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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2718.
Published online 2010 October 2. doi:  10.1107/S1600536810038778
PMCID: PMC3009364

N 2,N 2′-Bis[4-(dimethyl­amino)­benzyl­idene]pyridine-2,6-dicarbohydrazide monohydrate

Abstract

In the title compound, C25H27N7O2·H2O, the bis­[4-(dimethyl­amino)­benzyl­idene]pyridine-2,6-dicarbohydrazide mol­ecule and the water mol­ecule are located on a twofold rotation axis. The benzene and pyridine rings form a dihedral angle of 17.13 (7)°. In the crystal, inter­molecular N—H(...)O and O—H(...)O hydrogen bonds link the mol­ecules into a two-dimensional supermolecular structure parallel to the ab plane.

Related literature

For related structures, see: Cheng et al. (2007 [triangle]); Cheng & Liu (2008 [triangle]); Jia, Hu et al. (2006 [triangle]); Jia, Shi et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2718-scheme1.jpg

Experimental

Crystal data

  • C25H27N7O2·H2O
  • M r = 475.54
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2718-efi1.jpg
  • a = 8.5718 (11) Å
  • b = 10.2802 (14) Å
  • c = 27.112 (3) Å
  • β = 97.865 (1)°
  • V = 2366.7 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.36 × 0.31 × 0.16 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.968, T max = 0.986
  • 5774 measured reflections
  • 2076 independent reflections
  • 1348 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.204
  • S = 1.05
  • 2076 reflections
  • 163 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.59 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038778/rz2479sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038778/rz2479Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the financial support of the University Student Science and Technology Culture Foundation of Liaocheng University (No. SRT10057HX2).

supplementary crystallographic information

Comment

Schiff base ligands containing the pyridine ring have received considerable attention during the last decades, mainly because their coordinative and electronic properties. For this reason, much effort has been devoted to develop efficient routes for the synthesis of these classes of compounds. In this paper, we report the crystal structure of the title compound, obtained by the reaction of pyridine-2,6-dicarbohydrazide and 4-(dimethylamino)benzaldehyde.

In the title compound (Fig. 1), the bis(4-(dimethylamino)benzylidene)pyridine-2,6-dicarbohydrazide molecule and the water molecule possess crystallographic imposed twofold rotation symmetry. Bond lengths and angles are normal and correspond to those observed in related compounds (Cheng et al., 2007; Cheng & Liu, 2008; Jia, Hu et al., 2006; Jia, Shi et al., 2006). The dihedral angle formed by the benzene ring and the pyridine ring is 17.13 (7)°. In the crystal packing, a two-dimensional supermolecular structure parallel to the ab plane is formed by N—H···O and O—H···O intermolecular contacts (Table 1).

Experimental

To a solution of pyridine-2,6-dicarbohydrazide (3 mmol) in ethanol (30 ml) was added 4-(dimethylamino)benzaldehyde (6 mmol). The mixture was refluxed with stirring for 8 h. An red precipitate was then obtained. Red crystals suitable for X-ray diffraction analysis formed after several weeks on slow evaporation of an ethanol solution at room temperature. Elemental analysis: calculated for C25H29N7O3: C 63.14, H 6.15, N 20.62%; found: C 63.28, H 6.22, N 20.49%.

Refinement

The independent water H atom was located in a difference Fourier map and refined with the O—H bond constrained to 0.85 Å and Uiso(H) = 1.2 Ueq(O). All other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.96 Å, N—H =0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N) or 1.5 Ueq(C) for methyl H atoms

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme and 30% probability displacement ellipsoids. Unlabelled atoms are related to labelled atoms by (-x, y, 0.5-z).

