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Acta Cryst. (2007). E63, m2180    [ doi:10.1107/S1600536807034514 ]

cyclo-Tetrakis[[mu]-N-(2-hydroxybenzoyl)-N'-(2-hydroxy-3-methoxybenzylidene)hydrazine(2-)]tetrazinc(II) N,N-dimethylformamide tetrasolvate

Y.-X. Gao, L.-B. Wang and Y.-L. Niu

Abstract top

The title compound, [Zn4(C15H12N2O4)4]·4C3H7NO, is isostructural with its CoII analogue. The compound contains N-(2-hydroxybenzoyl)-N-(2-hydroxy-3-methoxybenzylidene)hydrazine anions and ZnII cations linked into tetrameric complexes about a position of \overline{4} point symmetry. Each ZnII cation is pentacoordinated with a distorted square-based pyramidal geometry. The ligand exhibits an intramolecular O-H...N hydrogen bond.

Comment top

The title compound, [Zn4(C15H12N2O4)4].4C3H7NO, is isostructural with its CoII analogue (Gao et al., 2007). As shown in Figure 1, each ZnII cation is penta-coordinated by four O atoms and one N atom, forming a distorted square-based pyramidal geometry. The Zn—O bond lengths are in the range 1.936 (3)–2.275 Å, and Zn—N = 1.961 (4) Å. The ZnII cations are linked into tetrameric complexes about positions of 4 point symmetry by four N-(2-hydroxybenzoyl)-N-(2-hydroxy-3-methoxybenzylidene)-hydrazine anions (Figure 2). The ligand exhibits an intramolecular O—H···N hydrogen bond.

Related literature top

One motivation to study hydrazine and its analogues is to understand better the mechanism of enzymes containing vitamin B6. For related literature, see: Maghler et al. (1982); Rath et al. (1997, 1998). For the analogous CoII complex, see: Gao et al. (2007).

Experimental top

All chemicals were used as purchased from Shanghai chemical Co. Ltd. A mixture of zinc(II) acetate (0.5 mmol) and N-(2-hydroxybenzoyl)-N-(2-hydroxy-3-methoxybenzylidene)-hydrazine (0.5 mmol) in DMF (30 ml) was refluxed for 1 h then filtered. Colourless crystals were obtained after a few days standing at room temperature with a yield of 15%. Elemental analysis calculated: C 51.09, H 4.49, N 9.93%; found: C 51.01, H 4.55, N 9.90%.

