π–π Stacks and C–H...O bonded sheets in 4-[(2-nitro­phenyl)­hydrazono]-4H-naphthalen-1-one

The title compound, C₁₆H₁₁N₃O₃, (I), exists in crystals as the pure hydrazone tautomer. Molecules form stacks stretched along [100]. AM1 calculations of the crystal electrostatic potential show that the crystal environment causes only a 24% increase in the molecular dipole moment of (I).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.108
• Data-to-parameter ratio = 12.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_353  Alert C Long  N-H Bond (0.87A)     N(1)   -   H(1)   =       1.05 Ang.


 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

Azo derivatives of α- and β-naphthols form a family of widely used dyes and pigments, but structure determinations the derivatives of α-naphthol have not been reported up to now.

The title compound, (I), is known to exist in solutions as the hydrazone tautomer (Koller & Zollinger, 1970; Korewa & Urbańska, 1972). The density functional theory (DFT) calculations for the isolated molecule showed that the hydrazone form is 28 kJ mol^-1 more stable than the azo form.

The molecule of (I) is close to being planar; its structure is shown in Fig. 1 and selected geometrical parameters are given in Table 1. The bond dimensions in the keto–hydrazone O1—C1—C2—C3—C4—N2—N1 chain indicate alternation of single and double bonds, thus only a moderate charge transfer from the hydrazone moiety to the keto group takes place. Neighbouring molecules within the stack are related by inversion centres, with interplanar distances of 3.347 (1) and 3.411 (1) Å. The nitro group forms an intramolecular hydrogen bond with the hydrazone H atom, thus precluding the formation of intermolecular hydrogen bonds. As shown in Fig. 2, the molecules are gathered together by C—H···O contacts to form flat sheets.

AM1 (Dewar et al., 1985) calculations predict that under the effect of the crystal electrostatic potential (Yatsenko & Paseshnichenko, 2000) the molecular dipole moment of (I) increases from 5.64 D for an isolated molecule to 6.99 D for a molecule within the crystal.

S2. Experimental

Compound (I) was prepared according to the established procedure of Elbs et al. (1924). Single crystals were grown by slow evaporation of a chloroform solution of (I). The DFT calculations were performed using the program provided by Dr D. N. Laikov (1997). Details of calculations employing the crystal electrostatic potentials have been reported elsewhere (Yatenko & Paseshnichenko, 2000).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PROFIT (Streltsov & Zavodnik, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2001).

Figures

	Fig. 1. A view of (I) with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii.
	Fig. 2. C—H···O Bonded sheets in the structure of (I).

4-[(2-nitrophenyl)hydrazono]-4H-naphthalen-1-one

Crystal data

C16H11N3O3	Dx = 1.479 Mg m^−3
Mr = 293.28	Melting point: 517 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.328 (2) Å	Cell parameters from 22 reflections
b = 16.366 (4) Å	θ = 14.7–16.3°
c = 11.131 (3) Å	µ = 0.11 mm^−1
β = 99.33 (2)°	T = 293 K
V = 1317.3 (6) Å^3	Needle, dark red
Z = 4	0.55 × 0.16 × 0.09 mm
F(000) = 608

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 2.2°
Graphite monochromator	h = −9→9
ω scans	k = 0→21
3173 measured reflections	l = 0→14
3025 independent reflections	3 standard reflections every 120 min
2041 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.045	All H-atom parameters refined
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.31	(Δ/σ)max = 0.006
3025 reflections	Δρmax = 0.20 e Å^−3
244 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (8)

