Acta Cryst. (2008). E64, o1584 [ doi:10.1107/S1600536808022708 ]
The title compound, C14H11BrN2O5·2H2O, crystallizes as hydrogen-bonded sheets. The 2-hydroxy group on the benzylidene group forms an intramolecular hydrogen bond to the N atom of the C=N double bond. The amino N atom is a hydrogen-bond donor to a water molecule. The hydroxy group on the benzohydrazide group is a hydrogen-bond donor to one acceptor site, whereas each water molecule is a hydrogen-bond donor to two acceptor sites.
3,4,5-Trihydroxybenzoylhydrazide (0.65 g, 3.5 mmol) and 5-bromo-2-hydroxybenzaldehyde (0.70 g, 3.5 mmol) were heated for 12 h in ethanol. The solvent was removed and the product recrystallized from ethanol.
Carbon and nitrogen-bound H-atoms were placed in calculated positions (C—H 0.95 Å; N–H 0.88 Å) and were included in the refinement in the riding model approximation, with Uiso(H) 1.2 Ueq(C). The hydroxy and water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01 Å and H···H 1.37±0.01 Å.
The final difference Fourier map had a peak of 1.37eÅ-3 at 0.69Å from Br1 and a hole of -1.81eÅ-3 at 1.33Å from C2.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
![[Figure 1]](./bt2751fig1thm.gif)
| Fig. 1. View (Barbour, 2001) of N-(5-bromo-2-hydroxybenzylidene)-3,4,5-trihydroxybenzohydrazide with displacement ellipsoids at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. |
| C14H11BrN2O5·2H2O | F000 = 816 |
| Mr = 403.19 | Dx = 1.779 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2758 reflections |
| a = 30.8424 (8) Å | θ = 3.2–27.4º |
| b = 3.7999 (1) Å | µ = 2.77 mm−1 |
| c = 12.8484 (4) Å | T = 100 (2) K |
| β = 90.280 (2)º | Needle, colorless |
| V = 1505.79 (7) Å3 | 0.30 × 0.03 × 0.03 mm |
| Z = 4 |
| Bruker SMART APEX diffractometer | 3424 independent reflections |
| Radiation source: fine-focus sealed tube | 2914 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.039 |
| T = 100(2) K | θmax = 27.5º |
| ω scans | θmin = 1.3º |
| Absorption correction: Multi-scan (SADABS; Sheldrick, 1996) | h = −38→40 |
| Tmin = 0.658, Tmax = 0.921 | k = −4→4 |
| 9964 measured reflections | l = −15→16 |
| 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)] = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.0499P)2 + 10.2476P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.22 | (Δ/σ)max = 0.001 |
| 3424 reflections | Δρmax = 1.08 e Å−3 |
| 241 parameters | Δρmin = −1.82 e Å−3 |
| 10 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| C14H11BrN2O5·2H2O | V = 1505.79 (7) Å3 |
| Mr = 403.19 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 30.8424 (8) Å | µ = 2.77 mm−1 |
