organic compounds
1-[(Bromomethyl)(phenyl)methylene]-2-(2,4-dinitrophenyl)hydrazine
aSchool of Chemical Sciences, Universiti Sains Malaysia, USM, Penang, 11800, Malaysia
*Correspondence e-mail: abdussalam@usm.my
The title compound, C14H11BrN4O4, comprises two crystallographically independent molecules (A and B) in the In molecule B, intramolecular bifurcated N—H⋯O and N—H⋯Br hydrogen bonds and in molecule A, an intramolecular N—H⋯O hydrogen bond generate S(6) ring motifs. The dihedral angle between the phenyl and benzene rings is 5.44 (6) in molecule A and 7.63 (6)° in molecule B. The ortho- and meta-nitro substituents make dihedral angles of 6.67 (15) and 2.26 (15)° to the attached benzene ring in molecule A and 6.37 (17) and 5.81 (16)° in molecule B. The Br atom in molecule B is disordered over two positions with a refined site-occupancy ratio of 0.61 (3):0.39 (3). Interesting features of the are the short Br⋯N [3.257 (3)–3.294 (4) Å], Br⋯O [3.279 (3)–3.307 (4) Å] and O⋯O [2.9319 (16)–2.9995 (16) Å] contacts, which are shorter than the sum of the van der Waals radii of these atoms. The is further stabilized by intermolecular C—H⋯O and π–π interactions [centroid–centroid distances = 3.6643 (8)–3.8514 (8) Å].
Related literature
For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures and bioactivity, see; for example: Salhin et al. (2007); Tameem et al. (2006, 2007, 2008); Rollas & Küçükgüzel (2007); Shao et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536809016225/at2763sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809016225/at2763Isup2.hkl
2,4-Dinitrophenylhydrazine (0.5 g, 2.5 mmol) was dissolved in ethanol (10 ml), and H2SO4 solution (98%, 1 ml) was added slowly with stirring. The solution was heated on a water bath for several minutes until it cleared. An ethanol solution (5 ml) of α-bromoacetophenone (0.5 g, 2.5 mmol) was dropped slowly into the above solution with continuous stirring. The mixture was heated for another 5 minutes on water bath. On cooling to room temperature, an orange precipitate was formed. Recrystallization from ethanol solution produced the crystals of the title compound.
The N-bound hydrogen atoms were located from the difference Fourier map and refined freely, see Table 1. The rest of the H atoms were positioned geometrically and refined as riding model with C—H = 0.93–0.97 and Uiso(H) = 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. | |
Fig. 2. The crystal packing of the title compound, viewed down the c-axis showing intermolecular interactions. Intermolecular interactions are shown as dashed lines. |
C14H11BrN4O4 | F(000) = 1520 |
Mr = 379.18 | Dx = 1.772 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9995 reflections |
a = 13.0803 (3) Å | θ = 2.2–33.8° |
b = 15.3626 (3) Å | µ = 2.92 mm−1 |
c = 14.1512 (2) Å | T = 100 K |
β = 91.903 (1)° | Block, orange |
V = 2842.08 (9) Å3 | 0.59 × 0.34 × 0.33 mm |
Z = 8 |
