Anthracene-9-carbaldehyde hydrazone

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.

Key indicators

• Single-crystal X-ray study
• T = 291 K, P = 0.0 kPa
• Mean [sigma](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

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S1. Comment

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).

S2. Experimental

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.

Computing details

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.

Figures

	Fig. 1. View of the title molecule with 40° probability displacement ellipsoids (PLATON; Spek, 2002).
	Fig. 2. Crystal packing view of the unit cell (PLATON; Spek, 2002).

1-(9-Anthrylmetylidene)hydrazine

Crystal data

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) Å^3	0.3 × 0.2 × 0.08 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0758P)^2 + 0.0918P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
27 constraints	Extinction coefficient: 0.107 (10)
Primary atom site location: structure-invariant direct methods

Special details

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
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N1^i	0.86 (2)	2.47 (2)	3.233 (2)	147.9 (19)

Symmetry code: (i) −x+1, −y+2, −z+1.