cyclo-Tetra­kis[μ-N-(2-hydroxy­benzo­yl)-N′-(2-hydr­oxy-3-methoxy­benzyl­idene)­hydrazinate(2–)]tetra­cobalt(II) N,N-dimethyl­formamide tetra­solvate

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

doi:10.1107/S1600536807033338

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Retracted: cyclo-Tetrakis[μ-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

The title compound, [Co₄(C₁₅H₁₂N₂O₄)₄]·4C₃H₇NO, contains N-(2-hydroxybenzoyl)-N-(2-hydroxy-3-methoxybenzylidene)hydrazine anions and Co^II cations linked into tetrameric complexes about positions of $\overline{4}$ point symmetry. Each Co^II 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].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033338/bi2200sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033338/bi2200Isup2.hkl Contains datablock I

CCDC reference: 1277974

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
R factor = 0.041
wR factor = 0.136
Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

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 Co^II cation. These are linked into tetrameric complexes about positions of 4 point symmetry. Each Co^II 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%.

Structure description top

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

	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.
	Fig. 2. Tetrameric complex formed about the position of 4 point symmetry.

cyclo-Tetrakis[µ-N-(2-hydroxybenzoyl)-N'-(2-hydroxy-3-µethoxybenzylidene)hydrazinate(2-)]tetracobalt(II)} N,N-dimethylformamide tetrasolvate top

