p-Methoxy­benz­aldehyde benzoyl­hydrazone monohydrate

The crystal structure of the title compound, C₁₅H₁₄N₂O₂·H₂O, is in the keto tautomeric form and the configuration at the azomethine C=N double bond is E. The mol­ecule is non-planar, with a dihedral angle of 27.3 (1)° between the aromatic rings. The crystal structure is stabilized by extensive hydrogen bonding involving the water mol­ecule and hydrazone moiety.

S1. Comment

Aroylhydrazone compounds are being studied extensively because of the strong coordinating hydrazone group to form polynuclear complexes. As a continuation of our work on the synthesis and characterization of aroylhydrazone compounds (Fun et al., 1999, 1996, 1997; Lu et al., 1999; Shanmuga Sundara Raj et al., 1999a), we report the crystal structure of the title compound, (I). \sch

The molecule is non-planar with a dihedral angle of 27.3 (1)° between the aromatic rings. The N1—N2 and C9—O2 bond distances, which are consistent with those in the related compounds, p-methoxybenzaldehyde isonicotinoylhydrazone monohydrate (Shanmuga Sundara Raj et al., 1999a) and its dihydrate derivative (Fun et al., 1996), indicate that these bonds correspond to single and double bonds. Thus the molecule is in a keto tautomeric form. Also, the configuration at the azomethine N1—C8 double bond is E. The C1—O1 and O1—C2 bond lengths in the hydroxyphenyl moiety is consistent with those [1.432 (2) and 1.370 (1) Å, and 1.436 (2) and 1.367 (2) Å, respectively] in the above related compounds. The keto group is in the plane of the central hydrazone bridge.

The asymmetry of the exocyclic angles at C5 is small: C4—C5—C8 = 122.3 (2), C6—C5—C8 = 120.0 (2)°, while that at C2 is larger: C3—C2—O1 = 114.7 (2), C7—C2—O1 = 125.0 (2)° and similar to that found usually in anisoles being caused by the tendency the methoxy group has to be coplanar with the phenyl ring. Conjugation of oxygen with phenyl, which is responsible for this coplanarity (Domiano et al., 1979), also causes some shortening of the C2—O1 bond. Some asymmetry is observed also for the exocyclic angles at C10: C9—C10—C11 = 118.2 (2) and C9—C10—C15 = 122.0 (2)° probably caused by the contacts: H11···O2 = 2.72 and H15···N2 = 2.74 Å. The torsion angles, C4—C5—C8—N1 = 11.7 (4) and N2—C9—C10—C15 = −44.7 (3)°, respectively, indicates that the methoxyphenyl and phenyl substituents are in syn-periplanar and syn-clinal orientations with respect to the central hydrazone plane. The methoxyphenyl ring makes a dihedral angle of 16.4 (1)° with the hydrazone bridge and the phenyl ring is twisted by an angle of 43.1 (1)° with the plane of the central hydrazone linkage.

The water and hydrazone group are involved in N—H···O and O—H···O hydrogen bonds to form a two-dimensional network. The H1W atom is involved in a three-center hydrogen bond.

S2. Experimental

The synthesis of the compound was carried out by reaction of p-methoxybenzaldehyde and benzoylhydrazine in ethanol solution under reflux for 3 h. Single crystals were obtained by recrystallization from ethanol.

S3. Refinement

Collection of intensity data was as described by Shanmuga Sundara Raj et al. (1999).