Refinement top

H atoms were placed geometrically and refined as riding with C—H = 0.93 or 0.96 Å, O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing displacement ellipsoids at 50% probability for non-H atoms. Atoms labeled with the subscript I are generated by the symmetry operator -y + 3/4, x - 1/4, -z + 3/4.
[Figure 2] Fig. 2. Tetrameric complex formed about the position of 4 point symmetry.
cyclo-Tetrakis[µ-N-(2-hydroxybenzoyl)-N'-(2-hydroxy-3-\ methoxybenzylidene)hydrazine(2-)]tetrazinc(II)} N,N-dimethylformamide tetrasolvate top
Crystal data top
[Zn4(C15H12N2O4)4]·4C3H7NODx = 1.474 Mg m−3
Mr = 1690.93Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3529 reflections
Hall symbol: -I 4adθ = 1.7–25.5°
a = 24.1202 (10) ŵ = 1.32 mm−1
c = 13.093 (2) ÅT = 293 K
V = 7617.2 (12) Å3Cube, colourless
Z = 40.15 × 0.15 × 0.15 mm
F(000) = 3488
Data collection top
Bruker APEXII CCD
diffractometer		3529 independent reflections
Radiation source: fine-focus sealed tube2249 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
φ and ω scansθmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −29→26
Tmin = 0.826, Tmax = 0.826k = −26→29
19270 measured reflectionsl = −15→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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters not refined
S = 1.00 w = 1/[σ2(Fo2) + (0.076P)2 + 20.3206P]
where P = (Fo2 + 2Fc2)/3
3529 reflections(Δ/σ)max < 0.001
248 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
[Zn4(C15H12N2O4)4]·4C3H7NOZ = 4
Mr = 1690.93Mo Kα radiation
Tetragonal, I41/aµ = 1.32 mm−1
a = 24.1202 (10) ÅT = 293 K
c = 13.093 (2) Å0.15 × 0.15 × 0.15 mm
V = 7617.2 (12) Å3
Data collection top
Bruker APEXII CCD
diffractometer		3529 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2249 reflections with I > 2σ(I)
Tmin = 0.826, Tmax = 0.826Rint = 0.052
19270 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.046 w = 1/[σ2(Fo2) + (0.076P)2 + 20.3206P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.154Δρmax = 0.43 e Å−3
S = 1.00Δρmin = −0.30 e Å−3
3529 reflectionsAbsolute structure: ?
248 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters not refined
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
C10.3405 (2)0.2402 (2)0.6596 (4)0.0602 (14)
H10.33770.24950.72840.072*
C20.3006 (2)0.2089 (2)0.6154 (4)0.0642 (15)
H20.27030.19750.65380.077*
C30.3046 (2)0.1934 (2)0.5123 (4)0.0579 (13)
H30.27670.17180.48330.069*
C40.34886 (19)0.20960 (19)0.4540 (3)0.0460 (11)
C50.3122 (3)0.1772 (4)0.2909 (5)0.116 (3)
H5A0.29970.14110.31180.175*
H5B0.32330.17590.22050.175*
H5C0.28270.20350.29890.175*
C60.39010 (18)0.24382 (18)0.4953 (3)0.0410 (10)
C70.38608 (19)0.25887 (19)0.6020 (3)0.0449 (11)
C80.42652 (19)0.29078 (19)0.6552 (3)0.0473 (11)
H80.42250.29520.72530.057*
C90.54307 (19)0.36577 (18)0.6185 (4)0.0451 (11)
C100.5861 (2)0.39546 (19)0.6751 (4)0.0496 (12)
C110.6263 (2)0.4233 (2)0.6198 (5)0.0648 (15)
H110.62460.42400.54890.078*
C120.6693 (3)0.4505 (3)0.6705 (7)0.089 (2)
H120.69640.46960.63410.107*
