N-(2,4-Dinitro­phen­yl)-N′-(2-pyridylmethyl­ene)hydrazine

The title compound [alternative name: pyridine-2-carbaldehyde 2,4-dinitro­phenyl­hydrazone], C₁₂H₉N₅O₄, was prepared using pyridine-2-carbaldehyde and N-(2,4-dinitro­phen­yl)hydrazine. In the crystal structure, weak inter­molecular C—H...O hydrogen-bonding inter­actions link adjacent mol­ecules to form a three-dimensional supramolecular network.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.118
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

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Alert level C
PLAT432_ALERT_2_C Short Inter X...Y Contact  O2     ..  C8      ..       2.97 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988),the synthesis of new and designed crystal structures has become the major strand of modern chemistry. In the present study, we report the synthesis and molecular structure of the title compound, (I).

A view of the molecule of (I) is shown in Fig. 1. In the molecular structure, the C6—N2 and N2—N3 bond lengths of 1.274 (2) and 1.369 (2) Å, respectively, are consistent with those found in a related structure (Jing et al., 2005). The dinitrophenylhydrazone moiety and the pyridine ring are both planar, with r.m.s. deviations of the fitted atoms of 0.039 (2) and 0.005 (2) Å, respectively. The dihedral angle between the dinitrophenylhydrazone and pyridine planes is 3.88 (8)°. A strong intramolecular N—H···O hydrogen bond (Table 1) stabilizes the molecular conformation. In the crystal packing, two weak C—H···O hydrogen-bond interactions are observed (Table 1), resulting in the formation of a three-dimensional supramolecular network.

S2. Experimental

An anhydrous ethanol solution of pyridine-2-carbaldehyde (1.22 g, 10 mmol) was added to an anhydrous ethanol solution of (2,4-dinitrophenyl)hydrazine (2.03 g, 10 mmol), and the mixture was stirred at 350 K for 8 h under nitrogen. The red–brown precipitate was isolated, recrystallized from ethanol, and dried in vacuo to give the pure compound (I) in 81% yield. Bright-red single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

S3. Refinement

H atoms bonded to C atoms were included in calculated positions (C—H = 0.93–0.96 Å) and refined using a riding-model approximation, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The H atom attached to N3 was located in a difference Fourier map and refined freely.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the title compound, shown with 30% probability displacement ellipsoids.

pyridine-2-carbaldehyde 2,4-dinitrophenylhydrazone

Crystal data

C12H9N5O4	F(000) = 592
Mr = 287.24	Dx = 1.507 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1875 reflections
a = 8.5690 (18) Å	θ = 2.9–25.9°
b = 6.3333 (13) Å	µ = 0.12 mm^−1
c = 23.340 (5) Å	T = 294 K
β = 91.532 (4)°	Block, red
V = 1266.2 (5) Å^3	0.34 × 0.26 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2564 independent reflections
Radiation source: fine-focus sealed tube	1567 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→10
Tmin = 0.929, Tmax = 0.977	k = −7→7
6807 measured reflections	l = −21→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 0.1982P] where P = (Fo^2 + 2Fc^2)/3
2564 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.14 e Å^−3
1 restraint	Δρmin = −0.19 e Å^−3