Crystal data top

[Co₄(C₁₅H₁₂N₂O₄)₄]·4C₃H₇NO	D_x = 1.460 Mg m⁻³
M_r = 1665.17	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 3308 reflections
Hall symbol: -I 4ad	θ = 1.7–25.0°
a = 23.996 (2) Å	µ = 0.94 mm⁻¹
c = 13.1605 (10) Å	T = 298 K
V = 7578.0 (11) Å³	Cube, red
Z = 4	0.10 × 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 tube	R_int = 0.060
Graphite monochromator	θ_max = 25.0°, θ_min = 1.7°
φ and ω scans	h = −28→25
18342 measured reflections	k = −26→28
3308 independent reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0641P)² + 15.4281P] where P = (F_o² + 2F_c²)/3
3308 reflections	(Δ/σ)_max < 0.001
249 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Co₄(C₁₅H₁₂N₂O₄)₄]·4C₃H₇NO	Z = 4
M_r = 1665.17	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.94 mm⁻¹
a = 23.996 (2) Å	T = 298 K
c = 13.1605 (10) Å	0.10 × 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 reflections	R_int = 0.060
3308 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0641P)² + 15.4281P] where P = (F_o² + 2F_c²)/3
3308 reflections	Δρ_max = 0.36 e Å⁻³
249 parameters	Δρ_min = −0.28 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Co1	0.48657 (2)	0.81667 (2)	1.03441 (3)	0.0390 (2)
C13	0.5884 (2)	0.8962 (2)	0.7148 (4)	0.0729 (14)
C14	0.6317 (3)	0.9226 (3)	0.6646 (6)	0.099 (2)
H14	0.6337	0.9224	0.5940	0.118*
C15	0.6710 (3)	0.9486 (3)	0.7205 (7)	0.105 (2)
H15	0.7005	0.9660	0.6873	0.126*
C16	0.6689 (2)	0.9502 (2)	0.8288 (7)	0.098 (2)
H16	0.6961	0.9694	0.8651	0.117*
C17	0.6263 (2)	0.9231 (2)	0.8797 (5)	0.0736 (14)
H17	0.6248	0.9235	0.9503	0.088*
C12	0.58614 (19)	0.89558 (18)	0.8248 (4)	0.0572 (11)
C11	0.54300 (18)	0.86555 (17)	0.8812 (3)	0.0516 (10)
C10	0.42641 (18)	0.79092 (18)	0.8447 (3)	0.0547 (11)
H10	0.4223	0.7953	0.7749	0.066*
C8	0.38607 (17)	0.75893 (18)	0.8983 (3)	0.0517 (10)
C7	0.3406 (2)	0.7401 (2)	0.8402 (4)	0.0681 (13)
H7	0.3380	0.7495	0.7717	0.082*
C6	0.3005 (2)	0.7085 (2)	0.8840 (4)	0.0723 (14)
H6	0.2702	0.6966	0.8458	0.087*
C5	0.3047 (2)	0.6933 (2)	0.9878 (4)	0.0668 (13)
H5	0.2767	0.6717	1.0168	0.080*
C4	0.34892 (18)	0.70962 (18)	1.0463 (3)	0.0528 (10)
C9	0.39024 (17)	0.74385 (17)	1.0048 (3)	0.0478 (10)
C3	0.3125 (3)	0.6763 (3)	1.2083 (5)	0.125 (3)
H3A	0.2843	0.7046	1.2079	0.188*
H3B	0.3249	0.6701	1.2767	0.188*
H3C	0.2973	0.6423	1.1815	0.188*
C18	0.2797 (4)	0.8669 (4)	0.8818 (8)	0.121 (2)
H2	0.2621	0.8535	0.8238	0.41 (11)*
N1	0.2578 (3)	0.8534 (3)	0.9732 (5)	0.124 (2)
N3	0.50473 (15)	0.84230 (15)	0.8251 (3)	0.0571 (9)
N2	0.46821 (15)	0.81391 (14)	0.8886 (3)	0.0526 (9)
O1	0.3210 (3)	0.8956 (3)	0.8710 (5)	0.174 (3)
O6	0.55073 (19)	0.87083 (19)	0.6544 (3)	0.0981 (13)
H6A	0.5288	0.8530	0.6895	0.147*
O5	0.54502 (12)	0.86371 (12)	0.9823 (2)	0.0579 (8)
O4	0.43272 (11)	0.75891 (12)	1.0661 (2)	0.0503 (7)
O3	0.35778 (12)	0.69341 (13)	1.1480 (2)	0.0643 (8)
C1	0.2100 (4)	0.8200 (4)	0.9791 (7)	0.146 (3)
H1A	0.1977	0.8106	0.9118	0.219*
H1B	0.1810	0.8400	1.0137	0.219*
H1C	0.2184	0.7865	1.0159	0.219*
C2	0.2841 (5)	0.8651 (5)	1.0693 (8)	0.205 (5)
H2A	0.3212	0.8786	1.0578	0.308*
H2B	0.2856	0.8317	1.1092	0.308*
H2C	0.2629	0.8929	1.1048	0.308*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0497 (3)	0.0468 (3)	0.0207 (3)	−0.0024 (2)	−0.0030 (2)	0.0027 (2)
C13	0.079 (3)	0.076 (3)	0.064 (3)	0.009 (3)	0.020 (3)	0.019 (3)
C14	0.104 (5)	0.095 (4)	0.097 (5)	0.007 (4)	0.041 (4)	0.031 (4)
C15	0.086 (5)	0.088 (4)	0.140 (7)	0.001 (4)	0.036 (5)	0.039 (5)
C16	0.069 (4)	0.083 (4)	0.141 (7)	−0.009 (3)	−0.003 (4)	0.032 (4)
C17	0.064 (3)	0.065 (3)	0.092 (4)	−0.003 (3)	0.000 (3)	0.019 (3)
C12	0.060 (3)	0.053 (2)	0.059 (3)	0.006 (2)	0.004 (2)	0.014 (2)
C11	0.060 (3)	0.054 (2)	0.040 (3)	0.006 (2)	0.000 (2)	0.011 (2)
C10	0.064 (3)	0.066 (3)	0.034 (2)	−0.002 (2)	−0.012 (2)	0.005 (2)
C8	0.055 (2)	0.060 (3)	0.040 (2)	−0.004 (2)	−0.006 (2)	0.002 (2)
C7	0.071 (3)	0.088 (3)	0.044 (3)	−0.005 (3)	−0.016 (2)	0.003 (2)
C6	0.065 (3)	0.087 (4)	0.064 (3)	−0.018 (3)	−0.015 (3)	0.001 (3)
C5	0.061 (3)	0.075 (3)	0.064 (3)	−0.014 (2)	−0.004 (2)	0.003 (3)
C4	0.058 (3)	0.060 (3)	0.041 (2)	−0.001 (2)	−0.002 (2)	0.001 (2)
C9	0.050 (2)	0.054 (2)	0.040 (2)	0.0002 (19)	−0.0044 (19)	−0.0029 (18)
C3	0.102 (5)	0.189 (8)	0.085 (5)	−0.056 (5)	0.000 (4)	0.053 (5)
C18	0.107 (6)	0.137 (7)	0.117 (7)	0.011 (5)	0.013 (6)	−0.005 (6)
N1	0.106 (5)	0.167 (6)	0.099 (5)	−0.006 (4)	0.019 (4)	−0.012 (4)
N3	0.063 (2)	0.072 (2)	0.037 (2)	−0.0066 (19)	−0.0005 (17)	0.0081 (18)
N2	0.062 (2)	0.062 (2)	0.0328 (19)	−0.0019 (17)	−0.0020 (17)	0.0070 (16)
O1	0.149 (5)	0.215 (7)	0.157 (6)	−0.027 (5)	0.030 (5)	0.007 (5)
O6	0.122 (3)	0.125 (3)	0.048 (2)	−0.025 (3)	0.013 (2)	0.010 (2)
O5	0.0687 (19)	0.0638 (18)	0.0412 (18)	−0.0062 (15)	−0.0044 (14)	0.0044 (14)
O4	0.0575 (17)	0.0633 (17)	0.0302 (14)	−0.0054 (13)	−0.0032 (13)	0.0038 (13)
O3	0.0636 (19)	0.082 (2)	0.0475 (19)	−0.0145 (16)	0.0005 (15)	0.0124 (16)
C1	0.122 (7)	0.136 (7)	0.181 (10)	−0.001 (6)	0.019 (6)	0.009 (6)
C2	0.219 (11)	0.282 (15)	0.115 (8)	−0.050 (11)	0.010 (8)	−0.015 (9)

