In the title compound, C15H12N2, the geometric parameters are normal, within experimental error. The molecules are arranged in pairs, with their hydrazone groups oriented towards one another.
Supporting information
CCDC reference: 214615
Key indicators
- Single-crystal X-ray study
- T = 291 K, P = 0.0 kPa
- Mean (C-C) = 0.002 Å
- R factor = 0.052
- wR factor = 0.140
- Data-to-parameter ratio = 12.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N2 - H2N2 ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
9-Anthraldehyde (1.4 g) was diluted in 30 ml of ethanol, and 0.34 ml of hydrazine hydrate was added under heating. After slow cooling the mixture was kept in a refrigerator overnight. The crystals formed were isolated, washed by ethanol and dried. The yield was 1 g of the title compound, whose identity and purity was checked by thin-layer chromatography and NMR spectra. If a half of the quantity of hydrazine hydrate was used and the mixture was refluxed for 5 h, the corresponding azine was produced. However, no suitable crystals could be obtained.
Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97.
1-(9-Anthrylmetylidene)hydrazine
top
Crystal data top
C15H12N2 | F(000) = 464 |
Mr = 220.27 | Dx = 1.325 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4704 reflections |
a = 17.7211 (9) Å | θ = 1.0–26.0° |
b = 3.9082 (2) Å | µ = 0.08 mm−1 |
c = 16.4115 (9) Å | T = 291 K |
β = 103.856 (3)° | Plate, yellow |
V = 1103.55 (10) Å3 | 0.3 × 0.2 × 0.08 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1628 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.000 |
Graphite monochromator | θmax = 26.0°, θmin = 2.6° |
ω scans | h = 0→21 |
2169 measured reflections | k = −4→4 |
2169 independent reflections | l = −20→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0758P)2 + 0.0918P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2169 reflections | Δρmax = 0.30 e Å−3 |
177 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
27 constraints | Extinction coefficient: 0.107 (10) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C15H12N2 | V = 1103.55 (10) Å3 |
Mr = 220.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.7211 (9) Å | µ = 0.08 mm−1 |
b = 3.9082 (2) Å | T = 291 K |
c = 16.4115 (9) Å | 0.3 × 0.2 × 0.08 mm |
β = 103.856 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 1628 reflections with I > 2σ(I) |
2169 measured reflections | Rint = 0.000 |
2169 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.30 e Å−3 |
2169 reflections | Δρmin = −0.24 e Å−3 |
177 parameters | |
Special details top
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 | Uiso*/Ueq | |
C1 | 0.18128 (9) | 0.7205 (4) | 0.47635 (10) | 0.0477 (4) | |
H1 | 0.2203 | 0.6382 | 0.5204 | 0.050 (4)* | |
C2 | 0.10649 (10) | 0.7134 (4) | 0.48320 (11) | 0.0559 (5) | |
