Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060667/is2249sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060667/is2249Isup2.hkl |
CCDC reference: 673084
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.086
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT352_ALERT_3_C Short N-H Bond (0.87A) N2 - H2 ... 0.75 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O2 .. C8 .. 2.99 Ang.
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 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).
An anhydrous ethanol solution (50 ml) of 5-bromo-2-hydroxybenzaldehyde (1.99 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 4-methoxybenzohydrazide (1.66 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N2, whereupon a red precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 94% yield. Red single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.
The N-bound H atom was located in a difference Fourier map and its positional parameters were refined, with Uiso(H) = 1.2Ueq(N). C-bound H atoms were included in calculated positions, with C—H = 0.93 (aromatic) or 0.96 Å (methyl), and refined using a riding model, with Uiso(H) = 1.2Ueq(C) for aromatic H or 1.5Ueq(C) for methyl H atoms.
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2005); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).
C14H11BrN2O3·C2H6O | F(000) = 1552 |
Mr = 381.23 | Dx = 1.589 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2324 reflections |
a = 17.873 (4) Å | θ = 2.3–25.0° |
b = 17.834 (4) Å | µ = 2.60 mm−1 |
c = 12.955 (3) Å | T = 113 K |
β = 129.48 (3)° | Block, red |
V = 3187.2 (19) Å3 | 0.14 × 0.10 × 0.04 mm |
Z = 8 |
Rigaku Saturn diffractometer | 2806 independent reflections |
Radiation source: rotating anode | 2367 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.047 |
ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | h = −21→19 |
Tmin = 0.712, Tmax = 0.903 | k = −21→18 |
9688 measured reflections | l = −14→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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3 |
2806 reflections | (Δ/σ)max = 0.002 |
219 parameters | Δρmax = 0.86 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
C14H11BrN2O3·C2H6O | V = 3187.2 (19) Å3 |
Mr = 381.23 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.873 (4) Å | µ = 2.60 mm−1 |
b = 17.834 (4) Å | T = 113 K |
c = 12.955 (3) Å | 0.14 × 0.10 × 0.04 mm |
β = 129.48 (3)° |
Rigaku Saturn diffractometer | 2806 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 2367 reflections with I > 2σ(I) |
Tmin = 0.712, Tmax = 0.903 | Rint = 0.047 |
9688 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.86 e Å−3 |
2806 reflections | Δρmin = −0.49 e Å−3 |
219 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 | 0.55893 (2) | 0.853491 (14) | 0.65804 (3) | 0.02871 (13) | |
O1 | 0.34688 (14) | 0.55776 (11) | 0.50624 (18) | 0.0256 (5) | |
H1 | 0.383 (2) | 0.5253 (18) | 0.538 (3) | 0.038* | |
O2 | 0.45039 (13) | 0.35423 (9) | 0.59475 (17) | 0.0204 (4) | |
O3 | 0.77352 (14) | 0.10340 (10) | 0.88829 (18) | 0.0239 (4) | |