| b = 3.7999 (1) Å | T = 100 (2) K |
| c = 12.8484 (4) Å | 0.30 × 0.03 × 0.03 mm |
| β = 90.280 (2)º |
| Bruker SMART APEX diffractometer | 3424 independent reflections |
| Absorption correction: Multi-scan (SADABS; Sheldrick, 1996) | 2914 reflections with I > 2σ(I) |
| Tmin = 0.658, Tmax = 0.921 | Rint = 0.039 |
| 9964 measured reflections |
| R[F2 > 2σ(F2)] = 0.064 | 10 restraints |
| wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.22 | w = 1/[σ2(Fo2) + (0.0499P)2 + 10.2476P] where P = (Fo2 + 2Fc2)/3 |
| 3424 reflections | Δρmax = 1.08 e Å−3 |
| 241 parameters | Δρmin = −1.82 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.467910 (16) | 0.31017 (16) | 0.89799 (4) | 0.01787 (17) | |
| O1 | 0.32358 (12) | 0.6446 (12) | 0.5944 (3) | 0.0201 (9) | |
| H1O | 0.3020 (15) | 0.745 (18) | 0.621 (5) | 0.030* | |
| O2 | 0.20078 (11) | 0.9755 (11) | 0.6545 (3) | 0.0182 (8) | |
| O3 | 0.05472 (13) | 1.3768 (13) | 0.7962 (4) | 0.0295 (11) | |
| H3O | 0.0335 (16) | 1.36 (2) | 0.836 (5) | 0.044* | |
| O4 | 0.05208 (14) | 1.1036 (15) | 0.9894 (4) | 0.0353 (12) | |
| H4O | 0.048 (3) | 0.933 (15) | 1.030 (6) | 0.053* | |
| O5 | 0.12324 (12) | 0.7692 (12) | 1.0737 (3) | 0.0182 (9) | |
| H5O | 0.1471 (12) | 0.682 (18) | 1.092 (5) | 0.027* | |
| O1W | 0.25912 (12) | 1.3152 (13) | 0.9988 (3) | 0.0209 (9) | |
| H1W1 | 0.2444 (17) | 1.382 (18) | 1.050 (3) | 0.031* | |
| H1W2 | 0.2806 (14) | 1.199 (17) | 1.020 (4) | 0.031* | |
| O2W | −0.02887 (15) | 1.3435 (17) | 0.8657 (5) | 0.0506 (16) | |
| H2W1 | −0.042 (3) | 1.30 (2) | 0.810 (4) | 0.076* | |
| H2W2 | −0.038 (3) | 1.534 (14) | 0.890 (7) | 0.076* | |
| N1 | 0.27850 (13) | 0.8683 (12) | 0.7531 (3) | 0.0139 (9) | |
| N2 | 0.24174 (13) | 0.9859 (13) | 0.8027 (3) | 0.0138 (9) | |
| H2N | 0.2431 | 1.0511 | 0.8684 | 0.017* | |
| C1 | 0.35563 (16) | 0.5778 (15) | 0.6648 (4) | 0.0144 (10) | |
| C2 | 0.39381 (16) | 0.4251 (16) | 0.6295 (4) | 0.0173 (11) | |
| H2 | 0.3970 | 0.3730 | 0.5576 | 0.021* | |
| C3 | 0.42746 (17) | 0.3479 (16) | 0.6985 (4) | 0.0193 (12) | |
| H3 | 0.4535 | 0.2431 | 0.6743 | 0.023* | |
| C4 | 0.42245 (16) | 0.4256 (16) | 0.8025 (4) | 0.0160 (11) | |
| C5 | 0.38470 (16) | 0.5781 (15) | 0.8398 (4) | 0.0143 (10) | |
| H5 | 0.3820 | 0.6294 | 0.9118 | 0.017* | |
| C6 | 0.35065 (15) | 0.6562 (15) | 0.7712 (4) | 0.0126 (10) | |
| C7 | 0.31105 (16) | 0.7988 (15) | 0.8138 (4) | 0.0130 (10) | |
| H7 | 0.3089 | 0.8415 | 0.8865 | 0.016* | |
| C8 | 0.20343 (16) | 1.0010 (13) | 0.7503 (4) | 0.0108 (10) | |
| C9 | 0.16507 (16) | 1.0460 (15) | 0.8180 (4) | 0.0130 (10) | |
| C10 | 0.12793 (16) | 1.2046 (16) | 0.7771 (4) | 0.0163 (11) | |
