In the title compound, C
17H
12N
4O
6, the dinitrophenyl and 2-hydroxy-5-methylphenyl groups are oriented with dihedral angles of 23.9 (1) and 13.1 (1)°, respectively, with respect to the pyrazole ring. The internal C—C—C ring angles at the
ortho and
para positions where NO
2 is bonded are 121.7 (2) and 121.9 (2)°. The dihedral angle between the phenyl rings is 11.2 (1)°. The crystal structure is stabilized by O—H
N intramolecular and by C—H
O intermolecular hydrogen bonds.
Supporting information
CCDC reference: 165676
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.050
- wR factor = 0.176
- Data-to-parameter ratio = 12.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
WEIGH_01 Alert C Extra text has been found in the
_refine_ls_weighting_scheme field. This should be in the
_refine_ls_weighting_details field.
Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.1P)^2^] where P
Weighting scheme identified as calc
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was synthesized as follows: 1.65 g (0.005 mol) of
2-hydroxy-5-methylacetophenone 2,4-dinitrophenylhydrazone was dissolved in
N,N-dimethylformamide (5 ml) and kept under ice-cold conditions.
To this, (1.4 ml) POCl3 was added dropwise with stirring over a period of 15 min. The reaction was stirred at room temperature for about 3–4 h, after
which time the contents were poured onto crushed ice (100 g). The yellow
precipitate obtained was filtered off, washed and dried. The product was
purified by column chromatography using 60–120 mesh and 20% ethyl
acetate–petroleum ether (yield 1.50 g) and recrystallized from ethyl acetate
by slow evaporation.
All H atoms are included at calculated positions and refined using a riding
model. The Uiso values for the H atoms of OH and CH2 or the CH3
groups were taken as 1.2Ueq or 1.5Ueq of the carrier atoms,
respectively.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: SDP (Frenz, 1978); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983; 1995).
1-(2,4-Dinitrophenyl)-3-(2-hydroxy-5-methylphenyl)pyrazole-4-carboxaldehyde
top
Crystal data top
C17H12N4O6 | Z = 2 |
Mr = 368.31 | F(000) = 380 |
Triclinic, P1 | Dx = 1.513 Mg m−3 |
a = 8.411 (2) Å | Cu Kα radiation, λ = 1.54180 Å |
b = 9.617 (3) Å | Cell parameters from 25 reflections |
c = 10.538 (3) Å | θ = 15–25° |
α = 102.62 (2)° | µ = 1.00 mm−1 |
β = 91.23 (2)° | T = 293 K |
γ = 102.94 (2)° | Block, orange |
V = 808.5 (4) Å3 | 0.25 × 0.18 × 0.15 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 69.9°, θmin = 4.3° |
Graphite monochromator | h = −10→10 |
ω/2θ scans | k = −11→11 |
3140 measured reflections | l = 0→12 |
2960 independent reflections | 3 standard reflections every 60 min |
1897 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.176 | Calculated w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.005 |
2960 reflections | Δρmax = 0.23 e Å−3 |