H3 | 0.827 (2) | 0.1135 (18) | 0.948 (3) | 0.036* | |
N1 | 0.51873 (15) | 0.49290 (11) | 0.64199 (19) | 0.0190 (5) | |
N2 | 0.57836 (16) | 0.43189 (12) | 0.6910 (2) | 0.0185 (5) | |
H2 | 0.632 (2) | 0.4377 (15) | 0.731 (3) | 0.022* | |
C1 | 0.3970 (2) | 0.62352 (15) | 0.5420 (2) | 0.0213 (6) | |
C2 | 0.3441 (2) | 0.69029 (15) | 0.4984 (3) | 0.0245 (6) | |
H2A | 0.2756 | 0.6888 | 0.4450 | 0.029* | |
C3 | 0.3913 (2) | 0.75889 (15) | 0.5328 (3) | 0.0239 (6) | |
H3A | 0.3553 | 0.8043 | 0.5034 | 0.029* | |
C4 | 0.4911 (2) | 0.76069 (14) | 0.6103 (2) | 0.0224 (6) | |
C5 | 0.54505 (19) | 0.69547 (15) | 0.6545 (2) | 0.0205 (6) | |
H5 | 0.6135 | 0.6978 | 0.7077 | 0.025* | |
C6 | 0.4982 (2) | 0.62563 (14) | 0.6204 (2) | 0.0199 (6) | |
C7 | 0.55798 (18) | 0.55823 (15) | 0.6696 (2) | 0.0201 (6) | |
H7 | 0.6263 | 0.5626 | 0.7224 | 0.024* | |
C8 | 0.53862 (19) | 0.36222 (13) | 0.6657 (2) | 0.0171 (6) | |
C9 | 0.60542 (18) | 0.29712 (14) | 0.7271 (2) | 0.0174 (5) | |
C10 | 0.70658 (19) | 0.30213 (14) | 0.8167 (2) | 0.0219 (6) | |
H10 | 0.7365 | 0.3501 | 0.8402 | 0.026* | |
C11 | 0.76376 (19) | 0.23865 (14) | 0.8716 (2) | 0.0213 (6) | |
H11 | 0.8324 | 0.2431 | 0.9323 | 0.026* | |
C12 | 0.72042 (19) | 0.16788 (14) | 0.8377 (2) | 0.0195 (6) | |
C13 | 0.61988 (19) | 0.16194 (14) | 0.7488 (3) | 0.0207 (6) | |
H13 | 0.5901 | 0.1140 | 0.7256 | 0.025* | |
C14 | 0.56334 (18) | 0.22577 (14) | 0.6941 (2) | 0.0183 (5) | |
H14 | 0.4947 | 0.2212 | 0.6331 | 0.022* | |
O4 | 0.27282 (13) | 0.02334 (10) | 0.29428 (17) | 0.0264 (4) | |
H4 | 0.2566 | −0.0001 | 0.2266 | 0.040* | |
C16 | 0.3665 (2) | 0.02035 (17) | 0.5312 (3) | 0.0368 (7) | |
H16A | 0.3933 | 0.0700 | 0.5395 | 0.055* | |
H16B | 0.4141 | −0.0089 | 0.6121 | 0.055* | |
H16C | 0.3071 | 0.0259 | 0.5200 | 0.055* | |
C15 | 0.3436 (2) | −0.01922 (16) | 0.4121 (3) | 0.0353 (8) | |
H15A | 0.4032 | −0.0245 | 0.4224 | 0.042* | |
H15B | 0.3181 | −0.0700 | 0.4045 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0351 (2) | 0.01993 (19) | 0.0299 (2) | −0.00043 (11) | 0.02010 (16) | 0.00053 (10) |
O1 | 0.0235 (11) | 0.0244 (11) | 0.0217 (10) | −0.0003 (8) | 0.0109 (9) | 0.0005 (8) |
O2 | 0.0182 (11) | 0.0245 (10) | 0.0174 (10) | 0.0002 (7) | 0.0107 (9) | 0.0006 (7) |
O3 | 0.0185 (10) | 0.0210 (10) | 0.0198 (10) | 0.0011 (8) | 0.0064 (8) | −0.0010 (8) |
N1 | 0.0241 (12) | 0.0200 (12) | 0.0159 (11) | 0.0024 (9) | 0.0141 (10) | 0.0023 (9) |
N2 | 0.0178 (11) | 0.0177 (12) | 0.0205 (12) | −0.0002 (9) | 0.0125 (10) | 0.0001 (9) |
C1 | 0.0262 (15) | 0.0247 (14) | 0.0163 (14) | −0.0029 (11) | 0.0151 (13) | −0.0010 (10) |
C2 | 0.0226 (15) | 0.0330 (16) | 0.0180 (13) | 0.0029 (11) | 0.0129 (12) | 0.0030 (11) |
C3 | 0.0330 (16) | 0.0218 (14) | 0.0204 (14) | 0.0064 (11) | 0.0186 (13) | 0.0050 (11) |
C4 | 0.0312 (16) | 0.0198 (14) | 0.0195 (14) | −0.0012 (11) | 0.0177 (13) | −0.0007 (10) |
C5 | 0.0213 (14) | 0.0268 (15) | 0.0146 (13) | 0.0001 (10) | 0.0119 (12) | −0.0007 (10) |
C6 | 0.0281 (16) | 0.0238 (14) | 0.0130 (13) | 0.0013 (11) | 0.0155 (12) | 0.0006 (10) |