| H10 | 0.1281 | 1.2984 | 0.7086 | 0.020* | |
| C11 | 0.09101 (17) | 1.2242 (15) | 0.8368 (4) | 0.0176 (12) | |
| C12 | 0.09010 (17) | 1.0775 (17) | 0.9364 (4) | 0.0204 (12) | |
| C13 | 0.12713 (17) | 0.9146 (15) | 0.9777 (4) | 0.0152 (11) | |
| C14 | 0.16479 (17) | 0.9040 (15) | 0.9188 (4) | 0.0149 (11) | |
| H14 | 0.1903 | 0.8006 | 0.9468 | 0.018* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0094 (2) | 0.0195 (3) | 0.0247 (3) | −0.0001 (2) | −0.00302 (17) | −0.0020 (3) |
| O1 | 0.0160 (18) | 0.032 (3) | 0.0125 (17) | 0.0031 (18) | −0.0028 (14) | −0.0016 (17) |
| O2 | 0.0127 (17) | 0.027 (2) | 0.0148 (18) | −0.0039 (16) | −0.0015 (14) | 0.0021 (17) |
| O3 | 0.0142 (19) | 0.041 (3) | 0.034 (2) | 0.0120 (19) | −0.0051 (17) | −0.005 (2) |
| O4 | 0.016 (2) | 0.060 (4) | 0.030 (2) | 0.009 (2) | 0.0035 (18) | −0.013 (2) |
| O5 | 0.0129 (17) | 0.031 (2) | 0.0110 (17) | −0.0007 (17) | 0.0027 (14) | −0.0045 (16) |
| O1W | 0.0162 (18) | 0.035 (2) | 0.0113 (17) | 0.0027 (18) | 0.0015 (14) | −0.0044 (18) |
| O2W | 0.016 (2) | 0.049 (4) | 0.087 (5) | 0.010 (2) | 0.010 (2) | 0.013 (3) |
| N1 | 0.0107 (19) | 0.014 (3) | 0.017 (2) | −0.0016 (17) | 0.0010 (16) | −0.0008 (18) |
| N2 | 0.0096 (19) | 0.019 (3) | 0.013 (2) | −0.0004 (18) | −0.0007 (15) | −0.0028 (18) |
| C1 | 0.014 (2) | 0.016 (3) | 0.014 (2) | −0.002 (2) | −0.0013 (19) | −0.002 (2) |
| C2 | 0.013 (2) | 0.025 (3) | 0.014 (2) | −0.001 (2) | 0.0024 (19) | 0.000 (2) |
| C3 | 0.013 (2) | 0.020 (3) | 0.025 (3) | 0.001 (2) | 0.006 (2) | −0.003 (2) |
| C4 | 0.012 (2) | 0.014 (3) | 0.021 (3) | −0.001 (2) | −0.003 (2) | 0.003 (2) |
| C5 | 0.015 (2) | 0.013 (3) | 0.015 (2) | −0.001 (2) | 0.0005 (19) | −0.002 (2) |
| C6 | 0.010 (2) | 0.015 (3) | 0.013 (2) | −0.003 (2) | 0.0008 (18) | 0.001 (2) |
| C7 | 0.013 (2) | 0.015 (3) | 0.012 (2) | −0.006 (2) | 0.0022 (18) | −0.003 (2) |
| C8 | 0.013 (2) | 0.004 (3) | 0.015 (2) | −0.0007 (18) | −0.0019 (18) | 0.0009 (19) |
| C9 | 0.011 (2) | 0.013 (3) | 0.015 (2) | 0.000 (2) | −0.0027 (19) | −0.003 (2) |
| C10 | 0.013 (2) | 0.016 (3) | 0.020 (3) | 0.001 (2) | −0.0034 (19) | 0.000 (2) |
| C11 | 0.017 (2) | 0.013 (3) | 0.022 (3) | 0.008 (2) | −0.007 (2) | −0.007 (2) |
| C12 | 0.012 (2) | 0.027 (3) | 0.022 (3) | 0.002 (2) | 0.001 (2) | −0.012 (2) |
| C13 | 0.016 (2) | 0.017 (3) | 0.013 (2) | 0.001 (2) | 0.0025 (19) | −0.008 (2) |
| C14 | 0.013 (2) | 0.016 (3) | 0.015 (2) | 0.001 (2) | −0.0022 (19) | −0.006 (2) |
| Br1—C4 | 1.909 (5) | C1—C6 | 1.408 (7) |
| O1—C1 | 1.361 (6) | C2—C3 | 1.393 (8) |
| O1—H1O | 0.840 (10) | C2—H2 | 0.9500 |