Bruker SMART APEXII CCD area-detector diffractometer | 11112 independent reflections |
Radiation source: fine-focus sealed tube | 8666 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 33.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −19→20 |
Tmin = 0.238, Tmax = 0.381 | k = −23→20 |
45788 measured reflections | l = −21→21 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0364P)2 + 1.0321P] where P = (Fo2 + 2Fc2)/3 |
11112 reflections | (Δ/σ)max = 0.007 |
433 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C14H11BrN4O4 | V = 2842.08 (9) Å3 |
Mr = 379.18 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.0803 (3) Å | µ = 2.92 mm−1 |
b = 15.3626 (3) Å | T = 100 K |
c = 14.1512 (2) Å | 0.59 × 0.34 × 0.33 mm |
β = 91.903 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 11112 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 8666 reflections with I > 2σ(I) |
Tmin = 0.238, Tmax = 0.381 | Rint = 0.031 |
45788 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.69 e Å−3 |
11112 reflections | Δρmin = −0.35 e Å−3 |
433 parameters |
Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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 | Occ. (<1) | |
Br1C | 0.9686 (2) | 0.1986 (2) | 0.2704 (3) | 0.0201 (6) | 0.39 (3) |
Br1A | 0.9789 (4) | 0.20086 (17) | 0.2662 (2) | 0.0351 (3) | 0.61 (3) |
O1A | 0.73417 (8) | 0.13615 (7) | 0.39559 (8) | 0.0233 (2) | |
O2A | 0.57980 (8) | 0.08996 (7) | 0.41372 (8) | 0.0265 (2) | |
O3A | 0.49748 (9) | −0.20591 (8) | 0.44038 (8) | 0.0278 (2) | |
O4A | 0.61595 (9) | −0.30399 (7) | 0.45462 (8) | 0.0279 (2) | |
N1A | 0.98576 (9) | 0.00033 (8) | 0.38344 (8) | 0.0160 (2) | |
N2A | 0.88776 (9) | 0.02751 (8) | 0.39522 (8) | 0.0169 (2) | |
N3A | 0.67186 (9) | 0.07666 (8) | 0.40818 (8) | 0.0184 (2) | |
N4A | 0.58779 (10) | −0.22801 (8) | 0.44372 (8) | 0.0214 (2) | |
C1A | 1.23883 (10) | 0.08672 (9) | 0.33786 (9) | 0.0182 (2) | |
H1AA | 1.2251 | 0.1460 | 0.3329 | 0.022* | |
C2A | 1.33726 (11) | 0.05613 (10) | 0.32338 (10) | 0.0207 (3) | |
H2AA | 1.3890 | 0.0951 | 0.3094 | 0.025* | |
C3A | 1.35843 (11) | −0.03208 (10) | 0.32978 (10) | 0.0210 (3) | |
H3AA | 1.4242 | −0.0524 | 0.3199 | 0.025* | |
C4A | 1.28092 (11) | −0.09024 (10) | 0.35096 (10) | 0.0204 (3) | |
H4AA | 1.2951 | −0.1495 | 0.3553 | 0.024* | |
C5A | 1.18284 (10) | −0.06035 (9) | 0.36562 (9) | 0.0177 (2) | |
H5AA | 1.1314 | −0.0997 | 0.3794 | 0.021* | |
C6A | 1.16034 (10) | 0.02883 (8) | 0.35980 (9) | 0.0149 (2) | |
C7A | 1.05537 (10) | 0.05985 (8) | 0.37716 (9) | 0.0154 (2) | |
C8A | 0.81403 (10) | −0.03332 (8) | 0.40698 (9) | 0.0155 (2) | |
C9A | 0.84032 (10) | −0.12258 (9) | 0.41293 (9) | 0.0171 (2) | |
H9AA | 0.9084 | −0.1388 | 0.4081 | 0.021* | |
C10A | 0.76784 (11) | −0.18574 (9) | 0.42569 (9) | 0.0188 (2) | |
H10A | 0.7866 | −0.2441 | 0.4294 | 0.023* | |
C11A | 0.66562 (11) | −0.16139 (9) | 0.43304 (9) | 0.0179 (2) | |
C12A | 0.63592 (10) | −0.07562 (9) | 0.42875 (9) | 0.0177 (2) | |
