Crystal structure of (E)-4-hy­droxy-N′-(3-hy­droxy­benzyl­idene)benzohydrazide monohydrate

In the title benzohydrazide hydrate, C₁₄H₁₂N₂O₃·H₂O, the dihedral angle between the aromatic rings is 58.11 (6)° and the C=O and N—H groups adopt an anti orientation. The main twist in the mol­ecule occurs about the C(=O)—C_ar (ar = aromatic) bond, with an N—C(=O)—C_ar—C_ar torsion angle of −43.5 (2)°. In the crystal, the components are linked by N—H...O, O—H...N and O—H...O hydrogen bonds. These inter­actions generate [10-1] chains, with adjacent organic mol­ecules linked by inversion symmetry generating either pairs of N—H...O links [R₂²(16) loops] or pairs of O—H...O links [R₂²(20) loops]. Pairs of water mol­ecules are located in the R₂²(20) loops and form their own O—H...O and O—H...N hydrogen bonds to adjacent organic mol­ecules in the chain. Finally, an inter­chain O—H...O hydrogen-bond link from the 4-hy­droxy group generates (010) sheets.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.044
• wR factor = 0.105
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

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PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.076 Check

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PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          2 Units
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          3 Why ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note

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S1. Synthesis and crystallization

Equimolar qu­anti­ties of 4-hy­droxy­benzohydrazide and 3-hy­droxy­benzaldehyde were refluxed in ethanol for several hours and then cooled to room temperature. Colourless chips of the title compound were obtained by slow evaporation of the solvent at room temperature after several days.

S2. Refinement

O- and N-bound H atoms were located in difference Fourier maps and their positions were freely refined. C-bound H atoms were placed in idealized positions (C—H = 0.93 Å) and refined as riding atoms. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases.

Related literature

For a related structure, see: Fun et al. (2011). A survey of the Cambridge Structural Database (Version 5.35 of November 2013; Allen, 2002) revealed no fewer than 581 distinct benzohydrazide fragments with different substituents on the aromatic rings and/or other chemical species in the crystal: all bond lengths for the central fragment of the title compound lie close to the mean values for these structures. The only parameter in the metrical survey that shows significant variation is the dihedral angle between the aromatic rings, with the most common value close to zero, and a roughly linear decrease to 90°.

Computing details

Data collection: CrystalClear (Rigaku, 2010); cell refinement: CrystalClear (Rigaku, 2010); data reduction: CrystalClear (Rigaku, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A fragment of a [101] chain in the structure of the title compound, with hydrogen bonds shown as double-dashed lines, showing the R2^2(16) loops and R2^2(20) loops between adjacent organic molecules (see Table 2 for details of the hydrogen bonding and the symmetry codes).
	Fig. 3. A histogram of dihedral angles between the aromatic rings of benzohydrazide structures in the Cambridge Structural Database (Version 5.35; Allen, 2002).

(E)-4-Hydroxy-N'-(3-hydroxybenzylidene)benzohydrazide monohydrate

Crystal data

C14H12N2O3·H2O	Z = 2
Mr = 274.27	F(000) = 288
Triclinic, P1	Dx = 1.407 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1826 (5) Å	Cell parameters from 6867 reflections
b = 9.2043 (6) Å	θ = 3.1–27.5°
c = 10.7568 (7) Å	µ = 0.11 mm^−1
α = 91.847 (7)°	T = 100 K
β = 102.433 (7)°	Chip, colourless
γ = 110.191 (8)°	0.09 × 0.05 × 0.02 mm
V = 647.37 (7) Å^3