The H atoms of the water molecule were refined isotropically while all the others were geometrically fixed and allowed to ride on the parent atoms to which they are attached.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

p-Methoxybenzaldehyde Benzoylhydrazone Monohydrate

Crystal data

C15H14N2O2·H2O	F(000) = 576
Mr = 272.30	Dx = 1.251 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9398 (6) Å	Cell parameters from 3248 reflections
b = 11.8595 (6) Å	θ = 1.9–29.4°
c = 11.3972 (6) Å	µ = 0.09 mm^−1
β = 116.389 (1)°	T = 293 K
V = 1445.68 (13) Å^3	Slab, colourless
Z = 4	0.40 × 0.24 × 0.16 mm

Data collection

Siemens SMART CCD area detector diffractometer	1704 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
Graphite monochromator	θmax = 29.3°, θmin = 1.9°
Detector resolution: 8.33 pixels mm^-1	h = −16→14
ω scans	k = −12→16
10036 measured reflections	l = −14→15
3650 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0764P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
2833 reflections	Δρmax = 0.23 e Å^−3
190 parameters	Δρmin = −0.21 e Å^−3
2 restraints	Extinction correction: SHELXTL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (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
O1	1.14877 (15)	0.41833 (15)	0.62626 (15)	0.0673 (5)
O2	0.48621 (14)	0.11530 (13)	0.60664 (14)	0.0546 (5)
N1	0.68145 (16)	0.25838 (15)	0.71384 (16)	0.0444 (5)
N2	0.59483 (15)	0.24386 (15)	0.76335 (16)	0.0440 (5)
H2	0.6013	0.2817	0.8305	0.053*
C1	1.2651 (2)	0.4674 (3)	0.7165 (3)	0.0843 (9)
H1A	1.3180	0.4775	0.6739	0.127*
H1B	1.3056	0.4184	0.7906	0.127*
H1C	1.2497	0.5392	0.7455	0.127*
C2	1.0620 (2)	0.39819 (19)	0.6718 (2)	0.0489 (6)
C3	0.9541 (2)	0.3440 (2)	0.5833 (2)	0.0590 (7)
H3	0.9448	0.3258	0.5001	0.071*
C4	0.8610 (2)	0.3174 (2)	0.6188 (2)	0.0541 (6)
H4	0.7895	0.2804	0.5594	0.065*
C5	0.87257 (19)	0.34513 (18)	0.74243 (19)	0.0425 (5)
C6	0.9807 (2)	0.39945 (19)	0.8279 (2)	0.0524 (6)
H6	0.9899	0.4189	0.9107	0.063*
C7	1.0761 (2)	0.4260 (2)	0.7946 (2)	0.0544 (6)
H7	1.1482	0.4619	0.8542	0.065*
C8	0.77408 (19)	0.32161 (18)	0.7817 (2)	0.0454 (5)
H8	0.7791	0.3536	0.8584	0.054*
C9	0.50076 (19)	0.16983 (18)	0.7048 (2)	0.0418 (5)
