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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): m38.
Published online 2008 December 10. doi:  10.1107/S1600536808040750
PMCID: PMC2967884

Dimethano­lbis[N′-(3-pyridylmethyl­ene)benzohydrazide]sodium(I) iodide

Abstract

The molecule of the title compound, [Na(C13H11N3O)2(CH3OH)2]I, is non-planar, with the Na atom chelated by the O atoms and the N atoms of two N′-(3-pyridylmethyl­ene)benzohydrazide ligands and both O atoms of two methanol ligands. The asymmetric unit consists of one half-mol­ecule. The Na atom is located on a crystallographic centre of inversion. The six-coordinate Na atom adopts a distorted octa­hedral coordination. In the crystal structure, inter­molecular N—H(...)I and O—H(...)N hydrogen bonds link the mol­ecules into a two-dimensional network.

Related literature

For general background, see: Lindoy et al. (1976 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-00m38-scheme1.jpg

Experimental

Crystal data

  • [Na(C13H11N3O)2(CH4O)2]I
  • M r = 664.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00m38-efi1.jpg
  • a = 8.6078 (15) Å
  • b = 13.1842 (16) Å
  • c = 13.2508 (17) Å
  • β = 101.6540 (10)°
  • V = 1472.8 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.15 mm−1
  • T = 298 (2) K
  • 0.54 × 0.43 × 0.40 mm

Data collection

  • Bruker SMART CCD area detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.577, T max = 0.657
  • 7140 measured reflections
  • 2586 independent reflections
  • 1919 reflections with I > 2σ(I)
  • R int = 0.078

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.104
  • S = 1.05
  • 2586 reflections
  • 185 parameters
  • H-atom parameters constrained
  • Δρmax = 0.69 e Å−3
  • Δρmin = −0.87 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
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040750/at2678sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040750/at2678Isup2.hkl

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

Acknowledgments

We acknowledge the National Natural Science Foundation of China (grant No. 20771053), Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University.

supplementary crystallographic information

Comment

Schiff bases have been known as effective ligands for metal ions in the preparation of dyes for many years, liquid crystals and powerful corrosion inhibitors. Furthermore, they are used in the mechanism of many biochemical processes (Lindoy et al., 1976). We report here the synthesis and crystal structure of the title compound (I).

The molecular structure of (I) is shown in Fig.1. The values of the geometric parameters in (I) are normal (Allen et al., 1987) (Table 1). In the crystal structure, there exist two intermolecular N—H···I and O—H···N hydrogen bonds (Table 2). As seen in Fig.2, the molecules are linked into two-dimensional network.

Experimental

A mixture of N'-(3-pyridylmethylene)benzohydrazide (3 mmol) and sodium methoxide (3 mmol) and bismuth iodide(1 mmol) in absolute ethanol (15 ml) was heated under reflux with stirring for 5 h and then filtered.The resulting clear colourless solution was diffused diethyl ether vapor at room temperature for 16 days, after which large colourless block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.

Refinement

All H-atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å (methylene) or 0.93 Å (aromatic),0.82 Å (hydroxyl) and Uiso(H) =1.2Ueq(C).

Figures

Fig. 1.
The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of the title compound, viewed approximately along the c axis.

Crystal data

[Na(C13H11N3O)2(CH4O)2]IF(000) = 672.0
Mr = 664.47Dx = 1.494 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3137 reflections
a = 8.6078 (15) Åθ = 2.2–27.2°
b = 13.1842 (16) ŵ = 1.15 mm1
c = 13.2508 (17) ÅT = 298 K
β = 101.654 (1)°Block, colourless
V = 1472.8 (4) Å30.54 × 0.43 × 0.40 mm
Z = 2

Data collection

Bruker SMART CCD area detector diffractometer2586 independent reflections
Radiation source: fine-focus sealed tube1919 reflections with I > 2σ(I)
graphiteRint = 0.078
phi and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→9
Tmin = 0.577, Tmax = 0.657k = −15→12
7140 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.104w = 1/[σ2(Fo2) + (0.028P)2 + 0.7317P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2586 reflectionsΔρmax = 0.69 e Å3
185 parametersΔρmin = −0.87 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0258 (18)