Data collection

Rigaku Saturn CCD diffractometer	2038 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −9→9
8728 measured reflections	k = −11→11
2962 independent reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.144P] where P = (Fo^2 + 2Fc^2)/3
2962 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2487 (2)	0.51249 (18)	0.02953 (16)	0.0151 (4)
H1	0.2596	0.6145	0.0499	0.018*
C2	0.2488 (2)	0.46303 (18)	−0.09366 (16)	0.0149 (4)
H2	0.2560	0.5306	−0.1564	0.018*
C3	0.2379 (2)	0.31187 (19)	−0.12226 (15)	0.0140 (4)
C4	0.2225 (2)	0.20863 (19)	−0.02998 (16)	0.0150 (4)
H4	0.2163	0.1077	−0.0499	0.018*
C5	0.2167 (2)	0.25738 (18)	0.09144 (16)	0.0145 (4)
H5	0.2022	0.1879	0.1527	0.017*
C6	0.2325 (2)	0.41045 (18)	0.12303 (15)	0.0133 (4)
C7	0.2265 (3)	0.45636 (18)	0.25514 (16)	0.0140 (4)
C8	0.5163 (3)	0.77584 (19)	0.48276 (16)	0.0164 (4)
H8	0.6243	0.8109	0.4432	0.020*
C9	0.5316 (3)	0.85792 (18)	0.60520 (16)	0.0145 (4)
C10	0.3753 (3)	0.80721 (18)	0.66983 (16)	0.0148 (4)
H10	0.2637	0.7159	0.6379	0.018*
C11	0.3865 (3)	0.89243 (18)	0.78093 (16)	0.0154 (4)
C12	0.5575 (3)	1.02744 (18)	0.83137 (16)	0.0158 (4)
H12	0.5659	1.0846	0.9066	0.019*
C13	0.7134 (3)	1.07503 (18)	0.76867 (16)	0.0162 (4)
H13	0.8278	1.1638	0.8029	0.019*
C14	0.7017 (3)	0.99231 (18)	0.65541 (16)	0.0167 (4)
H14	0.8066	1.0262	0.6132	0.020*
N1	0.3623 (2)	0.59830 (16)	0.30909 (13)	0.0156 (3)
H1N	0.469 (3)	0.647 (2)	0.2723 (17)	0.019*
N2	0.3584 (2)	0.65697 (15)	0.42830 (13)	0.0153 (3)
O1	0.24457 (19)	0.25851 (13)	−0.24143 (11)	0.0173 (3)
H1O	0.195 (3)	0.309 (2)	−0.3059 (19)	0.021*
O2	0.10482 (18)	0.37043 (13)	0.31151 (11)	0.0177 (3)
O3	0.23698 (19)	0.84893 (14)	0.84718 (12)	0.0198 (3)
H3O	0.125 (3)	0.776 (2)	0.7930 (18)	0.024*
O4	−0.0770 (2)	0.61780 (16)	0.42664 (13)	0.0236 (3)
H1W	0.047 (3)	0.624 (2)	0.4329 (19)	0.028*
H2W	−0.101 (3)	0.615 (2)	0.505 (2)	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0145 (8)	0.0140 (8)	0.0159 (9)	0.0042 (7)	0.0031 (7)	0.0012 (7)
C2	0.0147 (9)	0.0163 (8)	0.0138 (9)	0.0055 (7)	0.0035 (7)	0.0049 (7)
C3	0.0122 (8)	0.0206 (8)	0.0095 (8)	0.0067 (7)	0.0024 (6)	0.0007 (7)
C4	0.0157 (9)	0.0157 (8)	0.0140 (9)	0.0073 (7)	0.0021 (7)	0.0004 (7)
C5	0.0147 (8)	0.0154 (8)	0.0127 (9)	0.0047 (7)	0.0028 (7)	0.0046 (7)
C6	0.0117 (8)	0.0173 (8)	0.0111 (8)	0.0056 (7)	0.0021 (6)	0.0014 (6)
C7	0.0149 (8)	0.0163 (8)	0.0129 (9)	0.0081 (7)	0.0029 (7)	0.0024 (7)
C8	0.0164 (9)	0.0175 (8)	0.0164 (9)	0.0062 (7)	0.0057 (7)	0.0025 (7)
C9	0.0171 (9)	0.0139 (8)	0.0116 (9)	0.0058 (7)	0.0017 (7)	0.0015 (6)
C10	0.0164 (9)	0.0138 (8)	0.0124 (9)	0.0040 (7)	0.0019 (7)	0.0011 (7)
C11	0.0166 (9)	0.0168 (8)	0.0150 (9)	0.0076 (7)	0.0050 (7)	0.0048 (7)
C12	0.0194 (9)	0.0151 (8)	0.0120 (9)	0.0067 (7)	0.0014 (7)	−0.0009 (7)
C13	0.0159 (9)	0.0133 (8)	0.0167 (9)	0.0042 (7)	0.0001 (7)	0.0017 (7)
C14	0.0155 (9)	0.0174 (8)	0.0176 (9)	0.0062 (7)	0.0041 (7)	0.0055 (7)
N1	0.0175 (8)	0.0176 (7)	0.0117 (7)	0.0043 (6)	0.0071 (6)	0.0008 (6)
N2	0.0207 (8)	0.0176 (7)	0.0091 (7)	0.0081 (6)	0.0051 (6)	−0.0002 (6)
O1	0.0219 (7)	0.0225 (6)	0.0098 (6)	0.0104 (5)	0.0044 (5)	0.0018 (5)
O2	0.0195 (7)	0.0190 (6)	0.0136 (6)	0.0039 (5)	0.0068 (5)	0.0010 (5)
O3	0.0181 (7)	0.0203 (6)	0.0164 (7)	0.0001 (5)	0.0070 (5)	−0.0041 (5)
O4	0.0222 (7)	0.0391 (8)	0.0145 (7)	0.0154 (6)	0.0069 (6)	0.0081 (6)

Geometric parameters (Å, º)

