Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046533/dn3064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046533/dn3064Isup2.hkl |
CCDC reference: 663839
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.091
- wR factor = 0.176
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.04 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 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 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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 minitutes at 351 K, 3-Bromo-4-methoxybenzaldehyde (1 mmol 0.215 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 (I) was obtained after 1 d.
All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methy) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(Caromatic, N) or Uiso(H) = 1.5Ueq(methyl).
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 the synthesis and crystal structure of the title compound(I).
The 4-nitrophenyl group and the methyl benzene rings areslightly twisted making a dihedral angle of 9.9 (3)° (Fig. 1). The N1/O1/O2 nitro group is co-planar with its attached benzene ring [dihedral angle =1.4 (2)°].
The intermolecular N—H···O and C—H···O hydrogen bonds can help stabilizing the molecular structure·(Table 1, Fig.2)
For related literature, see: Okabe et al. (1993).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Bruker, 1997).
C14H12BrN3O3 | F(000) = 1408 |
Mr = 350.18 | Dx = 1.591 Mg m−3 |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 1248 reflections |
a = 7.2800 (15) Å | θ = 2.5–27.8° |
b = 14.678 (3) Å | µ = 2.82 mm−1 |
c = 27.368 (6) Å | T = 298 K |
V = 2924.4 (10) Å3 | Block, brown |
Z = 8 | 0.27 × 0.25 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 2980 independent reflections |
Radiation source: fine-focus sealed tube | 2456 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω scans | θmax = 26.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.486, Tmax = 0.548 | k = −18→18 |
30041 measured reflections | l = −34→34 |
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)] = 0.091 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.22 | w = 1/[σ2(Fo2) + (0.045P)2 + 6.3175P] where P = (Fo2 + 2Fc2)/3 |
2980 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
C14H12BrN3O3 | V = 2924.4 (10) Å3 |
Mr = 350.18 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 7.2800 (15) Å | µ = 2.82 mm−1 |
b = 14.678 (3) Å | T = 298 K |
c = 27.368 (6) Å | 0.27 × 0.25 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 2980 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2456 reflections with I > 2σ(I) |
Tmin = 0.486, Tmax = 0.548 | Rint = 0.060 |
30041 measured reflections |
R[F2 > 2σ(F2)] = 0.091 | 0 restraints |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.22 | Δρmax = 0.93 e Å−3 |
2980 reflections | Δρmin = −0.58 e Å−3 |
191 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 | ||
Br1 | 0.11817 (15) | 0.97770 (5) | 0.17684 (2) | 0.1058 (4) | |
O1 | 0.3606 (7) | 1.1359 (3) | 0.58357 (17) | 0.0930 (14) | |
O2 | 0.4495 (6) | 1.2106 (3) | 0.51958 (19) | 0.0857 (13) | |
O3 | 0.0204 (7) | 0.7930 (3) | 0.14235 (15) | 0.0887 (14) | |
N1 | 0.3772 (7) | 1.1431 (3) | 0.5392 (2) | 0.0687 (13) | |