H2 | 0.0952 | 0.6247 | 0.5315 | 0.069 (6)* | |
C3 | 0.04561 (10) | 0.8383 (5) | 0.41831 (12) | 0.0585 (5) | |
H3 | −0.0054 | 0.8309 | 0.4238 | 0.074 (6)* | |
C4 | 0.06163 (9) | 0.9688 (4) | 0.34813 (12) | 0.0537 (5) | |
H4 | 0.0212 | 1.0526 | 0.3058 | 0.068 (6)* | |
C5 | 0.37012 (10) | 1.0124 (4) | 0.30409 (10) | 0.0497 (4) | |
H5 | 0.4116 | 0.9162 | 0.3430 | 0.052 (5)* | |
C6 | 0.38282 (11) | 1.1584 (5) | 0.23336 (11) | 0.0586 (5) | |
H6 | 0.4330 | 1.1645 | 0.2253 | 0.068 (6)* | |
C7 | 0.32142 (12) | 1.3001 (4) | 0.17228 (11) | 0.0605 (5) | |
H7 | 0.3313 | 1.4036 | 0.1249 | 0.075 (6)* | |
C8 | 0.24828 (11) | 1.2864 (4) | 0.18225 (10) | 0.0544 (5) | |
H8 | 0.2079 | 1.3756 | 0.1407 | 0.074 (6)* | |
C9 | 0.27862 (8) | 0.8642 (3) | 0.39370 (9) | 0.0387 (4) | |
C10 | 0.15604 (10) | 1.1210 (4) | 0.26608 (10) | 0.0478 (4) | |
H10 | 0.1156 | 1.2066 | 0.2240 | 0.059 (5)* | |
C11 | 0.20133 (8) | 0.8516 (4) | 0.40300 (9) | 0.0404 (4) | |
C12 | 0.13899 (9) | 0.9813 (4) | 0.33731 (10) | 0.0439 (4) | |
C13 | 0.29429 (9) | 1.0040 (3) | 0.31968 (9) | 0.0406 (4) | |
C14 | 0.23133 (9) | 1.1372 (4) | 0.25553 (9) | 0.0445 (4) | |
C15 | 0.34009 (9) | 0.7253 (4) | 0.46235 (9) | 0.0421 (4) | |
N1 | 0.40544 (7) | 0.8693 (3) | 0.49051 (8) | 0.0455 (4) | |
N2 | 0.45402 (9) | 0.7240 (5) | 0.56097 (9) | 0.0580 (4) | |
H15 | 0.3280 (9) | 0.515 (5) | 0.4888 (11) | 0.054 (5)* | |
H1N2 | 0.5015 (13) | 0.765 (6) | 0.5600 (14) | 0.082 (7)* | |
H2N2 | 0.4443 (13) | 0.493 (7) | 0.5661 (16) | 0.100 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0532 (9) | 0.0462 (9) | 0.0429 (9) | −0.0038 (7) | 0.0096 (7) | 0.0008 (7) |
C2 | 0.0601 (11) | 0.0561 (10) | 0.0550 (11) | −0.0092 (8) | 0.0207 (9) | −0.0001 (8) |
C3 | 0.0463 (10) | 0.0615 (11) | 0.0695 (12) | −0.0073 (8) | 0.0172 (8) | −0.0072 (9) |
C4 | 0.0455 (9) | 0.0523 (10) | 0.0586 (11) | −0.0014 (7) | 0.0031 (8) | −0.0055 (8) |
C5 | 0.0546 (10) | 0.0539 (10) | 0.0405 (9) | −0.0037 (7) | 0.0114 (7) | −0.0066 (7) |
C6 | 0.0688 (12) | 0.0636 (11) | 0.0494 (10) | −0.0110 (9) | 0.0258 (9) | −0.0081 (8) |
C7 | 0.0887 (14) | 0.0566 (10) | 0.0406 (9) | −0.0094 (9) | 0.0240 (9) | −0.0010 (8) |
C8 | 0.0784 (12) | 0.0469 (9) | 0.0352 (8) | −0.0006 (8) | 0.0087 (8) | 0.0018 (7) |
C9 | 0.0461 (8) | 0.0333 (7) | 0.0348 (8) | −0.0035 (6) | 0.0057 (6) | −0.0051 (6) |
C10 | 0.0542 (9) | 0.0437 (8) | 0.0391 (9) | 0.0022 (7) | −0.0013 (7) | 0.0004 (7) |
C11 | 0.0478 (9) | 0.0345 (7) | 0.0370 (8) | −0.0040 (6) | 0.0066 (6) | −0.0058 (6) |
C12 | 0.0463 (9) | 0.0382 (8) | 0.0438 (9) | −0.0032 (6) | 0.0045 (7) | −0.0058 (6) |
C13 | 0.0504 (9) | 0.0352 (8) | 0.0349 (8) | −0.0043 (6) | 0.0077 (6) | −0.0056 (6) |
C14 | 0.0583 (10) | 0.0375 (8) | 0.0351 (8) | −0.0022 (7) | 0.0059 (7) | −0.0042 (6) |