H12A | 0.5676 | −0.0605 | 0.4348 | 0.021* | |
C13A | 0.70905 (10) | −0.01200 (9) | 0.41530 (9) | 0.0163 (2) | |
C14A | 1.03381 (11) | 0.15508 (9) | 0.38699 (9) | 0.0179 (2) | |
H14A | 0.9897 | 0.1645 | 0.4389 | 0.022* | 0.61 (3) |
H14B | 1.0965 | 0.1860 | 0.3998 | 0.022* | 0.61 (3) |
H14E | 1.0957 | 0.1854 | 0.4049 | 0.022* | 0.39 (3) |
H14F | 0.9853 | 0.1641 | 0.4355 | 0.022* | 0.39 (3) |
Br1B | 0.013792 (12) | 0.244826 (9) | 0.748873 (10) | 0.02245 (4) | |
O1B | −0.22221 (8) | 0.18339 (7) | 0.85993 (8) | 0.0230 (2) | |
O2B | −0.37193 (9) | 0.14659 (8) | 0.90464 (11) | 0.0387 (3) | |
O3B | −0.46689 (8) | −0.14664 (8) | 0.95307 (9) | 0.0301 (2) | |
O4B | −0.35034 (9) | −0.24598 (7) | 0.97032 (9) | 0.0286 (2) | |
N1B | 0.02449 (9) | 0.04055 (8) | 0.85746 (8) | 0.0164 (2) | |
N2B | −0.07206 (9) | 0.07090 (8) | 0.86865 (8) | 0.0172 (2) | |
N3B | −0.28334 (9) | 0.12826 (8) | 0.88791 (9) | 0.0201 (2) | |
N4B | −0.37744 (9) | −0.17037 (8) | 0.95376 (8) | 0.0200 (2) | |
C1B | 0.28568 (10) | 0.11582 (9) | 0.82555 (9) | 0.0181 (2) | |
H1BA | 0.2773 | 0.1759 | 0.8236 | 0.022* | |
C2B | 0.38267 (10) | 0.07996 (9) | 0.81648 (10) | 0.0202 (3) | |
H2BA | 0.4387 | 0.1163 | 0.8091 | 0.024* | |
C3B | 0.39609 (11) | −0.00974 (10) | 0.81839 (10) | 0.0202 (3) | |
H3BA | 0.4609 | −0.0336 | 0.8124 | 0.024* | |
C4B | 0.31187 (11) | −0.06353 (9) | 0.82929 (10) | 0.0211 (3) | |
H4BA | 0.3204 | −0.1236 | 0.8300 | 0.025* | |
C5B | 0.21560 (11) | −0.02835 (9) | 0.83908 (10) | 0.0189 (3) | |
H5BA | 0.1599 | −0.0651 | 0.8467 | 0.023* | |
C6B | 0.20080 (10) | 0.06198 (8) | 0.83760 (9) | 0.0150 (2) | |
C7B | 0.09677 (10) | 0.09733 (8) | 0.85066 (9) | 0.0153 (2) | |
C8B | −0.14694 (10) | 0.01355 (8) | 0.88991 (9) | 0.0151 (2) | |
C9B | −0.12331 (10) | −0.07567 (9) | 0.90438 (9) | 0.0169 (2) | |
H9BA | −0.0560 | −0.0943 | 0.9000 | 0.020* | |
C10B | −0.19764 (10) | −0.13504 (9) | 0.92470 (9) | 0.0176 (2) | |
H10B | −0.1811 | −0.1935 | 0.9329 | 0.021* | |
C11B | −0.29861 (10) | −0.10694 (9) | 0.93296 (9) | 0.0165 (2) | |
C12B | −0.32537 (10) | −0.02108 (9) | 0.92251 (9) | 0.0169 (2) | |
H12B | −0.3926 | −0.0033 | 0.9301 | 0.020* | |
C13B | −0.25005 (10) | 0.03894 (9) | 0.90035 (9) | 0.0158 (2) | |
C14B | 0.07976 (10) | 0.19299 (9) | 0.86268 (10) | 0.0183 (2) | |
H14C | 0.1449 | 0.2214 | 0.8757 | 0.022* | |
H14D | 0.0370 | 0.2026 | 0.9164 | 0.022* | |
H1NB | −0.0909 (14) | 0.1209 (13) | 0.8571 (13) | 0.026 (5)* | |
H1NA | 0.8714 (15) | 0.0766 (14) | 0.3890 (14) | 0.033 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1C | 0.0235 (14) | 0.0151 (5) | 0.0216 (5) | 0.0021 (5) | −0.0005 (4) | 0.0042 (4) |
Br1A | 0.0622 (9) | 0.0206 (5) | 0.0219 (3) | 0.0145 (5) | −0.0070 (5) | 0.0008 (3) |
O1A | 0.0180 (5) | 0.0153 (5) | 0.0366 (6) | 0.0002 (4) | −0.0001 (4) | 0.0009 (4) |
O2A | 0.0153 (5) | 0.0257 (6) | 0.0385 (6) | 0.0054 (4) | 0.0024 (4) | 0.0008 (5) |
O3A | 0.0225 (5) | 0.0295 (6) | 0.0319 (6) | −0.0083 (4) | 0.0058 (4) | −0.0021 (5) |