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
Na10.50000.50000.00000.0383 (5)
I10.00000.50000.50000.0439 (2)
N10.6395 (4)0.2735 (2)0.0500 (2)0.0384 (8)
H10.64450.20850.04620.046*
N20.5180 (3)0.3195 (2)0.0883 (2)0.0347 (7)
N30.0867 (4)0.2404 (3)0.2536 (3)0.0470 (9)
O10.7451 (3)0.42504 (19)0.0231 (2)0.0480 (7)
O20.4427 (3)0.4186 (2)−0.16052 (19)0.0492 (7)
H20.48790.3694−0.17930.074*
C10.7503 (4)0.3326 (3)0.0187 (3)0.0336 (8)
C20.8797 (4)0.2795 (3)−0.0193 (3)0.0319 (8)
C30.8939 (5)0.1758 (3)−0.0264 (3)0.0455 (10)
H30.81790.1337−0.00750.055*
C41.0197 (6)0.1342 (3)−0.0613 (3)0.0564 (12)
H41.02810.0641−0.06540.068*
C51.1334 (5)0.1946 (4)−0.0902 (3)0.0526 (11)
H51.21870.1658−0.11310.063*
C61.1193 (5)0.2980 (3)−0.0848 (3)0.0498 (11)
H61.19480.3398−0.10480.060*
C70.9930 (4)0.3401 (3)−0.0497 (3)0.0424 (9)
H70.98420.4103−0.04650.051*
C80.4330 (5)0.2585 (3)0.1286 (3)0.0382 (9)
H80.45640.18950.12990.046*
C90.2103 (5)0.2198 (3)0.2102 (3)0.0434 (10)
H90.23790.15220.20450.052*
C100.3003 (4)0.2933 (3)0.1730 (3)0.0329 (8)
C110.2568 (5)0.3933 (3)0.1804 (3)0.0439 (10)
H110.31290.44500.15610.053*
C120.1293 (5)0.4150 (3)0.2242 (3)0.0487 (10)
H120.09780.48190.22990.058*
C130.0492 (5)0.3378 (3)0.2592 (3)0.0471 (10)
H13−0.03680.35420.28870.057*
C140.3307 (7)0.4569 (4)−0.2446 (3)0.0740 (15)
H14A0.28570.5185−0.22450.111*
H14B0.24810.4078−0.26550.111*
H14C0.38210.4705−0.30110.111*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Na10.0414 (12)0.0344 (12)0.0424 (11)0.0097 (9)0.0161 (9)−0.0003 (9)
I10.0536 (3)0.0320 (3)0.0480 (3)0.00088 (16)0.01502 (17)−0.00036 (16)
N10.0429 (19)0.0277 (16)0.0514 (19)0.0058 (14)0.0258 (16)−0.0028 (14)
N20.0336 (17)0.0352 (17)0.0395 (17)0.0050 (14)0.0178 (14)−0.0020 (13)
N30.046 (2)0.054 (2)0.047 (2)−0.0037 (17)0.0229 (17)0.0043 (16)
O10.0430 (16)0.0313 (15)0.0748 (19)0.0031 (12)0.0237 (14)−0.0019 (13)
O20.0611 (19)0.0450 (17)0.0432 (15)0.0100 (14)0.0145 (14)−0.0067 (13)
C10.033 (2)0.033 (2)0.0365 (19)0.0057 (17)0.0096 (16)0.0026 (16)
C20.034 (2)0.033 (2)0.0294 (18)0.0052 (17)0.0082 (15)−0.0014 (15)
C30.057 (3)0.035 (2)0.052 (2)0.0053 (19)0.028 (2)0.0038 (18)
C40.067 (3)0.044 (3)0.067 (3)0.018 (2)0.035 (2)0.002 (2)
C50.044 (3)0.069 (3)0.050 (3)0.013 (2)0.024 (2)−0.006 (2)
C60.041 (2)0.064 (3)0.048 (2)−0.006 (2)0.020 (2)−0.003 (2)
C70.042 (2)0.040 (2)0.047 (2)−0.0017 (19)0.0153 (18)0.000 (2)
C80.044 (2)0.032 (2)0.042 (2)0.0015 (17)0.0164 (19)0.0000 (16)
C90.053 (3)0.037 (2)0.044 (2)−0.004 (2)0.0186 (19)0.0010 (19)
C100.031 (2)0.039 (2)0.0303 (18)−0.0002 (17)0.0116 (15)0.0001 (16)
C110.054 (3)0.037 (2)0.048 (2)−0.0022 (19)0.027 (2)−0.0001 (18)
C120.056 (3)0.039 (2)0.058 (3)0.004 (2)0.030 (2)−0.005 (2)
C130.041 (2)0.063 (3)0.042 (2)0.001 (2)0.0216 (18)−0.003 (2)
C140.095 (4)0.076 (3)0.049 (3)0.012 (3)0.009 (3)0.007 (3)