Geometric parameters (Å, º) top

Co1—N2	1.970 (3)	C6—C5	1.417 (7)
Co1—O4	1.941 (3)	C6—H6	0.930
Co1—O5	1.927 (3)	C5—C4	1.369 (6)
Co1—O4ⁱ	2.039 (3)	C5—H5	0.930
Co1—O3ⁱ	2.270 (3)	C4—C9	1.399 (6)
Co1—O4ⁱⁱ	2.686 (3)	C4—O3	1.409 (5)
C13—O6	1.349 (6)	C9—O4	1.350 (5)
C13—C14	1.385 (8)	C3—O3	1.408 (6)
C13—C12	1.450 (7)	C3—H3A	0.960
C14—C15	1.349 (9)	C3—H3B	0.960
C14—H14	0.930	C3—H3C	0.960
C15—C16	1.427 (10)	C18—O1	1.214 (9)
C15—H15	0.930	C18—N1	1.352 (10)
C16—C17	1.386 (7)	C18—H2	0.930
C16—H16	0.930	N1—C1	1.403 (9)
C17—C12	1.373 (7)	N1—C2	1.441 (11)
C17—H17	0.930	N3—N2	1.390 (5)
C12—C11	1.463 (6)	O6—H6A	0.820
C11—N3	1.304 (5)	O4—Co1ⁱⁱⁱ	2.039 (3)
C11—O5	1.332 (5)	O3—Co1ⁱⁱⁱ	2.270 (3)
C10—N2	1.282 (5)	C1—H1A	0.960
C10—C8	1.423 (6)	C1—H1B	0.960
C10—H10	0.930	C1—H1C	0.960
C8—C7	1.408 (6)	C2—H2A	0.960
C8—C9	1.450 (6)	C2—H2B	0.960
C7—C6	1.354 (7)	C2—H2C	0.960
C7—H7	0.930