N2 | 0.1160 (7) | 0.8638 (3) | 0.42050 (15) | 0.0642 (12) | |
H2 | 0.0786 | 0.8142 | 0.4340 | 0.077* | |
N3 | 0.1076 (6) | 0.8735 (3) | 0.37049 (16) | 0.0630 (12) | |
C1 | 0.3092 (7) | 1.0709 (4) | 0.50809 (19) | 0.0556 (13) | |
C2 | 0.2439 (8) | 0.9916 (4) | 0.5293 (2) | 0.0602 (13) | |
H2A | 0.2421 | 0.9849 | 0.5630 | 0.072* | |
C3 | 0.1816 (7) | 0.9227 (4) | 0.49932 (18) | 0.0573 (13) | |
H3 | 0.1378 | 0.8690 | 0.5131 | 0.069* | |
C4 | 0.1836 (7) | 0.9327 (3) | 0.44878 (18) | 0.0509 (12) | |
C5 | 0.2542 (8) | 1.0125 (4) | 0.42843 (19) | 0.0591 (13) | |
H5 | 0.2577 | 1.0196 | 0.3947 | 0.071* | |
C6 | 0.3184 (8) | 1.0802 (4) | 0.4581 (2) | 0.0615 (14) | |
H6 | 0.3683 | 1.1328 | 0.4445 | 0.074* | |
C7 | 0.0422 (8) | 0.8060 (4) | 0.3473 (2) | 0.0666 (15) | |
H7 | 0.0015 | 0.7557 | 0.3648 | 0.080* | |
C8 | 0.0284 (8) | 0.8046 (4) | 0.2942 (2) | 0.0622 (14) | |
C9 | 0.0654 (8) | 0.8806 (4) | 0.2657 (2) | 0.0621 (14) | |
H9 | 0.0943 | 0.9358 | 0.2805 | 0.075* | |
C10 | 0.0594 (8) | 0.8745 (4) | 0.2153 (2) | 0.0648 (15) | |
C11 | 0.0189 (8) | 0.7920 (4) | 0.1923 (2) | 0.0656 (15) | |
C12 | −0.0173 (9) | 0.7173 (4) | 0.2203 (3) | 0.0802 (19) | |
H12 | −0.0449 | 0.6620 | 0.2055 | 0.096* | |
C13 | −0.0130 (9) | 0.7237 (4) | 0.2705 (2) | 0.0745 (17) | |
H13 | −0.0388 | 0.6722 | 0.2891 | 0.089* | |
C14 | −0.0039 (13) | 0.7075 (5) | 0.1180 (3) | 0.112 (3) | |
H14A | 0.0900 | 0.6658 | 0.1284 | 0.167* | |
H14B | 0.0044 | 0.7163 | 0.0833 | 0.167* | |
H14C | −0.1224 | 0.6830 | 0.1260 | 0.167* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.1924 (10) | 0.0635 (4) | 0.0616 (4) | 0.0057 (5) | −0.0070 (5) | −0.0025 (3) |
O1 | 0.119 (4) | 0.090 (3) | 0.069 (3) | −0.005 (3) | −0.008 (3) | −0.017 (2) |
O2 | 0.091 (3) | 0.057 (2) | 0.108 (3) | −0.012 (2) | −0.009 (3) | −0.005 (2) |
O3 | 0.126 (4) | 0.075 (3) | 0.064 (2) | 0.023 (3) | −0.029 (3) | −0.030 (2) |
N1 | 0.063 (3) | 0.061 (3) | 0.082 (4) | 0.008 (3) | −0.007 (3) | −0.009 (3) |
N2 | 0.082 (3) | 0.059 (3) | 0.052 (2) | −0.010 (3) | −0.002 (2) | 0.008 (2) |
N3 | 0.071 (3) | 0.067 (3) | 0.051 (2) | −0.003 (2) | −0.003 (2) | 0.002 (2) |
C1 | 0.053 (3) | 0.052 (3) | 0.062 (3) | 0.006 (2) | −0.011 (3) | −0.002 (2) |
C2 | 0.063 (3) | 0.066 (3) | 0.052 (3) | 0.009 (3) | −0.001 (3) | 0.006 (3) |
C3 | 0.062 (3) | 0.054 (3) | 0.055 (3) | 0.000 (3) | −0.003 (3) | 0.009 (2) |
C4 | 0.045 (3) | 0.053 (3) | 0.055 (3) | 0.002 (2) | −0.003 (2) | 0.002 (2) |
C5 | 0.066 (3) | 0.060 (3) | 0.050 (3) | −0.009 (3) | −0.003 (3) | 0.009 (2) |
C6 | 0.062 (3) | 0.050 (3) | 0.072 (4) | −0.003 (3) | −0.004 (3) | 0.014 (3) |
C7 | 0.071 (4) | 0.057 (3) | 0.071 (4) | −0.006 (3) | −0.010 (3) | −0.002 (3) |
C8 | 0.056 (3) | 0.065 (4) | 0.065 (3) | −0.004 (3) | −0.007 (3) | −0.010 (3) |
C9 | 0.075 (4) | 0.053 (3) | 0.059 (3) | 0.006 (3) | −0.015 (3) | −0.012 (3) |
C10 | 0.083 (4) | 0.052 (3) | 0.060 (3) | 0.016 (3) | −0.013 (3) | −0.012 (3) |
C11 | 0.065 (4) | 0.066 (4) | 0.066 (3) | 0.014 (3) | −0.019 (3) | −0.019 (3) |
C12 | 0.088 (5) | 0.055 (3) | 0.098 (5) | −0.005 (3) | −0.023 (4) | −0.028 (3) |
C13 | 0.083 (4) | 0.062 (4) | 0.078 (4) | −0.010 (3) | −0.012 (3) | −0.004 (3) |
C14 | 0.161 (8) | 0.086 (5) | 0.088 (5) | 0.034 (5) | −0.040 (5) | −0.044 (4) |
Br1—C10 | 1.893 (6) | C5—C6 | 1.366 (7) |