C130.6710 (3)0.4484 (3)0.7795 (7)0.096 (2)
H130.70020.46560.81340.115*
C140.6319 (3)0.4226 (3)0.8351 (6)0.088 (2)
H140.63390.42250.90600.105*
C150.5884 (2)0.3959 (2)0.7857 (4)0.0642 (15)
C160.2793 (4)0.3665 (4)0.6165 (8)0.108 (3)
H160.26180.35290.67460.129*
C170.2830 (5)0.3663 (6)0.4320 (9)0.205 (6)
H17A0.26590.39880.40380.307*
H17B0.27820.33580.38570.307*
H17C0.32180.37300.44210.307*
C180.2097 (4)0.3197 (4)0.5211 (8)0.134 (3)
H18A0.19760.31050.58880.201*
H18B0.21820.28630.48430.201*
H18C0.18090.33960.48620.201*
N10.46812 (16)0.31377 (15)0.6114 (3)0.0445 (9)
N20.50458 (16)0.34242 (17)0.6749 (3)0.0494 (10)
N30.2579 (3)0.3533 (3)0.5269 (6)0.114 (2)
O10.3203 (3)0.3951 (3)0.6286 (6)0.157 (3)
O20.43283 (12)0.25892 (13)0.4338 (2)0.0425 (7)
O30.54506 (13)0.36375 (13)0.5177 (2)0.0488 (8)
O40.5508 (2)0.3710 (2)0.8454 (3)0.0883 (13)
H40.52810.35460.80970.133*
O50.35790 (13)0.19336 (14)0.3519 (2)0.0552 (9)
Zn10.48656 (2)0.31666 (2)0.46560 (4)0.0434 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.064 (3)0.079 (4)0.037 (3)−0.005 (3)0.016 (2)−0.003 (3)
C20.056 (3)0.079 (4)0.057 (3)−0.016 (3)0.016 (3)0.001 (3)
C30.053 (3)0.067 (3)0.054 (3)−0.012 (2)0.004 (2)−0.003 (3)
C40.051 (3)0.052 (3)0.034 (3)−0.001 (2)0.001 (2)0.000 (2)
C50.094 (5)0.182 (8)0.073 (5)−0.058 (5)0.002 (4)−0.053 (5)
C60.046 (3)0.046 (3)0.031 (2)0.000 (2)0.0032 (19)0.0023 (19)
C70.050 (3)0.053 (3)0.031 (2)−0.003 (2)0.007 (2)−0.001 (2)
C80.058 (3)0.060 (3)0.024 (2)−0.003 (2)0.011 (2)−0.006 (2)
C90.053 (3)0.046 (3)0.036 (3)0.006 (2)−0.002 (2)−0.010 (2)
C100.053 (3)0.045 (3)0.051 (3)0.007 (2)−0.004 (2)−0.014 (2)
C110.057 (3)0.059 (3)0.079 (4)0.000 (3)−0.001 (3)−0.019 (3)
C120.060 (4)0.072 (4)0.134 (7)−0.009 (3)0.004 (4)−0.032 (4)
C130.077 (5)0.078 (5)0.132 (7)0.001 (4)−0.036 (5)−0.039 (5)
C140.094 (5)0.087 (5)0.082 (5)0.010 (4)−0.039 (4)−0.030 (4)
C150.072 (4)0.067 (3)0.054 (3)0.009 (3)−0.017 (3)−0.017 (3)
C160.097 (6)0.123 (7)0.102 (7)0.008 (5)−0.005 (5)0.013 (5)
C170.198 (12)0.305 (18)0.111 (9)−0.080 (12)−0.029 (9)0.033 (10)
C180.114 (7)0.129 (7)0.159 (10)0.003 (6)−0.016 (6)−0.014 (7)
N10.055 (2)0.055 (2)0.0239 (19)−0.0004 (18)0.0017 (17)−0.0064 (17)
N20.055 (2)0.065 (3)0.028 (2)−0.004 (2)−0.0002 (18)−0.0077 (18)
N30.098 (5)0.161 (7)0.085 (5)−0.007 (5)−0.018 (4)0.011 (5)
O10.139 (6)0.199 (7)0.131 (6)−0.023 (5)−0.025 (5)−0.010 (5)
O20.0501 (18)0.0563 (18)0.0211 (14)−0.0046 (14)0.0036 (13)−0.0038 (13)
O30.061 (2)0.0550 (19)0.0307 (18)−0.0062 (15)0.0049 (15)−0.0041 (14)
O40.114 (4)0.114 (4)0.037 (2)−0.025 (3)−0.015 (2)−0.010 (2)
O50.056 (2)0.072 (2)0.0377 (19)−0.0142 (16)0.0000 (15)−0.0126 (16)
Zn10.0547 (4)0.0517 (4)0.0238 (3)−0.0025 (2)0.0031 (2)−0.0027 (2)
Geometric parameters (Å, º) top
C1—C21.352 (7)C12—H120.930
C1—C71.408 (6)C13—C141.343 (10)
C1—H10.930C13—H130.930
C2—C31.404 (8)C14—C151.390 (8)
C2—H20.930C14—H140.930
C3—C41.370 (6)C15—O41.342 (7)
C3—H30.930C16—O11.214 (10)
C4—C61.401 (6)C16—N31.321 (10)
C4—O51.411 (5)C16—H160.930
C5—O51.416 (7)C17—N31.418 (12)
C5—H5A0.960C17—H17A0.960
C5—H5B0.960C17—H17B0.960