O4A | 0.0369 (6) | 0.0174 (5) | 0.0295 (5) | −0.0069 (4) | 0.0016 (5) | 0.0009 (4) |
N1A | 0.0132 (5) | 0.0166 (5) | 0.0183 (5) | 0.0016 (4) | 0.0011 (4) | 0.0005 (4) |
N2A | 0.0151 (5) | 0.0134 (5) | 0.0223 (5) | 0.0013 (4) | 0.0014 (4) | 0.0004 (4) |
N3A | 0.0170 (5) | 0.0175 (5) | 0.0206 (5) | 0.0021 (4) | −0.0008 (4) | −0.0011 (4) |
N4A | 0.0263 (6) | 0.0212 (6) | 0.0169 (5) | −0.0075 (5) | 0.0036 (4) | −0.0019 (4) |
C1A | 0.0192 (6) | 0.0157 (6) | 0.0196 (6) | −0.0024 (5) | 0.0011 (5) | 0.0004 (5) |
C2A | 0.0166 (6) | 0.0243 (7) | 0.0215 (6) | −0.0056 (5) | 0.0022 (5) | 0.0000 (5) |
C3A | 0.0157 (6) | 0.0265 (7) | 0.0210 (6) | 0.0021 (5) | 0.0016 (5) | −0.0002 (5) |
C4A | 0.0194 (6) | 0.0180 (6) | 0.0237 (6) | 0.0037 (5) | 0.0005 (5) | 0.0001 (5) |
C5A | 0.0166 (6) | 0.0153 (6) | 0.0212 (6) | −0.0008 (5) | 0.0009 (5) | 0.0007 (5) |
C6A | 0.0148 (6) | 0.0148 (6) | 0.0150 (5) | −0.0004 (4) | −0.0006 (4) | −0.0003 (4) |
C7A | 0.0165 (6) | 0.0138 (6) | 0.0160 (5) | 0.0013 (4) | −0.0002 (4) | 0.0002 (4) |
C8A | 0.0153 (6) | 0.0158 (6) | 0.0155 (5) | 0.0000 (4) | −0.0001 (4) | −0.0003 (4) |
C9A | 0.0174 (6) | 0.0165 (6) | 0.0176 (5) | 0.0024 (5) | 0.0024 (4) | −0.0011 (4) |
C10A | 0.0240 (6) | 0.0153 (6) | 0.0172 (6) | −0.0004 (5) | 0.0013 (5) | −0.0009 (4) |
C11A | 0.0210 (6) | 0.0171 (6) | 0.0156 (5) | −0.0044 (5) | 0.0020 (5) | −0.0007 (4) |
C12A | 0.0162 (6) | 0.0208 (6) | 0.0161 (5) | −0.0016 (5) | 0.0002 (4) | −0.0013 (5) |
C13A | 0.0166 (6) | 0.0155 (6) | 0.0169 (5) | 0.0011 (5) | 0.0005 (4) | −0.0004 (4) |
C14A | 0.0190 (6) | 0.0161 (6) | 0.0186 (6) | 0.0011 (5) | −0.0003 (5) | −0.0003 (4) |
Br1B | 0.02671 (7) | 0.01604 (7) | 0.02483 (7) | 0.00470 (5) | 0.00414 (5) | 0.00186 (5) |
O1B | 0.0200 (5) | 0.0146 (5) | 0.0345 (6) | 0.0001 (4) | 0.0014 (4) | 0.0018 (4) |
O2B | 0.0189 (5) | 0.0243 (6) | 0.0738 (9) | 0.0085 (5) | 0.0131 (6) | 0.0068 (6) |
O3B | 0.0159 (5) | 0.0297 (6) | 0.0446 (7) | −0.0018 (4) | 0.0024 (4) | 0.0081 (5) |
O4B | 0.0277 (6) | 0.0174 (5) | 0.0410 (7) | −0.0017 (4) | 0.0071 (5) | 0.0046 (4) |
N1B | 0.0132 (5) | 0.0160 (5) | 0.0200 (5) | 0.0013 (4) | 0.0017 (4) | −0.0007 (4) |
N2B | 0.0137 (5) | 0.0134 (5) | 0.0245 (5) | 0.0016 (4) | 0.0025 (4) | −0.0003 (4) |
N3B | 0.0174 (5) | 0.0158 (5) | 0.0272 (6) | 0.0027 (4) | 0.0011 (4) | −0.0003 (4) |
N4B | 0.0190 (5) | 0.0214 (6) | 0.0197 (5) | −0.0031 (4) | 0.0022 (4) | 0.0011 (4) |
C1B | 0.0182 (6) | 0.0151 (6) | 0.0211 (6) | −0.0017 (5) | 0.0024 (5) | −0.0008 (5) |
C2B | 0.0154 (6) | 0.0209 (7) | 0.0243 (6) | −0.0029 (5) | 0.0030 (5) | −0.0009 (5) |
C3B | 0.0158 (6) | 0.0228 (7) | 0.0220 (6) | 0.0035 (5) | 0.0020 (5) | 0.0010 (5) |
C4B | 0.0191 (6) | 0.0162 (6) | 0.0280 (7) | 0.0028 (5) | 0.0029 (5) | 0.0019 (5) |
C5B | 0.0167 (6) | 0.0155 (6) | 0.0247 (6) | −0.0011 (5) | 0.0029 (5) | 0.0009 (5) |
C6B | 0.0149 (6) | 0.0148 (6) | 0.0152 (5) | −0.0001 (4) | 0.0006 (4) | −0.0011 (4) |