C10	0.4136 (2)	0.15748 (17)	0.7660 (2)	0.0436 (5)
C11	0.2865 (2)	0.1510 (2)	0.6843 (2)	0.0574 (6)
H11	0.2570	0.1557	0.5940	0.069*
C12	0.2038 (3)	0.1375 (2)	0.7380 (3)	0.0721 (8)
H12	0.1183	0.1351	0.6836	0.087*
C13	0.2470 (3)	0.1277 (2)	0.8707 (3)	0.0786 (9)
H13	0.1909	0.1180	0.9061	0.094*
C14	0.3720 (3)	0.1324 (2)	0.9509 (3)	0.0830 (9)
H14	0.4012	0.1248	1.0410	0.100*
C15	0.4561 (2)	0.1483 (2)	0.8985 (2)	0.0637 (7)
H15	0.5414	0.1527	0.9537	0.076*
O1W	0.62976 (17)	0.09820 (14)	0.46274 (16)	0.0563 (5)
H1W	0.608 (3)	0.120 (2)	0.525 (2)	0.093 (10)*
H2W	0.590 (3)	0.034 (2)	0.430 (3)	0.151 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0623 (10)	0.0798 (12)	0.0741 (12)	−0.0249 (9)	0.0431 (9)	−0.0175 (10)
O2	0.0630 (10)	0.0546 (9)	0.0576 (10)	−0.0128 (8)	0.0370 (8)	−0.0159 (8)
N1	0.0451 (10)	0.0466 (11)	0.0492 (11)	−0.0019 (9)	0.0279 (9)	−0.0016 (9)
N2	0.0463 (10)	0.0489 (11)	0.0450 (10)	−0.0055 (9)	0.0277 (8)	−0.0062 (9)
C1	0.0660 (17)	0.094 (2)	0.112 (2)	−0.0388 (16)	0.0571 (17)	−0.0394 (18)
C2	0.0467 (13)	0.0501 (13)	0.0559 (14)	−0.0083 (11)	0.0281 (11)	−0.0050 (11)
C3	0.0578 (14)	0.0761 (17)	0.0492 (14)	−0.0159 (13)	0.0294 (12)	−0.0146 (12)
C4	0.0459 (13)	0.0664 (16)	0.0482 (14)	−0.0133 (12)	0.0194 (11)	−0.0121 (12)
C5	0.0404 (12)	0.0444 (12)	0.0439 (12)	−0.0027 (10)	0.0199 (10)	−0.0020 (10)
C6	0.0545 (14)	0.0602 (15)	0.0441 (13)	−0.0065 (12)	0.0235 (11)	−0.0088 (11)
C7	0.0456 (13)	0.0617 (15)	0.0539 (14)	−0.0126 (11)	0.0204 (11)	−0.0118 (12)
C8	0.0484 (13)	0.0469 (12)	0.0445 (12)	−0.0032 (11)	0.0240 (10)	−0.0030 (10)
C9	0.0448 (12)	0.0410 (12)	0.0433 (12)	0.0019 (10)	0.0229 (10)	0.0001 (10)
C10	0.0499 (13)	0.0395 (12)	0.0475 (13)	−0.0045 (10)	0.0273 (11)	−0.0048 (10)
C11	0.0534 (14)	0.0599 (15)	0.0622 (15)	−0.0020 (12)	0.0287 (12)	0.0006 (12)
C12	0.0546 (15)	0.0656 (18)	0.106 (2)	−0.0037 (13)	0.0442 (16)	−0.0031 (16)
C13	0.091 (2)	0.0673 (18)	0.115 (3)	−0.0282 (16)	0.080 (2)	−0.0243 (17)
C14	0.112 (2)	0.094 (2)	0.0644 (17)	−0.0472 (19)	0.0585 (18)	−0.0202 (16)
C15	0.0684 (16)	0.0753 (17)	0.0534 (15)	−0.0253 (14)	0.0323 (13)	−0.0064 (13)
O1W	0.0772 (12)	0.0511 (10)	0.0555 (10)	−0.0067 (9)	0.0430 (9)	−0.0023 (8)