Crystal data

C25H27N7O2·H2OF(000) = 1008
Mr = 475.54Dx = 1.332 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1533 reflections
a = 8.5718 (11) Åθ = 3.0–24.4°
b = 10.2802 (14) ŵ = 0.09 mm1
c = 27.112 (3) ÅT = 298 K
β = 97.865 (1)°Block, red
V = 2366.7 (5) Å30.36 × 0.31 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2076 independent reflections
Radiation source: fine-focus sealed tube1348 reflections with I > 2σ(I)
graphiteRint = 0.039
phi and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.968, Tmax = 0.986k = −12→12
5774 measured reflectionsl = −32→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.204H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.1275P)2] where P = (Fo2 + 2Fc2)/3
2076 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.17 e Å3
1 restraintΔρmin = −0.59 e Å3

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 (Å2)

xyzUiso*/Ueq
N10.00000.0318 (3)0.25000.0419 (8)
N20.1517 (3)0.1645 (2)0.18533 (9)0.0456 (6)
H2A0.07210.19380.19810.068*
N30.2319 (3)0.2465 (2)0.15743 (8)0.0448 (7)
N40.4368 (3)0.7693 (2)0.05148 (10)0.0556 (7)
O10.3055 (3)−0.0104 (2)0.17635 (9)0.0669 (7)
O21.00000.3442 (4)0.25000.0927 (13)
H20.934 (4)0.398 (3)0.2352 (16)0.111*
C10.1949 (3)0.0402 (3)0.19306 (10)0.0445 (7)
C20.0935 (3)−0.0351 (3)0.22381 (10)0.0411 (7)
C30.0976 (3)−0.1702 (3)0.22298 (11)0.0488 (8)
H30.1650−0.21410.20460.059*
C40.0000−0.2371 (4)0.25000.0535 (11)
H40.0000−0.32760.25000.064*
C50.1730 (3)0.3604 (3)0.15200 (10)0.0462 (7)
H50.08170.37860.16570.055*
C60.2429 (3)0.4630 (3)0.12527 (10)0.0424 (7)
C70.3772 (3)0.4455 (3)0.10227 (11)0.0452 (7)
H70.42550.36430.10350.054*
C80.4387 (3)0.5447 (3)0.07816 (11)0.0474 (8)
H80.52760.52920.06280.057*
C90.3728 (3)0.6699 (3)0.07561 (10)0.0420 (7)
C100.2390 (3)0.6870 (3)0.09890 (11)0.0494 (8)
H100.19170.76850.09820.059*
C110.1755 (3)0.5864 (3)0.12276 (11)0.0489 (8)
H110.08540.60100.13760.059*
C120.5716 (4)0.7484 (3)0.02620 (13)0.0685 (10)
H12A0.65670.71410.04920.103*
H12B0.60310.82950.01300.103*
H12C0.54500.6877−0.00050.103*
C130.3639 (4)0.8964 (3)0.04783 (13)0.0639 (9)
H13A0.26690.89230.02550.096*
H13B0.43350.95760.03540.096*
H13C0.34300.92350.08020.096*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0486 (18)0.0423 (18)0.0350 (17)0.0000.0068 (15)0.000
N20.0534 (14)0.0424 (14)0.0433 (13)−0.0004 (11)0.0155 (11)0.0021 (11)
N30.0518 (14)0.0457 (15)0.0376 (13)−0.0025 (11)0.0082 (11)0.0021 (11)
N40.0561 (15)0.0533 (16)0.0613 (16)−0.0005 (12)0.0220 (13)0.0100 (13)
O10.0674 (14)0.0616 (14)0.0780 (16)0.0146 (11)0.0330 (13)0.0048 (12)
O20.100 (3)0.081 (3)0.101 (3)0.0000.030 (3)0.000
C10.0497 (16)0.0449 (17)0.0392 (16)0.0056 (13)0.0068 (13)−0.0040 (12)
C20.0472 (15)0.0377 (15)0.0370 (15)0.0009 (12)0.0013 (13)−0.0015 (12)
C30.0497 (17)0.0461 (17)0.0495 (17)0.0057 (14)0.0031 (14)−0.0055 (14)
C40.055 (3)0.036 (2)0.066 (3)0.000−0.005 (2)0.000
C50.0480 (16)0.0520 (18)0.0400 (15)0.0003 (14)0.0107 (13)0.0012 (13)
C60.0466 (15)0.0469 (16)0.0341 (14)−0.0018 (13)0.0072 (12)0.0000 (12)
C70.0443 (15)0.0449 (16)0.0472 (16)0.0026 (13)0.0091 (13)−0.0015 (13)
C80.0422 (15)0.0556 (18)0.0472 (17)0.0008 (13)0.0162 (13)−0.0020 (14)
C90.0415 (15)0.0484 (17)0.0369 (15)−0.0024 (13)0.0080 (12)0.0008 (13)
C100.0512 (17)0.0456 (17)0.0533 (18)0.0064 (14)0.0134 (14)0.0008 (14)
C110.0503 (16)0.0510 (18)0.0496 (17)0.0024 (14)0.0220 (14)0.0010 (14)
C120.069 (2)0.072 (2)0.071 (2)−0.0130 (17)0.0331 (19)0.0018 (18)
C130.073 (2)0.057 (2)0.065 (2)−0.0058 (17)0.0188 (18)0.0117 (17)