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	0.26494 (16)	0.2947 (2)	0.23555 (6)	0.0596 (4)
O2	0.40822 (19)	0.0197 (3)	0.24571 (6)	0.0798 (5)
O3	0.6692 (2)	−0.1588 (3)	0.41983 (8)	0.0844 (6)
O4	0.67334 (18)	0.0620 (3)	0.49017 (7)	0.0762 (5)
N1	−0.06722 (18)	1.1709 (2)	0.31995 (7)	0.0527 (4)
N2	0.18293 (17)	0.7369 (2)	0.34905 (7)	0.0438 (4)
N3	0.23738 (17)	0.5665 (2)	0.31952 (7)	0.0447 (4)
N4	0.35286 (18)	0.1818 (3)	0.26474 (7)	0.0455 (4)
N5	0.6303 (2)	0.0074 (3)	0.44178 (8)	0.0574 (5)
C1	−0.1236 (2)	1.3413 (3)	0.34645 (11)	0.0629 (6)
H1	−0.1865	1.4329	0.3249	0.075*
C2	−0.0952 (3)	1.3901 (3)	0.40282 (11)	0.0656 (6)
H2	−0.1377	1.5107	0.4189	0.079*
C3	−0.0030 (3)	1.2570 (4)	0.43476 (10)	0.0662 (6)
H3	0.0192	1.2861	0.4732	0.079*
C4	0.0568 (2)	1.0800 (3)	0.40959 (8)	0.0528 (5)
H4	0.1189	0.9867	0.4309	0.063*
C5	0.02352 (19)	1.0417 (3)	0.35219 (8)	0.0407 (4)
C6	0.0859 (2)	0.8572 (3)	0.32272 (8)	0.0431 (5)
H6	0.0549	0.8280	0.2851	0.052*
C7	0.3331 (2)	0.4275 (3)	0.34758 (7)	0.0399 (4)
C8	0.39047 (19)	0.2404 (3)	0.32318 (7)	0.0369 (4)
C9	0.48744 (19)	0.1024 (3)	0.35370 (8)	0.0415 (4)
H9	0.5242	−0.0198	0.3366	0.050*
C10	0.5279 (2)	0.1491 (3)	0.40914 (8)	0.0447 (5)
C11	0.4739 (3)	0.3304 (3)	0.43502 (9)	0.0599 (6)
H11	0.5024	0.3593	0.4729	0.072*
C12	0.3794 (2)	0.4666 (3)	0.40538 (8)	0.0564 (6)
H12	0.3443	0.5879	0.4234	0.068*
H3A	0.209 (2)	0.541 (3)	0.2831 (5)	0.050 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0645 (9)	0.0642 (9)	0.0491 (8)	0.0122 (8)	−0.0161 (7)	−0.0087 (7)
O2	0.0893 (12)	0.0878 (11)	0.0614 (10)	0.0418 (10)	−0.0166 (8)	−0.0360 (9)
O3	0.1006 (13)	0.0644 (11)	0.0875 (12)	0.0325 (10)	−0.0119 (10)	0.0018 (10)
O4	0.0758 (11)	0.0953 (12)	0.0563 (10)	0.0098 (9)	−0.0212 (8)	0.0111 (9)
N1	0.0535 (10)	0.0463 (10)	0.0578 (11)	0.0057 (8)	−0.0068 (8)	0.0111 (8)
N2	0.0458 (9)	0.0369 (9)	0.0483 (9)	0.0016 (7)	−0.0027 (7)	−0.0033 (7)
N3	0.0505 (9)	0.0398 (9)	0.0434 (10)	0.0040 (7)	−0.0055 (8)	−0.0068 (8)
N4	0.0422 (9)	0.0503 (10)	0.0438 (9)	0.0024 (8)	−0.0019 (7)	−0.0092 (8)
N5	0.0550 (10)	0.0596 (12)	0.0574 (12)	0.0044 (9)	−0.0042 (9)	0.0117 (10)
C1	0.0580 (13)	0.0485 (13)	0.0818 (17)	0.0120 (10)	−0.0060 (12)	0.0135 (12)
C2	0.0629 (14)	0.0514 (13)	0.0830 (17)	0.0101 (11)	0.0110 (13)	−0.0042 (13)
C3	0.0737 (15)	0.0666 (15)	0.0581 (14)	0.0111 (12)	0.0006 (11)	−0.0108 (12)
C4	0.0558 (12)	0.0520 (12)	0.0502 (12)	0.0107 (10)	−0.0059 (9)	0.0018 (10)
C5	0.0361 (9)	0.0393 (10)	0.0467 (11)	−0.0027 (8)	−0.0017 (8)	0.0053 (9)
C6	0.0446 (10)	0.0414 (10)	0.0429 (10)	−0.0034 (9)	−0.0059 (8)	0.0022 (9)
C7	0.0403 (10)	0.0372 (10)	0.0420 (10)	−0.0045 (8)	−0.0021 (8)	−0.0009 (8)
C8	0.0366 (9)	0.0376 (10)	0.0365 (10)	−0.0059 (8)	0.0010 (7)	−0.0038 (8)
C9	0.0396 (10)	0.0362 (10)	0.0490 (11)	−0.0017 (8)	0.0053 (8)	−0.0032 (9)
C10	0.0475 (11)	0.0430 (11)	0.0432 (11)	0.0021 (9)	−0.0047 (9)	0.0047 (9)
C11	0.0813 (15)	0.0539 (13)	0.0435 (12)	0.0092 (12)	−0.0177 (11)	−0.0089 (10)
C12	0.0742 (14)	0.0441 (12)	0.0505 (12)	0.0099 (10)	−0.0100 (11)	−0.0121 (10)

Geometric parameters (Å, º)

O1—N4	1.2309 (19)	C3—C4	1.371 (3)
O2—N4	1.2200 (19)	C3—H3	0.9300
O3—N5	1.221 (2)	C4—C5	1.384 (3)
O4—N5	1.228 (2)	C4—H4	0.9300
N1—C1	1.341 (3)	C5—C6	1.465 (2)
N1—C5	1.345 (2)	C6—H6	0.9300
N2—C6	1.274 (2)	C7—C8	1.409 (2)
N2—N3	1.369 (2)	C7—C12	1.418 (2)
N3—C7	1.360 (2)	C8—C9	1.389 (2)
N3—H3A	0.894 (9)	C9—C10	1.363 (2)
N4—C8	1.441 (2)	C9—H9	0.9300
N5—C10	1.456 (2)	C10—C11	1.383 (3)
C1—C2	1.367 (3)	C11—C12	1.360 (3)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.364 (3)	C12—H12	0.9300
C2—H2	0.9300
C1—N1—C5	116.21 (18)	N1—C5—C6	115.81 (17)
C6—N2—N3	117.09 (16)	C4—C5—C6	121.76 (17)
C7—N3—N2	118.51 (15)	N2—C6—C5	119.50 (17)
C7—N3—H3A	119.4 (12)	N2—C6—H6	120.3
N2—N3—H3A	122.1 (12)	C5—C6—H6	120.3
O2—N4—O1	121.70 (16)	N3—C7—C8	124.21 (16)
O2—N4—C8	118.80 (16)	N3—C7—C12	119.68 (17)
O1—N4—C8	119.49 (15)	C8—C7—C12	116.11 (16)
O3—N5—O4	123.36 (19)	C9—C8—C7	122.13 (16)
O3—N5—C10	118.63 (18)	C9—C8—N4	116.04 (15)
O4—N5—C10	118.01 (18)	C7—C8—N4	121.83 (16)
N1—C1—C2	124.7 (2)	C10—C9—C8	118.95 (17)
N1—C1—H1	117.7	C10—C9—H9	120.5
C2—C1—H1	117.7	C8—C9—H9	120.5
C3—C2—C1	118.2 (2)	C9—C10—C11	121.00 (17)
C3—C2—H2	120.9	C9—C10—N5	119.84 (17)
C1—C2—H2	120.9	C11—C10—N5	119.16 (17)
C2—C3—C4	119.2 (2)	C12—C11—C10	120.42 (18)
C2—C3—H3	120.4	C12—C11—H11	119.8
C4—C3—H3	120.4	C10—C11—H11	119.8
C3—C4—C5	119.25 (19)	C11—C12—C7	121.39 (18)
C3—C4—H4	120.4	C11—C12—H12	119.3
C5—C4—H4	120.4	C7—C12—H12	119.3
N1—C5—C4	122.42 (18)
C6—N2—N3—C7	−175.76 (16)	O2—N4—C8—C9	−0.7 (2)
C5—N1—C1—C2	−0.1 (3)	O1—N4—C8—C9	178.54 (16)
N1—C1—C2—C3	0.1 (3)	O2—N4—C8—C7	178.76 (17)
C1—C2—C3—C4	−0.4 (3)	O1—N4—C8—C7	−2.0 (2)
C2—C3—C4—C5	0.8 (3)	C7—C8—C9—C10	0.3 (3)
C1—N1—C5—C4	0.4 (3)	N4—C8—C9—C10	179.75 (16)
C1—N1—C5—C6	−179.39 (16)	C8—C9—C10—C11	0.0 (3)
C3—C4—C5—N1	−0.8 (3)	C8—C9—C10—N5	−179.57 (16)
C3—C4—C5—C6	179.03 (18)	O3—N5—C10—C9	−5.1 (3)
N3—N2—C6—C5	179.91 (15)	O4—N5—C10—C9	174.85 (18)
N1—C5—C6—N2	174.29 (16)	O3—N5—C10—C11	175.33 (19)
C4—C5—C6—N2	−5.5 (3)	O4—N5—C10—C11	−4.8 (3)
N2—N3—C7—C8	176.51 (15)	C9—C10—C11—C12	−0.3 (3)
N2—N3—C7—C12	−2.7 (3)	N5—C10—C11—C12	179.36 (19)
N3—C7—C8—C9	−179.62 (16)	C10—C11—C12—C7	0.2 (3)
C12—C7—C8—C9	−0.4 (2)	N3—C7—C12—C11	179.44 (19)
N3—C7—C8—N4	0.9 (3)	C8—C7—C12—C11	0.1 (3)
C12—C7—C8—N4	−179.81 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.89 (1)	1.98 (2)	2.624 (2)	128 (2)
C4—H4···O4^i	0.93	2.55	3.368 (2)	147
C1—H1···O2^ii	0.93	2.54	3.402 (3)	154

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