247 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (2) |
Crystal data top
C17H12N4O6 | γ = 102.94 (2)° |
Mr = 368.31 | V = 808.5 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.411 (2) Å | Cu Kα radiation |
b = 9.617 (3) Å | µ = 1.00 mm−1 |
c = 10.538 (3) Å | T = 293 K |
α = 102.62 (2)° | 0.25 × 0.18 × 0.15 mm |
β = 91.23 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.016 |
3140 measured reflections | 3 standard reflections every 60 min |
2960 independent reflections | intensity decay: 1% |
1897 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.23 e Å−3 |
2960 reflections | Δρmin = −0.28 e Å−3 |
247 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.0068 (2) | 0.6797 (2) | 0.9573 (2) | 0.0580 (6) | |
N2 | 0.1554 (2) | 0.7008 (2) | 0.9047 (2) | 0.0567 (6) | |
N3 | 0.3091 (4) | 0.2692 (3) | 0.5045 (3) | 0.0797 (7) | |
N4 | −0.1040 (3) | 0.4938 (4) | 0.7176 (3) | 0.0821 (8) | |
O1 | 0.3816 (2) | 1.1051 (2) | 1.1384 (2) | 0.0836 (7) | |
O2 | −0.3074 (2) | 0.5996 (2) | 0.9783 (2) | 0.0871 (7) | |
H2 | −0.2182 | 0.5900 | 0.9529 | 0.131* | |
O3 | 0.4517 (3) | 0.2780 (3) | 0.4849 (3) | 0.1106 (9) | |
O4 | 0.1970 (4) | 0.1695 (3) | 0.4472 (2) | 0.1036 (8) | |
O5 | −0.1391 (3) | 0.6027 (4) | 0.6960 (2) | 0.1128 (10) | |
O6 | −0.1996 (3) | 0.3875 (3) | 0.7366 (4) | 0.1385 (13) | |
C1 | 0.1903 (3) | 0.5938 (3) | 0.8017 (3) | 0.0553 (6) | |
C2 | 0.3525 (3) | 0.5888 (3) | 0.7852 (3) | 0.0668 (7) | |
H2A | 0.4351 | 0.6561 | 0.8412 | 0.080* | |
C3 | 0.3918 (3) | 0.4848 (3) | 0.6864 (3) | 0.0698 (8) | |
H3 | 0.5007 | 0.4839 | 0.6735 | 0.084* | |
C4 | 0.2691 (3) | 0.3833 (3) | 0.6077 (3) | 0.0644 (7) | |
C5 | 0.1082 (3) | 0.3833 (3) | 0.6222 (3) | 0.0667 (7) | |
H5 | 0.0261 | 0.3119 | 0.5691 | 0.080* | |
C6 | 0.0704 (3) | 0.4911 (3) | 0.7168 (3) | 0.0595 (7) | |
C1' | −0.1336 (3) | 0.8160 (3) | 1.1204 (2) | 0.0546 (6) | |
C2' | −0.2859 (3) | 0.7197 (3) | 1.0785 (3) | 0.0635 (7) | |
C3' | −0.4242 (3) | 0.7448 (3) | 1.1392 (3) | 0.0739 (8) | |
H3' | −0.5249 | 0.6803 | 1.1108 | 0.089* | |
C4' | −0.4148 (3) | 0.8627 (4) | 1.2399 (3) | 0.0747 (8) | |
H4' | −0.5098 | 0.8791 | 1.2778 | 0.090* | |
C5' | −0.2662 (4) | 0.9587 (3) | 1.2871 (3) | 0.0733 (8) | |
C6' | −0.1278 (3) | 0.9316 (3) | 1.2274 (3) | 0.0684 (8) | |
H6' | −0.0267 | 0.9931 | 1.2602 | 0.082* | |
C7' | −0.2548 (5) | 1.0892 (4) | 1.4002 (4) | 0.1107 (14) | |
H7'1 | −0.2309 | 1.0630 | 1.4801 | 0.166* | |
H7'2 | −0.3570 | 1.1181 | 1.4036 | 0.166* | |
H7'3 | −0.1693 | 1.1692 | 1.3886 | 0.166* | |
C3A | 0.2537 (3) | 0.8304 (3) | 0.9633 (3) | 0.0574 (6) | |
H3A | 0.3600 | 0.8668 | 0.9436 | 0.069* | |
C4A | 0.1693 (3) | 0.8995 (3) | 1.0573 (2) | 0.0536 (6) | |
C5A | 0.0127 (3) | 0.8001 (3) | 1.0495 (2) | 0.0515 (6) | |
C6A | 0.2388 (3) | 1.0472 (3) | 1.1340 (3) | 0.0694 (8) | |
H6A | 0.1699 | 1.0987 | 1.1814 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0420 (10) | 0.0565 (11) | 0.0688 (14) | 0.0089 (8) | 0.0132 (9) | 0.0019 (10) |