C7 | 0.0211 (14) | 0.0253 (15) | 0.0149 (13) | 0.0006 (10) | 0.0118 (12) | 0.0004 (10) |
C8 | 0.0187 (15) | 0.0240 (15) | 0.0105 (13) | −0.0005 (10) | 0.0101 (12) | −0.0006 (10) |
C9 | 0.0181 (14) | 0.0230 (14) | 0.0116 (12) | 0.0009 (10) | 0.0096 (11) | 0.0010 (10) |
C10 | 0.0250 (15) | 0.0188 (13) | 0.0198 (13) | −0.0029 (10) | 0.0133 (12) | −0.0016 (10) |
C11 | 0.0153 (13) | 0.0249 (14) | 0.0178 (13) | −0.0012 (10) | 0.0078 (11) | −0.0019 (10) |
C12 | 0.0204 (14) | 0.0224 (14) | 0.0166 (13) | 0.0025 (10) | 0.0122 (12) | 0.0011 (10) |
C13 | 0.0228 (15) | 0.0189 (13) | 0.0203 (14) | −0.0031 (10) | 0.0135 (13) | −0.0025 (10) |
C14 | 0.0173 (14) | 0.0233 (14) | 0.0142 (12) | −0.0016 (10) | 0.0100 (11) | −0.0006 (10) |
O4 | 0.0260 (11) | 0.0288 (10) | 0.0183 (10) | 0.0027 (8) | 0.0112 (9) | −0.0029 (8) |
C16 | 0.0380 (18) | 0.0439 (18) | 0.0231 (15) | 0.0096 (14) | 0.0169 (14) | 0.0026 (13) |
C15 | 0.0336 (18) | 0.0304 (16) | 0.0251 (16) | 0.0104 (13) | 0.0108 (14) | −0.0008 (12) |
Br1—C4 | 1.907 (3) | C7—H7 | 0.9500 |
O1—C1 | 1.366 (3) | C8—C9 | 1.483 (3) |
O1—H1 | 0.77 (3) | C9—C10 | 1.398 (4) |
O2—C8 | 1.228 (3) | C9—C14 | 1.400 (3) |
O3—C12 | 1.364 (3) | C10—C11 | 1.381 (3) |
O3—H3 | 0.78 (3) | C10—H10 | 0.9500 |
N1—C7 | 1.288 (3) | C11—C12 | 1.398 (4) |
N1—N2 | 1.365 (3) | C11—H11 | 0.9500 |
N2—C8 | 1.364 (3) | C12—C13 | 1.391 (4) |
N2—H2 | 0.76 (3) | C13—C14 | 1.381 (4) |
C1—C2 | 1.397 (4) | C13—H13 | 0.9500 |
C1—C6 | 1.402 (4) | C14—H14 | 0.9500 |
C2—C3 | 1.389 (4) | O4—C15 | 1.432 (3) |
C2—H2A | 0.9500 | O4—H4 | 0.8400 |
C3—C4 | 1.383 (4) | C16—C15 | 1.497 (4) |
C3—H3A | 0.9500 | C16—H16A | 0.9800 |
C4—C5 | 1.381 (4) | C16—H16B | 0.9800 |
C5—C6 | 1.406 (4) | C16—H16C | 0.9800 |
C5—H5 | 0.9500 | C15—H15A | 0.9900 |
C6—C7 | 1.459 (4) | C15—H15B | 0.9900 |
C1—O1—H1 | 108 (3) | C10—C9—C8 | 124.8 (2) |
C12—O3—H3 | 109 (2) | C14—C9—C8 | 117.1 (2) |
C7—N1—N2 | 117.8 (2) | C11—C10—C9 | 121.2 (2) |
C8—N2—N1 | 118.8 (2) | C11—C10—H10 | 119.4 |
C8—N2—H2 | 122 (2) | C9—C10—H10 | 119.4 |
N1—N2—H2 | 119 (2) | C10—C11—C12 | 119.8 (2) |
O1—C1—C2 | 117.7 (2) | C10—C11—H11 | 120.1 |
O1—C1—C6 | 122.3 (2) | C12—C11—H11 | 120.1 |
C2—C1—C6 | 120.0 (2) | O3—C12—C13 | 118.1 (2) |
C3—C2—C1 | 120.3 (3) | O3—C12—C11 | 122.2 (2) |
C3—C2—H2A | 119.9 | C13—C12—C11 | 119.7 (2) |
C1—C2—H2A | 119.9 | C14—C13—C12 | 120.0 (2) |
C4—C3—C2 | 119.5 (2) | C14—C13—H13 | 120.0 |
C4—C3—H3A | 120.2 | C12—C13—H13 | 120.0 |
C2—C3—H3A | 120.2 | C13—C14—C9 | 121.1 (2) |
C5—C4—C3 | 121.3 (2) | C13—C14—H14 | 119.4 |
C5—C4—Br1 | 117.7 (2) | C9—C14—H14 | 119.4 |
C3—C4—Br1 | 121.04 (19) | C15—O4—H4 | 109.5 |
C4—C5—C6 | 119.7 (2) | C15—C16—H16A | 109.5 |
C4—C5—H5 | 120.1 | C15—C16—H16B | 109.5 |
C6—C5—H5 | 120.1 | H16A—C16—H16B | 109.5 |
C1—C6—C5 | 119.2 (2) | C15—C16—H16C | 109.5 |
C1—C6—C7 | 122.9 (2) | H16A—C16—H16C | 109.5 |
C5—C6—C7 | 117.9 (2) | H16B—C16—H16C | 109.5 |
N1—C7—C6 | 120.4 (2) | O4—C15—C16 | 109.0 (2) |
N1—C7—H7 | 119.8 | O4—C15—H15A | 109.9 |
C6—C7—H7 | 119.8 | C16—C15—H15A | 109.9 |
O2—C8—N2 | 120.7 (2) | O4—C15—H15B | 109.9 |
O2—C8—C9 | 121.6 (2) | C16—C15—H15B | 109.9 |
