Literature DB >> 21579067

A tetra-nuclear cobalt(III) cluster with 2-(hydroxy-meth-yl)pyridine ligands.

Fang-Ming Wang1, Chang-Sheng Lu, Yi-Zhi Li, Qing-Jin Meng.   

Abstract

In the title compound, tetra-kis[μ(3)-(2-pyrid-yl)methano-lato]tetra-kis[bromido(methanol)cobalt(III)] tetra-bromide 2-(hydroxy-meth-yl)pyridine tetra-solvate dihydrate, [Co(4)Br(4)(C(6)H(6)NO)(4)(CH(3)OH)(4)]Br(4)·4C(6)H(7)NO(4)·2H(2)O, the cation comprises a [Co(4)O(4)] cubane-type core ( symmetry). The four Co(III) ions and bridging O atoms from four (2-pyrid-yl)methano-late anions are located at alternating vertices of the cube, with bromide ions and methanol ligands on the exterior of the core, completing a distorted octa-hedral geometry. The structure is stablized by inter-molecular O-H⋯Br and O-H⋯O inter-actions.

Entities:  

Year:  2010        PMID： 21579067      PMCID： PMC2979208          DOI： 10.1107/S1600536810015369

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For related structures and magnetic properties, see: Tong et al. (2002 ▶); Yang et al. (2002 ▶); Zhao et al. (2004 ▶).

