Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051719/xu2338sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051719/xu2338Isup2.hkl |
CCDC reference: 667420
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.005 Å
- R factor = 0.051
- wR factor = 0.088
- Data-to-parameter ratio = 8.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.43 From the CIF: _reflns_number_total 1687 Count of symmetry unique reflns 1721 Completeness (_total/calc) 98.02% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
4-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous methanol, H2SO4 (98% 0.5 ml) was added to this, the mixture was stirred for several minutes at 351 K, 1,3-Benzodioxole-5-carbaldehyde (1 mmol, 0.150 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane, brown single crystals of the title compound were obtained after 2 d.
Imino H atom was located in a difference Fourier map and positional parameters were refined, Uiso(H) = 1.2Ueq(N). Other H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene), and refined in riding mode with Uiso(H)=1.2Ueq(C). Friedel pairs were merged.
4-Nitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). As a continuation of this work, we report here the crystal structure of the title compound.
The structure of the title compound is shown in Fig. 1, Selected bond lengths and angles are listed in Table 1. The C6—C1 and C6—C5 bond, close to the imino group, are longer than other aromatic C—C bonds in the same benzene ring, which are consistent with the reported by Shan et al. (2002, 2003).
The title molecule crystallizes in the E conformation, with an N2—N1—C7—C1 torsion angle of -176.6 (3)°. The two benzene rings make a dihedral angle of 5.2 (16)°.
The intermolecular N—H···O hydrogen bonding (Table 2) helps to stabilize the crystal structure (Fig. 2).
For general background, see: Okabe et al. (1993). For related structures, see: Shan et al. (2002, 2003).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
C14H11N3O4 | F(000) = 592 |
Mr = 285.26 | Dx = 1.318 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 1143 reflections |
a = 23.719 (3) Å | θ = 2.1–25.6° |
b = 4.9052 (18) Å | µ = 0.10 mm−1 |
c = 12.353 (2) Å | T = 291 K |
V = 1437.2 (6) Å3 | Block, brown |
Z = 4 | 0.30 × 0.26 × 0.24 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1316 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 27.4°, θmin = 2.4° |
φ and ω scans | h = −30→29 |
14432 measured reflections | k = −6→6 |
1687 independent reflections | l = −15→15 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
1687 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.14 e Å−3 |
1 restraint | Δρmin = −0.14 e Å−3 |
C14H11N3O4 | V = 1437.2 (6) Å3 |
Mr = 285.26 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 23.719 (3) Å | µ = 0.10 mm−1 |
b = 4.9052 (18) Å | T = 291 K |
c = 12.353 (2) Å | 0.30 × 0.26 × 0.24 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1316 reflections with I > 2σ(I) |
14432 measured reflections | Rint = 0.062 |
1687 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.14 e Å−3 |
1687 reflections | Δρmin = −0.14 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 | ||
C1 | 0.97237 (14) | −0.2533 (5) | 0.2885 (3) | 0.0355 (7) | |
H1 | 0.9499 | −0.2448 | 0.3502 | 0.043* | |
C2 | 1.01832 (13) | −0.4287 (7) | 0.2850 (3) | 0.0405 (8) | |
H2 | 1.0268 | −0.5372 | 0.3446 | 0.049* | |
