organic compounds
(1E,2E)-1,2-Bis(2,3-dihydro-1H-inden-1-ylidene)hydrazine
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
In the title compound, C18H16N2, there are two independent half-molecules (A and B) in the 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 et al. (2004). For the reactivity of towards Fe2(CO)9, see: Dönnecke et al. (2004a,b); Wu et al. (2006).
see: ChoytunExperimental
Crystal data
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Data collection
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Refinement
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Data collection: COLLECT (Nonius, 1998); cell 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
10.1107/S160053681203560X/bg2471sup1.cif
contains datablocks I, global. DOI: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
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%).
Hydrogen atoms have been placed in idealized positions and were refined using the riding model approximation with C—H distances of 0.95 and 0.99 Å for aromatic and methylene groups, respectively, with Uiso(H) = 1.2 Ueq(C).
Data collection: COLLECT (Nonius, 1998); cell
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).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. |
C18H16N2 | Z = 2 |
Mr = 260.33 | F(000) = 276 |
Triclinic, P1 | Dx = 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 |
Nonius KappaCCD diffractometer | 1901 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 1.8° |
phi–scan, ω–scan | h = −6→6 |
4726 measured reflections | k = −14→15 |
2999 independent reflections | l = −15→15 |
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(Fo2) + (0.050P)2] where P = (Fo2 + 2Fc2)/3 |
2999 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C18H16N2 | γ = 100.47 (3)° |
Mr = 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)° |
Nonius KappaCCD diffractometer | 1901 reflections with I > 2σ(I) |
4726 measured reflections | Rint = 0.037 |
2999 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.19 e Å−3 |
2999 reflections | Δρmin = −0.19 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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. |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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).
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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).