O1—N1 | 1.226 (6) | C5—H5 | 0.9300 |
O2—N1 | 1.244 (6) | C6—H6 | 0.9300 |
O3—C11 | 1.367 (7) | C7—C8 | 1.456 (8) |
O3—C14 | 1.432 (7) | C7—H7 | 0.9300 |
N1—C1 | 1.447 (7) | C8—C13 | 1.385 (8) |
N2—C4 | 1.364 (6) | C8—C9 | 1.389 (8) |
N2—N3 | 1.377 (6) | C9—C10 | 1.382 (7) |
N2—H2 | 0.8600 | C9—H9 | 0.9300 |
N3—C7 | 1.269 (7) | C10—C11 | 1.398 (7) |
C1—C6 | 1.376 (7) | C11—C12 | 1.363 (9) |
C1—C2 | 1.384 (7) | C12—C13 | 1.379 (9) |
C2—C3 | 1.379 (7) | C12—H12 | 0.9300 |
C2—H2A | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.391 (7) | C14—H14A | 0.9600 |
C3—H3 | 0.9300 | C14—H14B | 0.9600 |
C4—C5 | 1.396 (7) | C14—H14C | 0.9600 |
C11—O3—C14 | 117.0 (5) | N3—C7—H7 | 118.8 |
O1—N1—O2 | 122.5 (5) | C8—C7—H7 | 118.8 |
O1—N1—C1 | 119.1 (5) | C13—C8—C9 | 117.8 (5) |
O2—N1—C1 | 118.4 (5) | C13—C8—C7 | 119.6 (6) |
C4—N2—N3 | 120.3 (4) | C9—C8—C7 | 122.4 (5) |
C4—N2—H2 | 119.9 | C10—C9—C8 | 120.2 (5) |
N3—N2—H2 | 119.9 | C10—C9—H9 | 119.9 |
C7—N3—N2 | 115.7 (5) | C8—C9—H9 | 119.9 |
C6—C1—C2 | 121.1 (5) | C9—C10—C11 | 120.8 (6) |
C6—C1—N1 | 119.7 (5) | C9—C10—Br1 | 119.7 (4) |
C2—C1—N1 | 119.2 (5) | C11—C10—Br1 | 119.4 (4) |
C3—C2—C1 | 118.8 (5) | C12—C11—O3 | 125.0 (5) |
C3—C2—H2A | 120.6 | C12—C11—C10 | 118.9 (5) |
C1—C2—H2A | 120.6 | O3—C11—C10 | 116.1 (6) |
C2—C3—C4 | 120.7 (5) | C11—C12—C13 | 120.1 (5) |
C2—C3—H3 | 119.7 | C11—C12—H12 | 119.9 |
C4—C3—H3 | 119.7 | C13—C12—H12 | 119.9 |
N2—C4—C3 | 118.8 (5) | C12—C13—C8 | 122.0 (6) |
N2—C4—C5 | 121.9 (5) | C12—C13—H13 | 119.0 |
C3—C4—C5 | 119.3 (5) | C8—C13—H13 | 119.0 |
C6—C5—C4 | 120.0 (5) | O3—C14—H14A | 109.5 |
C6—C5—H5 | 120.0 | O3—C14—H14B | 109.5 |
C4—C5—H5 | 120.0 | H14A—C14—H14B | 109.5 |
C5—C6—C1 | 120.2 (5) | O3—C14—H14C | 109.5 |
C5—C6—H6 | 119.9 | H14A—C14—H14C | 109.5 |
C1—C6—H6 | 119.9 | H14B—C14—H14C | 109.5 |
N3—C7—C8 | 122.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.86 | 2.19 | 3.035 (6) | 166 |
C7—H7···O1i | 0.93 | 2.48 | 3.400 (8) | 172 |
Symmetry code: (i) x−1/2, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H12BrN3O3 |
Mr | 350.18 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 298 |
a, b, c (Å) | 7.2800 (15), 14.678 (3), 27.368 (6) |
V (Å3) | 2924.4 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.82 |
Crystal size (mm) | 0.27 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.486, 0.548 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30041, 2980, 2456 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.091, 0.176, 1.22 |
No. of reflections | 2980 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.93, −0.58 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.86 | 2.19 | 3.035 (6) | 166.1 |
C7—H7···O1i | 0.93 | 2.48 | 3.400 (8) | 172.0 |
Symmetry code: (i) x−1/2, y−1/2, −z+1. |
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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 the synthesis and crystal structure of the title compound(I).
The 4-nitrophenyl group and the methyl benzene rings areslightly twisted making a dihedral angle of 9.9 (3)° (Fig. 1). The N1/O1/O2 nitro group is co-planar with its attached benzene ring [dihedral angle =1.4 (2)°].
The intermolecular N—H···O and C—H···O hydrogen bonds can help stabilizing the molecular structure·(Table 1, Fig.2)