N2—C8—C9 | 117.8 (2) | H15A—C15—H15B | 108.3 |
C10—C9—C14 | 118.1 (2) | ||
C7—N1—N2—C8 | 178.4 (2) | N1—N2—C8—O2 | 3.5 (4) |
O1—C1—C2—C3 | 179.3 (2) | N1—N2—C8—C9 | −176.2 (2) |
C6—C1—C2—C3 | −0.2 (4) | O2—C8—C9—C10 | −175.0 (2) |
C1—C2—C3—C4 | 0.2 (4) | N2—C8—C9—C10 | 4.7 (4) |
C2—C3—C4—C5 | −0.1 (4) | O2—C8—C9—C14 | 3.9 (4) |
C2—C3—C4—Br1 | 179.13 (19) | N2—C8—C9—C14 | −176.4 (2) |
C3—C4—C5—C6 | 0.0 (4) | C14—C9—C10—C11 | −0.2 (4) |
Br1—C4—C5—C6 | −179.20 (18) | C8—C9—C10—C11 | 178.7 (2) |
O1—C1—C6—C5 | −179.4 (2) | C9—C10—C11—C12 | 0.0 (4) |
C2—C1—C6—C5 | 0.2 (4) | C10—C11—C12—O3 | 179.5 (2) |
O1—C1—C6—C7 | 0.3 (4) | C10—C11—C12—C13 | 0.0 (4) |
C2—C1—C6—C7 | 179.8 (2) | O3—C12—C13—C14 | −179.3 (2) |
C4—C5—C6—C1 | −0.1 (3) | C11—C12—C13—C14 | 0.1 (4) |
C4—C5—C6—C7 | −179.8 (2) | C12—C13—C14—C9 | −0.3 (4) |
N2—N1—C7—C6 | −179.9 (2) | C10—C9—C14—C13 | 0.3 (4) |
C1—C6—C7—N1 | −0.1 (4) | C8—C9—C14—C13 | −178.6 (2) |
C5—C6—C7—N1 | 179.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.84 | 2.55 | 3.085 (3) | 123 |
O4—H4···O3ii | 0.84 | 2.21 | 2.983 (3) | 153 |
N2—H2···O4iii | 0.76 (3) | 2.20 (3) | 2.932 (3) | 163 (3) |
O3—H3···O2iii | 0.78 (3) | 1.86 (3) | 2.639 (3) | 174 (3) |
O1—H1···N1 | 0.77 (3) | 1.96 (3) | 2.645 (3) | 148 (3) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y, −z+1; (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11BrN2O3·C2H6O |
Mr | 381.23 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 113 |
a, b, c (Å) | 17.873 (4), 17.834 (4), 12.955 (3) |
β (°) | 129.48 (3) |
V (Å3) | 3187.2 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.60 |
Crystal size (mm) | 0.14 × 0.10 × 0.04 |
Data collection | |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.712, 0.903 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9688, 2806, 2367 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.00 |
No. of reflections | 2806 |
No. of parameters | 219 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.86, −0.49 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalStructure (Rigaku/MSC, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.84 | 2.55 | 3.085 (3) | 122.9 |
O4—H4···O3ii | 0.84 | 2.21 | 2.983 (3) | 153.3 |
N2—H2···O4iii | 0.76 (3) | 2.20 (3) | 2.932 (3) | 163 (3) |
O3—H3···O2iii | 0.78 (3) | 1.86 (3) | 2.639 (3) | 174 (3) |
O1—H1···N1 | 0.77 (3) | 1.96 (3) | 2.645 (3) | 148 (3) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y, −z+1; (iii) x+1/2, −y+1/2, z+1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of the active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and crystal structure of the title compound, (I).
In the molecular structure of the compound, (I), the geometric parameters are normal (Fig. 1). The dihedral angle between two benzene planes is 6.10 (2)°. An intramolecular O—H···N hydrogen bond (Table 1) stabilizes the molecular structure. The Schiff base and ethanol molecules are linked via weak intermolecular O—H···O and N—H···O hydrogen bonds (Table 1), forming a three-dimensional framework, as illustrated in Fig. 2.