Experimental

Crystal data

[Co4Br4(C6H6NO)4(CH4O)4]Br4·4C6H7NO4·2H2O M = 1908.10 Tetragonal, a = 16.5302 (6) Å c = 29.875 (2) Å V = 8163.3 (8) Å3 Z = 4 Mo Kα radiation μ = 4.77 mm−1 T = 291 K 0.30 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.265, T max = 0.350 21461 measured reflections 4018 independent reflections 3180 reflections with I > 2σ(I) R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.052 wR(F 2) = 0.113 S = 0.99 4018 reflections 200 parameters H-atom parameters constrained Δρmax = 0.75 e Å−3 Δρmin = −0.56 e Å−3 Absolute structure: Flack (1983 ▶), 1822 Friedel pairs Flack parameter: 0.025 (18) Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015369/bx2274sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015369/bx2274Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Co4Br4(C6H6NO)4(CH4O)4]Br4·4C6H7NO4·2H2ODx = 1.553 Mg m−3
Mr = 1908.10Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42dCell parameters from 4154 reflections
Hall symbol: I -4 2bwθ = 2.2–23.1°
a = 16.5302 (6) ŵ = 4.77 mm−1
c = 29.875 (2) ÅT = 291 K
V = 8163.3 (8) Å3Block, purple
Z = 40.30 × 0.24 × 0.22 mm
F(000) = 3760
Bruker SMART APEX CCD area-detector diffractometer4018 independent reflections
Radiation source: sealed tube3180 reflections with I > 2σ(I)
graphiteRint = 0.056
phi and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −15→20
Tmin = 0.265, Tmax = 0.350k = −20→17
21461 measured reflectionsl = −32→36
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.113w = 1/[σ2(Fo2) + (0.0635P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
4018 reflectionsΔρmax = 0.75 e Å−3
200 parametersΔρmin = −0.56 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1822 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.025 (18)
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.
xyzUiso*/UeqOcc. (<1)
Br1−0.05719 (4)0.72378 (5)0.20269 (3)0.04360 (19)
Br20.27436 (4)0.77454 (4)0.29686 (2)0.04162 (18)
C10.0376 (4)0.6172 (5)0.1104 (3)0.0415 (17)
H1−0.00350.65540.11260.050*
C20.0725 (5)0.6005 (5)0.0696 (2)0.0423 (18)
H20.05560.62850.04430.051*
C30.1331 (5)0.5422 (5)0.0658 (2)0.0417 (18)
H30.15640.53110.03810.050*
C40.1584 (5)0.5003 (5)0.1042 (3)0.0453 (18)
H40.19740.46000.10210.054*
C50.1241 (5)0.5198 (5)0.1460 (2)0.0422 (17)
C60.1358 (5)0.4721 (5)0.1851 (2)0.0385 (16)
H6A0.13560.41560.17630.046*
H6B0.18910.48400.19690.046*
C70.1841 (5)0.7172 (5)0.1922 (3)0.0460 (18)
H7A0.22470.68760.17600.069*
H7B0.20960.75670.21100.069*
H7C0.14880.74390.17140.069*
C80.5885 (5)−0.0934 (5)0.1084 (2)0.0432 (18)
H80.5728−0.14720.11110.052*
C90.6092 (5)−0.0630 (5)0.0676 (3)0.0415 (17)
H90.6083−0.09670.04260.050*
C100.6315 (5)0.0173 (5)0.0626 (3)0.0468 (19)
H100.64410.03780.03450.056*
C110.6350 (4)0.0673 (5)0.1005 (3)0.0454 (19)
H110.65120.12100.09780.055*
