Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033090/sg2187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033090/sg2187Isup2.hkl |
CCDC reference: 659076
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.086
- Data-to-parameter ratio = 22.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.17
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 0 ALERT type 5 Informative message, check
For related structures, see: 2-bromo-N'-[(E)-(4-fluorophenyl)methylene]-5-methoxybenzohydrazide monohydrate (Narayana, Sunil et al., 2007); 2-bromo-5-methoxy-N'-[(E)-(2-nitrophenyl)methylene]benzohydrazide (Yathirajan, Sarojini et al., 2007); N'-[(1E)-(4-fluorophenyl)methylene]-6-methoxy-2-naphthohydrazide (Yathirajan, Narayana et al., (2007).
For related literature, see: Swain (1959); Hodnett & Dunn (1970); Cajocorius et al. (1977); Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Narayana, Vijayaraj et al. (2005); Narayana, Ashalatha et al. (2005); Liu et al. (2006).
A mixture of 2-bromo-5-methoxybenzohydrazide (2.45 g, 0.01 mol) and acetone (1.2 g, 0.02 mol) in 15 ml of absolute ethanol containing 1 drop of dilute sulfuric acid was refluxed for about 4 h. On cooling, the solid that separated was filtered and recrystallized from ethyl acetate (m.p.: 404–406 K). Analysis for C11H13BrN2O2: Found (Calculated): C: 46.21 (46.33); H: 4.54 (4.60); N: 9.73% (9.82%).
H atoms were found in a difference map, but they were refined using a riding model with C—H = 0.95Å and Uiso(H) = 1.2Ueq(C).
Hydrazides and their Schiff bases are useful precursors in the synthesis of several heterocyclic systems. Some substituted hydrazides and their Schiff bases are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity It is also used as an intermediate in many pharmaceutically important compounds. A new Schiff base of the hydrazide, C11H13BrN2O2 was synthesized and its crystal structure is reported.
Geometric parameters of the title compound (Fig. 1) are in the usual ranges. All seven non-H atoms of the acetone hydrazone moiety lie in a common plane (r.m.s. deviation 0.007 Å) which is almost perpendicular [88.52 (6)°] to the aromatic ring. In the crystal, the molecules are connected by N—H···O hydrogen bonds to form centrosymmetric dimers (Fig. 2).
For related structures, see: 2-bromo-N'-[(E)-(4-fluorophenyl)methylene]-5-methoxybenzohydrazide monohydrate (Narayana, Sunil et al., 2007); 2-bromo-5-methoxy-N'-[(E)-(2-nitrophenyl)methylene]benzohydrazide (Yathirajan, Sarojini et al., 2007); N'-[(1E)-(4-fluorophenyl)methylene]-6-methoxy-2-naphthohydrazide (Yathirajan, Narayana et al., (2007).
For related literature, see: Swain (1959); Hodnett & Dunn (1970); Cajocorius et al. (1977); Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Narayana, Vijayaraj et al. (2005); Narayana, Ashalatha et al. (2005); Liu et al. (2006).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level. |