C3 | 1.05156 (14) | −0.4423 (7) | 0.1928 (3) | 0.0422 (8) | |
C4 | 1.03942 (13) | −0.2802 (7) | 0.1041 (3) | 0.0443 (8) | |
C5 | 0.99349 (14) | −0.1041 (7) | 0.1062 (3) | 0.0427 (8) | |
H5 | 0.9851 | 0.0034 | 0.0463 | 0.051* | |
C6 | 0.95999 (13) | −0.0902 (6) | 0.1992 (3) | 0.0350 (7) | |
C7 | 0.91205 (14) | 0.0874 (7) | 0.2049 (3) | 0.0452 (8) | |
H7 | 0.8909 | 0.0741 | 0.2680 | 0.054* | |
C8 | 1.11926 (16) | −0.5179 (8) | 0.0645 (3) | 0.0512 (9) | |
H8A | 1.1557 | −0.4302 | 0.0722 | 0.061* | |
H8B | 1.1232 | −0.6724 | 0.0161 | 0.061* | |
C9 | 0.82653 (14) | 0.6057 (7) | 0.0746 (3) | 0.0415 (8) | |
C10 | 0.85405 (17) | 0.6553 (7) | −0.0236 (3) | 0.0464 (9) | |
H10 | 0.8865 | 0.5586 | −0.0414 | 0.056* | |
C11 | 0.83259 (14) | 0.8510 (6) | −0.0950 (3) | 0.0410 (8) | |
H11 | 0.8513 | 0.8880 | −0.1596 | 0.049* | |
C12 | 0.78322 (13) | 0.9903 (7) | −0.0692 (3) | 0.0392 (8) | |
C13 | 0.75576 (14) | 0.9381 (6) | 0.0283 (3) | 0.0360 (7) | |
H13 | 0.7229 | 1.0317 | 0.0456 | 0.043* | |
C14 | 0.77741 (13) | 0.7470 (8) | 0.0995 (3) | 0.0473 (9) | |
H14 | 0.7590 | 0.7129 | 0.1646 | 0.057* | |
N1 | 0.89330 (11) | 0.2693 (6) | 0.1327 (2) | 0.0411 (7) | |
N2 | 0.84735 (12) | 0.4281 (5) | 0.1523 (2) | 0.0346 (6) | |
H2A | 0.8303 (14) | 0.416 (7) | 0.210 (3) | 0.042* | |
N3 | 0.76391 (11) | 1.2097 (5) | −0.1526 (2) | 0.0377 (6) | |
O1 | 1.09794 (10) | −0.6063 (5) | 0.1701 (2) | 0.0479 (6) | |
O2 | 1.07755 (9) | −0.3256 (4) | 0.0227 (2) | 0.0419 (5) | |
O3 | 0.78600 (10) | 1.2221 (4) | −0.23909 (18) | 0.0416 (6) | |
O4 | 0.71404 (9) | 1.3080 (5) | −0.1304 (2) | 0.0454 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0421 (19) | 0.0279 (13) | 0.0365 (17) | −0.0115 (12) | −0.0002 (14) | −0.0008 (13) |
C2 | 0.0315 (17) | 0.0506 (19) | 0.039 (2) | −0.0092 (15) | −0.0065 (14) | 0.0090 (15) |
C3 | 0.0454 (19) | 0.0382 (18) | 0.043 (2) | 0.0026 (14) | −0.0013 (16) | 0.0078 (16) |
C4 | 0.0420 (19) | 0.0357 (17) | 0.055 (2) | −0.0038 (14) | 0.0117 (17) | 0.0213 (16) |
C5 | 0.0334 (19) | 0.053 (2) | 0.042 (2) | −0.0006 (14) | −0.0035 (15) | 0.0153 (17) |
C6 | 0.0373 (17) | 0.0304 (14) | 0.0372 (18) | −0.0116 (12) | −0.0058 (15) | −0.0018 (14) |
C7 | 0.0354 (18) | 0.056 (2) | 0.044 (2) | −0.0034 (15) | −0.0021 (16) | 0.0095 (17) |
C8 | 0.054 (2) | 0.0439 (19) | 0.056 (2) | 0.0059 (17) | 0.0079 (17) | 0.0071 (17) |
C9 | 0.0350 (17) | 0.0442 (18) | 0.045 (2) | −0.0027 (14) | 0.0084 (15) | 0.0062 (16) |
C10 | 0.067 (2) | 0.0361 (16) | 0.037 (2) | 0.0120 (16) | 0.0168 (18) | −0.0051 (15) |
C11 | 0.0433 (18) | 0.0350 (17) | 0.045 (2) | −0.0080 (14) | 0.0096 (15) | 0.0024 (15) |
C12 | 0.0322 (16) | 0.0409 (17) | 0.0444 (19) | −0.0121 (14) | −0.0005 (16) | 0.0025 (14) |
C13 | 0.0408 (18) | 0.0266 (13) | 0.0407 (19) | −0.0054 (13) | 0.0035 (15) | −0.0078 (15) |
C14 | 0.0349 (18) | 0.048 (2) | 0.059 (2) | −0.0019 (14) | 0.0173 (16) | 0.0171 (17) |
N1 | 0.0356 (14) | 0.0468 (15) | 0.0409 (16) | −0.0009 (13) | 0.0149 (12) | 0.0120 (13) |
N2 | 0.0391 (16) | 0.0358 (13) | 0.0290 (14) | −0.0037 (12) | 0.0019 (11) | −0.0101 (12) |
N3 | 0.0377 (16) | 0.0385 (14) | 0.0369 (17) | −0.0112 (11) | −0.0082 (14) | −0.0055 (12) |
O1 | 0.0472 (15) | 0.0455 (13) | 0.0509 (16) | 0.0054 (10) | −0.0010 (12) | 0.0072 (11) |
O2 | 0.0417 (13) | 0.0405 (12) | 0.0436 (13) | −0.0056 (10) | 0.0021 (11) | 0.0026 (11) |
O3 | 0.0494 (13) | 0.0406 (12) | 0.0346 (14) | 0.0218 (10) | −0.0060 (12) | −0.0059 (10) |
