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Acta Cryst. (2007). E63, m2128    [ doi:10.1107/S1600536807033338 ]

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

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

Abstract top

The title compound, [Co4(C15H12N2O4)4]·4C3H7NO, contains N-(2-hydroxybenzoyl)-N-(2-hydroxy-3-methoxybenzylidene)hydrazine anions and CoII cations linked into tetrameric complexes about positions of \overline{4} point symmetry. Each CoII cation is pentacoordinated and adopts a distorted square-based pyramidal geometry. There is one O-H...N hydrogen bond [O...N = 2.595 (6) Å].

Comment top

Owing to their biological activity and chemical/industrial versatility, metal-hydrazine complexes have received considerable attention. For instance, Schiff base hydrazine and its analogues have been well studied in order to understand better the mechanism of enzymes containing vitamin B6 (Maghler et al., 1982; Rath et al., 1997; Rath et al., 1998)

Herein, we report the structure of the title compound, [Co4(C15H12N2O4)4].4C3H7NO. As shown in Fig. 1, the asymmetric unit comprises one N-(2-hydroxy-benzoyl)-N-(2-hydroxy-3-methoxo-benzoylidene)hydrazine anion and one CoII cation. These are linked into tetrameric complexes about positions of 4 point symmetry. Each CoII cation adopts a distorted 6-coordinate geometry through one N and three O atoms lying in the equatorial plane, with the Co1—O3 bond lying to one side of this plane and the longer Co1—O4 bond lying on the opposite side.

Related literature top

One motivation to study the Schiff base 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).

Experimental top

All chemicals were used as purchased from Shanghai Sci & Tec Co. Ltd. A solution of cobalt(II) acetate (0.5 mmol) and N-(2-hydroxy-benzoyl)-N-(2-hydroxy-3-methoxo-benzoylidene)hydrazine (0.5 mmol) in DMF (10 ml) was refluxed for 2 h then filtered. Red crystals were obtained after a few days standing at room temperature with a yield of 25%. Elemental analysis calculated: C 51.89, H 4.56, N 10.09%; found: C 51.82, H 4.60, N 10.01%.