C7B | 0.0160 (6) | 0.0135 (6) | 0.0163 (5) | 0.0003 (4) | 0.0009 (4) | −0.0013 (4) |
C8B | 0.0142 (6) | 0.0154 (6) | 0.0157 (5) | 0.0007 (4) | 0.0006 (4) | −0.0015 (4) |
C9B | 0.0152 (6) | 0.0153 (6) | 0.0202 (6) | 0.0024 (5) | 0.0009 (4) | −0.0002 (4) |
C10B | 0.0189 (6) | 0.0148 (6) | 0.0192 (6) | 0.0015 (5) | 0.0014 (5) | 0.0001 (4) |
C11B | 0.0150 (6) | 0.0179 (6) | 0.0167 (5) | −0.0015 (5) | 0.0006 (4) | 0.0014 (4) |
C12B | 0.0141 (6) | 0.0189 (6) | 0.0179 (6) | 0.0008 (5) | 0.0012 (4) | −0.0003 (4) |
C13B | 0.0145 (6) | 0.0143 (6) | 0.0186 (6) | 0.0023 (4) | 0.0003 (4) | −0.0005 (4) |
C14B | 0.0179 (6) | 0.0150 (6) | 0.0221 (6) | 0.0003 (5) | 0.0014 (5) | −0.0023 (5) |
Br1C—C14A | 1.949 (4) | C14A—H14F | 0.9601 |
Br1A—C14A | 1.962 (3) | Br1B—C14B | 1.9699 (14) |
O1A—N3A | 1.2413 (15) | O1B—N3B | 1.2388 (16) |
O2A—N3A | 1.2265 (15) | O2B—N3B | 1.2232 (16) |
O3A—N4A | 1.2286 (17) | O3B—N4B | 1.2252 (16) |
O4A—N4A | 1.2321 (17) | O4B—N4B | 1.2347 (16) |
N1A—C7A | 1.2955 (17) | N1B—C7B | 1.2922 (17) |
N1A—N2A | 1.3636 (16) | N1B—N2B | 1.3604 (16) |
N2A—C8A | 1.3572 (17) | N2B—C8B | 1.3584 (17) |
N2A—H1NA | 0.79 (2) | N2B—H1NB | 0.82 (2) |
N3A—C13A | 1.4487 (17) | N3B—C13B | 1.4486 (17) |
N4A—C11A | 1.4549 (18) | N4B—C11B | 1.4559 (18) |
C1A—C2A | 1.392 (2) | C1B—C2B | 1.3928 (19) |
C1A—C6A | 1.4010 (18) | C1B—C6B | 1.3995 (18) |
C1A—H1AA | 0.9300 | C1B—H1BA | 0.9300 |
C2A—C3A | 1.386 (2) | C2B—C3B | 1.389 (2) |
C2A—H2AA | 0.9300 | C2B—H2BA | 0.9300 |
C3A—C4A | 1.392 (2) | C3B—C4B | 1.390 (2) |
C3A—H3AA | 0.9300 | C3B—H3BA | 0.9300 |
C4A—C5A | 1.3847 (19) | C4B—C5B | 1.382 (2) |
C4A—H4AA | 0.9300 | C4B—H4BA | 0.9300 |
C5A—C6A | 1.4031 (19) | C5B—C6B | 1.4011 (19) |
C5A—H5AA | 0.9300 | C5B—H5BA | 0.9300 |
C6A—C7A | 1.4816 (18) | C6B—C7B | 1.4824 (18) |
C7A—C14A | 1.4973 (18) | C7B—C14B | 1.4969 (18) |
C8A—C9A | 1.4155 (19) | C8B—C13B | 1.4164 (18) |
C8A—C13A | 1.4205 (19) | C8B—C9B | 1.4185 (18) |
C9A—C10A | 1.3727 (19) | C9B—C10B | 1.3706 (19) |
C9A—H9AA | 0.9300 | C9B—H9BA | 0.9300 |
C10A—C11A | 1.396 (2) | C10B—C11B | 1.3980 (19) |
C10A—H10A | 0.9300 | C10B—H10B | 0.9300 |
C11A—C12A | 1.375 (2) | C11B—C12B | 1.3714 (19) |
C12A—C13A | 1.3851 (19) | C12B—C13B | 1.3928 (19) |
C12A—H12A | 0.9300 | C12B—H12B | 0.9300 |
C14A—H14A | 0.9600 | C14B—H14C | 0.9700 |
C14A—H14B | 0.9600 | C14B—H14D | 0.9700 |
C14A—H14E | 0.9600 | ||
C7A—N1A—N2A | 117.26 (11) | H14A—C14A—H14E | 104.4 |
C8A—N2A—N1A | 118.61 (11) | C7A—C14A—H14F | 109.8 |
C8A—N2A—H1NA | 118.8 (15) | Br1C—C14A—H14F | 106.0 |
N1A—N2A—H1NA | 122.1 (15) | Br1A—C14A—H14F | 109.9 |
O2A—N3A—O1A | 122.50 (12) | H14B—C14A—H14F | 112.0 |
O2A—N3A—C13A | 118.70 (12) | H14E—C14A—H14F | 108.2 |
O1A—N3A—C13A | 118.80 (11) | C7B—N1B—N2B | 117.50 (11) |
O3A—N4A—O4A | 123.35 (13) | C8B—N2B—N1B | 118.85 (11) |
O3A—N4A—C11A | 118.47 (13) | C8B—N2B—H1NB | 115.9 (13) |
O4A—N4A—C11A | 118.17 (12) | N1B—N2B—H1NB | 124.8 (14) |
C2A—C1A—C6A | 120.43 (13) | O2B—N3B—O1B | 122.01 (12) |