C5—H5C0.960C17—H17C0.960
C6—O21.358 (5)C18—N31.418 (10)
C6—C71.446 (6)C18—H18A0.960
C7—C81.424 (6)C18—H18B0.960
C8—N11.282 (6)C18—H18C0.960
C8—H80.930N1—N21.393 (5)
C9—N21.313 (6)O2—Zn1i2.028 (3)
C9—O31.322 (5)O4—H40.820
C9—C101.463 (6)O5—Zn1i2.275 (3)
C10—C111.383 (7)Zn1—N11.961 (4)
C10—C151.449 (7)Zn1—O21.948 (3)
C11—C121.395 (8)Zn1—O31.936 (3)
C11—H110.930Zn1—O2ii2.028 (3)
C12—C131.429 (11)Zn1—O5ii2.275 (3)
C2—C1—C7120.3 (5)C15—C14—H14120.3
C2—C1—H1119.9O4—C15—C14116.6 (6)
C7—C1—H1119.9O4—C15—C10123.6 (5)
C1—C2—C3120.8 (5)C14—C15—C10119.8 (6)
C1—C2—H2119.6O1—C16—N3124.8 (9)
C3—C2—H2119.6O1—C16—H16117.6
C4—C3—C2120.8 (5)N3—C16—H16117.6
C4—C3—H3119.6N3—C17—H17A109.4
C2—C3—H3119.6N3—C17—H17B109.5
C3—C4—C6120.5 (4)H17A—C17—H17B109.5
C3—C4—O5124.7 (4)N3—C17—H17C109.5
C6—C4—O5114.8 (4)H17A—C17—H17C109.5
O5—C5—H5A109.5H17B—C17—H17C109.5
O5—C5—H5B109.5N3—C18—H18A109.5
H5A—C5—H5B109.5N3—C18—H18B109.5
O5—C5—H5C109.5H18A—C18—H18B109.5
H5A—C5—H5C109.5N3—C18—H18C109.5
H5B—C5—H5C109.5H18A—C18—H18C109.5
O2—C6—C4117.9 (4)H18B—C18—H18C109.5
O2—C6—C7123.8 (4)C8—N1—N2116.3 (4)
C4—C6—C7118.2 (4)C8—N1—Zn1128.9 (3)
C1—C7—C8116.5 (4)N2—N1—Zn1114.8 (3)
C1—C7—C6119.3 (4)C9—N2—N1108.9 (4)
C8—C7—C6124.2 (4)C16—N3—C17123.9 (9)
N1—C8—C7123.5 (4)C16—N3—C18120.4 (8)
N1—C8—H8118.3C17—N3—C18115.4 (8)
C7—C8—H8118.3C6—O2—Zn1124.7 (3)
N2—C9—O3124.8 (4)C6—O2—Zn1i120.3 (3)
N2—C9—C10115.3 (4)Zn1—O2—Zn1i113.10 (14)
O3—C9—C10119.9 (4)C9—O3—Zn1110.3 (3)
C11—C10—C15119.5 (5)C15—O4—H4109.5
C11—C10—C9118.0 (5)C4—O5—C5119.4 (4)
C15—C10—C9122.5 (5)C4—O5—Zn1i111.4 (3)
C10—C11—C12120.0 (6)C5—O5—Zn1i122.0 (4)
C10—C11—H11120.0O3—Zn1—O2168.57 (13)
C12—C11—H11120.0O3—Zn1—N180.97 (14)
C11—C12—C13118.6 (7)O2—Zn1—N191.83 (14)
C11—C12—H12120.7O3—Zn1—O2ii98.19 (13)
C13—C12—H12120.7O2—Zn1—O2ii88.56 (12)
C14—C13—C12122.5 (6)N1—Zn1—O2ii177.14 (14)
C14—C13—H13118.7O3—Zn1—O5ii90.08 (13)
C12—C13—H13118.7O2—Zn1—O5ii100.61 (13)
C13—C14—C15119.5 (7)N1—Zn1—O5ii107.61 (13)
C13—C14—H14120.3O2ii—Zn1—O5ii75.09 (11)
Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+3/4, −z+3/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···N20.821.882.589 (5)144
Selected bond lengths (Å) top
Zn1—N11.961 (4)Zn1—O2i2.028 (3)
Zn1—O21.948 (3)Zn1—O5i2.275 (3)
Zn1—O31.936 (3)
Symmetry code: (i) y+1/4, −x+3/4, −z+3/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···N20.821.882.589 (5)144
Acknowledgements top

The authors thank the NSFC (grant No. 20501017) and Tonghua Teachers' College.

references
References top

Bruker (2001). SADABS, SAINT-Plus and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison , Wisconsin, USA.

Gao, Y.-X., Wang, L.-B., Niu, Y.-L. & Hao, L.-J. (2007). Acta Cryst. E63, BI2200.

Maghler, H. R., Cordes, E. H., Dawes, H. M., Waters, J. M. & Waters, T. N. (1982). Inorg. Chim. Acta, 66, 2930–2936.

Rath, S. P., Mondal, S. & Chakravorty, A. (1997). Inorg. Chim. Acta, 263, 247–253.

Rath, S. P., Rajak, K. K. & Mondal, S. (1998). J. Chem. Soc. Dalton Trans. pp. 2097–2109.

Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.