Refinement top

H atoms were placed geometrically and refined as riding with C—H = 0.93, N—H = 0.86 and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C/N) or 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2001); 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 - 1/4, -x + 5/4, -z + 9/4.
[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)hydrazinate(2-)]tetracobalt(II)} N,N-dimethylformamide tetrasolvate top
Crystal data top
[Co4(C15H12N2O4)4]·4C3H7NODx = 1.460 Mg m−3
Mr = 1665.17Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3308 reflections
Hall symbol: -I 4adθ = 1.7–25.0°
a = 23.996 (2) ŵ = 0.94 mm−1
c = 13.1605 (10) ÅT = 298 K
V = 7578.0 (11) Å3Cube, red
Z = 40.10 × 0.10 × 0.10 mm
F(000) = 3440
Data collection top
Bruker APEXII CCD
diffractometer		2180 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.060
Graphite monochromatorθmax = 25.0°, θmin = 1.7°
φ and ω scansh = −28→25
18342 measured reflectionsk = −26→28
3308 independent 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0641P)2 + 15.4281P]
where P = (Fo2 + 2Fc2)/3
3308 reflections(Δ/σ)max < 0.001
249 parametersΔρmax = 0.36 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
[Co4(C15H12N2O4)4]·4C3H7NOZ = 4
Mr = 1665.17Mo Kα radiation
Tetragonal, I41/aµ = 0.94 mm−1
a = 23.996 (2) ÅT = 298 K
c = 13.1605 (10) Å0.10 × 0.10 × 0.10 mm
V = 7578.0 (11) Å3
Data collection top
Bruker APEXII CCD
diffractometer		2180 reflections with I > 2σ(I)
18342 measured reflectionsRint = 0.060
3308 independent reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0641P)2 + 15.4281P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136Δρmax = 0.36 e Å−3
S = 1.00Δρmin = −0.28 e Å−3
3308 reflectionsAbsolute structure: ?
249 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
Co10.48657 (2)0.81667 (2)1.03441 (3)0.0390 (2)
C130.5884 (2)0.8962 (2)0.7148 (4)0.0729 (14)
C140.6317 (3)0.9226 (3)0.6646 (6)0.099 (2)
H140.63370.92240.59400.118*
C150.6710 (3)0.9486 (3)0.7205 (7)0.105 (2)
H150.70050.96600.68730.126*
C160.6689 (2)0.9502 (2)0.8288 (7)0.098 (2)
H160.69610.96940.86510.117*
C170.6263 (2)0.9231 (2)0.8797 (5)0.0736 (14)
H170.62480.92350.95030.088*
C120.58614 (19)0.89558 (18)0.8248 (4)0.0572 (11)
C110.54300 (18)0.86555 (17)0.8812 (3)0.0516 (10)
C100.42641 (18)0.79092 (18)0.8447 (3)0.0547 (11)
H100.42230.79530.77490.066*
C80.38607 (17)0.75893 (18)0.8983 (3)0.0517 (10)
C70.3406 (2)0.7401 (2)0.8402 (4)0.0681 (13)
H70.33800.74950.77170.082*
C60.3005 (2)0.7085 (2)0.8840 (4)0.0723 (14)
H60.27020.69660.84580.087*
C50.3047 (2)0.6933 (2)0.9878 (4)0.0668 (13)
H50.27670.67171.01680.080*
C40.34892 (18)0.70962 (18)1.0463 (3)0.0528 (10)
C90.39024 (17)0.74385 (17)1.0048 (3)0.0478 (10)
C30.3125 (3)0.6763 (3)1.2083 (5)0.125 (3)
H3A0.28430.70461.20790.188*
H3B0.32490.67011.27670.188*
H3C0.29730.64231.18150.188*
C180.2797 (4)0.8669 (4)0.8818 (8)0.121 (2)
H20.26210.85350.82380.41 (11)*
N10.2578 (3)0.8534 (3)0.9732 (5)0.124 (2)
N30.50473 (15)0.84230 (15)0.8251 (3)0.0571 (9)
N20.46821 (15)0.81391 (14)0.8886 (3)0.0526 (9)
O10.3210 (3)0.8956 (3)0.8710 (5)0.174 (3)
O60.55073 (19)0.87083 (19)0.6544 (3)0.0981 (13)
H6A0.52880.85300.68950.147*
O50.54502 (12)0.86371 (12)0.9823 (2)0.0579 (8)
O40.43272 (11)0.75891 (12)1.0661 (2)0.0503 (7)
O30.35778 (12)0.69341 (13)1.1480 (2)0.0643 (8)
C10.2100 (4)0.8200 (4)0.9791 (7)0.146 (3)
H1A0.19770.81060.91180.219*
H1B0.18100.84001.01370.219*
H1C0.21840.78651.01590.219*
C20.2841 (5)0.8651 (5)1.0693 (8)0.205 (5)
H2A0.32120.87861.05780.308*
H2B0.28560.83171.10920.308*
H2C0.26290.89291.10480.308*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0497 (3)0.0468 (3)0.0207 (3)−0.0024 (2)−0.0030 (2)0.0027 (2)
C130.079 (3)0.076 (3)0.064 (3)0.009 (3)0.020 (3)0.019 (3)
C140.104 (5)0.095 (4)0.097 (5)0.007 (4)0.041 (4)0.031 (4)
C150.086 (5)0.088 (4)0.140 (7)0.001 (4)0.036 (5)0.039 (5)
C160.069 (4)0.083 (4)0.141 (7)−0.009 (3)−0.003 (4)0.032 (4)
C170.064 (3)0.065 (3)0.092 (4)−0.003 (3)0.000 (3)0.019 (3)
C120.060 (3)0.053 (2)0.059 (3)0.006 (2)0.004 (2)0.014 (2)
C110.060 (3)0.054 (2)0.040 (3)0.006 (2)0.000 (2)0.011 (2)
C100.064 (3)0.066 (3)0.034 (2)−0.002 (2)−0.012 (2)0.005 (2)