C120.6141 (5)0.0361 (5)0.1423 (3)0.0446 (18)
C130.6198 (5)0.0845 (5)0.1836 (3)0.0458 (19)
H13A0.67360.08030.19640.055*
H13B0.60850.14090.17740.055*
Co10.02308 (6)0.59361 (6)0.21302 (3)0.0396 (2)
N10.0641 (4)0.5764 (3)0.1481 (2)0.0367 (14)
N20.5908 (4)−0.0430 (4)0.1466 (2)0.0407 (14)
O10.0801 (3)0.4821 (3)0.21907 (16)0.0415 (11)
O20.1369 (3)0.6610 (3)0.21993 (16)0.0384 (11)
H2B0.17410.61620.22380.046*
O30.5652 (3)0.0547 (3)0.21175 (16)0.0445 (12)
H3A0.59270.03230.23720.053*
O40.5585 (6)0.7840 (6)0.2123 (3)0.044 (2)0.50
H4A0.59640.75210.22970.053*0.50
H4B0.51150.78460.23180.053*0.50
U11U22U33U12U13U23
Br10.0435 (4)0.0479 (4)0.0394 (4)0.0080 (3)0.0066 (3)0.0131 (3)
Br20.0410 (4)0.0412 (4)0.0427 (4)−0.0152 (3)0.0104 (3)0.0128 (3)
C10.037 (4)0.046 (4)0.041 (4)0.014 (3)0.018 (3)0.001 (3)
C20.042 (4)0.050 (4)0.035 (4)0.008 (3)0.010 (3)0.014 (3)
C30.047 (4)0.042 (4)0.035 (4)0.011 (3)0.020 (3)0.002 (3)
C40.049 (4)0.043 (4)0.044 (4)0.009 (3)0.012 (4)0.006 (3)
C50.049 (4)0.041 (4)0.036 (4)0.004 (3)0.008 (3)0.010 (3)
C60.037 (4)0.041 (4)0.037 (4)0.012 (3)0.013 (3)0.010 (3)
C70.048 (4)0.039 (4)0.051 (5)−0.003 (3)0.007 (3)0.010 (4)
C80.046 (4)0.044 (4)0.040 (4)0.023 (3)0.010 (3)0.015 (3)
C90.042 (4)0.045 (4)0.038 (4)0.011 (3)0.006 (3)0.018 (3)
C100.051 (5)0.054 (5)0.035 (4)−0.009 (4)−0.011 (3)0.019 (4)
C110.038 (4)0.049 (5)0.050 (5)0.014 (3)0.013 (3)0.008 (4)
C120.044 (4)0.044 (4)0.046 (4)−0.020 (3)0.008 (3)−0.006 (3)
C130.054 (5)0.031 (4)0.052 (5)0.007 (3)0.005 (4)−0.008 (3)
Co10.0400 (5)0.0405 (5)0.0384 (6)0.0002 (4)0.0028 (4)0.0029 (4)
N10.037 (3)0.029 (3)0.044 (3)−0.009 (2)0.013 (3)0.002 (2)
N20.040 (3)0.038 (3)0.044 (4)−0.001 (3)0.012 (3)0.011 (3)
O10.041 (3)0.042 (3)0.041 (3)0.004 (2)0.018 (2)0.005 (2)
O20.036 (3)0.044 (3)0.035 (3)0.0024 (19)0.000 (2)0.010 (2)
O30.052 (3)0.052 (3)0.029 (3)−0.012 (2)−0.014 (2)−0.008 (2)
O40.050 (6)0.040 (5)0.041 (6)−0.001 (5)0.009 (5)0.008 (5)
Br1—Co12.5467 (12)C9—C101.386 (11)
C1—C21.376 (10)C9—H90.9300
C1—N11.384 (10)C10—C111.403 (12)
C1—H10.9300C10—H100.9300
C2—C31.394 (11)C11—C121.394 (11)
C2—H20.9300C11—H110.9300
C3—C41.405 (11)C12—N21.370 (9)
C3—H30.9300C12—C131.474 (11)
C4—C51.407 (10)C13—O31.328 (10)
C4—H40.9300C13—H13A0.9700
C5—N11.366 (10)C13—H13B0.9700
C5—C61.422 (10)Co1—O1i2.043 (5)
C6—O11.381 (8)Co1—N12.073 (6)
C6—H6A0.9700Co1—O12.079 (5)
C6—H6B0.9700Co1—O1ii2.123 (5)
C7—O21.469 (9)Co1—O22.196 (5)
C7—H7A0.9600O1—Co1iii2.043 (5)
C7—H7B0.9600O1—Co1ii2.123 (5)
C7—H7C0.9600O2—H2B0.9700
C8—C91.362 (10)O3—H3A0.9601
C8—N21.415 (10)O4—H4A0.9700
C8—H80.9300O4—H4B0.9700
C2—C1—N1119.4 (6)N2—C12—C11120.5 (7)
C2—C1—H1120.3N2—C12—C13117.2 (7)
N1—C1—H1120.3C11—C12—C13122.3 (7)
C1—C2—C3120.8 (7)O3—C13—C12106.6 (7)
C1—C2—H2119.6O3—C13—H13A110.4
C3—C2—H2119.6C12—C13—H13A110.4
C2—C3—C4119.2 (6)O3—C13—H13B110.4