C11H13BrN2O2 | F(000) = 576 |
Mr = 285.14 | Dx = 1.558 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 13368 reflections |
a = 7.8311 (5) Å | θ = 3.6–29.5° |
b = 13.6460 (7) Å | µ = 3.37 mm−1 |
c = 11.3800 (8) Å | T = 173 K |
β = 92.005 (5)° | Block, colourless |
V = 1215.36 (13) Å3 | 0.29 × 0.27 × 0.25 mm |
Z = 4 |
Stoe IPDS II two-circle- diffractometer | 3404 independent reflections |
Radiation source: fine-focus sealed tube | 2995 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
ω scans | θmax = 29.6°, θmin = 3.6° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −10→10 |
Tmin = 0.398, Tmax = 0.438 | k = −18→16 |
27762 measured reflections | l = −15→15 |
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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.086 | w = 1/[σ2(Fo2) + (0.0262P)2 + 0.9527P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
3404 reflections | Δρmax = 0.47 e Å−3 |
153 parameters | Δρmin = −0.53 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: 0.0108 (9) |
C11H13BrN2O2 | V = 1215.36 (13) Å3 |
Mr = 285.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8311 (5) Å | µ = 3.37 mm−1 |
b = 13.6460 (7) Å | T = 173 K |
c = 11.3800 (8) Å | 0.29 × 0.27 × 0.25 mm |
β = 92.005 (5)° |
Stoe IPDS II two-circle- diffractometer | 3404 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2995 reflections with I > 2σ(I) |
Tmin = 0.398, Tmax = 0.438 | Rint = 0.080 |
27762 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.47 e Å−3 |
3404 reflections | Δρmin = −0.53 e Å−3 |
153 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 | −0.02400 (3) | 0.755039 (17) | 0.73418 (2) | 0.03436 (10) | |
N1 | 0.1881 (2) | 0.56917 (15) | 0.92316 (15) | 0.0241 (4) | |
H1 | 0.163 (4) | 0.553 (2) | 0.992 (2) | 0.029 (7)* | |
N2 | 0.3432 (2) | 0.61293 (15) | 0.89571 (15) | 0.0263 (4) | |
O1 | −0.0623 (2) | 0.50527 (13) | 0.85582 (13) | 0.0299 (4) | |
O2 | 0.3225 (2) | 0.42571 (13) | 0.48012 (14) | 0.0322 (4) | |
C1 | 0.0758 (3) | 0.54460 (15) | 0.83589 (17) | 0.0213 (4) | |
C2 | 0.4445 (3) | 0.63696 (17) | 0.98164 (19) | 0.0266 (4) | |
C3 | 0.4144 (3) | 0.6235 (2) | 1.11038 (19) | 0.0342 (5) | |
H3A | 0.3039 | 0.6521 | 1.1292 | 0.051* | |
H3B | 0.5056 | 0.6561 | 1.1568 | 0.051* | |
H3C | 0.4141 | 0.5534 | 1.1291 | 0.051* | |
C4 | 0.6117 (3) | 0.6825 (2) | 0.9500 (2) | 0.0433 (7) | |
H4A | 0.6176 | 0.6864 | 0.8642 | 0.065* | |
H4B | 0.7062 | 0.6422 | 0.9814 | 0.065* | |
H4C | 0.6201 | 0.7485 | 0.9836 | 0.065* | |
C11 | 0.1243 (2) | 0.56409 (16) | 0.71060 (16) | 0.0200 (4) | |
C12 | 0.0821 (3) | 0.65109 (16) | 0.65255 (18) | 0.0229 (4) | |
C13 | 0.1178 (3) | 0.66386 (17) | 0.53468 (18) | 0.0274 (4) | |
H13 | 0.0881 | 0.7235 | 0.4961 | 0.033* | |
C14 | 0.1971 (3) | 0.58937 (17) | 0.47296 (17) | 0.0264 (4) | |
H14 | 0.2215 | 0.5980 | 0.3924 | 0.032* | |
C15 | 0.2403 (3) | 0.50254 (16) | 0.52987 (17) | 0.0230 (4) | |
