0.0112 (7)	0.0137 (7)	0.0126 (7)
C14	0.0261 (8)	0.0256 (8)	0.0229 (8)	0.0052 (6)	0.0064 (6)	0.0092 (7)
C15	0.0284 (8)	0.0268 (8)	0.0243 (8)	0.0078 (6)	0.0084 (7)	0.0106 (7)
C16	0.0368 (9)	0.0296 (8)	0.0318 (9)	0.0154 (7)	0.0131 (7)	0.0152 (7)
C17	0.0321 (8)	0.0325 (8)	0.0271 (8)	0.0126 (7)	0.0110 (7)	0.0136 (7)
C18	0.0267 (8)	0.0248 (8)	0.0242 (8)	0.0070 (6)	0.0070 (7)	0.0096 (7)

Geometric parameters (Å, º) top

N1—C7	1.2895 (18)	C9—H9B	0.9900
N1—N1ⁱ	1.412 (2)	C9—H9A	0.9900
C1—C2	1.381 (2)	C10—C11	1.379 (2)
C1—C6	1.393 (2)	C10—C15	1.385 (2)
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.393 (2)	C11—C12	1.396 (2)
C2—H2	0.9500	C11—H11	0.9500
N2—C18	1.2847 (19)	C12—C13	1.377 (2)
N2—N2ⁱⁱ	1.415 (2)	C12—H12	0.9500
C3—C4	1.385 (2)	C13—C14	1.395 (2)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.386 (2)	C14—C15	1.394 (2)
C4—H4	0.9500	C14—C18	1.467 (2)
C5—C6	1.393 (2)	C15—C16	1.512 (2)
C5—C9	1.505 (2)	C16—C17	1.541 (2)
C6—C7	1.464 (2)	C16—H16B	0.9900
C7—C8	1.509 (2)	C16—H16A	0.9900
C8—C9	1.544 (2)	C17—C18	1.506 (2)
C8—H8B	0.9900	C17—H17B	0.9900
C8—H8A	0.9900	C17—H17A	0.9900

C7—N1—N1ⁱ	111.59 (15)	H9B—C9—H9A	108.9
C2—C1—C6	118.82 (14)	C11—C10—C15	119.20 (14)
C2—C1—H1	120.6	C11—C10—H10	120.4
C6—C1—H1	120.6	C15—C10—H10	120.4
C1—C2—C3	120.35 (15)	C10—C11—C12	121.08 (15)
C1—C2—H2	119.8	C10—C11—H11	119.5
C3—C2—H2	119.8	C12—C11—H11	119.5
C18—N2—N2ⁱⁱ	111.52 (15)	C13—C12—C11	120.29 (15)
C4—C3—C2	120.84 (14)	C13—C12—H12	119.9
C4—C3—H3	119.6	C11—C12—H12	119.9
C2—C3—H3	119.6	C12—C13—C14	118.55 (15)
C5—C4—C3	119.13 (14)	C12—C13—H13	120.7
C5—C4—H4	120.4	C14—C13—H13	120.7
C3—C4—H4	120.4	C13—C14—C15	121.22 (14)
C4—C5—C6	119.98 (14)	C13—C14—C18	128.93 (15)
C4—C5—C9	128.68 (13)	C15—C14—C18	109.84 (13)
C6—C5—C9	111.34 (12)	C10—C15—C14	119.64 (14)
C1—C6—C5	120.89 (14)	C10—C15—C16	129.42 (14)
C1—C6—C7	129.37 (14)	C14—C15—C16	110.94 (13)
C5—C6—C7	109.75 (13)	C15—C16—C17	104.84 (12)
N1—C7—C6	122.75 (14)	C15—C16—H16B	110.8
N1—C7—C8	128.85 (14)	C17—C16—H16B	110.8
C6—C7—C8	108.39 (12)	C15—C16—H16A	110.8
C7—C8—C9	105.79 (12)	C17—C16—H16A	110.8
C7—C8—H8B	110.6	H16B—C16—H16A	108.9
C9—C8—H8B	110.6	C18—C17—C16	105.91 (12)
C7—C8—H8A	110.6	C18—C17—H17B	110.6
C9—C8—H8A	110.6	C16—C17—H17B	110.6
H8B—C8—H8A	108.7	C18—C17—H17A	110.6
C5—C9—C8	104.71 (12)	C16—C17—H17A	110.6
C5—C9—H9B	110.8	H17B—C17—H17A	108.7
C8—C9—H9B	110.8	N2—C18—C14	122.08 (14)
C5—C9—H9A	110.8	N2—C18—C17	129.46 (14)
C8—C9—H9A	110.8	C14—C18—C17	108.45 (13)

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···Cg1	0.99	2.76	3.687 (3)	157
C16—H16B···Cg2ⁱⁱⁱ	0.99	2.79	3.649 (2)	146

Symmetry code: (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂
M_r	260.33
Crystal system, space group	Triclinic, P1
Temperature (K)	183
a, b, c (Å)	5.1161 (10), 11.877 (2), 12.245 (2)
α, β, γ (°)	109.59 (3), 99.93 (3), 100.47 (3)
V (Å³)	667.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.6 × 0.1 × 0.1

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4726, 2999, 1901
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.114, 1.02
No. of reflections	2999
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···Cg1	0.99	2.76	3.687 (3)	156.5
C16—H16B···Cg2ⁱ	0.99	2.79	3.649 (2)	145.9

Symmetry code: (i) x−1, y, z.

Acknowledgements

Financial support by the Deutsche Forschungsgemeinschaft is gratefully acknowledged.

References

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COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2741

doi:10.1107/S160053681203560X

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