catena-Poly[[(2,2′-bipyridine-κ²N,N′)cobalt(II)]-μ-oxalato-κ⁴O¹,O²:O^1′,O^2′]

In the title compound, [Co(C₂O₄)(C₁₀H₈N₂)]_n, the oxalate group chelates two adjacent metal atoms, resulting in a zigzag chain running along the a axis. The Co^II centre exists in an all cis-octa­hedral coordination geometry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.026
• wR factor = 0.068
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.49
           From the CIF: _reflns_number_total               2698
           Count of symmetry unique reflns         1422
           Completeness (_total/calc)            189.73%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1276
           Fraction of Friedel pairs measured     0.897
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The oxalate group chelates two adjacent metal atoms in Co(C₁₀H₈N₂)(C₂O₄) resulting in a zigzag chain running along the a-axis of the orthorhombic unit cell. The cobalt atom exists in an all cis-octahedral coordination geometry.

Related literature

The Mn(II), Fe(II), Ni(II), Cu(II) and Zn(II) analogs are isostructural; see: Deguenon et al. (1990); Fun et al. (1999); Lin et al. (2006); Luo et al. (2001); Yu et al. (2006).

S2. Experimental

An aqueous solution of 2M sodium hydroxide (0.2 ml) was added to a water/DMF (2:7 v/v) solution (9 ml) of cobalt(II) oxalate dihdyrate (0.01 g, 0.05 mmol) and 2,2'-bipyridine (0.01 g, 0.05 mmol). Pink blocks separated from the solution after several days in 30% yield. CH&N elemental analysis. Calculated for C₁₂H₈CoN₂O₄: C 47.55, H 2.66, N 9.24%. Found: C 47.27, H 2.94, N 9.40%.

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of a section of the chain structure of Co(C10H8N2)(C2O4) at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

catena-Poly[[(2,2'-bipyridine-κ²N,N')cobalt(II)]-µ- oxalato-κ⁴O¹,O²:O^1',O^2']

Crystal data

[Co(C2O4)(C10H8N2)]	F(000) = 612
Mr = 303.13	Dx = 1.683 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4493 reflections
a = 9.1275 (8) Å	θ = 2.6–26.1°
b = 9.2323 (8) Å	µ = 1.45 mm^−1
c = 14.1929 (12) Å	T = 293 K
V = 1196.00 (18) Å^3	Prism, pink
Z = 4	0.36 × 0.25 × 0.18 mm

Data collection

Bruker APEXII diffractometer	2698 independent reflections
Radiation source: fine-focus sealed tube	2456 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.624, Tmax = 0.781	k = −11→11
9371 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0436P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2698 reflections	Δρmax = 0.17 e Å^−3
172 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1277 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

