Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680502934X/rz6111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680502934X/rz6111Isup2.hkl |
CCDC reference: 287697
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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.
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.
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.
Fig. 1. A view of the title compound, shown with 30% probability displacement ellipsoids. |
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) Å3 | 0.34 × 0.26 × 0.20 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H 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 parameters | Δρmax = 0.14 e Å−3 |
1 restraint | Δρmin = −0.19 e Å−3 |
C12H9N5O4 | V = 1266.2 (5) Å3 |
Mr = 287.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.5690 (18) Å | µ = 0.12 mm−1 |
b = 6.3333 (13) Å | T = 294 K |
c = 23.340 (5) Å | 0.34 × 0.26 × 0.20 mm |
β = 91.532 (4)° |
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 = 0.977 | Rint = 0.037 |
6807 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 1 restraint |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.14 e Å−3 |
2564 reflections | Δρmin = −0.19 e Å−3 |
194 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···O4i | 0.93 | 2.55 | 3.368 (2) | 147 |
C1—H1···O2ii | 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. |
Experimental details
Crystal data | |
Chemical formula | C12H9N5O4 |
Mr | 287.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.5690 (18), 6.3333 (13), 23.340 (5) |
β (°) | 91.532 (4) |
V (Å3) | 1266.2 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.34 × 0.26 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.929, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6807, 2564, 1567 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.118, 0.99 |
No. of reflections | 2564 |
No. of parameters | 194 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.19 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.894 (9) | 1.982 (16) | 2.624 (2) | 127.5 (15) |
C4—H4···O4i | 0.93 | 2.55 | 3.368 (2) | 147 |
C1—H1···O2ii | 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. |
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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.