C2A—C1A—H1AA | 119.8 | O2B—N3B—C13B | 118.52 (12) |
C6A—C1A—H1AA | 119.8 | O1B—N3B—C13B | 119.46 (11) |
C3A—C2A—C1A | 120.29 (13) | O3B—N4B—O4B | 123.33 (13) |
C3A—C2A—H2AA | 119.9 | O3B—N4B—C11B | 118.80 (12) |
C1A—C2A—H2AA | 119.9 | O4B—N4B—C11B | 117.86 (12) |
C2A—C3A—C4A | 119.77 (13) | C2B—C1B—C6B | 120.41 (13) |
C2A—C3A—H3AA | 120.1 | C2B—C1B—H1BA | 119.8 |
C4A—C3A—H3AA | 120.1 | C6B—C1B—H1BA | 119.8 |
C5A—C4A—C3A | 120.31 (13) | C3B—C2B—C1B | 120.36 (13) |
C5A—C4A—H4AA | 119.8 | C3B—C2B—H2BA | 119.8 |
C3A—C4A—H4AA | 119.8 | C1B—C2B—H2BA | 119.8 |
C4A—C5A—C6A | 120.56 (13) | C2B—C3B—C4B | 119.46 (13) |
C4A—C5A—H5AA | 119.7 | C2B—C3B—H3BA | 120.3 |
C6A—C5A—H5AA | 119.7 | C4B—C3B—H3BA | 120.3 |
C1A—C6A—C5A | 118.62 (12) | C5B—C4B—C3B | 120.46 (13) |
C1A—C6A—C7A | 121.50 (12) | C5B—C4B—H4BA | 119.8 |
C5A—C6A—C7A | 119.87 (12) | C3B—C4B—H4BA | 119.8 |
N1A—C7A—C6A | 116.21 (11) | C4B—C5B—C6B | 120.79 (13) |
N1A—C7A—C14A | 123.25 (12) | C4B—C5B—H5BA | 119.6 |
C6A—C7A—C14A | 120.54 (12) | C6B—C5B—H5BA | 119.6 |
N2A—C8A—C9A | 120.14 (12) | C1B—C6B—C5B | 118.52 (12) |
N2A—C8A—C13A | 122.97 (12) | C1B—C6B—C7B | 122.27 (12) |
C9A—C8A—C13A | 116.88 (12) | C5B—C6B—C7B | 119.20 (12) |
C10A—C9A—C8A | 121.67 (13) | N1B—C7B—C6B | 116.03 (12) |
C10A—C9A—H9AA | 119.2 | N1B—C7B—C14B | 122.85 (12) |
C8A—C9A—H9AA | 119.2 | C6B—C7B—C14B | 120.95 (11) |
C9A—C10A—C11A | 119.21 (13) | N2B—C8B—C13B | 122.72 (12) |
C9A—C10A—H10A | 120.4 | N2B—C8B—C9B | 120.22 (12) |
C11A—C10A—H10A | 120.4 | C13B—C8B—C9B | 117.05 (12) |
C12A—C11A—C10A | 121.58 (13) | C10B—C9B—C8B | 121.37 (12) |
C12A—C11A—N4A | 118.77 (13) | C10B—C9B—H9BA | 119.3 |
C10A—C11A—N4A | 119.64 (13) | C8B—C9B—H9BA | 119.3 |
C11A—C12A—C13A | 119.15 (13) | C9B—C10B—C11B | 119.39 (12) |
C11A—C12A—H12A | 120.4 | C9B—C10B—H10B | 120.3 |
C13A—C12A—H12A | 120.4 | C11B—C10B—H10B | 120.3 |
C12A—C13A—C8A | 121.50 (12) | C12B—C11B—C10B | 121.76 (13) |
C12A—C13A—N3A | 116.18 (12) | C12B—C11B—N4B | 119.05 (12) |
C8A—C13A—N3A | 122.30 (12) | C10B—C11B—N4B | 119.18 (12) |
C7A—C14A—Br1C | 109.55 (14) | C11B—C12B—C13B | 118.76 (12) |
C7A—C14A—Br1A | 109.50 (11) | C11B—C12B—H12B | 120.6 |
C7A—C14A—H14A | 109.8 | C13B—C12B—H12B | 120.6 |
Br1C—C14A—H14A | 109.8 | C12B—C13B—C8B | 121.62 (12) |
Br1A—C14A—H14A | 113.6 | C12B—C13B—N3B | 116.26 (12) |
C7A—C14A—H14B | 109.8 | C8B—C13B—N3B | 122.11 (12) |
Br1C—C14A—H14B | 109.7 | C7B—C14B—Br1B | 111.51 (9) |
Br1A—C14A—H14B | 105.8 | C7B—C14B—H14C | 109.3 |
H14A—C14A—H14B | 108.2 | Br1B—C14B—H14C | 109.3 |
C7A—C14A—H14E | 109.8 | C7B—C14B—H14D | 109.3 |
Br1C—C14A—H14E | 113.5 | Br1B—C14B—H14D | 109.3 |
Br1A—C14A—H14E | 109.7 | H14C—C14B—H14D | 108.0 |
C7A—N1A—N2A—C8A | −176.60 (12) | C6A—C7A—C14A—Br1A | 98.2 (2) |
C6A—C1A—C2A—C3A | 0.5 (2) | C7B—N1B—N2B—C8B | −170.40 (12) |
C1A—C2A—C3A—C4A | −0.1 (2) | C6B—C1B—C2B—C3B | 0.6 (2) |
C2A—C3A—C4A—C5A | 0.0 (2) | C1B—C2B—C3B—C4B | 0.1 (2) |
C3A—C4A—C5A—C6A | −0.3 (2) | C2B—C3B—C4B—C5B | −0.6 (2) |