C2—C3—H3120.4C12—C13—H13B110.4
C4—C3—H3120.4H13A—C13—H13B108.6
C3—C4—C5119.5 (7)O1i—Co1—N1158.0 (2)
C3—C4—H4120.3O1i—Co1—O180.55 (19)
C5—C4—H4120.3N1—Co1—O179.1 (2)
N1—C5—C4119.4 (7)O1i—Co1—O1ii79.5 (2)
N1—C5—C6116.1 (6)N1—Co1—O1ii105.2 (2)
C4—C5—C6123.1 (7)O1—Co1—O1ii80.5 (2)
O1—C6—C5116.6 (6)O1i—Co1—O289.86 (19)
O1—C6—H6A108.1N1—Co1—O282.9 (2)
C5—C6—H6A108.1O1—Co1—O293.03 (19)
O1—C6—H6B108.1O1ii—Co1—O2168.29 (18)
C5—C6—H6B108.1O1i—Co1—Br1101.00 (14)
H6A—C6—H6B107.3N1—Co1—Br199.94 (17)
O2—C7—H7A109.5O1—Co1—Br1175.05 (15)
O2—C7—H7B109.5O1ii—Co1—Br195.13 (14)
H7A—C7—H7B109.5O2—Co1—Br191.68 (13)
O2—C7—H7C109.5C5—N1—C1121.6 (6)
H7A—C7—H7C109.5C5—N1—Co1112.1 (5)
H7B—C7—H7C109.5C1—N1—Co1126.3 (5)
C9—C8—N2119.9 (8)C12—N2—C8119.6 (6)
C9—C8—H8120.0C6—O1—Co1iii130.8 (4)
N2—C8—H8120.0C6—O1—Co1110.1 (4)
C8—C9—C10121.0 (8)Co1iii—O1—Co199.9 (2)
C8—C9—H9119.5C6—O1—Co1ii113.7 (5)
C10—C9—H9119.5Co1iii—O1—Co1ii98.49 (19)
C9—C10—C11119.3 (7)Co1—O1—Co1ii98.7 (2)
C9—C10—H10120.3C7—O2—Co1136.3 (4)
C11—C10—H10120.3C7—O2—H2B102.3
C12—C11—C10119.6 (8)Co1—O2—H2B99.6
C12—C11—H11120.2C13—O3—H3A108.8
C10—C11—H11120.2H4A—O4—H4B101.6
N1—C1—C2—C31.3 (12)O2—Co1—N1—C1−102.6 (6)
C1—C2—C3—C4−0.1 (12)Br1—Co1—N1—C1−12.1 (6)
C2—C3—C4—C5−2.0 (12)C11—C12—N2—C80.3 (11)
C3—C4—C5—N13.0 (12)C13—C12—N2—C8−176.7 (7)
C3—C4—C5—C6169.2 (8)C9—C8—N2—C12−0.1 (11)
N1—C5—C6—O16.7 (11)C5—C6—O1—Co1iii−146.0 (6)
C4—C5—C6—O1−159.9 (7)C5—C6—O1—Co1−22.0 (8)
N2—C8—C9—C10−1.0 (11)C5—C6—O1—Co1ii87.7 (7)
C8—C9—C10—C111.8 (12)O1i—Co1—O1—C6−150.0 (5)
C9—C10—C11—C12−1.5 (11)N1—Co1—O1—C621.6 (5)
C10—C11—C12—N20.5 (12)O1ii—Co1—O1—C6129.2 (4)
C10—C11—C12—C13177.4 (7)O2—Co1—O1—C6−60.7 (5)
N2—C12—C13—O3−30.4 (10)Br1—Co1—O1—C6101.3 (16)
C11—C12—C13—O3152.6 (7)O1i—Co1—O1—Co1iii−9.59 (19)
C4—C5—N1—C1−1.9 (10)N1—Co1—O1—Co1iii162.0 (3)
C6—C5—N1—C1−169.1 (7)O1ii—Co1—O1—Co1iii−90.4 (2)
C4—C5—N1—Co1179.5 (6)O2—Co1—O1—Co1iii79.8 (2)
C6—C5—N1—Co112.4 (8)Br1—Co1—O1—Co1iii−118.2 (15)
C2—C1—N1—C5−0.2 (11)O1i—Co1—O1—Co1ii90.7 (2)
C2—C1—N1—Co1178.1 (6)N1—Co1—O1—Co1ii−97.7 (2)
O1i—Co1—N1—C54.2 (9)O1ii—Co1—O1—Co1ii9.9 (3)
O1—Co1—N1—C5−18.6 (5)O2—Co1—O1—Co1ii−179.97 (19)
O1ii—Co1—N1—C5−95.5 (5)Br1—Co1—O1—Co1ii−18.0 (17)
O2—Co1—N1—C575.9 (5)O1i—Co1—O2—C7−160.9 (6)
Br1—Co1—N1—C5166.4 (5)N1—Co1—O2—C739.9 (6)
O1i—Co1—N1—C1−174.3 (6)O1—Co1—O2—C7118.6 (6)
O1—Co1—N1—C1163.0 (6)O1ii—Co1—O2—C7174.5 (9)
O1ii—Co1—N1—C186.1 (6)Br1—Co1—O2—C7−59.9 (6)
D—H···AD—HH···AD···AD—H···A
O2—H2B···Br1iii0.972.543.217 (5)127
O3—H3A···O3iv0.962.313.030 (9)132
O3—H3A···O4v0.962.573.370 (11)141
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O2—H2B⋯Br1i0.972.543.217 (5)127
O3—H3A⋯O3ii0.962.313.030 (9)132
O3—H3A⋯O4iii0.962.573.370 (11)141

Symmetry codes: (i) ; (ii) ; (iii) .

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