| O2—C8 | 1.236 (6) | C3—C4 | 1.378 (8) |
| O3—C11 | 1.362 (6) | C3—H3 | 0.9500 |
| O3—H3O | 0.838 (10) | C4—C5 | 1.388 (7) |
| O4—C12 | 1.362 (7) | C5—C6 | 1.400 (7) |
| O4—H4O | 0.840 (10) | C5—H5 | 0.9500 |
| O5—C13 | 1.357 (7) | C6—C7 | 1.446 (7) |
| O5—H5O | 0.841 (10) | C7—H7 | 0.9500 |
| O1W—H1W1 | 0.839 (10) | C8—C9 | 1.482 (7) |
| O1W—H1W2 | 0.838 (10) | C9—C10 | 1.395 (7) |
| O2W—H2W1 | 0.838 (10) | C9—C14 | 1.403 (7) |
| O2W—H2W2 | 0.839 (10) | C10—C11 | 1.378 (7) |
| N1—C7 | 1.296 (7) | C10—H10 | 0.9500 |
| N1—N2 | 1.378 (6) | C11—C12 | 1.396 (8) |
| N2—C8 | 1.359 (6) | C12—C13 | 1.401 (8) |
| N2—H2N | 0.8800 | C13—C14 | 1.390 (7) |
| C1—C2 | 1.391 (7) | C14—H14 | 0.9500 |
| C1—O1—H1O | 113 (5) | C5—C6—C7 | 118.3 (4) |
| C11—O3—H3O | 111 (6) | C1—C6—C7 | 122.9 (5) |
| C12—O4—H4O | 112 (6) | N1—C7—C6 | 120.1 (4) |
| C13—O5—H5O | 110 (5) | N1—C7—H7 | 120.0 |
| H1W1—O1W—H1W2 | 109.6 (18) | C6—C7—H7 | 120.0 |
| H2W1—O2W—H2W2 | 109.5 (18) | O2—C8—N2 | 122.9 (4) |
| C7—N1—N2 | 115.1 (4) | O2—C8—C9 | 123.0 (4) |
| C8—N2—N1 | 120.0 (4) | N2—C8—C9 | 114.1 (4) |
| C8—N2—H2N | 120.0 | C10—C9—C14 | 120.3 (5) |
| N1—N2—H2N | 120.0 | C10—C9—C8 | 119.0 (5) |
| O1—C1—C2 | 118.3 (5) | C14—C9—C8 | 120.4 (5) |
| O1—C1—C6 | 121.6 (5) | C11—C10—C9 | 119.5 (5) |
| C2—C1—C6 | 120.1 (5) | C11—C10—H10 | 120.2 |
| C1—C2—C3 | 120.6 (5) | C9—C10—H10 | 120.2 |
| C1—C2—H2 | 119.7 | O3—C11—C10 | 119.3 (5) |
| C3—C2—H2 | 119.7 | O3—C11—C12 | 120.1 (5) |
| C4—C3—C2 | 119.1 (5) | C10—C11—C12 | 120.6 (5) |
| C4—C3—H3 | 120.5 | O4—C12—C11 | 116.7 (5) |
| C2—C3—H3 | 120.5 | O4—C12—C13 | 123.0 (5) |
| C3—C4—C5 | 121.5 (5) | C11—C12—C13 | 120.3 (5) |
| C3—C4—Br1 | 119.2 (4) | O5—C13—C14 | 124.1 (5) |
| C5—C4—Br1 | 119.3 (4) | O5—C13—C12 | 116.7 (5) |
| C4—C5—C6 | 120.0 (5) | C14—C13—C12 | 119.2 (5) |
| C4—C5—H5 | 120.0 | C13—C14—C9 | 120.0 (5) |
| C6—C5—H5 | 120.0 | C13—C14—H14 | 120.0 |
| C5—C6—C1 | 118.7 (5) | C9—C14—H14 | 120.0 |
| C7—N1—N2—C8 | −167.2 (5) | N2—C8—C9—C10 | 154.0 (5) |
| O1—C1—C2—C3 | −179.3 (5) | O2—C8—C9—C14 | 147.8 (5) |
| C6—C1—C2—C3 | 0.1 (9) | N2—C8—C9—C14 | −31.4 (7) |
| C1—C2—C3—C4 | −0.1 (9) | C14—C9—C10—C11 | 0.6 (9) |
| C2—C3—C4—C5 | 0.1 (9) | C8—C9—C10—C11 | 175.2 (5) |
| C2—C3—C4—Br1 | 178.5 (4) | C9—C10—C11—O3 | −179.5 (5) |
| C3—C4—C5—C6 | 0.0 (9) | C9—C10—C11—C12 | −2.0 (9) |
| Br1—C4—C5—C6 | −178.4 (4) | O3—C11—C12—O4 | −1.4 (8) |
| C4—C5—C6—C1 | −0.1 (8) | C10—C11—C12—O4 | −178.9 (6) |
| C4—C5—C6—C7 | 177.0 (5) | O3—C11—C12—C13 | 178.9 (5) |
| O1—C1—C6—C5 | 179.4 (5) | C10—C11—C12—C13 | 1.4 (9) |
| C2—C1—C6—C5 | 0.1 (8) | O4—C12—C13—O5 | 2.2 (9) |