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
O1	0.60667 (17)	0.57864 (7)	0.93712 (9)	0.0572 (4)
O2	0.23492 (18)	0.27875 (7)	0.44880 (11)	0.0656 (4)
O3	0.1408 (2)	0.20724 (7)	0.28875 (13)	0.0759 (4)
N1	0.21431 (17)	0.43700 (7)	0.44329 (10)	0.0401 (3)
N2	0.23925 (16)	0.51405 (7)	0.48507 (10)	0.0380 (3)
N3	0.15886 (19)	0.27320 (8)	0.34107 (13)	0.0498 (4)
C1	0.5250 (2)	0.56377 (9)	0.83466 (13)	0.0386 (4)
C2	0.5072 (2)	0.48104 (9)	0.78856 (14)	0.0425 (4)
C3	0.4199 (2)	0.46339 (9)	0.67641 (14)	0.0426 (4)
C4	0.33440 (19)	0.52586 (8)	0.59335 (12)	0.0336 (3)
C5	0.2814 (2)	0.67590 (9)	0.55850 (14)	0.0445 (4)
C6	0.2949 (2)	0.75520 (10)	0.59902 (16)	0.0517 (4)
C7	0.3810 (2)	0.77243 (9)	0.71679 (16)	0.0523 (4)
C8	0.4546 (2)	0.71045 (10)	0.79169 (15)	0.0469 (4)
C9	0.4430 (2)	0.62964 (9)	0.75147 (13)	0.0366 (3)
C10	0.35333 (19)	0.61141 (8)	0.63376 (12)	0.0352 (3)
C11	0.11540 (19)	0.42454 (8)	0.32735 (12)	0.0356 (3)
C12	0.0890 (2)	0.34606 (9)	0.27546 (13)	0.0390 (4)
C13	−0.0090 (2)	0.33540 (11)	0.15852 (15)	0.0478 (4)
C14	−0.0833 (2)	0.40066 (11)	0.09289 (15)	0.0523 (5)
C15	−0.0601 (2)	0.47837 (11)	0.14233 (15)	0.0491 (4)
C16	0.0393 (2)	0.49030 (9)	0.25649 (14)	0.0416 (4)
H2	0.555 (2)	0.4411 (10)	0.8370 (14)	0.053 (5)*
H3	0.419 (2)	0.4083 (11)	0.6500 (16)	0.069 (5)*
H5	0.226 (2)	0.6630 (10)	0.4827 (15)	0.051 (5)*
H6	0.241 (2)	0.7953 (11)	0.5459 (14)	0.061 (5)*
H7	0.383 (2)	0.8270 (10)	0.7417 (13)	0.055 (5)*
H8	0.508 (2)	0.7184 (11)	0.8724 (16)	0.062 (5)*
H13	−0.022 (3)	0.2800 (12)	0.1302 (16)	0.072 (6)*
H14	−0.153 (2)	0.3925 (10)	0.0167 (15)	0.060 (5)*
H15	−0.114 (2)	0.5221 (10)	0.0985 (14)	0.055 (5)*
H16	0.054 (2)	0.5419 (10)	0.2910 (13)	0.052 (5)*
H1	0.257 (2)	0.3828 (10)	0.4895 (13)	0.047 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0728 (8)	0.0503 (7)	0.0403 (6)	−0.0017 (6)	−0.0153 (6)	−0.0015 (5)
O2	0.0868 (10)	0.0455 (7)	0.0558 (8)	0.0033 (6)	−0.0150 (7)	0.0075 (6)
O3	0.0982 (11)	0.0346 (6)	0.0878 (10)	−0.0061 (7)	−0.0059 (8)	−0.0118 (6)
N1	0.0484 (8)	0.0330 (6)	0.0355 (7)	0.0011 (6)	−0.0037 (6)	−0.0011 (5)
N2	0.0417 (7)	0.0341 (6)	0.0367 (7)	0.0005 (5)	0.0020 (6)	−0.0021 (5)
N3	0.0534 (8)	0.0344 (7)	0.0595 (9)	−0.0051 (6)	0.0027 (7)	0.0012 (6)
C1	0.0382 (8)	0.0396 (8)	0.0358 (8)	−0.0017 (7)	−0.0007 (6)	0.0008 (6)
C2	0.0485 (10)	0.0361 (8)	0.0392 (9)	0.0059 (7)	−0.0042 (7)	0.0071 (7)
C3	0.0488 (10)	0.0332 (7)	0.0436 (9)	0.0025 (7)	0.0004 (7)	−0.0009 (7)
C4	0.0345 (8)	0.0338 (7)	0.0314 (7)	0.0002 (6)	0.0017 (6)	0.0000 (6)
C5	0.0506 (10)	0.0373 (8)	0.0409 (9)	−0.0003 (7)	−0.0064 (8)	0.0043 (7)
C6	0.0576 (11)	0.0356 (8)	0.0572 (10)	0.0016 (8)	−0.0048 (8)	0.0092 (8)
C7	0.0586 (11)	0.0305 (8)	0.0637 (11)	−0.0027 (8)	−0.0019 (9)	−0.0037 (8)
C8	0.0507 (10)	0.0406 (8)	0.0454 (9)	−0.0040 (7)	−0.0042 (8)	−0.0055 (7)
C9	0.0349 (8)	0.0368 (7)	0.0365 (7)	−0.0022 (6)	0.0006 (6)	−0.0005 (6)
C10	0.0337 (8)	0.0351 (7)	0.0361 (8)	−0.0004 (6)	0.0030 (6)	0.0028 (6)
C11	0.0334 (8)	0.0387 (8)	0.0333 (8)	−0.0018 (6)	0.0015 (6)	−0.0004 (6)
C12	0.0365 (8)	0.0387 (8)	0.0409 (8)	−0.0037 (6)	0.0036 (6)	−0.0011 (6)
C13	0.0471 (10)	0.0511 (10)	0.0445 (9)	−0.0116 (8)	0.0049 (7)	−0.0095 (8)
C14	0.0491 (10)	0.0681 (12)	0.0359 (9)	−0.0104 (9)	−0.0045 (7)	−0.0030 (8)
C15	0.0465 (10)	0.0566 (10)	0.0417 (9)	0.0030 (8)	−0.0002 (8)	0.0102 (8)
C16	0.0449 (9)	0.0376 (8)	0.0405 (9)	0.0026 (7)	0.0014 (7)	−0.0002 (7)