C16 | 0.2025 (3) | 0.48971 (16) | 0.64868 (17) | 0.0226 (4) | |
H16 | 0.2306 | 0.4297 | 0.6870 | 0.027* | |
C17 | 0.3679 (3) | 0.4361 (2) | 0.35960 (19) | 0.0350 (5) | |
H17A | 0.2639 | 0.4419 | 0.3097 | 0.053* | |
H17B | 0.4329 | 0.3785 | 0.3358 | 0.053* | |
H17C | 0.4379 | 0.4951 | 0.3511 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.04829 (16) | 0.02903 (13) | 0.02596 (13) | 0.00271 (11) | 0.00392 (9) | −0.00287 (9) |
N1 | 0.0230 (8) | 0.0368 (10) | 0.0127 (7) | −0.0085 (7) | 0.0021 (6) | 0.0033 (7) |
N2 | 0.0242 (9) | 0.0351 (10) | 0.0199 (8) | −0.0105 (7) | 0.0052 (7) | −0.0027 (7) |
O1 | 0.0236 (8) | 0.0489 (10) | 0.0173 (7) | −0.0125 (7) | −0.0005 (6) | 0.0073 (7) |
O2 | 0.0361 (9) | 0.0403 (9) | 0.0204 (7) | 0.0059 (7) | 0.0062 (6) | −0.0018 (7) |
C1 | 0.0222 (9) | 0.0275 (10) | 0.0142 (8) | −0.0030 (7) | 0.0018 (7) | 0.0038 (7) |
C2 | 0.0251 (10) | 0.0322 (11) | 0.0226 (10) | −0.0060 (8) | 0.0032 (8) | −0.0028 (8) |
C3 | 0.0315 (12) | 0.0510 (15) | 0.0199 (10) | −0.0089 (11) | −0.0038 (8) | 0.0015 (10) |
C4 | 0.0359 (13) | 0.0602 (18) | 0.0341 (13) | −0.0239 (13) | 0.0062 (11) | −0.0121 (12) |
C11 | 0.0192 (9) | 0.0281 (10) | 0.0129 (8) | −0.0068 (7) | 0.0004 (7) | 0.0020 (7) |
C12 | 0.0263 (10) | 0.0255 (10) | 0.0169 (9) | −0.0041 (8) | 0.0005 (7) | −0.0020 (7) |
C13 | 0.0375 (12) | 0.0279 (10) | 0.0166 (9) | −0.0039 (9) | −0.0007 (8) | 0.0055 (8) |
C14 | 0.0298 (11) | 0.0376 (12) | 0.0119 (8) | −0.0059 (9) | 0.0012 (7) | 0.0032 (8) |
C15 | 0.0205 (9) | 0.0321 (11) | 0.0164 (8) | −0.0039 (8) | −0.0002 (7) | −0.0009 (8) |
C16 | 0.0225 (10) | 0.0282 (10) | 0.0168 (9) | −0.0028 (8) | −0.0006 (7) | 0.0045 (7) |
C17 | 0.0291 (11) | 0.0572 (16) | 0.0189 (10) | 0.0024 (11) | 0.0031 (8) | −0.0072 (10) |
Br1—C12 | 1.902 (2) | C4—H4B | 0.9800 |
N1—C1 | 1.346 (3) | C4—H4C | 0.9800 |
N1—N2 | 1.398 (2) | C11—C16 | 1.390 (3) |
N1—H1 | 0.85 (3) | C11—C12 | 1.393 (3) |
N2—C2 | 1.280 (3) | C12—C13 | 1.391 (3) |
O1—C1 | 1.235 (2) | C13—C14 | 1.394 (3) |
O2—C15 | 1.364 (3) | C13—H13 | 0.9500 |
O2—C17 | 1.436 (3) | C14—C15 | 1.386 (3) |
C1—C11 | 1.512 (3) | C14—H14 | 0.9500 |
C2—C3 | 1.503 (3) | C15—C16 | 1.405 (3) |
C2—C4 | 1.505 (3) | C16—H16 | 0.9500 |
C3—H3A | 0.9800 | C17—H17A | 0.9800 |
C3—H3B | 0.9800 | C17—H17B | 0.9800 |
C3—H3C | 0.9800 | C17—H17C | 0.9800 |
C4—H4A | 0.9800 | ||
C1—N1—N2 | 119.46 (16) | C16—C11—C1 | 118.64 (18) |
C1—N1—H1 | 116.7 (19) | C12—C11—C1 | 122.28 (18) |
N2—N1—H1 | 123.7 (19) | C13—C12—C11 | 120.8 (2) |
C2—N2—N1 | 117.28 (17) | C13—C12—Br1 | 118.92 (17) |
C15—O2—C17 | 117.17 (19) | C11—C12—Br1 | 120.29 (15) |
O1—C1—N1 | 121.77 (18) | C12—C13—C14 | 120.2 (2) |
O1—C1—C11 | 120.00 (18) | C12—C13—H13 | 119.9 |
N1—C1—C11 | 118.21 (17) | C14—C13—H13 | 119.9 |
N2—C2—C3 | 126.8 (2) | C15—C14—C13 | 119.57 (18) |
N2—C2—C4 | 116.3 (2) | C15—C14—H14 | 120.2 |
C3—C2—C4 | 116.8 (2) | C13—C14—H14 | 120.2 |
C2—C3—H3A | 109.5 | O2—C15—C14 | 125.03 (18) |