N2 | 0.0425 (10) | 0.0540 (11) | 0.0667 (13) | 0.0091 (8) | 0.0126 (9) | 0.0008 (10) |
N3 | 0.0863 (18) | 0.0889 (19) | 0.0686 (17) | 0.0394 (16) | 0.0201 (14) | 0.0068 (15) |
N4 | 0.0536 (14) | 0.102 (2) | 0.0751 (18) | 0.0212 (14) | 0.0030 (11) | −0.0158 (15) |
O1 | 0.0615 (11) | 0.0693 (12) | 0.0985 (16) | −0.0086 (9) | 0.0191 (10) | −0.0029 (11) |
O2 | 0.0551 (11) | 0.0953 (15) | 0.0810 (14) | −0.0109 (10) | 0.0158 (10) | −0.0145 (12) |
O3 | 0.0986 (18) | 0.131 (2) | 0.1046 (19) | 0.0558 (16) | 0.0391 (15) | −0.0010 (16) |
O4 | 0.118 (2) | 0.0959 (17) | 0.0827 (17) | 0.0339 (16) | 0.0071 (14) | −0.0187 (14) |
O5 | 0.0983 (18) | 0.170 (3) | 0.0892 (18) | 0.0804 (19) | 0.0040 (13) | 0.0204 (18) |
O6 | 0.0572 (13) | 0.113 (2) | 0.201 (3) | −0.0105 (14) | 0.0294 (17) | −0.027 (2) |
C1 | 0.0469 (12) | 0.0535 (13) | 0.0616 (15) | 0.0128 (10) | 0.0105 (11) | 0.0035 (12) |
C2 | 0.0463 (13) | 0.0636 (15) | 0.0825 (19) | 0.0124 (11) | 0.0112 (12) | −0.0003 (14) |
C3 | 0.0517 (14) | 0.0713 (17) | 0.086 (2) | 0.0208 (13) | 0.0185 (14) | 0.0098 (15) |
C4 | 0.0655 (16) | 0.0657 (16) | 0.0624 (17) | 0.0243 (13) | 0.0161 (13) | 0.0050 (13) |
C5 | 0.0609 (15) | 0.0704 (17) | 0.0622 (17) | 0.0177 (13) | 0.0060 (12) | −0.0010 (14) |
C6 | 0.0454 (12) | 0.0663 (15) | 0.0609 (16) | 0.0146 (11) | 0.0067 (11) | 0.0004 (13) |
C1' | 0.0442 (12) | 0.0568 (13) | 0.0590 (15) | 0.0093 (10) | 0.0113 (10) | 0.0075 (12) |
C2' | 0.0486 (13) | 0.0728 (17) | 0.0617 (16) | 0.0062 (12) | 0.0083 (11) | 0.0076 (14) |
C3' | 0.0458 (14) | 0.094 (2) | 0.0735 (19) | 0.0058 (13) | 0.0132 (12) | 0.0119 (17) |
C4' | 0.0537 (15) | 0.092 (2) | 0.084 (2) | 0.0256 (14) | 0.0225 (14) | 0.0230 (18) |
C5' | 0.0617 (16) | 0.0675 (16) | 0.088 (2) | 0.0199 (13) | 0.0238 (14) | 0.0060 (15) |
C6' | 0.0538 (14) | 0.0625 (16) | 0.0797 (19) | 0.0103 (12) | 0.0167 (13) | −0.0008 (14) |
C7' | 0.096 (3) | 0.089 (2) | 0.129 (3) | 0.023 (2) | 0.049 (2) | −0.020 (2) |
C3A | 0.0448 (12) | 0.0532 (13) | 0.0675 (16) | 0.0062 (10) | 0.0097 (11) | 0.0044 (12) |
C4A | 0.0457 (12) | 0.0506 (13) | 0.0586 (15) | 0.0073 (10) | 0.0088 (10) | 0.0040 (11) |
C5A | 0.0430 (11) | 0.0519 (13) | 0.0574 (15) | 0.0109 (9) | 0.0078 (10) | 0.0081 (11) |
C6A | 0.0601 (15) | 0.0589 (15) | 0.0766 (19) | 0.0033 (12) | 0.0220 (13) | −0.0016 (14) |
Geometric parameters (Å, º) top
N1—C5A | 1.329 (3) | C5—H5 | 0.9300 |
N1—N2 | 1.370 (3) | C1'—C2' | 1.400 (3) |
N2—C3A | 1.341 (3) | C1'—C6' | 1.391 (4) |
N2—C1 | 1.409 (3) | C1'—C5A | 1.472 (3) |
N3—O3 | 1.209 (3) | C2'—C3' | 1.382 (4) |
N3—O4 | 1.220 (4) | C3'—C4' | 1.360 (4) |
N3—C4 | 1.470 (3) | C3'—H3' | 0.9300 |
N4—O6 | 1.209 (4) | C4'—C5' | 1.385 (4) |
N4—O5 | 1.214 (4) | C4'—H4' | 0.9300 |
N4—C6 | 1.473 (3) | C5'—C6' | 1.384 (4) |
O1—C6A | 1.201 (3) | C5'—C7' | 1.514 (4) |
O2—C2' | 1.359 (3) | C6'—H6' | 0.9300 |
O2—H2 | 0.8200 | C7'—H7'1 | 0.9600 |