Geometric parameters (Å, º)

O1—C1	1.2235 (17)	C6—C7	1.389 (2)
O2—N3	1.2410 (16)	C6—H6	0.929 (17)
O3—N3	1.2235 (16)	C7—C8	1.367 (2)
N1—N2	1.3462 (17)	C7—H7	0.935 (16)
N1—C11	1.3889 (17)	C8—C9	1.394 (2)
N1—H1	1.047 (15)	C8—H8	0.929 (17)
N2—C4	1.3053 (17)	C9—C10	1.3995 (19)
N3—C12	1.4479 (19)	C11—C16	1.396 (2)
C1—C2	1.446 (2)	C11—C12	1.409 (2)
C1—C9	1.483 (2)	C12—C13	1.392 (2)
C2—C3	1.339 (2)	C13—C14	1.357 (2)
C2—H2	0.884 (16)	C13—H13	0.960 (19)
C3—C4	1.451 (2)	C14—C15	1.385 (2)
C3—H3	0.949 (18)	C14—H14	0.926 (17)
C4—C10	1.4703 (19)	C15—C16	1.372 (2)
C5—C6	1.372 (2)	C15—H15	0.918 (16)
C5—C10	1.397 (2)	C16—H16	0.927 (16)
C5—H5	0.900 (16)
N2—N1—C11	118.67 (12)	C7—C8—C9	120.70 (15)
N2—N1—H1	127.6 (8)	C7—C8—H8	123.3 (11)
C11—N1—H1	113.7 (8)	C9—C8—H8	115.9 (11)
C4—N2—N1	118.69 (12)	C8—C9—C10	119.84 (14)
O3—N3—O2	121.44 (14)	C8—C9—C1	119.45 (13)
O3—N3—C12	118.97 (14)	C10—C9—C1	120.71 (13)
O2—N3—C12	119.59 (13)	C5—C10—C9	118.35 (13)
O1—C1—C2	121.28 (14)	C5—C10—C4	121.90 (13)
O1—C1—C9	121.65 (14)	C9—C10—C4	119.75 (12)
C2—C1—C9	117.06 (13)	N1—C11—C16	120.81 (13)
C3—C2—C1	122.32 (14)	N1—C11—C12	122.09 (13)
C3—C2—H2	119.5 (10)	C16—C11—C12	117.10 (13)
C1—C2—H2	118.2 (10)	C13—C12—C11	120.90 (14)
C2—C3—C4	122.28 (14)	C13—C12—N3	117.07 (14)
C2—C3—H3	118.1 (11)	C11—C12—N3	122.02 (13)
C4—C3—H3	119.5 (11)	C14—C13—C12	120.39 (16)
N2—C4—C3	126.51 (13)	C14—C13—H13	123.9 (11)
N2—C4—C10	115.68 (12)	C12—C13—H13	115.7 (11)
C3—C4—C10	117.81 (12)	C13—C14—C15	119.73 (15)
C6—C5—C10	121.16 (15)	C13—C14—H14	119.6 (11)
C6—C5—H5	121.9 (11)	C15—C14—H14	120.6 (11)
C10—C5—H5	117.0 (11)	C16—C15—C14	120.73 (16)
C5—C6—C7	119.99 (15)	C16—C15—H15	119.9 (10)
C5—C6—H6	117.3 (11)	C14—C15—H15	119.3 (10)
C7—C6—H6	122.7 (11)	C15—C16—C11	121.12 (15)
C8—C7—C6	119.93 (15)	C15—C16—H16	121.5 (10)
C8—C7—H7	122.9 (10)	C11—C16—H16	117.3 (10)
C6—C7—H7	117.1 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	1.05 (2)	1.76 (2)	2.594 (2)	133 (1)
C2—H2···O3^i	0.88 (2)	2.58 (2)	3.233 (2)	131 (1)
C6—H6···O1^ii	0.93 (2)	2.51 (2)	3.426 (2)	169 (1)
C13—H13···O2^iii	0.96 (2)	2.65 (2)	3.323 (2)	128 (1)
C15—H15···O1^iv	0.92 (2)	2.66 (2)	3.474 (2)	148 (1)

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1, y, z−1.