C80.055 (2)0.060 (3)0.040 (2)−0.004 (2)−0.006 (2)0.002 (2)
C70.071 (3)0.088 (3)0.044 (3)−0.005 (3)−0.016 (2)0.003 (2)
C60.065 (3)0.087 (4)0.064 (3)−0.018 (3)−0.015 (3)0.001 (3)
C50.061 (3)0.075 (3)0.064 (3)−0.014 (2)−0.004 (2)0.003 (3)
C40.058 (3)0.060 (3)0.041 (2)−0.001 (2)−0.002 (2)0.001 (2)
C90.050 (2)0.054 (2)0.040 (2)0.0002 (19)−0.0044 (19)−0.0029 (18)
C30.102 (5)0.189 (8)0.085 (5)−0.056 (5)0.000 (4)0.053 (5)
C180.107 (6)0.137 (7)0.117 (7)0.011 (5)0.013 (6)−0.005 (6)
N10.106 (5)0.167 (6)0.099 (5)−0.006 (4)0.019 (4)−0.012 (4)
N30.063 (2)0.072 (2)0.037 (2)−0.0066 (19)−0.0005 (17)0.0081 (18)
N20.062 (2)0.062 (2)0.0328 (19)−0.0019 (17)−0.0020 (17)0.0070 (16)
O10.149 (5)0.215 (7)0.157 (6)−0.027 (5)0.030 (5)0.007 (5)
O60.122 (3)0.125 (3)0.048 (2)−0.025 (3)0.013 (2)0.010 (2)
O50.0687 (19)0.0638 (18)0.0412 (18)−0.0062 (15)−0.0044 (14)0.0044 (14)
O40.0575 (17)0.0633 (17)0.0302 (14)−0.0054 (13)−0.0032 (13)0.0038 (13)
O30.0636 (19)0.082 (2)0.0475 (19)−0.0145 (16)0.0005 (15)0.0124 (16)
C10.122 (7)0.136 (7)0.181 (10)−0.001 (6)0.019 (6)0.009 (6)
C20.219 (11)0.282 (15)0.115 (8)−0.050 (11)0.010 (8)−0.015 (9)
Geometric parameters (Å, º) top
Co1—N21.970 (3)C6—C51.417 (7)
Co1—O41.941 (3)C6—H60.930
Co1—O51.927 (3)C5—C41.369 (6)
Co1—O4i2.039 (3)C5—H50.930
Co1—O3i2.270 (3)C4—C91.399 (6)
Co1—O4ii2.686 (3)C4—O31.409 (5)
C13—O61.349 (6)C9—O41.350 (5)
C13—C141.385 (8)C3—O31.408 (6)
C13—C121.450 (7)C3—H3A0.960
C14—C151.349 (9)C3—H3B0.960
C14—H140.930C3—H3C0.960
C15—C161.427 (10)C18—O11.214 (9)
C15—H150.930C18—N11.352 (10)
C16—C171.386 (7)C18—H20.930
C16—H160.930N1—C11.403 (9)
C17—C121.373 (7)N1—C21.441 (11)
C17—H170.930N3—N21.390 (5)
C12—C111.463 (6)O6—H6A0.820
C11—N31.304 (5)O4—Co1iii2.039 (3)
C11—O51.332 (5)O3—Co1iii2.270 (3)
C10—N21.282 (5)C1—H1A0.960
C10—C81.423 (6)C1—H1B0.960
C10—H100.930C1—H1C0.960
C8—C71.408 (6)C2—H2A0.960
C8—C91.450 (6)C2—H2B0.960
C7—C61.354 (7)C2—H2C0.960
C7—H70.930
O5—Co1—O4168.50 (12)C4—C5—H5119.2
O5—Co1—N280.55 (13)C6—C5—H5119.2
O4—Co1—N292.10 (13)C5—C4—C9119.8 (4)
O5—Co1—O4i98.51 (12)C5—C4—O3124.9 (4)
O4—Co1—O4i88.43 (11)C9—C4—O3115.2 (4)
N2—Co1—O4i177.24 (13)O4—C9—C4117.3 (4)
O5—Co1—O3i90.22 (12)O4—C9—C8124.3 (4)
O4—Co1—O3i100.50 (12)C4—C9—C8118.4 (4)
N2—Co1—O3i107.87 (13)O3—C3—H3A109.5
O4i—Co1—O3i74.68 (11)O3—C3—H3B109.5
O6—C13—C14115.4 (6)H3A—C3—H3B109.5
O6—C13—C12124.0 (4)O3—C3—H3C109.5
C14—C13—C12120.6 (6)H3A—C3—H3C109.5
C15—C14—C13118.4 (7)H3B—C3—H3C109.5
C15—C14—H14120.8O1—C18—N1123.8 (10)
C13—C14—H14120.8O1—C18—H2118.1
C14—C15—C16122.3 (6)N1—C18—H2118.1
C14—C15—H15118.9C18—N1—C1120.3 (8)
C16—C15—H15118.9C18—N1—C2124.4 (8)
C17—C16—C15119.7 (6)C1—N1—C2114.9 (8)
C17—C16—H16120.1C11—N3—N2108.3 (3)
C15—C16—H16120.2C10—N2—N3115.7 (3)
C12—C17—C16119.3 (6)C10—N2—Co1128.9 (3)
C12—C17—H17120.3N3—N2—Co1115.4 (3)
C16—C17—H17120.3C13—O6—H6A109.5
C17—C12—C13119.6 (5)C11—O5—Co1110.4 (3)
C17—C12—C11117.8 (5)C9—O4—Co1124.4 (3)
C13—C12—C11122.5 (4)C9—O4—Co1iii120.8 (2)
N3—C11—O5125.3 (4)Co1—O4—Co1iii112.99 (13)
N3—C11—C12115.0 (4)C4—O3—C3120.0 (4)
O5—C11—C12119.8 (4)C4—O3—Co1iii111.5 (2)
N2—C10—C8122.7 (4)C3—O3—Co1iii121.9 (3)
N2—C10—H10118.6N1—C1—H1A109.5
C8—C10—H10118.6N1—C1—H1B109.5
C7—C8—C10115.5 (4)H1A—C1—H1B109.5
C7—C8—C9119.9 (4)N1—C1—H1C109.5
C10—C8—C9124.5 (4)H1A—C1—H1C109.5
C6—C7—C8119.9 (5)H1B—C1—H1C109.5
C6—C7—H7120.1N1—C2—H2A109.5
C8—C7—H7120.1N1—C2—H2B109.5
C7—C6—C5120.4 (4)H2A—C2—H2B109.5
C7—C6—H6119.8N1—C2—H2C109.5
C5—C6—H6119.8H2A—C2—H2C109.5
C4—C5—C6121.5 (4)H2B—C2—H2C109.5
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z; (iii) −y+5/4, x+1/4, −z+9/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···N30.821.892.595 (6)143
Selected bond lengths (Å) top
Co1—N21.970 (3)Co1—O4i2.039 (3)
Co1—O41.941 (3)Co1—O3i2.270 (3)
Co1—O51.927 (3)Co1—O4ii2.686 (3)
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···N30.821.892.595 (6)143
Acknowledgements top

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

references
References top

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

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. 187, 2097–2109.

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