O4 | 0.0431 (13) | 0.0433 (12) | 0.0497 (15) | −0.0070 (10) | 0.0105 (12) | 0.0169 (12) |
C1—C2 | 1.389 (5) | C8—H8B | 0.9700 |
C1—C6 | 1.394 (5) | C9—N2 | 1.388 (4) |
C1—H1 | 0.9300 | C9—C14 | 1.390 (5) |
C2—C3 | 1.387 (5) | C9—C10 | 1.399 (5) |
C2—H2 | 0.9300 | C10—C11 | 1.399 (5) |
C3—C4 | 1.385 (5) | C10—H10 | 0.9300 |
C3—O1 | 1.392 (4) | C11—C12 | 1.393 (5) |
C4—O2 | 1.371 (4) | C11—H11 | 0.9300 |
C4—C5 | 1.391 (5) | C12—C13 | 1.393 (4) |
C5—C6 | 1.399 (5) | C12—N3 | 1.558 (4) |
C5—H5 | 0.9300 | C13—C14 | 1.384 (5) |
C6—C7 | 1.434 (4) | C13—H13 | 0.9300 |
C7—N1 | 1.338 (4) | C14—H14 | 0.9300 |
C7—H7 | 0.9300 | N1—N2 | 1.361 (4) |
C8—O2 | 1.461 (4) | N2—H2A | 0.82 (4) |
C8—O1 | 1.464 (5) | N3—O3 | 1.192 (4) |
C8—H8A | 0.9700 | N3—O4 | 1.307 (3) |
C2—C1—C6 | 119.8 (3) | N2—C9—C14 | 117.2 (3) |
C2—C1—H1 | 120.1 | N2—C9—C10 | 122.9 (3) |
C6—C1—H1 | 120.1 | C14—C9—C10 | 119.8 (3) |
C3—C2—C1 | 120.1 (3) | C9—C10—C11 | 119.7 (3) |
C3—C2—H2 | 120.0 | C9—C10—H10 | 120.1 |
C1—C2—H2 | 120.0 | C11—C10—H10 | 120.1 |
C4—C3—C2 | 120.3 (3) | C12—C11—C10 | 119.9 (3) |
C4—C3—O1 | 109.7 (3) | C12—C11—H11 | 120.1 |
C2—C3—O1 | 130.0 (3) | C10—C11—H11 | 120.1 |
O2—C4—C3 | 110.5 (3) | C11—C12—C13 | 120.1 (3) |
O2—C4—C5 | 129.1 (3) | C11—C12—N3 | 115.8 (3) |
C3—C4—C5 | 120.3 (3) | C13—C12—N3 | 124.1 (3) |
C4—C5—C6 | 119.4 (3) | C14—C13—C12 | 120.0 (3) |
C4—C5—H5 | 120.3 | C14—C13—H13 | 120.0 |
C6—C5—H5 | 120.3 | C12—C13—H13 | 120.0 |
C1—C6—C5 | 120.2 (3) | C13—C14—C9 | 120.5 (3) |
C1—C6—C7 | 118.5 (3) | C13—C14—H14 | 119.8 |
C5—C6—C7 | 121.3 (3) | C9—C14—H14 | 119.8 |
N1—C7—C6 | 129.5 (3) | C7—N1—N2 | 121.9 (3) |
N1—C7—H7 | 115.2 | N1—N2—C9 | 121.4 (3) |
C6—C7—H7 | 115.2 | N1—N2—H2A | 121 (2) |
O2—C8—O1 | 105.8 (3) | C9—N2—H2A | 118 (2) |
O2—C8—H8A | 110.6 | O3—N3—O4 | 124.6 (3) |
O1—C8—H8A | 110.6 | O3—N3—C12 | 119.9 (3) |
O2—C8—H8B | 110.6 | O4—N3—C12 | 112.5 (2) |
O1—C8—H8B | 110.6 | C3—O1—C8 | 106.4 (2) |
H8A—C8—H8B | 108.7 | C4—O2—C8 | 107.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4i | 0.82 (4) | 2.30 (4) | 3.110 (4) | 171 (3) |
Symmetry code: (i) −x+3/2, y−1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11N3O4 |
Mr | 285.26 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 291 |
a, b, c (Å) | 23.719 (3), 4.9052 (18), 12.353 (2) |
V (Å3) | 1437.2 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14432, 1687, 1316 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.088, 1.07 |
No. of reflections | 1687 |
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, −0.14 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4i | 0.82 (4) | 2.30 (4) | 3.110 (4) | 171 (3) |
Symmetry code: (i) −x+3/2, y−1, z+1/2. |
4-Nitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). As a continuation of this work, we report here the crystal structure of the title compound.
The structure of the title compound is shown in Fig. 1, Selected bond lengths and angles are listed in Table 1. The C6—C1 and C6—C5 bond, close to the imino group, are longer than other aromatic C—C bonds in the same benzene ring, which are consistent with the reported by Shan et al. (2002, 2003).
The title molecule crystallizes in the E conformation, with an N2—N1—C7—C1 torsion angle of -176.6 (3)°. The two benzene rings make a dihedral angle of 5.2 (16)°.
The intermolecular N—H···O hydrogen bonding (Table 2) helps to stabilize the crystal structure (Fig. 2).