Di-μ-oxo-bis[(2,2′-bipyridine)cobalt(III)] bis(perchlorate)

In the title compound, [Co₂O₂(C₁₀H₈N₂)₂](ClO₄)₂, the binuclear complex cation has 2/m symmetry, and the perchlorate ion has mirror symmetry. The Co^III atoms are coordinated by two N atoms of the 2,2′-bipyridine ligand and two bridging O atoms in a square-planar geometry. The Co...Co distance in the complex is 2.8784 (19) Å.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.072
• wR factor = 0.162
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    -   N2      ..       6.35 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL.

Bis(2,2'-bipyridine)-bis(oxo)dicobalt(III) diperchlorate

Crystal data

[Co2(C10H8N2)2O2](ClO4)2	F(000) = 664
Mr = 661.13	Dx = 1.823 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 8119 reflections
a = 13.646 (5) Å	θ = 2.1–28.4°
b = 15.289 (6) Å	µ = 1.66 mm^−1
c = 6.309 (2) Å	T = 298 K
β = 113.798 (6)°	Block, blue
V = 1204.4 (8) Å^3	0.24 × 0.16 × 0.08 mm
Z = 2

Data collection

Bruker Apex CCD diffractometer	1567 independent reflections
Radiation source: fine-focus sealed tube	1301 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ω scan	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −18→18
Tmin = 0.691, Tmax = 0.878	k = −20→20
8119 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.162	H-atom parameters constrained
S = 1.24	w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 2.5649P] where P = (Fo^2 + 2Fc^2)/3
1567 reflections	(Δ/σ)max < 0.001
93 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3

Special details

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. The maximum residual electron-density is 0.66 e Å^-3 at 0.84 Å from Co1 and the minimum one -0.53 e Å^-3 at 0.73 Å from Co1. 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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.40587 (5)	1.0000	0.0367 (3)
Cl1	0.25142 (15)	0.0000	0.9369 (3)	0.0506 (5)
O1	0.5469 (5)	0.5000	1.2227 (9)	0.0583 (14)
O2	0.3624 (5)	0.0000	1.0917 (10)	0.0717 (17)
O3	0.2005 (4)	0.0769 (2)	0.9759 (8)	0.0677 (12)
O4	0.2422 (5)	0.0000	0.6999 (9)	0.0654 (16)
C1	0.4675 (4)	0.2261 (3)	0.8730 (8)	0.0400 (10)
N2	0.4466 (3)	0.3071 (3)	0.7763 (7)	0.0452 (10)
C3	0.3898 (4)	0.3138 (4)	0.5449 (9)	0.0522 (13)
H3	0.3751	0.3690	0.4774	0.063*
C4	0.3532 (4)	0.2413 (4)	0.4068 (9)	0.0551 (14)
H4	0.3150	0.2476	0.2479	0.066*
C5	0.3734 (5)	0.1592 (4)	0.5049 (10)	0.0583 (14)
H5	0.3480	0.1097	0.4137	0.070*
C6	0.4321 (4)	0.1517 (4)	0.7412 (9)	0.0508 (12)
H6	0.4475	0.0968	0.8104	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0443 (5)	0.0231 (4)	0.0354 (5)	0.000	0.0086 (4)	0.000
Cl1	0.0511 (10)	0.0448 (10)	0.0419 (9)	0.000	0.0043 (8)	0.000
O1	0.073 (4)	0.039 (3)	0.046 (3)	0.000	0.005 (3)	0.000
O2	0.054 (3)	0.076 (4)	0.059 (4)	0.000	−0.004 (3)	0.000
O3	0.074 (3)	0.045 (2)	0.078 (3)	0.0068 (19)	0.024 (2)	−0.0074 (19)
O4	0.079 (4)	0.064 (4)	0.040 (3)	0.000	0.010 (3)	0.000
C1	0.043 (3)	0.039 (3)	0.035 (2)	0.003 (2)	0.013 (2)	0.0007 (18)
N2	0.051 (2)	0.040 (2)	0.039 (2)	0.0022 (18)	0.0129 (19)	0.0016 (17)
C3	0.060 (3)	0.051 (3)	0.038 (3)	0.009 (2)	0.012 (2)	0.007 (2)
C4	0.050 (3)	0.068 (4)	0.035 (3)	−0.001 (3)	0.005 (2)	−0.006 (2)
C5	0.057 (3)	0.053 (3)	0.056 (3)	−0.005 (3)	0.014 (3)	−0.013 (3)
C6	0.056 (3)	0.039 (3)	0.052 (3)	0.000 (2)	0.016 (2)	−0.006 (2)

Geometric parameters (Å, º)

Co1—O1	1.931 (3)	C1—C6	1.377 (6)
Co1—O1^i	1.931 (3)	C1—C1^ii	1.486 (9)
Co1—N2	1.994 (4)	N2—C3	1.353 (6)
Co1—N2^ii	1.994 (4)	C3—C4	1.373 (8)
Co1—Co1^i	2.8784 (19)	C3—H3	0.9300
Cl1—O2	1.433 (6)	C4—C5	1.376 (8)
Cl1—O3^iii	1.437 (4)	C4—H4	0.9300
Cl1—O3	1.437 (4)	C5—C6	1.384 (7)
Cl1—O4	1.450 (6)	C5—H5	0.9300
C1—N2	1.359 (6)	C6—H6	0.9300
O1—Co1—O1^i	83.6 (2)	N2—C1—C1^ii	114.2 (2)
O1—Co1—N2	177.3 (2)	C6—C1—C1^ii	124.2 (3)
O1^i—Co1—N2	97.50 (16)	C3—N2—C1	118.6 (4)
O1—Co1—N2^ii	97.50 (16)	C3—N2—Co1	126.4 (4)
O1^i—Co1—N2^ii	177.3 (2)	C1—N2—Co1	115.0 (3)
N2—Co1—N2^ii	81.5 (2)	N2—C3—C4	121.8 (5)
O1—Co1—Co1^i	41.81 (11)	N2—C3—H3	119.1
O1^i—Co1—Co1^i	41.81 (11)	C4—C3—H3	119.1
N2—Co1—Co1^i	139.25 (11)	C3—C4—C5	119.7 (5)
N2^ii—Co1—Co1^i	139.25 (11)	C3—C4—H4	120.2
O2—Cl1—O3^iii	109.6 (2)	C5—C4—H4	120.2
O2—Cl1—O3	109.6 (2)	C4—C5—C6	119.0 (5)
O3^iii—Cl1—O3	109.9 (4)	C4—C5—H5	120.5
O2—Cl1—O4	109.3 (4)	C6—C5—H5	120.5
O3^iii—Cl1—O4	109.3 (2)	C1—C6—C5	119.4 (5)
O3—Cl1—O4	109.3 (2)	C1—C6—H6	120.3
Co1—O1—Co1^i	96.4 (2)	C5—C6—H6	120.3
N2—C1—C6	121.5 (4)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, y, −z+2; (iii) x, −y, z.