C1—C6 | 1.386 (4) | C7'—H7'2 | 0.9600 |
C1—C2 | 1.389 (3) | C7'—H7'3 | 0.9600 |
C2—C3 | 1.379 (4) | C3A—C4A | 1.371 (3) |
C2—H2A | 0.9300 | C3A—H3A | 0.9300 |
C3—C4 | 1.366 (4) | C4A—C5A | 1.433 (3) |
C3—H3 | 0.9300 | C4A—C6A | 1.456 (3) |
C4—C5 | 1.365 (4) | C6A—H6A | 0.9300 |
C5—C6 | 1.371 (3) | | |
| | | |
C5A—N1—N2 | 105.8 (2) | O2—C2'—C1' | 123.2 (2) |
C3A—N2—N1 | 111.6 (2) | C3'—C2'—C1' | 120.1 (3) |
C3A—N2—C1 | 127.5 (2) | C4'—C3'—C2' | 120.8 (3) |
N1—N2—C1 | 120.9 (2) | C4'—C3'—H3' | 119.6 |
O3—N3—O4 | 124.4 (3) | C2'—C3'—H3' | 119.6 |
O3—N3—C4 | 117.6 (3) | C3'—C4'—C5' | 121.1 (3) |
O4—N3—C4 | 118.0 (3) | C3'—C4'—H4' | 119.4 |
O6—N4—O5 | 125.7 (3) | C5'—C4'—H4' | 119.4 |
O6—N4—C6 | 117.8 (3) | C6'—C5'—C4' | 117.8 (3) |
O5—N4—C6 | 116.4 (3) | C6'—C5'—C7' | 120.9 (3) |
C2'—O2—H2 | 109.5 | C4'—C5'—C7' | 121.3 (3) |
C6—C1—C2 | 118.1 (2) | C5'—C6'—C1' | 122.7 (3) |
C6—C1—N2 | 123.3 (2) | C5'—C6'—H6' | 118.6 |
C2—C1—N2 | 118.7 (2) | C1'—C6'—H6' | 118.6 |
C3—C2—C1 | 120.5 (3) | C5'—C7'—H7'1 | 109.5 |
C3—C2—H2A | 119.7 | C5'—C7'—H7'2 | 109.5 |
C1—C2—H2A | 119.7 | H7'1—C7'—H7'2 | 109.5 |
C4—C3—C2 | 119.2 (2) | C5'—C7'—H7'3 | 109.5 |
C4—C3—H3 | 120.4 | H7'1—C7'—H7'3 | 109.5 |
C2—C3—H3 | 120.4 | H7'2—C7'—H7'3 | 109.5 |
C3—C4—C5 | 121.9 (2) | N2—C3A—C4A | 107.7 (2) |
C3—C4—N3 | 119.8 (2) | N2—C3A—H3A | 126.1 |
C5—C4—N3 | 118.3 (3) | C4A—C3A—H3A | 126.1 |
C6—C5—C4 | 118.5 (3) | C3A—C4A—C5A | 105.0 (2) |
C6—C5—H5 | 120.8 | C3A—C4A—C6A | 121.5 (2) |
C4—C5—H5 | 120.8 | C5A—C4A—C6A | 133.4 (2) |
C5—C6—C1 | 121.7 (2) | N1—C5A—C4A | 109.9 (2) |
C5—C6—N4 | 115.4 (2) | N1—C5A—C1' | 119.4 (2) |
C1—C6—N4 | 122.8 (2) | C4A—C5A—C1' | 130.6 (2) |
C2'—C1'—C6' | 117.3 (2) | O1—C6A—C4A | 122.6 (3) |
C2'—C1'—C5A | 121.2 (2) | O1—C6A—H6A | 118.7 |
C6'—C1'—C5A | 121.4 (2) | C4A—C6A—H6A | 118.7 |
O2—C2'—C3' | 116.6 (2) | | |
| | | |
C5A—N1—N2—C3A | 0.8 (3) | C5A—C1'—C2'—O2 | 5.6 (4) |
C5A—N1—N2—C1 | −179.1 (2) | C6'—C1'—C2'—C3' | 2.8 (4) |
C3A—N2—C1—C6 | −155.9 (3) | C5A—C1'—C2'—C3' | −174.0 (3) |
N1—N2—C1—C6 | 23.9 (4) | O2—C2'—C3'—C4' | −179.6 (3) |
C3A—N2—C1—C2 | 25.2 (4) | C1'—C2'—C3'—C4' | 0.0 (5) |
N1—N2—C1—C2 | −154.9 (2) | C2'—C3'—C4'—C5' | −1.8 (5) |
C6—C1—C2—C3 | 0.4 (4) | C3'—C4'—C5'—C6' | 0.7 (5) |
N2—C1—C2—C3 | 179.3 (3) | C3'—C4'—C5'—C7' | −179.3 (3) |
C1—C2—C3—C4 | −2.4 (5) | C4'—C5'—C6'—C1' | 2.4 (5) |
C2—C3—C4—C5 | 1.3 (5) | C7'—C5'—C6'—C1' | −177.7 (3) |
C2—C3—C4—N3 | −178.2 (3) | C2'—C1'—C6'—C5' | −4.1 (4) |
O3—N3—C4—C3 | −6.9 (4) | C5A—C1'—C6'—C5' | 172.7 (3) |
O4—N3—C4—C3 | 170.7 (3) | N1—N2—C3A—C4A | −0.4 (3) |
O3—N3—C4—C5 | 173.5 (3) | C1—N2—C3A—C4A | 179.4 (2) |
O4—N3—C4—C5 | −8.8 (4) | N2—C3A—C4A—C5A | −0.1 (3) |
C3—C4—C5—C6 | 1.6 (5) | N2—C3A—C4A—C6A | −176.4 (2) |
N3—C4—C5—C6 | −178.9 (3) | N2—N1—C5A—C4A | −0.8 (3) |
C4—C5—C6—C1 | −3.6 (4) | N2—N1—C5A—C1' | 176.4 (2) |
C4—C5—C6—N4 | 173.7 (3) | C3A—C4A—C5A—N1 | 0.5 (3) |
C2—C1—C6—C5 | 2.6 (4) | C6A—C4A—C5A—N1 | 176.2 (3) |
