Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680502934X/rz6111sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680502934X/rz6111Isup2.hkl
Contains datablock I

CCDC reference: 287697

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

No syntax errors found



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

Comment top

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.

Experimental top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The H atom attached to N3 was located in a difference Fourier map and refined freely.

Computing details top

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 top
[Figure 1] Fig. 1. A view of the title compound, shown with 30% probability displacement ellipsoids.
pyridine-2-carbaldehyde 2,4-dinitrophenylhydrazone top
Crystal data top
C12H9N5O4F(000) = 592
Mr = 287.24Dx = 1.507 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1875 reflections
a = 8.5690 (18) Åθ = 2.9–25.9°
b = 6.3333 (13) ŵ = 0.12 mm1
c = 23.340 (5) ÅT = 294 K
β = 91.532 (4)°Block, red
V = 1266.2 (5) Å30.34 × 0.26 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2564 independent reflections
Radiation source: fine-focus sealed tube1567 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scansθmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 810
Tmin = 0.929, Tmax = 0.977k = 77
6807 measured reflectionsl = 2129
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0543P)2 + 0.1982P]
where P = (Fo2 + 2Fc2)/3
2564 reflections(Δ/σ)max < 0.001
194 parametersΔρmax = 0.14 e Å3
1 restraintΔρmin = 0.19 e Å3
Crystal data top
C12H9N5O4V = 1266.2 (5) Å3
Mr = 287.24Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.5690 (18) ŵ = 0.12 mm1
b = 6.3333 (13) ÅT = 294 K
c = 23.340 (5) Å0.34 × 0.26 × 0.20 mm
β = 91.532 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2564 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1567 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.977Rint = 0.037
6807 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0401 restraint
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.14 e Å3
2564 reflectionsΔρmin = 0.19 e Å3
194 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.26494 (16)0.2947 (2)0.23555 (6)0.0596 (4)
O20.40822 (19)0.0197 (3)0.24571 (6)0.0798 (5)
O30.6692 (2)0.1588 (3)0.41983 (8)0.0844 (6)
O40.67334 (18)0.0620 (3)0.49017 (7)0.0762 (5)
N10.06722 (18)1.1709 (2)0.31995 (7)0.0527 (4)
N20.18293 (17)0.7369 (2)0.34905 (7)0.0438 (4)
N30.23738 (17)0.5665 (2)0.31952 (7)0.0447 (4)
N40.35286 (18)0.1818 (3)0.26474 (7)0.0455 (4)
N50.6303 (2)0.0074 (3)0.44178 (8)0.0574 (5)
C10.1236 (2)1.3413 (3)0.34645 (11)0.0629 (6)
H10.18651.43290.32490.075*
C20.0952 (3)1.3901 (3)0.40282 (11)0.0656 (6)
H20.13771.51070.41890.079*
C30.0030 (3)1.2570 (4)0.43476 (10)0.0662 (6)
H30.01921.28610.47320.079*
C40.0568 (2)1.0800 (3)0.40959 (8)0.0528 (5)
H40.11890.98670.43090.063*
C50.02352 (19)1.0417 (3)0.35219 (8)0.0407 (4)
C60.0859 (2)0.8572 (3)0.32272 (8)0.0431 (5)
H60.05490.82800.28510.052*
C70.3331 (2)0.4275 (3)0.34758 (7)0.0399 (4)
C80.39047 (19)0.2404 (3)0.32318 (7)0.0369 (4)
C90.48744 (19)0.1024 (3)0.35370 (8)0.0415 (4)
H90.52420.01980.33660.050*
C100.5279 (2)0.1491 (3)0.40914 (8)0.0447 (5)
C110.4739 (3)0.3304 (3)0.43502 (9)0.0599 (6)
H110.50240.35930.47290.072*
C120.3794 (2)0.4666 (3)0.40538 (8)0.0564 (6)
H120.34430.58790.42340.068*
H3A0.209 (2)0.541 (3)0.2831 (5)0.050 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0645 (9)0.0642 (9)0.0491 (8)0.0122 (8)0.0161 (7)0.0087 (7)
O20.0893 (12)0.0878 (11)0.0614 (10)0.0418 (10)0.0166 (8)0.0360 (9)
O30.1006 (13)0.0644 (11)0.0875 (12)0.0325 (10)0.0119 (10)0.0018 (10)
O40.0758 (11)0.0953 (12)0.0563 (10)0.0098 (9)0.0212 (8)0.0111 (9)
N10.0535 (10)0.0463 (10)0.0578 (11)0.0057 (8)0.0068 (8)0.0111 (8)
N20.0458 (9)0.0369 (9)0.0483 (9)0.0016 (7)0.0027 (7)0.0033 (7)
N30.0505 (9)0.0398 (9)0.0434 (10)0.0040 (7)0.0055 (8)0.0068 (8)