C1—C2	1.387 (2)	C9—C14	1.394 (2)
C1—C6	1.394 (2)	C9—C10	1.399 (2)
C1—H1	0.9300	C10—C11	1.380 (2)
C2—C3	1.387 (2)	C10—H10	0.9300
C2—H2	0.9300	C11—O3	1.3685 (19)
C3—O1	1.3743 (19)	C11—C12	1.401 (2)
C3—C4	1.391 (2)	C12—C13	1.381 (2)
C4—C5	1.381 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.387 (2)
C5—C6	1.398 (2)	C13—H13	0.9300
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.483 (2)	N1—N2	1.3847 (18)
C7—O2	1.2404 (19)	N1—H1N	0.922 (18)
C7—N1	1.350 (2)	O1—H1O	0.92 (2)
C8—N2	1.281 (2)	O3—H3O	0.92 (2)
C8—C9	1.461 (2)	O4—H1W	0.86 (2)
C8—H8	0.9300	O4—H2W	0.89 (2)
C2—C1—C6	120.52 (15)	C14—C9—C8	119.08 (15)
C2—C1—H1	119.7	C10—C9—C8	121.08 (14)
C6—C1—H1	119.7	C11—C10—C9	120.12 (15)
C3—C2—C1	119.34 (15)	C11—C10—H10	119.9
C3—C2—H2	120.3	C9—C10—H10	119.9
C1—C2—H2	120.3	O3—C11—C10	122.49 (15)
O1—C3—C2	121.75 (15)	O3—C11—C12	117.45 (15)
O1—C3—C4	117.34 (15)	C10—C11—C12	120.05 (15)
C2—C3—C4	120.90 (15)	C13—C12—C11	119.56 (15)
C5—C4—C3	119.41 (15)	C13—C12—H12	120.2
C5—C4—H4	120.3	C11—C12—H12	120.2
C3—C4—H4	120.3	C12—C13—C14	120.89 (15)
C4—C5—C6	120.53 (15)	C12—C13—H13	119.6
C4—C5—H5	119.7	C14—C13—H13	119.6
C6—C5—H5	119.7	C13—C14—C9	119.56 (15)
C1—C6—C5	119.25 (15)	C13—C14—H14	120.2
C1—C6—C7	122.63 (15)	C9—C14—H14	120.2
C5—C6—C7	118.11 (15)	C7—N1—N2	119.60 (14)
O2—C7—N1	122.60 (15)	C7—N1—H1N	119.1 (11)
O2—C7—C6	122.25 (14)	N2—N1—H1N	120.5 (11)
N1—C7—C6	115.15 (14)	C8—N2—N1	114.82 (14)
N2—C8—C9	121.91 (15)	C3—O1—H1O	112.8 (11)
N2—C8—H8	119.0	C11—O3—H3O	106.5 (11)
C9—C8—H8	119.0	H1W—O4—H2W	108.6 (18)
C14—C9—C10	119.79 (15)
C6—C1—C2—C3	−1.7 (2)	N2—C8—C9—C10	1.6 (3)
C1—C2—C3—O1	−177.71 (15)	C14—C9—C10—C11	1.9 (3)
C1—C2—C3—C4	1.4 (2)	C8—C9—C10—C11	−175.61 (16)
O1—C3—C4—C5	179.58 (14)	C9—C10—C11—O3	179.33 (16)
C2—C3—C4—C5	0.4 (2)	C9—C10—C11—C12	−1.9 (3)
C3—C4—C5—C6	−2.0 (2)	O3—C11—C12—C13	179.29 (16)
C2—C1—C6—C5	0.2 (2)	C10—C11—C12—C13	0.5 (3)
C2—C1—C6—C7	−178.43 (15)	C11—C12—C13—C14	1.0 (3)
C4—C5—C6—C1	1.7 (2)	C12—C13—C14—C9	−1.0 (3)
C4—C5—C6—C7	−179.64 (15)	C10—C9—C14—C13	−0.4 (3)
C1—C6—C7—O2	136.31 (18)	C8—C9—C14—C13	177.13 (15)
C5—C6—C7—O2	−42.3 (2)	O2—C7—N1—N2	−4.7 (3)
C1—C6—C7—N1	−43.5 (2)	C6—C7—N1—N2	175.08 (14)
C5—C6—C7—N1	137.90 (16)	C9—C8—N2—N1	176.21 (15)
N2—C8—C9—C14	−175.95 (16)	C7—N1—N2—C8	166.42 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.922 (18)	2.044 (19)	2.9357 (19)	162.2 (16)
O1—H1O···O4^ii	0.92 (2)	1.68 (2)	2.6025 (18)	172.6 (17)
O3—H3O···O2^iii	0.92 (2)	1.83 (2)	2.7512 (17)	178.1 (17)
O4—H1W···N2	0.86 (2)	2.16 (2)	3.018 (2)	172.5 (19)
O4—H2W···O2^iii	0.89 (2)	1.98 (2)	2.8676 (17)	170.5 (18)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) −x, −y+1, −z+1.