Buy article online - an online subscription or single-article purchase is required to access this article.
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.
Supporting information
CCDC reference: 150351
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.
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.
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).
p-Methoxybenzaldehyde Benzoylhydrazone Monohydrate
top
Crystal data top
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) Å3 | Slab, colourless |
Z = 4 | 0.40 × 0.24 × 0.16 mm |
Data collection top
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 top
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)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0764P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (3) |
Crystal data top
C15H14N2O2·H2O | V = 1445.68 (13) Å3 |
Mr = 272.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.9398 (6) Å | µ = 0.09 mm−1 |
b = 11.8595 (6) Å | T = 293 K |
c = 11.3972 (6) Å | 0.40 × 0.24 × 0.16 mm |
β = 116.389 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 1704 reflections with I > 2σ(I) |
10036 measured reflections | Rint = 0.067 |
3650 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 2 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.23 e Å−3 |
2833 reflections | Δρmin = −0.21 e Å−3 |
190 parameters | |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O1Wi | 0.86 | 1.99 | 2.829 (2) | 165 |
O1W—H2W···O2ii | 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. |
Experimental details
Crystal data |
Chemical formula | C15H14N2O2·H2O |
Mr | 272.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.9398 (6), 11.8595 (6), 11.3972 (6) |
β (°) | 116.389 (1) |
V (Å3) | 1445.68 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.24 × 0.16 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10036, 3650, 1704 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.689 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.120, 0.93 |
No. of reflections | 2833 |
No. of parameters | 190 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Selected geometric parameters (Å, º) topO1—C2 | 1.371 (2) | N1—N2 | 1.392 (2) |
O1—C1 | 1.434 (3) | N2—C9 | 1.346 (3) |
O2—C9 | 1.236 (2) | C5—C8 | 1.459 (3) |
N1—C8 | 1.274 (3) | C10—C15 | 1.368 (3) |
| | | |
C8—N1—N2 | 115.3 (2) | O2—C9—C10 | 121.6 (2) |
C9—N2—N1 | 119.1 (2) | N2—C9—C10 | 115.7 (2) |
O2—C9—N2 | 122.7 (2) | | |
| | | |
C8—N1—N2—C9 | −173.6 (2) | N1—N2—C9—C10 | 178.7 (2) |
N2—N1—C8—C5 | −179.9 (2) | | |
Hydrogen-bond geometry (Å, º) top
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···O1Wi | 0.86 | 1.99 | 2.829 (2) | 165 |
O1W—H2W···O2ii | 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. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
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.