N40.0422 (9)0.0503 (10)0.0438 (9)0.0024 (8)0.0019 (7)0.0092 (8)
N50.0550 (10)0.0596 (12)0.0574 (12)0.0044 (9)0.0042 (9)0.0117 (10)
C10.0580 (13)0.0485 (13)0.0818 (17)0.0120 (10)0.0060 (12)0.0135 (12)
C20.0629 (14)0.0514 (13)0.0830 (17)0.0101 (11)0.0110 (13)0.0042 (13)
C30.0737 (15)0.0666 (15)0.0581 (14)0.0111 (12)0.0006 (11)0.0108 (12)
C40.0558 (12)0.0520 (12)0.0502 (12)0.0107 (10)0.0059 (9)0.0018 (10)
C50.0361 (9)0.0393 (10)0.0467 (11)0.0027 (8)0.0017 (8)0.0053 (9)
C60.0446 (10)0.0414 (10)0.0429 (10)0.0034 (9)0.0059 (8)0.0022 (9)
C70.0403 (10)0.0372 (10)0.0420 (10)0.0045 (8)0.0021 (8)0.0009 (8)
C80.0366 (9)0.0376 (10)0.0365 (10)0.0059 (8)0.0010 (7)0.0038 (8)
C90.0396 (10)0.0362 (10)0.0490 (11)0.0017 (8)0.0053 (8)0.0032 (9)
C100.0475 (11)0.0430 (11)0.0432 (11)0.0021 (9)0.0047 (9)0.0047 (9)
C110.0813 (15)0.0539 (13)0.0435 (12)0.0092 (12)0.0177 (11)0.0089 (10)
C120.0742 (14)0.0441 (12)0.0505 (12)0.0099 (10)0.0100 (11)0.0121 (10)
Geometric parameters (Å, º) top
O1—N41.2309 (19)C3—C41.371 (3)
O2—N41.2200 (19)C3—H30.9300
O3—N51.221 (2)C4—C51.384 (3)
O4—N51.228 (2)C4—H40.9300
N1—C11.341 (3)C5—C61.465 (2)
N1—C51.345 (2)C6—H60.9300
N2—C61.274 (2)C7—C81.409 (2)
N2—N31.369 (2)C7—C121.418 (2)
N3—C71.360 (2)C8—C91.389 (2)
N3—H3A0.894 (9)C9—C101.363 (2)
N4—C81.441 (2)C9—H90.9300
N5—C101.456 (2)C10—C111.383 (3)
C1—C21.367 (3)C11—C121.360 (3)
C1—H10.9300C11—H110.9300
C2—C31.364 (3)C12—H120.9300
C2—H20.9300
C1—N1—C5116.21 (18)N1—C5—C6115.81 (17)
C6—N2—N3117.09 (16)C4—C5—C6121.76 (17)
C7—N3—N2118.51 (15)N2—C6—C5119.50 (17)
C7—N3—H3A119.4 (12)N2—C6—H6120.3
N2—N3—H3A122.1 (12)C5—C6—H6120.3
O2—N4—O1121.70 (16)N3—C7—C8124.21 (16)
O2—N4—C8118.80 (16)N3—C7—C12119.68 (17)
O1—N4—C8119.49 (15)C8—C7—C12116.11 (16)
O3—N5—O4123.36 (19)C9—C8—C7122.13 (16)
O3—N5—C10118.63 (18)C9—C8—N4116.04 (15)
O4—N5—C10118.01 (18)C7—C8—N4121.83 (16)
N1—C1—C2124.7 (2)C10—C9—C8118.95 (17)
N1—C1—H1117.7C10—C9—H9120.5
C2—C1—H1117.7C8—C9—H9120.5
C3—C2—C1118.2 (2)C9—C10—C11121.00 (17)
C3—C2—H2120.9C9—C10—N5119.84 (17)
C1—C2—H2120.9C11—C10—N5119.16 (17)
C2—C3—C4119.2 (2)C12—C11—C10120.42 (18)
C2—C3—H3120.4C12—C11—H11119.8
C4—C3—H3120.4C10—C11—H11119.8
C3—C4—C5119.25 (19)C11—C12—C7121.39 (18)
C3—C4—H4120.4C11—C12—H12119.3
C5—C4—H4120.4C7—C12—H12119.3
N1—C5—C4122.42 (18)
C6—N2—N3—C7175.76 (16)O2—N4—C8—C90.7 (2)
C5—N1—C1—C20.1 (3)O1—N4—C8—C9178.54 (16)
N1—C1—C2—C30.1 (3)O2—N4—C8—C7178.76 (17)
C1—C2—C3—C40.4 (3)O1—N4—C8—C72.0 (2)
C2—C3—C4—C50.8 (3)C7—C8—C9—C100.3 (3)
C1—N1—C5—C40.4 (3)N4—C8—C9—C10179.75 (16)
C1—N1—C5—C6179.39 (16)C8—C9—C10—C110.0 (3)
C3—C4—C5—N10.8 (3)C8—C9—C10—N5179.57 (16)
C3—C4—C5—C6179.03 (18)O3—N5—C10—C95.1 (3)
N3—N2—C6—C5179.91 (15)O4—N5—C10—C9174.85 (18)
N1—C5—C6—N2174.29 (16)O3—N5—C10—C11175.33 (19)
C4—C5—C6—N25.5 (3)O4—N5—C10—C114.8 (3)
N2—N3—C7—C8176.51 (15)C9—C10—C11—C120.3 (3)
N2—N3—C7—C122.7 (3)N5—C10—C11—C12179.36 (19)
N3—C7—C8—C9179.62 (16)C10—C11—C12—C70.2 (3)
C12—C7—C8—C90.4 (2)N3—C7—C12—C11179.44 (19)
N3—C7—C8—N40.9 (3)C8—C7—C12—C110.1 (3)
C12—C7—C8—N4179.81 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.89 (1)1.98 (2)2.624 (2)128 (2)
C4—H4···O4i0.932.553.368 (2)147
C1—H1···O2ii0.932.543.402 (3)154
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H9N5O4
Mr287.24
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)8.5690 (18), 6.3333 (13), 23.340 (5)
β (°) 91.532 (4)
V3)1266.2 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.34 × 0.26 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.929, 0.977
No. of measured, independent and
observed [I > 2σ(I)] reflections
6807, 2564, 1567
Rint0.037
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.118, 0.99
No. of reflections2564
No. of parameters194
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.894 (9)1.982 (16)2.624 (2)127.5 (15)
C4—H4···O4i0.932.553.368 (2)147
C1—H1···O2ii0.932.543.402 (3)154
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+3/2, z+1/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds