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Acta Cryst. (2007). E63, o2899    [ doi:10.1107/S1600536807022635 ]

Pyridine-2,6-dicarbaldehyde bis(benzylidenehydrazone) monohydrate

C.-X. Cheng, H.-W. Liu, F.-H. Luo, M.-N. Cao and Z.-Q. Hu

Abstract top

The crystal structure of the title compound, C21H17N5O2·H2O, is stabilized by intermolecular hydrogen bonds.

Comment top

Tridentate ligands containing the 2,6-dipicolinoyhydrazone moiety have been intensively studied due to their interesting coordination mode (Chen et al., 1997; Thompson et al.,2002; Zhao et al., 2004).

The molecules are linked into a three dimensional framework by a combination of N–H···O C—H···O and O—H···O hydrogen bonds.

Related literature top

For related literature, see: Chen et al. (1997); Thompson (2002); Zhao et al. (2004).

Experimental top

To a solution of benzaldehyde (1.166 g, 11 mmol) in absolute ethanol (40 ml) a suspension of 2,6-dipicolinoyhydrazine in the same solvent (50 ml) was added at 353 K. The mixture was left to react at reflux for 8 h. Then, the white product was filtered, washed with hot ethanol (20 ml) three times and dried in vacuo. Crystals suitable for X-ray diffraction were obtained from dimethylformamide–methanol (3:1 v/v) over a period of about three weeks.

Refinement top

All H atoms were located in difference maps. H atoms bonded to C were then treated as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The coordinates of the remaining H atoms were refined, but Uiso(H) was set to 1.2Ueq(N,O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART-Plus (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines.
Pyridine-2,6-dicarbaldehyde bis(benzylidenehydrazone) monohydrate top
Crystal data top
C21H17N5O2·H2ODx = 1.297 Mg m−3
Mr = 389.41Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 1982 reflections
a = 10.3490 (8) Åθ = 2.5–21.4°
b = 16.2487 (12) ŵ = 0.09 mm−1
c = 11.8556 (9) ÅT = 298 K
V = 1993.6 (3) Å3Block, colourless
Z = 40.20 × 0.10 × 0.10 mm
F(000) = 816
Data collection top
Bruker SMART CCD area-detector
diffractometer		1653 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.077
graphiteθmax = 27.0°, θmin = 2.1°
φ and ω scansh = −9→13
11761 measured reflectionsk = −20→20
2278 independent reflectionsl = −12→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0503P)2]
where P = (Fo2 + 2Fc2)/3
2278 reflections(Δ/σ)max < 0.001
274 parametersΔρmax = 0.14 e Å−3
1 restraintΔρmin = −0.16 e Å−3
Crystal data top
C21H17N5O2·H2OV = 1993.6 (3) Å3
Mr = 389.41Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 10.3490 (8) ŵ = 0.09 mm−1
b = 16.2487 (12) ÅT = 298 K
c = 11.8556 (9) Å0.20 × 0.10 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1653 reflections with I > 2σ(I)
11761 measured reflectionsRint = 0.077
2278 independent reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108Δρmax = 0.14 e Å−3
S = 0.98Δρmin = −0.16 e Å−3
2278 reflectionsAbsolute structure: ?
274 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
C10.1229 (3)0.68779 (19)0.7135 (3)0.0417 (7)
C20.0307 (3)0.6861 (2)0.7975 (3)0.0560 (9)
H2−0.04760.71330.78850.067*
C30.0570 (4)0.6437 (2)0.8943 (3)0.0674 (10)
H3−0.00350.64160.95220.081*
C40.1735 (3)0.6041 (2)0.9053 (3)0.0575 (9)
H40.19340.57480.97040.069*
C50.2607 (3)0.60884 (18)0.8169 (3)0.0426 (7)
C60.0924 (3)0.73123 (18)0.6064 (3)0.0456 (7)
C70.2320 (4)0.7503 (2)0.3423 (3)0.0591 (10)
H70.30230.71570.35410.071*
C80.2124 (3)0.7865 (2)0.2314 (3)0.0538 (8)
C90.2824 (4)0.7571 (2)0.1402 (3)0.0693 (11)
H90.34390.71610.15120.083*
C100.2617 (4)0.7881 (3)0.0331 (3)0.0757 (12)
H100.30820.7673−0.02770.091*
C110.1732 (4)0.8494 (3)0.0162 (4)0.0751 (12)
H110.15980.8704−0.05580.090*
C120.1055 (4)0.8790 (2)0.1043 (3)0.0689 (11)
H120.04550.92080.09230.083*
C130.1232 (3)0.8489 (2)0.2117 (3)0.0597 (9)
H130.07530.87030.27120.072*
C140.3879 (3)0.56512 (19)0.8299 (3)0.0463 (8)
C150.6689 (3)0.5587 (2)0.6706 (3)0.0515 (8)
H150.64090.59090.61060.062*
C160.8009 (3)0.5264 (2)0.6703 (3)0.0546 (9)
C170.8874 (3)0.5537 (2)0.5896 (3)0.0621 (9)
H170.86170.59240.53650.075*
C181.0127 (4)0.5230 (3)0.5881 (4)0.0775 (13)
H181.07080.54130.53370.093*
C191.0508 (4)0.4663 (3)0.6659 (5)0.0834 (14)
H191.13490.44610.66490.100*
C200.9653 (4)0.4391 (3)0.7455 (5)0.0863 (13)
H200.99150.40020.79820.104*
C210.8410 (3)0.4687 (2)0.7486 (4)0.0705 (11)
H210.78370.44980.80320.085*
N10.2374 (2)0.64974 (15)0.7219 (2)0.0418 (6)
N20.1809 (3)0.72613 (19)0.5239 (3)0.0575 (8)
N30.1550 (2)0.76508 (16)0.4236 (2)0.0553 (7)
N40.4704 (3)0.57779 (18)0.7442 (2)0.0497 (7)
N50.5920 (2)0.54337 (16)0.7514 (2)0.0514 (7)
O1−0.0089 (2)0.76993 (14)0.5958 (2)0.0605 (6)
O20.4109 (2)0.52270 (15)0.9118 (2)0.0654 (7)
O30.3994 (3)0.60103 (18)0.4627 (3)0.0724 (8)
H4A0.454 (4)0.605 (2)0.683 (4)0.087*
H2A0.244 (4)0.693 (3)0.535 (4)0.087*
H3B0.431 (4)0.551 (3)0.445 (4)0.109*
H3A0.458 (4)0.637 (3)0.470 (5)0.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0390 (16)0.0443 (16)0.0419 (18)0.0012 (13)0.0026 (13)0.0021 (13)
C20.051 (2)0.063 (2)0.054 (2)0.0104 (16)0.0116 (17)0.0085 (18)
C30.061 (2)0.088 (3)0.053 (2)0.0149 (19)0.0240 (18)0.017 (2)
C40.064 (2)0.064 (2)0.044 (2)0.0074 (17)0.0107 (16)0.0135 (17)
C50.0456 (18)0.0419 (16)0.0403 (18)−0.0040 (13)0.0027 (14)0.0041 (14)
C60.0435 (17)0.0439 (17)0.0495 (19)0.0039 (14)0.0022 (15)0.0026 (15)
C70.055 (2)0.065 (2)0.057 (2)0.0169 (17)0.0111 (17)0.0182 (19)
C80.0539 (19)0.057 (2)0.051 (2)0.0010 (16)0.0118 (16)0.0071 (17)
C90.075 (3)0.066 (2)0.067 (3)−0.002 (2)0.023 (2)0.000 (2)
C100.092 (3)0.085 (3)0.049 (2)−0.026 (3)0.026 (2)−0.014 (2)
C110.085 (3)0.094 (3)0.046 (2)−0.025 (3)−0.004 (2)0.012 (2)
C120.067 (2)0.085 (3)0.055 (2)0.0016 (19)−0.004 (2)0.018 (2)
C130.059 (2)0.072 (2)0.048 (2)0.0052 (18)0.0053 (17)0.0113 (18)
C140.0490 (19)0.0480 (18)0.0418 (18)−0.0008 (14)−0.0016 (14)0.0046 (15)
C150.0486 (19)0.0551 (19)0.051 (2)0.0092 (15)−0.0054 (16)−0.0033 (17)
C160.0448 (18)0.055 (2)0.064 (2)0.0056 (15)−0.0024 (17)−0.0187 (18)
C170.053 (2)0.064 (2)0.069 (3)−0.0008 (17)0.0032 (18)−0.016 (2)
C180.056 (2)0.084 (3)0.093 (3)−0.011 (2)0.020 (2)−0.034 (3)
C190.052 (2)0.087 (3)0.112 (4)0.017 (2)−0.012 (3)−0.033 (3)
C200.062 (2)0.094 (3)0.102 (4)0.024 (2)−0.010 (3)−0.003 (3)
C210.055 (2)0.082 (3)0.074 (3)0.0168 (19)0.003 (2)−0.001 (2)
N10.0399 (13)0.0447 (13)0.0409 (15)−0.0007 (11)0.0034 (11)0.0062 (12)
N20.0509 (17)0.072 (2)0.0499 (17)0.0186 (14)0.0112 (14)0.0248 (15)
N30.0534 (16)0.0626 (17)0.0498 (18)0.0096 (13)0.0082 (14)0.0172 (15)
N40.0430 (14)0.0621 (17)0.0441 (16)0.0105 (12)−0.0008 (12)0.0084 (13)
N50.0440 (15)0.0594 (16)0.0508 (17)0.0110 (12)−0.0021 (13)0.0029 (14)
O10.0526 (13)0.0707 (15)0.0581 (15)0.0241 (11)0.0065 (12)0.0106 (13)
O20.0650 (15)0.0791 (16)0.0521 (15)0.0141 (12)0.0000 (11)0.0228 (14)
O30.0643 (17)0.0628 (16)0.090 (2)0.0070 (13)0.0042 (14)−0.0171 (15)
Geometric parameters (Å, °) top
C1—N11.340 (4)C12—H120.9300
C1—C21.380 (4)C13—H130.9300
C1—C61.486 (4)C14—O21.214 (4)
C2—C31.366 (5)C14—N41.343 (4)
C2—H20.9300C15—N51.271 (4)
C3—C41.373 (5)C15—C161.463 (4)
C3—H30.9300C15—H150.9300
C4—C51.385 (4)C16—C171.383 (5)
C4—H40.9300C16—C211.383 (5)
C5—N11.330 (4)C17—C181.389 (5)
C5—C141.504 (4)C17—H170.9300
C6—O11.229 (3)C18—C191.363 (7)
C6—N21.343 (4)C18—H180.9300
C7—N31.274 (4)C19—C201.367 (7)
C7—C81.454 (5)C19—H190.9300
C7—H70.9300C20—C211.373 (5)
C8—C91.387 (5)C20—H200.9300
C8—C131.391 (5)C21—H210.9300
C9—C101.383 (6)N2—N31.374 (4)
C9—H90.9300N2—H2A0.86 (4)
C10—C111.367 (6)N4—N51.380 (3)
C10—H100.9300N4—H4A0.87 (4)
C11—C121.347 (6)O3—H3B0.90 (4)
C11—H110.9300O3—H3A0.85 (5)
C12—C131.376 (5)
N1—C1—C2123.2 (3)C12—C13—H13119.9
N1—C1—C6118.1 (2)C8—C13—H13119.9
C2—C1—C6118.6 (3)O2—C14—N4124.6 (3)
C3—C2—C1118.6 (3)O2—C14—C5121.5 (3)
C3—C2—H2120.7N4—C14—C5114.0 (3)
C1—C2—H2120.7N5—C15—C16121.1 (3)
C2—C3—C4119.4 (3)N5—C15—H15119.4
C2—C3—H3120.3C16—C15—H15119.4
C4—C3—H3120.3C17—C16—C21119.2 (3)
C3—C4—C5118.3 (3)C17—C16—C15119.4 (3)
C3—C4—H4120.9C21—C16—C15121.4 (3)
C5—C4—H4120.9C16—C17—C18119.9 (4)
N1—C5—C4123.4 (3)C16—C17—H17120.0
N1—C5—C14118.8 (3)C18—C17—H17120.0
C4—C5—C14117.8 (3)C19—C18—C17120.2 (4)
O1—C6—N2122.6 (3)C19—C18—H18119.9
O1—C6—C1120.8 (3)C17—C18—H18119.9
N2—C6—C1116.6 (3)C18—C19—C20119.9 (4)
N3—C7—C8121.4 (3)C18—C19—H19120.0
N3—C7—H7119.3C20—C19—H19120.0
C8—C7—H7119.3C19—C20—C21120.8 (5)
C9—C8—C13117.8 (3)C19—C20—H20119.6
C9—C8—C7119.5 (3)C21—C20—H20119.6
C13—C8—C7122.6 (3)C20—C21—C16120.0 (4)
C10—C9—C8120.6 (4)C20—C21—H21120.0
C10—C9—H9119.7C16—C21—H21120.0
C8—C9—H9119.7C5—N1—C1117.0 (2)
C11—C10—C9120.3 (4)C6—N2—N3118.0 (3)
C11—C10—H10119.9C6—N2—H2A117 (3)
C9—C10—H10119.9N3—N2—H2A125 (3)
C12—C11—C10119.7 (4)C7—N3—N2116.5 (3)
C12—C11—H11120.2C14—N4—N5118.1 (3)
C10—C11—H11120.2C14—N4—H4A126 (3)
C11—C12—C13121.4 (4)N5—N4—H4A116 (3)
C11—C12—H12119.3C15—N5—N4116.5 (3)
C13—C12—H12119.3H3B—O3—H3A113 (4)
C12—C13—C8120.2 (3)
N1—C1—C2—C30.0 (5)C4—C5—C14—N4−175.4 (3)
C6—C1—C2—C3177.6 (3)N5—C15—C16—C17−170.8 (3)
C1—C2—C3—C40.0 (6)N5—C15—C16—C219.7 (5)
C2—C3—C4—C50.0 (6)C21—C16—C17—C18−0.1 (5)
C3—C4—C5—N10.0 (5)C15—C16—C17—C18−179.6 (3)
C3—C4—C5—C14−179.9 (3)C16—C17—C18—C19−0.1 (6)
N1—C1—C6—O1−177.0 (3)C17—C18—C19—C200.3 (6)
C2—C1—C6—O15.2 (4)C18—C19—C20—C21−0.4 (7)
N1—C1—C6—N22.6 (4)C19—C20—C21—C160.2 (7)
C2—C1—C6—N2−175.2 (3)C17—C16—C21—C200.0 (6)
N3—C7—C8—C9−167.6 (4)C15—C16—C21—C20179.5 (4)
N3—C7—C8—C1310.9 (6)C4—C5—N1—C10.0 (4)
C13—C8—C9—C10−1.2 (6)C14—C5—N1—C1179.9 (3)
C7—C8—C9—C10177.3 (4)C2—C1—N1—C50.0 (4)
C8—C9—C10—C111.1 (6)C6—C1—N1—C5−177.7 (3)
C9—C10—C11—C12−0.4 (6)O1—C6—N2—N3−0.9 (5)
C10—C11—C12—C13−0.1 (6)C1—C6—N2—N3179.5 (3)
C11—C12—C13—C80.0 (6)C8—C7—N3—N2178.5 (3)
C9—C8—C13—C120.7 (5)C6—N2—N3—C7−171.0 (3)
C7—C8—C13—C12−177.8 (4)O2—C14—N4—N5−3.0 (5)
N1—C5—C14—O2−175.3 (3)C5—C14—N4—N5176.9 (3)
C4—C5—C14—O24.6 (5)C16—C15—N5—N4179.0 (3)
N1—C5—C14—N44.7 (4)C14—N4—N5—C15−177.9 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O30.932.483.305 (5)148
N2—H2A···O30.86 (4)2.35 (4)3.126 (4)150 (4)
O3—H3B···O2i0.90 (4)2.06 (4)2.874 (3)149 (4)
N4—H4A···O1ii0.87 (4)2.32 (4)3.044 (4)142 (4)
O3—H3A···O1ii0.85 (5)2.14 (5)2.790 (4)133 (5)
Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) x+1/2, −y+3/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O30.932.483.305 (5)148
N2—H2A···O30.86 (4)2.35 (4)3.126 (4)150 (4)
O3—H3B···O2i0.90 (4)2.06 (4)2.874 (3)149 (4)
N4—H4A···O1ii0.87 (4)2.32 (4)3.044 (4)142 (4)
O3—H3A···O1ii0.85 (5)2.14 (5)2.790 (4)133 (5)
Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) x+1/2, −y+3/2, z.
Acknowledgements top

This work was supported by Hubei Education Government of China (grant No. 20050131).

references
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