Geometric parameters (Å, °)

N1—C21.333 (3)C5—H50.9300
N1—C2i1.333 (3)C6—C111.392 (4)
N2—C11.339 (3)C6—C71.394 (4)
N2—N31.378 (3)C7—C81.356 (4)
N2—H2A0.8600C7—H70.9300
N3—C51.276 (3)C8—C91.404 (4)
N4—C91.368 (3)C8—H80.9300
N4—C121.438 (4)C9—C101.394 (4)
N4—C131.446 (4)C10—C111.371 (4)
O1—C11.222 (3)C10—H100.9300
O2—H20.85 (3)C11—H110.9300
C1—C21.499 (4)C12—H12A0.9600
C2—C31.390 (4)C12—H12B0.9600
C3—C41.370 (3)C12—H12C0.9600
C3—H30.9300C13—H13A0.9600
C4—C3i1.370 (3)C13—H13B0.9600
C4—H40.9300C13—H13C0.9600
C5—C61.455 (4)
C2—N1—C2i117.8 (3)C8—C7—H7119.4
C1—N2—N3121.5 (2)C6—C7—H7119.4
C1—N2—H2A119.3C7—C8—C9122.2 (3)
N3—N2—H2A119.3C7—C8—H8118.9
C5—N3—N2114.0 (2)C9—C8—H8118.9
C9—N4—C12121.2 (3)N4—C9—C10122.1 (3)
C9—N4—C13120.6 (2)N4—C9—C8121.5 (2)
C12—N4—C13118.0 (2)C10—C9—C8116.3 (2)
O1—C1—N2124.1 (3)C11—C10—C9121.6 (3)
O1—C1—C2121.7 (3)C11—C10—H10119.2
N2—C1—C2114.3 (2)C9—C10—H10119.2
N1—C2—C3122.9 (3)C10—C11—C6121.4 (3)
N1—C2—C1117.8 (2)C10—C11—H11119.3
C3—C2—C1119.3 (2)C6—C11—H11119.3
C4—C3—C2118.3 (3)N4—C12—H12A109.5
C4—C3—H3120.8N4—C12—H12B109.5
C2—C3—H3120.8H12A—C12—H12B109.5
C3—C4—C3i119.8 (4)N4—C12—H12C109.5
C3—C4—H4120.1H12A—C12—H12C109.5
C3i—C4—H4120.1H12B—C12—H12C109.5
N3—C5—C6122.7 (3)N4—C13—H13A109.5
N3—C5—H5118.7N4—C13—H13B109.5
C6—C5—H5118.7H13A—C13—H13B109.5
C11—C6—C7117.3 (2)N4—C13—H13C109.5
C11—C6—C5119.2 (2)H13A—C13—H13C109.5
C7—C6—C5123.4 (3)H13B—C13—H13C109.5
C8—C7—C6121.2 (3)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O2ii0.862.232.967 (4)143
O2—H2···O1iii0.85 (3)2.04 (4)2.844 (3)157 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2479).

References

  • Cheng, C. & Liu, H. (2008). Acta Cryst. E64, o155. [PMC free article] [PubMed]
  • Cheng, C.-X., Liu, H.-W., Luo, F.-H., Cao, M.-N. & Hu, Z.-Q. (2007). Acta Cryst. E63, o2899.
  • Jia, B., Hu, Z.-Q., Deng, X.-T., Cheng, C.-X. & Shi, S.-M. (2006). Acta Cryst. E62, o4902–o4903.
  • Jia, B., Shi, S., Luo, F. & Hu, Z. (2006). Acta Cryst. E62, o3326–o3327.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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