C15 | 0.0482 (9) | 0.0400 (8) | 0.0380 (8) | 0.0000 (7) | 0.0100 (7) | −0.0001 (6) |
N1 | 0.0437 (7) | 0.0523 (7) | 0.0384 (7) | 0.0016 (6) | 0.0055 (6) | −0.0005 (6) |
N2 | 0.0450 (9) | 0.0806 (12) | 0.0449 (8) | 0.0043 (8) | 0.0038 (6) | 0.0084 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.357 (2) | C8—C14 | 1.432 (2) |
C1—C11 | 1.429 (2) | C8—H8 | 0.9300 |
C1—H1 | 0.9300 | C9—C11 | 1.415 (2) |
C2—C3 | 1.409 (2) | C9—C13 | 1.419 (2) |
C2—H2 | 0.9300 | C9—C15 | 1.471 (2) |
C3—C4 | 1.350 (2) | C10—C14 | 1.387 (2) |
C3—H3 | 0.9300 | C10—C12 | 1.388 (2) |
C4—C12 | 1.425 (2) | C10—H10 | 0.9300 |
C4—H4 | 0.9300 | C11—C12 | 1.438 (2) |
C5—C6 | 1.360 (2) | C13—C14 | 1.436 (2) |
C5—C13 | 1.427 (2) | C15—N1 | 1.2709 (19) |
C5—H5 | 0.9300 | C15—H15 | 0.977 (18) |
C6—C7 | 1.405 (3) | N1—N2 | 1.3870 (19) |
C6—H6 | 0.9300 | N2—H1N2 | 0.86 (2) |
C7—C8 | 1.346 (3) | N2—H2N2 | 0.93 (3) |
C7—H7 | 0.9300 | | |
| | | |
C2—C1—C11 | 121.45 (15) | C11—C9—C15 | 117.57 (13) |
C2—C1—H1 | 119.3 | C13—C9—C15 | 122.50 (13) |
C11—C1—H1 | 119.3 | C14—C10—C12 | 122.21 (14) |
C1—C2—C3 | 121.10 (16) | C14—C10—H10 | 118.9 |
C1—C2—H2 | 119.4 | C12—C10—H10 | 118.9 |
C3—C2—H2 | 119.4 | C9—C11—C1 | 123.08 (13) |
C4—C3—C2 | 119.74 (16) | C9—C11—C12 | 119.77 (14) |
C4—C3—H3 | 120.1 | C1—C11—C12 | 117.14 (14) |
C2—C3—H3 | 120.1 | C10—C12—C4 | 121.91 (15) |
C3—C4—C12 | 121.61 (16) | C10—C12—C11 | 119.14 (14) |
C3—C4—H4 | 119.2 | C4—C12—C11 | 118.94 (15) |
C12—C4—H4 | 119.2 | C9—C13—C5 | 123.23 (14) |
C6—C5—C13 | 121.21 (16) | C9—C13—C14 | 119.37 (14) |
C6—C5—H5 | 119.4 | C5—C13—C14 | 117.38 (14) |
C13—C5—H5 | 119.4 | C10—C14—C8 | 121.67 (14) |
C5—C6—C7 | 121.09 (17) | C10—C14—C13 | 119.57 (14) |
C5—C6—H6 | 119.5 | C8—C14—C13 | 118.76 (15) |
C7—C6—H6 | 119.5 | N1—C15—C9 | 123.94 (15) |
C8—C7—C6 | 120.10 (16) | N1—C15—H15 | 119.2 (10) |
C8—C7—H7 | 120.0 | C9—C15—H15 | 116.8 (10) |
C6—C7—H7 | 120.0 | C15—N1—N2 | 116.84 (15) |
C7—C8—C14 | 121.35 (16) | N1—N2—H1N2 | 108.9 (15) |
C7—C8—H8 | 119.3 | N1—N2—H2N2 | 112.5 (15) |
C14—C8—H8 | 119.3 | H1N2—N2—H2N2 | 112.7 (19) |
C11—C9—C13 | 119.92 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···N1i | 0.86 (2) | 2.47 (2) | 3.233 (2) | 147.9 (19) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C15H12N2 |
Mr | 220.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 17.7211 (9), 3.9082 (2), 16.4115 (9) |
β (°) | 103.856 (3) |
V (Å3) | 1103.55 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.08 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2169, 2169, 1628 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.140, 1.10 |
No. of reflections | 2169 |
No. of parameters | 177 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.24 |
Selected geometric parameters (Å, º) topC1—C2 | 1.357 (2) | C9—C11 | 1.415 (2) |
C1—C11 | 1.429 (2) | C9—C13 | 1.419 (2) |