N2—C1—C6—C5 | −176.3 (3) | C3A—C4A—C5A—C1' | −176.2 (3) |
C2—C1—C6—N4 | −174.5 (3) | C6A—C4A—C5A—C1' | −0.5 (5) |
N2—C1—C6—N4 | 6.7 (4) | C2'—C1'—C5A—N1 | −10.8 (4) |
O6—N4—C6—C5 | 61.7 (4) | C6'—C1'—C5A—N1 | 172.5 (3) |
O5—N4—C6—C5 | −116.7 (3) | C2'—C1'—C5A—C4A | 165.6 (3) |
O6—N4—C6—C1 | −121.0 (3) | C6'—C1'—C5A—C4A | −11.0 (4) |
O5—N4—C6—C1 | 60.6 (4) | C3A—C4A—C6A—O1 | −15.0 (5) |
C6'—C1'—C2'—O2 | −177.6 (3) | C5A—C4A—C6A—O1 | 169.9 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1 | 0.82 | 1.89 | 2.610 (3) | 146 |
C2—H2A···O1i | 0.93 | 2.43 | 3.202 (3) | 141 |
C3A—H3A···O1i | 0.93 | 2.34 | 3.244 (3) | 165 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Experimental details
Crystal data |
Chemical formula | C17H12N4O6 |
Mr | 368.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.411 (2), 9.617 (3), 10.538 (3) |
α, β, γ (°) | 102.62 (2), 91.23 (2), 102.94 (2) |
V (Å3) | 808.5 (4) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.25 × 0.18 × 0.15 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3140, 2960, 1897 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.176, 1.17 |
No. of reflections | 2960 |
No. of parameters | 247 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.28 |
Selected geometric parameters (Å, º) topN3—C4 | 1.470 (3) | N4—C6 | 1.473 (3) |
| | | |
C5A—N1—N2 | 105.8 (2) | C5—C6—N4 | 115.4 (2) |
C3A—N2—N1 | 111.6 (2) | C1—C6—N4 | 122.8 (2) |
C3A—N2—C1 | 127.5 (2) | O2—C2'—C3' | 116.6 (2) |
N1—N2—C1 | 120.9 (2) | O2—C2'—C1' | 123.2 (2) |
O3—N3—C4 | 117.6 (3) | N2—C3A—C4A | 107.7 (2) |
O4—N3—C4 | 118.0 (3) | C3A—C4A—C5A | 105.0 (2) |
O6—N4—C6 | 117.8 (3) | C3A—C4A—C6A | 121.5 (2) |
O5—N4—C6 | 116.4 (3) | C5A—C4A—C6A | 133.4 (2) |
C6—C1—N2 | 123.3 (2) | N1—C5A—C4A | 109.9 (2) |
C2—C1—N2 | 118.7 (2) | N1—C5A—C1' | 119.4 (2) |
C3—C4—N3 | 119.8 (2) | C4A—C5A—C1' | 130.6 (2) |
C5—C4—N3 | 118.3 (3) | O1—C6A—C4A | 122.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1 | 0.82 | 1.89 | 2.610 (3) | 146 |
C2—H2A···O1i | 0.93 | 2.43 | 3.202 (3) | 141 |
C3A—H3A···O1i | 0.93 | 2.34 | 3.244 (3) | 165 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Pyrazole derivatives are principally used in medicine; many alkyl pyrazoles have shown quite significant bacteriostatic, bacteriocidal and fungicidal, analgesic and antipyretic activity (Malhotra et al., 1997; Potts, 1986). Nitrogen heterocycles, such as pyrazoles, imidazoles and trizoles, either in isolation or in a fused system, are well documented for their antifertility activity (Omodei-Sale et al., 1976). Pyrazole derivatives have been found to have moderate antimalarial activity (Garg et al., 1973) and are also used as anti-inflammatory (Mani Naidu et al., 1996; Lesyk et al., 1998; Asero, 1998), antihyperglycaemic (Kees et al., 1996), multidrug resistance (MDR) modulating (Chiba et al.,1998) agents and analgesic (Sobczak and Pawlaczyk, 1998), and they have many important applications in the areas of medicine, agriculture, and also in synthetic organic chemistry (Weily & Wiley, 1964; Taki et al., 1992). Pyrazole compounds are widely used as extractions in the separation of trace metals (Akama et al., 1995). In view of the wide biological applications of the pyrazole derivatives, the crystal structure of the title compound, (I), has been determined.