C2A—C1A—C6A—C5A | −0.80 (19) | C3B—C4B—C5B—C6B | 0.4 (2) |
C2A—C1A—C6A—C7A | 178.94 (12) | C2B—C1B—C6B—C5B | −0.80 (19) |
C4A—C5A—C6A—C1A | 0.70 (19) | C2B—C1B—C6B—C7B | 177.96 (12) |
C4A—C5A—C6A—C7A | −179.04 (12) | C4B—C5B—C6B—C1B | 0.3 (2) |
N2A—N1A—C7A—C6A | −177.18 (11) | C4B—C5B—C6B—C7B | −178.51 (13) |
N2A—N1A—C7A—C14A | 3.11 (18) | N2B—N1B—C7B—C6B | −179.43 (11) |
C1A—C6A—C7A—N1A | 170.46 (12) | N2B—N1B—C7B—C14B | 5.26 (19) |
C5A—C6A—C7A—N1A | −9.80 (18) | C1B—C6B—C7B—N1B | 177.49 (12) |
C1A—C6A—C7A—C14A | −9.82 (18) | C5B—C6B—C7B—N1B | −3.76 (18) |
C5A—C6A—C7A—C14A | 169.92 (12) | C1B—C6B—C7B—C14B | −7.11 (19) |
N1A—N2A—C8A—C9A | 4.05 (18) | C5B—C6B—C7B—C14B | 171.65 (12) |
N1A—N2A—C8A—C13A | −176.93 (12) | N1B—N2B—C8B—C13B | −178.28 (12) |
N2A—C8A—C9A—C10A | 179.39 (12) | N1B—N2B—C8B—C9B | 2.88 (18) |
C13A—C8A—C9A—C10A | 0.31 (19) | N2B—C8B—C9B—C10B | −179.15 (12) |
C8A—C9A—C10A—C11A | 0.0 (2) | C13B—C8B—C9B—C10B | 1.94 (19) |
C9A—C10A—C11A—C12A | −0.7 (2) | C8B—C9B—C10B—C11B | −1.1 (2) |
C9A—C10A—C11A—N4A | 178.16 (12) | C9B—C10B—C11B—C12B | −0.9 (2) |
O3A—N4A—C11A—C12A | 6.17 (18) | C9B—C10B—C11B—N4B | 179.49 (12) |
O4A—N4A—C11A—C12A | −174.63 (12) | O3B—N4B—C11B—C12B | 6.41 (19) |
O3A—N4A—C11A—C10A | −172.69 (12) | O4B—N4B—C11B—C12B | −174.33 (13) |
O4A—N4A—C11A—C10A | 6.51 (18) | O3B—N4B—C11B—C10B | −173.95 (13) |
C10A—C11A—C12A—C13A | 1.1 (2) | O4B—N4B—C11B—C10B | 5.31 (18) |
N4A—C11A—C12A—C13A | −177.78 (11) | C10B—C11B—C12B—C13B | 1.9 (2) |
C11A—C12A—C13A—C8A | −0.76 (19) | N4B—C11B—C12B—C13B | −178.46 (12) |
C11A—C12A—C13A—N3A | 177.91 (11) | C11B—C12B—C13B—C8B | −0.99 (19) |
N2A—C8A—C13A—C12A | −178.96 (12) | C11B—C12B—C13B—N3B | 178.53 (12) |
C9A—C8A—C13A—C12A | 0.09 (19) | N2B—C8B—C13B—C12B | −179.76 (12) |
N2A—C8A—C13A—N3A | 2.5 (2) | C9B—C8B—C13B—C12B | −0.88 (19) |
C9A—C8A—C13A—N3A | −178.49 (11) | N2B—C8B—C13B—N3B | 0.7 (2) |
O2A—N3A—C13A—C12A | −0.45 (18) | C9B—C8B—C13B—N3B | 179.62 (12) |
O1A—N3A—C13A—C12A | −179.62 (12) | O2B—N3B—C13B—C12B | 5.65 (19) |
O2A—N3A—C13A—C8A | 178.20 (12) | O1B—N3B—C13B—C12B | −173.60 (12) |
O1A—N3A—C13A—C8A | −0.97 (19) | O2B—N3B—C13B—C8B | −174.83 (14) |
N1A—C7A—C14A—Br1C | −77.37 (17) | O1B—N3B—C13B—C8B | 5.92 (19) |
C6A—C7A—C14A—Br1C | 102.93 (15) | N1B—C7B—C14B—Br1B | −77.67 (14) |
N1A—C7A—C14A—Br1A | −82.1 (2) | C6B—C7B—C14B—Br1B | 107.25 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H1NB···Br1B | 0.82 (2) | 2.826 (19) | 3.3764 (12) | 126.2 (15) |
N2B—H1NB···O1B | 0.82 (2) | 1.969 (19) | 2.6159 (16) | 135.1 (17) |
N2A—H1NA···O1A | 0.79 (2) | 2.02 (2) | 2.6120 (16) | 131.8 (19) |
C2B—H2BA···Br1Ai | 0.93 | 2.93 | 3.673 (3) | 138 |
C14B—H14C···O1Ai | 0.97 | 2.49 | 3.3352 (17) | 145 |
C14B—H14D···O3Aii | 0.97 | 2.52 | 3.3745 (18) | 147 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11BrN4O4 |
Mr | 379.18 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 13.0803 (3), 15.3626 (3), 14.1512 (2) |
β (°) | 91.903 (1) |
