Crystal structure of di-μ-hydroxido-κ⁴O:O-bis[bis(acetyl­acetonato-κ²O,O′)cobalt(III)]

[Co(acac)₂(μ-OH)]₂ (acac = acetyl­acetonate) is the first crystal structure reported of a dimeric transition metal bis-acac complex with OH⁻ as the bridging group. The centrosymmetric mol­ecular structure is a [Co₂(μ₂-OH)₂] dimer with each metal coordinated by two acac ligands in a κ²-O,O′ mode.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.093
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT303_ALERT_2_G Full Occupancy H-Atom  H1     with # Connections       3.00 Check
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         23 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013/4 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008), CrystalMaker (CrystalMaker, 1994); software used to prepare material for publication: XCIF (Bruker, 2013) and publCIF (Westrip, 2010).

Di-µ-hydroxido-κ⁴O:O-bis[bis(acetylacetonato-κ²O,O')cobalt(III)]

Crystal data

[Co2(C5H7O2)4(OH)2]	Z = 1
Mr = 548.30	F(000) = 284
Triclinic, P1	Dx = 1.560 Mg m^−3
a = 7.8610 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2481 (11) Å	Cell parameters from 3791 reflections
c = 9.8372 (13) Å	θ = 2.6–25.5°
α = 100.786 (8)°	µ = 1.47 mm^−1
β = 106.708 (8)°	T = 173 K
γ = 99.492 (9)°	Plate, blue
V = 583.67 (14) Å^3	0.23 × 0.19 × 0.04 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2617 independent reflections
Radiation source: fine-focus sealed tube	2228 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
profile data from φ and ω scans	θmax = 27.3°, θmin = 2.2°
Absorption correction: integration (SADABS; Bruker, 2012)	h = −10→10
Tmin = 0.776, Tmax = 0.945	k = −10→10
16164 measured reflections	l = −12→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0366P)^2 + 0.1984P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2617 reflections	Δρmax = 0.39 e Å^−3
152 parameters	Δρmin = −0.53 e Å^−3

Special details

Experimental. One distinct cell was identified using APEX2 (Bruker, 2013). Fourteen frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2013) then corrected for absorption by integration using SAINT/SADABS, v2012/1 (Bruker, 2012) to sort, merge, and scale the combined data. No decay correction was applied.

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. Structure was phased by direct methods (Sheldrick, 2008). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude and resolution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.08356 (4)	0.96491 (4)	0.63894 (3)	0.01839 (12)
O1	0.0955 (2)	1.1492 (2)	0.54669 (18)	0.0197 (4)
H1	0.182 (4)	1.158 (4)	0.530 (3)	0.030*
O2	0.0442 (2)	0.7772 (2)	0.71880 (18)	0.0244 (4)
O3	0.2682 (2)	0.9024 (2)	0.56955 (18)	0.0220 (4)
C1	0.0467 (4)	0.5042 (3)	0.7559 (3)	0.0294 (6)
H1A	0.1238	0.5263	0.8584	0.044*
H1B	0.0576	0.3969	0.7002	0.044*
H1C	−0.0808	0.4967	0.7508	0.044*
C2	0.1074 (3)	0.6460 (3)	0.6920 (2)	0.0216 (5)
C3	0.2293 (3)	0.6301 (3)	0.6154 (3)	0.0239 (5)
H3	0.2605	0.5236	0.5962	0.029*
C4	0.3092 (3)	0.7594 (3)	0.5647 (2)	0.0204 (5)
C5	0.4588 (3)	0.7360 (3)	0.5010 (3)	0.0291 (6)
H5A	0.4703	0.8171	0.4411	0.044*
H5B	0.4290	0.6201	0.4398	0.044*
H5C	0.5745	0.7556	0.5805	0.044*
O4	−0.1041 (2)	1.0298 (2)	0.70365 (18)	0.0211 (3)
O5	0.2764 (2)	1.0871 (2)	0.81009 (18)	0.0258 (4)
C6	−0.2501 (3)	1.1417 (4)	0.8641 (3)	0.0302 (6)
H6A	−0.2682	1.2526	0.8490	0.045*
H6B	−0.2371	1.1397	0.9658	0.045*
H6C	−0.3556	1.0527	0.7980	0.045*
C7	−0.0812 (3)	1.1114 (3)	0.8328 (3)	0.0216 (5)
C8	0.0873 (3)	1.1769 (3)	0.9434 (3)	0.0265 (5)
H8	0.0877	1.2323	1.0373	0.032*
C9	0.2534 (3)	1.1666 (3)	0.9258 (3)	0.0245 (5)
C10	0.4268 (4)	1.2530 (4)	1.0500 (3)	0.0383 (7)
H10A	0.4992	1.1698	1.0733	0.057*
H10B	0.3972	1.3033	1.1363	0.057*
H10C	0.4973	1.3424	1.0215	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01960 (18)	0.01881 (19)	0.02005 (19)	0.00636 (13)	0.01007 (13)	0.00540 (13)
O1	0.0196 (8)	0.0184 (8)	0.0237 (9)	0.0052 (7)	0.0118 (7)	0.0033 (7)
O2	0.0309 (9)	0.0253 (9)	0.0253 (9)	0.0113 (7)	0.0164 (7)	0.0102 (7)
O3	0.0223 (8)	0.0223 (9)	0.0267 (9)	0.0086 (7)	0.0130 (7)	0.0083 (7)
C1	0.0407 (15)	0.0259 (13)	0.0245 (13)	0.0060 (11)	0.0144 (11)	0.0090 (10)
C2	0.0227 (12)	0.0217 (12)	0.0162 (11)	0.0041 (9)	0.0015 (9)	0.0035 (9)
C3	0.0276 (12)	0.0198 (12)	0.0253 (13)	0.0091 (10)	0.0091 (10)	0.0041 (10)
C4	0.0199 (11)	0.0214 (12)	0.0166 (11)	0.0057 (9)	0.0023 (9)	0.0018 (9)
C5	0.0292 (13)	0.0297 (14)	0.0366 (15)	0.0149 (11)	0.0175 (11)	0.0099 (11)
O4	0.0210 (8)	0.0233 (9)	0.0218 (8)	0.0066 (7)	0.0114 (7)	0.0042 (7)
O5	0.0216 (9)	0.0323 (10)	0.0231 (9)	0.0069 (7)	0.0088 (7)	0.0033 (7)
C6	0.0301 (13)	0.0399 (15)	0.0278 (14)	0.0147 (12)	0.0167 (11)	0.0085 (12)
C7	0.0292 (12)	0.0188 (12)	0.0231 (12)	0.0075 (10)	0.0155 (10)	0.0080 (9)
C8	0.0317 (13)	0.0303 (14)	0.0196 (12)	0.0094 (11)	0.0120 (10)	0.0034 (10)
C9	0.0282 (13)	0.0260 (13)	0.0214 (12)	0.0074 (10)	0.0098 (10)	0.0074 (10)
C10	0.0313 (14)	0.0479 (18)	0.0277 (15)	0.0049 (13)	0.0074 (12)	−0.0021 (13)