The bond lengths in the five-membered ring [N1—N2 1.370 (3), N2—C3A 1.341 (3), C3A—C4A 1.371 (3), C4A—C5A 1.433 (3) and C5A—N1 1.329 (3) Å] agree well with several related pyrazole derivatives (Bonati & Bovio, 1990; Allen et al., 1987; Fronczek et al., 1989; Panneerselvam et al., 1996; Mani Naidu et al., 1996; Malhotra et al., 1997). The C—O [1.359 (3) Å] and C═O [1.201 (3) Å] distances compare well with those found in related pyrazole derivatives (Allen et al., 1987; Malhotra et al., 1997). The Csp2—N bonds associated with the nitro groups are clearly single bonds, while the C1—N2 [1.409 (3) Å] bond shows partial double-bond character (Jeyakanthan et al., 1999) which is also evidence for conjugation. The experimental values of the internal C—C—C ring angles [121.7 (2)° and 121.9 (2)°] of the phenyl ring to which NO2 is bonded at ortho and para positions agree with the value of 122.3 (1)° from MO calculations and 122.7 (1)° for nitrobenzene in a crystalline environment (Domenicano et al., 1990). Also, absence of π–π-stacking interactions indicates that the electronic interaction of the nitro group with the ring occurs primarily at the σ level, with limited transfer of π electrons from the ring to the substituent.
The carboxaldehyde group is twisted by 13.5 (2)° from the best plane of the pyrazole ring, the C5A—C4A—C6A—O1 [169.9 (3)°] and C5A—C1'—C2'—O2 [5.6 (4)°] torsion angles give the orientations of the carboxaldehyde group and the primed phenyl group with respect to the pyrazole ring. The interplanar angle between the phenyl rings is 11.2 (1)°. The dihedral angles between the phenyl and pyrazole rings are 23.9 (1) (dinitrophenyl) and 13.1 (1)° (2-hydroxy-5-methylphenyl). There is conjugation between the phenyl and pyrazole rings.
The bond lengths and bond angles in the NO2 groups [N3—O3 1.209 (3), N3—O4 1.220 (4), N4—O5 1.214 (4) and N4—O6 1.209 (4) Å; O3–N3—-O4 124.4 (3) and O5—N4—O6 125.7 (3)°] are comparable to those found in several related pyrazole derivatives (Fronczek et al., 1989; Aygün et al., 1998). The nitro group in the ortho position is twisted 62.1 (1)° from the plane of the phenyl ring, whereas the nitro group in the para position is almost coplanar [dihedral angle 9.1 (2)° with the ring].
Apart from normal Van der Waals interactions, the molecular structure is stabilized by O—H···N-type intramolecular hydrogen bonds, while the molecular packing in the solid state is stabilized by four C—H···O intermolecular hydrogen bonds (Table 2).