Geometric parameters (Å, °)

Na1—O12.294 (3)C4—C51.375 (6)
Na1—O1i2.294 (3)C4—H40.9300
Na1—O2i2.344 (2)C5—C61.371 (6)
Na1—O22.344 (2)C5—H50.9300
Na1—N22.642 (3)C6—C71.382 (5)
Na1—N2i2.642 (3)C6—H60.9300
Na1—C1i3.059 (4)C7—H70.9300
N1—C11.360 (4)C8—C101.461 (5)
N1—N21.390 (4)C8—H80.9300
N1—H10.8600C9—C101.391 (5)
N2—C81.276 (5)C9—H90.9300
N3—C131.330 (5)C10—C111.379 (5)
N3—C91.335 (5)C11—C121.371 (5)
O1—C11.222 (4)C11—H110.9300
O2—C141.412 (5)C12—C131.362 (6)
O2—H20.8200C12—H120.9300
C1—C21.487 (5)C13—H130.9300
C2—C31.377 (5)C14—H14A0.9600
C2—C71.382 (5)C14—H14B0.9600
C3—C41.375 (6)C14—H14C0.9600
C3—H30.9300
O1—Na1—O1i180.0C4—C3—H3119.8
O1—Na1—O2i93.26 (10)C2—C3—H3119.8
O1i—Na1—O2i86.74 (10)C3—C4—C5121.1 (4)
O1—Na1—O286.74 (10)C3—C4—H4119.5
O1i—Na1—O293.26 (10)C5—C4—H4119.5
O2i—Na1—O2180.0C6—C5—C4119.0 (4)
O1—Na1—N265.34 (9)C6—C5—H5120.5
O1i—Na1—N2114.66 (9)C4—C5—H5120.5
O2i—Na1—N291.60 (9)C5—C6—C7120.0 (4)
O2—Na1—N288.40 (9)C5—C6—H6120.0
O1—Na1—N2i114.66 (9)C7—C6—H6120.0
O1i—Na1—N2i65.34 (9)C2—C7—C6121.0 (4)
O2i—Na1—N2i88.40 (9)C2—C7—H7119.5
O2—Na1—N2i91.60 (9)C6—C7—H7119.5
N2—Na1—N2i180.00 (6)N2—C8—C10122.1 (3)
O1—Na1—C1i159.30 (9)N2—C8—H8118.9
O1i—Na1—C1i20.70 (9)C10—C8—H8118.9
O2i—Na1—C1i76.04 (9)N3—C9—C10124.1 (4)
O2—Na1—C1i103.96 (9)N3—C9—H9118.0
N2—Na1—C1i131.53 (9)C10—C9—H9118.0
N2i—Na1—C1i48.47 (9)C11—C10—C9117.5 (3)
C1—N1—N2119.1 (3)C11—C10—C8125.1 (3)
C1—N1—H1120.4C9—C10—C8117.4 (3)
N2—N1—H1120.4C12—C11—C10118.8 (4)
C8—N2—N1114.5 (3)C12—C11—H11120.6
C8—N2—Na1140.1 (3)C10—C11—H11120.6
N1—N2—Na1102.3 (2)C13—C12—C11119.4 (4)
C13—N3—C9116.3 (3)C13—C12—H12120.3
C1—O1—Na1117.7 (2)C11—C12—H12120.3
C14—O2—Na1122.5 (3)N3—C13—C12123.9 (4)
C14—O2—H2109.5N3—C13—H13118.0
Na1—O2—H2127.7C12—C13—H13118.0