V (Å3) | 2842.08 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.92 |
Crystal size (mm) | 0.59 × 0.34 × 0.33 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.238, 0.381 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45788, 11112, 8666 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.777 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.077, 1.01 |
No. of reflections | 11112 |
No. of parameters | 433 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.69, −0.35 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H1NB···Br1B | 0.82 (2) | 2.826 (19) | 3.3764 (12) | 126.2 (15) |
N2B—H1NB···O1B | 0.82 (2) | 1.969 (19) | 2.6159 (16) | 135.1 (17) |
N2A—H1NA···O1A | 0.79 (2) | 2.02 (2) | 2.6120 (16) | 131.8 (19) |
C2B—H2BA···Br1Ai | 0.9300 | 2.9300 | 3.673 (3) | 138.00 |
C14B—H14C···O1Ai | 0.9700 | 2.4900 | 3.3352 (17) | 145.00 |
C14B—H14D···O3Aii | 0.9700 | 2.5200 | 3.3745 (18) | 147.00 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+3/2. |
Acknowledgements
We thank the Malysian Government and Universiti Sains Malaysia for the Science Fund grant No. 1001/229/PKIMIA/811055.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In view of the importance of hydrazone derivatives in chemical and biological applications (Rollas & Küçükgüzel, 2007; Shao et al., 2008), a series of hydrazone derivatives has been prepared in our laboratory, from which several X-ray structures have been reported (Salhin et al., 2007; Tameem et al., 2006, 2007 and 2008).
The title compound, C14H11BrN4O4, comprises two crystallographically independent molecules (A, B) in the asymmetric unit. In molecule B, intramolecular bifurcated N—H···O and N—H···Br hydrogen bonds and in molecule A, an intramolecular N—H···O hydrogen bond generate S(6) ring motifs. The dihedral angle between the phenyl rings in molecules A and B are 5.44 (6) and 7.63 (6)°, respectively. The ortho and meta nitro-substituents make the dihedral angles of 6.67 (15) and 2.26 (15)° in molecule A and 6.37917) and 5.81 (16)° to the benzene ring they are attached. The bromine group was disordered over two positins with a refined site-occupancy ratio of 0.61 (3)/0.39 (3) in molecule B. The crystal structure is further stabilized by intermolecular C—H···O and π-π [Cg1··· Cg1iii = 3.6643 (8) Å, (iii) 2 - x, -y, 1 - z; Cg1··· Cg4iv = 3.7308 (8) Å, (iv) 1 - x, -y, 1 - z; Cg1···Cg2iv = 3.7013 (8) Å; Cg2···Cg3iv = 3.7012 (8) Å; Cg3···Cg4v = 3.8514 (8) Å, (v) -x, -y, 2 - z: Cg1, Cg2, Cg3, Cg4 are the centroids of the C1A–C6A, C8A–C13A, C1B–C6B, and C8B–C13b rings].
The interesting features of the crystal structure are short Br1A···N4Avi [3.257 (3), (vi) 3/2-x,1/2+y,1/2-z], Br1C···N4Avi [3.294 (4) Å], Br1A···O3Aviii [3.279 (3), (viii) 3/2-x,-1/2+y,1/2-z], Br1C···O3Avii [3.307 (4) Å], O2A···O3Aiv [2.9319 (16) Å], and O1A···O4Bvii [2.9995(160 Å, (vii) 1/2-x,1/2+y,3/2-z] contacts which are shorter than the sum of the van der Waals radii of these atoms.