C2—C3—H3B | 109.5 | O2—C15—C16 | 114.97 (19) |
H3A—C3—H3B | 109.5 | C14—C15—C16 | 120.0 (2) |
C2—C3—H3C | 109.5 | C11—C16—C15 | 120.54 (19) |
H3A—C3—H3C | 109.5 | C11—C16—H16 | 119.7 |
H3B—C3—H3C | 109.5 | C15—C16—H16 | 119.7 |
C2—C4—H4A | 109.5 | O2—C17—H17A | 109.5 |
C2—C4—H4B | 109.5 | O2—C17—H17B | 109.5 |
H4A—C4—H4B | 109.5 | H17A—C17—H17B | 109.5 |
C2—C4—H4C | 109.5 | O2—C17—H17C | 109.5 |
H4A—C4—H4C | 109.5 | H17A—C17—H17C | 109.5 |
H4B—C4—H4C | 109.5 | H17B—C17—H17C | 109.5 |
C16—C11—C12 | 118.91 (17) | ||
C1—N1—N2—C2 | 178.5 (2) | C1—C11—C12—Br1 | 5.2 (3) |
N2—N1—C1—O1 | 179.5 (2) | C11—C12—C13—C14 | −0.2 (3) |
N2—N1—C1—C11 | 1.0 (3) | Br1—C12—C13—C14 | 179.32 (17) |
N1—N2—C2—C3 | −0.2 (4) | C12—C13—C14—C15 | −0.1 (3) |
N1—N2—C2—C4 | 179.1 (2) | C17—O2—C15—C14 | 0.2 (3) |
O1—C1—C11—C16 | −85.5 (3) | C17—O2—C15—C16 | −178.48 (19) |
N1—C1—C11—C16 | 93.0 (2) | C13—C14—C15—O2 | −178.0 (2) |
O1—C1—C11—C12 | 89.7 (3) | C13—C14—C15—C16 | 0.6 (3) |
N1—C1—C11—C12 | −91.8 (3) | C12—C11—C16—C15 | 0.8 (3) |
C16—C11—C12—C13 | −0.2 (3) | C1—C11—C16—C15 | 176.12 (18) |
C1—C11—C12—C13 | −175.3 (2) | O2—C15—C16—C11 | 177.74 (19) |
C16—C11—C12—Br1 | −179.67 (15) | C14—C15—C16—C11 | −1.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (3) | 2.08 (3) | 2.916 (2) | 168 (3) |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H13BrN2O2 |
Mr | 285.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 7.8311 (5), 13.6460 (7), 11.3800 (8) |
β (°) | 92.005 (5) |
V (Å3) | 1215.36 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.37 |
Crystal size (mm) | 0.29 × 0.27 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle- diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.398, 0.438 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27762, 3404, 2995 |
Rint | 0.080 |
(sin θ/λ)max (Å−1) | 0.696 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.086, 1.17 |
No. of reflections | 3404 |
No. of parameters | 153 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.53 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (3) | 2.08 (3) | 2.916 (2) | 168 (3) |
Symmetry code: (i) −x, −y+1, −z+2. |
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Hydrazides and their Schiff bases are useful precursors in the synthesis of several heterocyclic systems. Some substituted hydrazides and their Schiff bases are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity It is also used as an intermediate in many pharmaceutically important compounds. A new Schiff base of the hydrazide, C11H13BrN2O2 was synthesized and its crystal structure is reported.
Geometric parameters of the title compound (Fig. 1) are in the usual ranges. All seven non-H atoms of the acetone hydrazone moiety lie in a common plane (r.m.s. deviation 0.007 Å) which is almost perpendicular [88.52 (6)°] to the aromatic ring. In the crystal, the molecules are connected by N—H···O hydrogen bonds to form centrosymmetric dimers (Fig. 2).