C2—C3 | 1.409 (2) | C9—C15 | 1.471 (2) |
C3—C4 | 1.350 (2) | C10—C14 | 1.387 (2) |
C4—C12 | 1.425 (2) | C10—C12 | 1.388 (2) |
C5—C6 | 1.360 (2) | C11—C12 | 1.438 (2) |
C5—C13 | 1.427 (2) | C13—C14 | 1.436 (2) |
C6—C7 | 1.405 (3) | C15—N1 | 1.2709 (19) |
C7—C8 | 1.346 (3) | N1—N2 | 1.3870 (19) |
C8—C14 | 1.432 (2) | | |
| | | |
N1—C15—C9 | 123.94 (15) | C15—N1—N2 | 116.84 (15) |
N1—C15—H15 | 119.2 (10) | N1—N2—H1N2 | 108.9 (15) |
C9—C15—H15 | 116.8 (10) | N1—N2—H2N2 | 112.5 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···N1i | 0.86 (2) | 2.47 (2) | 3.233 (2) | 147.9 (19) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
During our investigation of chemical and electrochemical properties of the azine grouping >C═N—N═C< (Riedl et al., 1996; Zuman & Ludv\'ιk, 2000), various azine and hydrazone derivatives were synthesized, including the title compound, (I), derived from anthracene-9-carbaldehyde.
In order to compare the distances in (I), a search of the Cambridge Structural Database (CSD, Version 5.21; Allen, 2002) was carried out and yielded 24 hits. The search considered structures containing anthracene, not involved in the π-bonding with a metal and with R factors < 0.09. The bond lengths within the anthracene ring of (I) are in accordance with those found in the search, except for slight deviations of the bond-lengths of the pairs C9—C11, C9—C13 and C10—C12, C10—C14 (Fig. 1), which are ~0.022 Å longer and 0.008 Å shorter, respectively, than in pure anthracene. The reason why the chemically equivalent bonds C9—C11, C9—C13 are longer than C10—C12, C10—C14 (Table 1) is probably due to the substituent on C9.
Neither atom N1 nor atom N2 lie in the plane of the central aromatic ring A (C9/C11/C12/C10/C14/C13). The dihedral angle between the plane through atoms N1, C15, C9 and plane A is 42.9 (2)°. The bond length N1—N2 of 1.387 (2) Å is significantly longer than the N═N bond length in azo-compounds (~1.25 Å), as shown by a search of the CSD. [Compounds with a fragment C···C···N···N···C···C were searched while the coordination number on C was 3 and 2 on N. The value of ~1.25 Å corresponds to the maximum (more than 700 hits) in the distribution of N···N bond lengths.] On the other hand the N1—N2 bond length is shorter than that in hydrazine: the average N—N bond in hydrazinium(1+) is 1.435 (7) Å, according to 36 hits from the CSD.
This comparison shows that the N—N bond in (I) (Table 1) has a bond order close to one. The bond length between atoms C15 and N1 [1.272 (2) Å] corresponds, however, to a typical double bond, that is ~1.28 Å (Box \& Yu, 1997).
The hydrazone groups are oriented towards each other, ordering the molecules into hydrogen bonded pairs (Fig. 2). The geometry of the N2-H1N2···N1 contact points to a weak hydrogen bond (Table 2).