O1—C1—N1121.5 (3)O2—C14—H14A109.5
O1—C1—C2121.5 (3)O2—C14—H14B109.5
N1—C1—C2117.0 (3)H14A—C14—H14B109.5
C3—C2—C7118.4 (3)O2—C14—H14C109.5
C3—C2—C1125.0 (3)H14A—C14—H14C109.5
C7—C2—C1116.6 (3)H14B—C14—H14C109.5
C4—C3—C2120.4 (4)
C1—N1—N2—C8−170.8 (3)N2—N1—C1—C2178.6 (3)
C1—N1—N2—Na125.1 (3)O1—C1—C2—C3179.9 (4)
O1—Na1—N2—C8175.8 (4)N1—C1—C2—C31.0 (5)
O1i—Na1—N2—C8−4.2 (4)O1—C1—C2—C7−0.2 (5)
O2i—Na1—N2—C882.9 (4)N1—C1—C2—C7−179.1 (3)
O2—Na1—N2—C8−97.1 (4)C7—C2—C3—C41.1 (6)
C1i—Na1—N2—C810.2 (4)C1—C2—C3—C4−179.0 (4)
O1—Na1—N2—N1−27.19 (19)C2—C3—C4—C5−0.3 (6)
O1i—Na1—N2—N1152.81 (19)C3—C4—C5—C6−0.6 (7)
O2i—Na1—N2—N1−120.0 (2)C4—C5—C6—C70.6 (6)
O2—Na1—N2—N160.0 (2)C3—C2—C7—C6−1.1 (6)
C1i—Na1—N2—N1167.28 (18)C1—C2—C7—C6179.1 (4)
O2i—Na1—O1—C1122.2 (3)C5—C6—C7—C20.2 (6)
O2—Na1—O1—C1−57.8 (3)N1—N2—C8—C10179.9 (3)
N2—Na1—O1—C131.9 (3)Na1—N2—C8—C10−24.9 (6)
N2i—Na1—O1—C1−148.1 (3)C13—N3—C9—C100.9 (6)
C1i—Na1—O1—C1180.0N3—C9—C10—C11−1.0 (6)
O1—Na1—O2—C14−153.5 (3)N3—C9—C10—C8179.3 (4)
O1i—Na1—O2—C1426.5 (3)N2—C8—C10—C11−2.9 (6)
N2—Na1—O2—C14141.2 (3)N2—C8—C10—C9176.7 (4)
N2i—Na1—O2—C14−38.8 (3)C9—C10—C11—C120.5 (5)
C1i—Na1—O2—C148.6 (4)C8—C10—C11—C12−179.9 (4)
Na1—O1—C1—N1−32.3 (4)C10—C11—C12—C130.0 (6)
Na1—O1—C1—C2148.9 (3)C9—N3—C13—C12−0.3 (6)
N2—N1—C1—O1−0.3 (5)C11—C12—C13—N3−0.1 (7)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···I1ii0.863.033.816 (3)153
O2—H2···N3iii0.821.982.792 (5)171

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2678).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Lindoy, L. F., Lip, H. C., Power, L. F. & Rea, T. H. (1976). Inorg. Chem.15, 1724–1727.
  • 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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