Geometric parameters (Å, º)

Co1—O3	1.8770 (16)	C4—C5	1.506 (3)
Co1—O4	1.8814 (16)	C5—H5A	0.9800
Co1—O5	1.8820 (17)	C5—H5B	0.9800
Co1—O2	1.8830 (16)	C5—H5C	0.9800
Co1—O1^i	1.9087 (17)	O4—C7	1.268 (3)
Co1—O1	1.9131 (16)	O5—C9	1.279 (3)
Co1—Co1^i	2.8829 (7)	C6—C7	1.495 (3)
O1—Co1^i	1.9087 (17)	C6—H6A	0.9800
O1—H1	0.74 (3)	C6—H6B	0.9800
O2—C2	1.278 (3)	C6—H6C	0.9800
O3—C4	1.269 (3)	C7—C8	1.395 (3)
C1—C2	1.502 (3)	C8—C9	1.380 (3)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.502 (3)
C1—H1C	0.9800	C10—H10A	0.9800
C2—C3	1.387 (3)	C10—H10B	0.9800
C3—C4	1.393 (3)	C10—H10C	0.9800
C3—H3	0.9500
O3—Co1—O4	178.37 (6)	C2—C3—C4	124.5 (2)
O3—Co1—O5	85.06 (7)	C2—C3—H3	117.8
O4—Co1—O5	95.92 (7)	C4—C3—H3	117.8
O3—Co1—O2	95.73 (7)	O3—C4—C3	125.0 (2)
O4—Co1—O2	85.55 (7)	O3—C4—C5	115.1 (2)
O5—Co1—O2	91.96 (7)	C3—C4—C5	120.0 (2)
O3—Co1—O1^i	90.26 (7)	C4—C5—H5A	109.5
O4—Co1—O1^i	88.67 (7)	C4—C5—H5B	109.5
O5—Co1—O1^i	173.53 (7)	H5A—C5—H5B	109.5
O2—Co1—O1^i	92.95 (7)	C4—C5—H5C	109.5
O3—Co1—O1	88.10 (7)	H5A—C5—H5C	109.5
O4—Co1—O1	90.54 (7)	H5B—C5—H5C	109.5
O5—Co1—O1	93.29 (7)	C7—O4—Co1	124.45 (16)
O2—Co1—O1	173.75 (7)	C9—O5—Co1	123.82 (16)
O1^i—Co1—O1	82.07 (7)	C7—C6—H6A	109.5
O3—Co1—Co1^i	88.91 (5)	C7—C6—H6B	109.5
O4—Co1—Co1^i	89.47 (5)	H6A—C6—H6B	109.5
O5—Co1—Co1^i	134.10 (5)	C7—C6—H6C	109.5
O2—Co1—Co1^i	133.93 (6)	H6A—C6—H6C	109.5
O1^i—Co1—Co1^i	41.09 (5)	H6B—C6—H6C	109.5
O1—Co1—Co1^i	40.98 (5)	O4—C7—C8	125.1 (2)
Co1^i—O1—Co1	97.93 (7)	O4—C7—C6	116.0 (2)
Co1^i—O1—H1	103 (2)	C8—C7—C6	118.9 (2)
Co1—O1—H1	106 (2)	C9—C8—C7	124.4 (2)
C2—O2—Co1	123.65 (15)	C9—C8—H8	117.8
C4—O3—Co1	124.41 (15)	C7—C8—H8	117.8
C2—C1—H1A	109.5	O5—C9—C8	125.7 (2)
C2—C1—H1B	109.5	O5—C9—C10	114.7 (2)
H1A—C1—H1B	109.5	C8—C9—C10	119.6 (2)
C2—C1—H1C	109.5	C9—C10—H10A	109.5
H1A—C1—H1C	109.5	C9—C10—H10B	109.5
H1B—C1—H1C	109.5	H10A—C10—H10B	109.5
O2—C2—C3	125.1 (2)	C9—C10—H10C	109.5
O2—C2—C1	115.2 (2)	H10A—C10—H10C	109.5
C3—C2—C1	119.6 (2)	H10B—C10—H10C	109.5

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1^ii	0.98	2.42	3.395 (3)	174

Symmetry code: (ii) x, y−1, z.