| O1—C1—C6—C7 | 2.5 (9) | C11—C12—C13—O5 | −178.1 (5) |
| C2—C1—C6—C7 | −176.9 (5) | O4—C12—C13—C14 | −179.1 (6) |
| N2—N1—C7—C6 | 176.8 (5) | C11—C12—C13—C14 | 0.6 (9) |
| C5—C6—C7—N1 | −178.7 (5) | O5—C13—C14—C9 | 176.7 (5) |
| C1—C6—C7—N1 | −1.8 (8) | C12—C13—C14—C9 | −1.9 (8) |
| N1—N2—C8—O2 | −13.6 (8) | C10—C9—C14—C13 | 1.3 (8) |
| N1—N2—C8—C9 | 165.7 (5) | C8—C9—C14—C13 | −173.2 (5) |
| O2—C8—C9—C10 | −26.7 (8) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1o···N1 | 0.84 (1) | 1.91 (5) | 2.616 (6) | 141 (7) |
| O3—H3o···O2w | 0.84 (1) | 1.96 (4) | 2.736 (6) | 153 (7) |
| O4—H4o···O2wi | 0.84 (1) | 1.81 (3) | 2.623 (8) | 163 (9) |
| O5—H5o···O2ii | 0.84 (1) | 1.93 (2) | 2.764 (5) | 171 (7) |
| O1w—H1w1···O2iii | 0.84 (1) | 1.98 (2) | 2.812 (5) | 170 (6) |
| O1w—H1w2···O1ii | 0.84 (1) | 2.09 (2) | 2.914 (6) | 167 (6) |
| O2w—H2w1···O3iv | 0.84 (1) | 2.13 (5) | 2.845 (9) | 142 (8) |
| O2w—H2w2···O4v | 0.84 (1) | 2.12 (4) | 2.900 (8) | 154 (8) |
| Symmetry codes: (i) −x, −y+2, −z+2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+5/2, z+1/2; (iv) −x, y−1/2, −z+3/2; (v) −x, −y+3, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1o···N1 | 0.84 (1) | 1.91 (5) | 2.616 (6) | 141 (7) |
| O3—H3o···O2w | 0.84 (1) | 1.96 (4) | 2.736 (6) | 153 (7) |
| O4—H4o···O2wi | 0.84 (1) | 1.81 (3) | 2.623 (8) | 163 (9) |
| O5—H5o···O2ii | 0.84 (1) | 1.93 (2) | 2.764 (5) | 171 (7) |
| O1w—H1w1···O2iii | 0.84 (1) | 1.98 (2) | 2.812 (5) | 170 (6) |
| O1w—H1w2···O1ii | 0.84 (1) | 2.09 (2) | 2.914 (6) | 167 (6) |
| O2w—H2w1···O3iv | 0.84 (1) | 2.13 (5) | 2.845 (9) | 142 (8) |
| O2w—H2w2···O4v | 0.84 (1) | 2.12 (4) | 2.900 (8) | 154 (8) |
| Symmetry codes: (i) −x, −y+2, −z+2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+5/2, z+1/2; (iv) −x, y−1/2, −z+3/2; (v) −x, −y+3, −z+2. |
We thank the Science Fund (12–02-03–2031, 12–02-03–2051) and the University of Malaya (PJP) for supporting this study. We are grateful to the University of Malaya for the purchase of the diffractometer.
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Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Liu, H.-Y., Wang, H.-Y., Gao, F., Lu, Z.-S. & Niu, D.-Z. (2006). Acta Cryst. E62, o4495–o4496.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2008). publCIF. In preparation.
This study extends the structural study on the Schiff base, 5-bromosalicylaldehyde benzoylhydrazone (Liu et al., 2006) as the title compound (Scheme I, Fig. 1) has several hydroxy groups on one of the aromatic rings. The compound crystallizes with two lattice water molecules. Hydrogen bonding interactions (Table 1) give rise to a layer motif.