Geometric parameters (Å, º)

O1—C2	1.371 (2)	C6—C7	1.387 (3)
O1—C1	1.434 (3)	C6—H6	0.9300
O2—C9	1.236 (2)	C7—H7	0.9300
N1—C8	1.274 (3)	C8—H8	0.9300
N1—N2	1.392 (2)	C9—C10	1.495 (3)
N2—C9	1.346 (3)	C10—C15	1.368 (3)
N2—H2	0.8600	C10—C11	1.386 (3)
C1—H1A	0.9600	C11—C12	1.383 (3)
C1—H1B	0.9600	C11—H11	0.9300
C1—H1C	0.9600	C12—C13	1.369 (4)
C2—C7	1.373 (3)	C12—H12	0.9300
C2—C3	1.391 (3)	C13—C14	1.361 (4)
C3—C4	1.378 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.391 (3)
C4—C5	1.393 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.383 (3)	O1W—H1W	0.895 (17)
C5—C8	1.459 (3)	O1W—H2W	0.890 (19)
C2—O1—C1	117.0 (2)	C2—C7—H7	120.6
C8—N1—N2	115.3 (2)	C6—C7—H7	120.6
C9—N2—N1	119.1 (2)	N1—C8—C5	121.75 (19)
C9—N2—H2	120.4	N1—C8—H8	119.1
N1—N2—H2	120.4	C5—C8—H8	119.1
O1—C1—H1A	109.5	O2—C9—N2	122.7 (2)
O1—C1—H1B	109.5	O2—C9—C10	121.6 (2)
H1A—C1—H1B	109.5	N2—C9—C10	115.7 (2)
O1—C1—H1C	109.5	C15—C10—C11	119.7 (2)
H1A—C1—H1C	109.5	C15—C10—C9	122.0 (2)
H1B—C1—H1C	109.5	C11—C10—C9	118.30 (19)
O1—C2—C7	125.0 (2)	C12—C11—C10	119.6 (2)
O1—C2—C3	114.72 (19)	C12—C11—H11	120.2
C7—C2—C3	120.3 (2)	C10—C11—H11	120.2
C4—C3—C2	120.1 (2)	C13—C12—C11	120.4 (3)
C4—C3—H3	120.0	C13—C12—H12	119.8
C2—C3—H3	120.0	C11—C12—H12	119.8
C3—C4—C5	120.8 (2)	C14—C13—C12	120.0 (2)
C3—C4—H4	119.6	C14—C13—H13	120.0
C5—C4—H4	119.6	C12—C13—H13	120.0
C6—C5—C4	117.64 (19)	C13—C14—C15	120.2 (3)
C6—C5—C8	120.03 (19)	C13—C14—H14	119.9
C4—C5—C8	122.31 (19)	C15—C14—H14	119.9
C5—C6—C7	122.4 (2)	C10—C15—C14	120.0 (2)
C5—C6—H6	118.8	C10—C15—H15	120.0
C7—C6—H6	118.8	C14—C15—H15	120.0
C2—C7—C6	118.7 (2)	H1W—O1W—H2W	107 (3)
C8—N1—N2—C9	−173.6 (2)	C4—C5—C8—N1	11.7 (3)
C1—O1—C2—C7	3.0 (3)	N1—N2—C9—O2	−1.5 (3)
C1—O1—C2—C3	−176.1 (2)	N1—N2—C9—C10	178.7 (2)
O1—C2—C3—C4	178.8 (2)	O2—C9—C10—C15	135.4 (2)
C7—C2—C3—C4	−0.4 (4)	N2—C9—C10—C15	−44.7 (3)
C2—C3—C4—C5	0.7 (4)	O2—C9—C10—C11	−42.1 (3)
C3—C4—C5—C6	−0.4 (3)	N2—C9—C10—C11	137.8 (2)
C3—C4—C5—C8	177.9 (2)	C15—C10—C11—C12	1.3 (3)
C4—C5—C6—C7	−0.3 (3)	C9—C10—C11—C12	178.8 (2)
C8—C5—C6—C7	−178.6 (2)	C10—C11—C12—C13	−1.6 (4)
O1—C2—C7—C6	−179.4 (2)	C11—C12—C13—C14	0.6 (4)
C3—C2—C7—C6	−0.3 (4)	C12—C13—C14—C15	0.7 (4)
C5—C6—C7—C2	0.6 (4)	C11—C10—C15—C14	0.1 (4)
N2—N1—C8—C5	−179.9 (2)	C9—C10—C15—C14	−177.4 (2)
C6—C5—C8—N1	−170.0 (2)	C13—C14—C15—C10	−1.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N1	0.90 (3)	2.53 (2)	3.257 (2)	138 (3)
O1W—H1W···O2	0.90 (3)	2.05 (4)	2.858 (3)	150 (3)
N2—H2···O1W^i	0.86	1.99	2.829 (2)	165
O1W—H2W···O2^ii	0.89 (3)	1.95 (3)	2.825 (2)	169 (3)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1.