O5—Co1—O4	168.50 (12)	C4—C5—H5	119.2
O5—Co1—N2	80.55 (13)	C6—C5—H5	119.2
O4—Co1—N2	92.10 (13)	C5—C4—C9	119.8 (4)
O5—Co1—O4ⁱ	98.51 (12)	C5—C4—O3	124.9 (4)
O4—Co1—O4ⁱ	88.43 (11)	C9—C4—O3	115.2 (4)
N2—Co1—O4ⁱ	177.24 (13)	O4—C9—C4	117.3 (4)
O5—Co1—O3ⁱ	90.22 (12)	O4—C9—C8	124.3 (4)
O4—Co1—O3ⁱ	100.50 (12)	C4—C9—C8	118.4 (4)
N2—Co1—O3ⁱ	107.87 (13)	O3—C3—H3A	109.5
O4ⁱ—Co1—O3ⁱ	74.68 (11)	O3—C3—H3B	109.5
O6—C13—C14	115.4 (6)	H3A—C3—H3B	109.5
O6—C13—C12	124.0 (4)	O3—C3—H3C	109.5
C14—C13—C12	120.6 (6)	H3A—C3—H3C	109.5
C15—C14—C13	118.4 (7)	H3B—C3—H3C	109.5
C15—C14—H14	120.8	O1—C18—N1	123.8 (10)
C13—C14—H14	120.8	O1—C18—H2	118.1
C14—C15—C16	122.3 (6)	N1—C18—H2	118.1
C14—C15—H15	118.9	C18—N1—C1	120.3 (8)
C16—C15—H15	118.9	C18—N1—C2	124.4 (8)
C17—C16—C15	119.7 (6)	C1—N1—C2	114.9 (8)
C17—C16—H16	120.1	C11—N3—N2	108.3 (3)
C15—C16—H16	120.2	C10—N2—N3	115.7 (3)
C12—C17—C16	119.3 (6)	C10—N2—Co1	128.9 (3)
C12—C17—H17	120.3	N3—N2—Co1	115.4 (3)
C16—C17—H17	120.3	C13—O6—H6A	109.5
C17—C12—C13	119.6 (5)	C11—O5—Co1	110.4 (3)
C17—C12—C11	117.8 (5)	C9—O4—Co1	124.4 (3)
C13—C12—C11	122.5 (4)	C9—O4—Co1ⁱⁱⁱ	120.8 (2)
N3—C11—O5	125.3 (4)	Co1—O4—Co1ⁱⁱⁱ	112.99 (13)
N3—C11—C12	115.0 (4)	C4—O3—C3	120.0 (4)
O5—C11—C12	119.8 (4)	C4—O3—Co1ⁱⁱⁱ	111.5 (2)
N2—C10—C8	122.7 (4)	C3—O3—Co1ⁱⁱⁱ	121.9 (3)
N2—C10—H10	118.6	N1—C1—H1A	109.5
C8—C10—H10	118.6	N1—C1—H1B	109.5
C7—C8—C10	115.5 (4)	H1A—C1—H1B	109.5
C7—C8—C9	119.9 (4)	N1—C1—H1C	109.5
C10—C8—C9	124.5 (4)	H1A—C1—H1C	109.5
C6—C7—C8	119.9 (5)	H1B—C1—H1C	109.5
C6—C7—H7	120.1	N1—C2—H2A	109.5
C8—C7—H7	120.1	N1—C2—H2B	109.5
C7—C6—C5	120.4 (4)	H2A—C2—H2B	109.5
C7—C6—H6	119.8	N1—C2—H2C	109.5
C5—C6—H6	119.8	H2A—C2—H2C	109.5
C4—C5—C6	121.5 (4)	H2B—C2—H2C	109.5

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···A	D—H	H···A	D···A	D—H···A
O6—H6A···N3	0.82	1.89	2.595 (6)	143

Experimental details

Crystal data
Chemical formula	[Co₄(C₁₅H₁₂N₂O₄)₄]·4C₃H₇NO
M_r	1665.17
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	298
a, c (Å)	23.996 (2), 13.1605 (10)
V (Å³)	7578.0 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18342, 3308, 2180
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.136, 1.00
No. of reflections	3308
No. of parameters	249
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0641P)² + 15.4281P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Selected bond lengths (Å) top

Co1—N2	1.970 (3)	Co1—O4ⁱ	2.039 (3)
Co1—O4	1.941 (3)	Co1—O3ⁱ	2.270 (3)
Co1—O5	1.927 (3)	Co1—O4ⁱⁱ	2.686 (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···A	D—H	H···A	D···A	D—H···A
O6—H6A···N3	0.82	1.89	2.595 (6)	143

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Retracted: cyclo-Tetra­kis[μ-N-(2-hydroxy­benzo­yl)-N′-(2-hydr­oxy-3-methoxy­benzyl­idene)­hydrazinate(2–)]tetra­cobalt(II) N,N-dimethyl­formamide tetra­solvate