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

	x	y	z	Uiso*/Ueq
Co1	0.38104 (3)	0.58866 (2)	0.49966 (4)	0.03408 (9)
N1	0.3016 (2)	0.4155 (2)	0.41608 (15)	0.0413 (5)
N2	0.4481 (2)	0.40387 (19)	0.57666 (14)	0.0390 (4)
O1	0.27899 (18)	0.75569 (19)	0.42055 (11)	0.0445 (4)
O2	0.07533 (18)	0.88996 (17)	0.42286 (12)	0.0409 (4)
O3	0.19137 (17)	0.61940 (16)	0.57821 (11)	0.0389 (3)
O4	−0.00808 (15)	0.75786 (19)	0.58323 (12)	0.0449 (4)
C1	0.2256 (3)	0.4294 (3)	0.3354 (2)	0.0551 (7)
H1	0.1995	0.5218	0.3153	0.066*
C2	0.1847 (3)	0.3113 (4)	0.2810 (2)	0.0674 (8)
H2	0.1334	0.3240	0.2250	0.081*
C3	0.2216 (4)	0.1757 (4)	0.3117 (2)	0.0710 (9)
H3	0.1954	0.0948	0.2765	0.085*
C4	0.2974 (3)	0.1594 (3)	0.3946 (2)	0.0574 (7)
H4	0.3222	0.0675	0.4162	0.069*
C5	0.3367 (3)	0.2817 (3)	0.44589 (16)	0.0385 (5)
C6	0.4169 (3)	0.2747 (3)	0.53643 (18)	0.0390 (5)
C7	0.4574 (4)	0.1460 (3)	0.5795 (2)	0.0583 (7)
H7	0.4359	0.0578	0.5511	0.070*
C8	0.5303 (4)	0.1498 (4)	0.6653 (2)	0.0661 (8)
H8	0.5587	0.0642	0.6947	0.079*
C9	0.5598 (3)	0.2808 (4)	0.70638 (19)	0.0635 (8)
H9	0.6075	0.2857	0.7642	0.076*
C10	0.5172 (3)	0.4054 (3)	0.6601 (2)	0.0531 (7)
H110	0.5373	0.4944	0.6880	0.064*
C11	0.1593 (2)	0.7943 (2)	0.45489 (15)	0.0329 (4)
C12	0.1106 (2)	0.7173 (3)	0.54720 (15)	0.0329 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03270 (14)	0.03499 (14)	0.03454 (13)	−0.00016 (11)	0.00143 (14)	−0.00307 (16)
N1	0.0463 (11)	0.0436 (11)	0.0339 (10)	−0.0047 (8)	−0.0038 (8)	−0.0021 (8)
N2	0.0408 (11)	0.0406 (11)	0.0356 (10)	0.0037 (8)	−0.0018 (8)	−0.0021 (8)
O1	0.0411 (9)	0.0516 (10)	0.0409 (9)	0.0057 (7)	0.0145 (8)	0.0104 (8)
O2	0.0398 (8)	0.0430 (9)	0.0401 (9)	0.0032 (7)	0.0070 (7)	0.0130 (7)
O3	0.0377 (8)	0.0401 (8)	0.0388 (8)	0.0037 (7)	0.0054 (7)	0.0105 (7)
O4	0.0397 (9)	0.0536 (10)	0.0413 (9)	0.0093 (7)	0.0125 (8)	0.0179 (8)
C1	0.0618 (17)	0.0630 (17)	0.0404 (13)	−0.0075 (13)	−0.0131 (12)	−0.0006 (12)
C2	0.0740 (19)	0.085 (2)	0.0435 (15)	−0.0175 (17)	−0.0170 (14)	−0.0103 (14)
C3	0.082 (2)	0.069 (2)	0.0628 (18)	−0.0255 (17)	−0.0066 (16)	−0.0259 (16)
C4	0.0692 (18)	0.0465 (15)	0.0565 (16)	−0.0145 (13)	−0.0005 (14)	−0.0107 (12)
C5	0.0407 (11)	0.0403 (12)	0.0346 (12)	−0.0044 (11)	0.0034 (10)	−0.0051 (10)
C6	0.0429 (12)	0.0341 (11)	0.0402 (12)	0.0035 (10)	0.0077 (10)	−0.0023 (9)
C7	0.0777 (19)	0.0428 (14)	0.0544 (15)	0.0149 (14)	−0.0004 (15)	−0.0044 (13)
C8	0.086 (2)	0.0576 (17)	0.0546 (16)	0.0271 (16)	0.0024 (16)	0.0105 (15)
C9	0.0727 (18)	0.077 (2)	0.0406 (15)	0.0236 (16)	−0.0064 (13)	0.0052 (14)
C10	0.0622 (17)	0.0555 (16)	0.0416 (13)	0.0124 (12)	−0.0082 (13)	−0.0062 (11)
C11	0.0342 (10)	0.0332 (11)	0.0312 (10)	−0.0055 (10)	0.0024 (9)	0.0017 (9)
C12	0.0318 (11)	0.0349 (11)	0.0321 (11)	−0.0025 (9)	0.0030 (8)	0.0025 (9)

Geometric parameters (Å, º)

Co1—O3	2.0786 (16)	C1—H1	0.9300
Co1—O2^i	2.0909 (16)	C2—C3	1.367 (5)
Co1—O4^i	2.1068 (16)	C2—H2	0.9300
Co1—N1	2.119 (2)	C3—C4	1.374 (5)
Co1—N2	2.1165 (19)	C3—H3	0.9300
Co1—O1	2.1228 (17)	C4—C5	1.391 (4)
N1—C1	1.344 (3)	C4—H4	0.9300
N1—C5	1.344 (3)	C5—C6	1.480 (3)
N2—C10	1.342 (3)	C6—C7	1.386 (4)
N2—C6	1.352 (3)	C7—C8	1.388 (4)
O1—C11	1.248 (3)	C7—H7	0.9300
O2—C11	1.255 (3)	C8—C9	1.369 (5)
O2—Co1^ii	2.0909 (16)	C8—H8	0.9300
O3—C12	1.247 (3)	C9—C10	1.381 (4)
O4—C12	1.255 (2)	C9—H9	0.9300
O4—Co1^ii	2.1068 (16)	C10—H110	0.9300
C1—C2	1.388 (4)	C11—C12	1.555 (2)
O3—Co1—O2^i	166.68 (6)	C2—C3—C4	119.8 (3)
O3—Co1—O4^i	90.36 (6)	C2—C3—H3	120.1
O2^i—Co1—O4^i	79.78 (6)	C4—C3—H3	120.1
O3—Co1—N1	96.78 (8)	C3—C4—C5	119.3 (3)
O2^i—Co1—N1	94.00 (7)	C3—C4—H4	120.4
O4^i—Co1—N1	170.80 (7)	C5—C4—H4	120.4
O3—Co1—N2	94.24 (7)	N1—C5—C4	121.3 (2)
O2^i—Co1—N2	95.74 (7)	N1—C5—C6	115.6 (2)
O4^i—Co1—N2	96.46 (8)	C4—C5—C6	123.1 (3)
N1—Co1—N2	77.29 (7)	N2—C6—C7	120.9 (3)
O3—Co1—O1	79.57 (6)	N2—C6—C5	115.6 (2)
O2^i—Co1—O1	91.60 (7)	C7—C6—C5	123.5 (3)
O4^i—Co1—O1	91.15 (7)	C8—C7—C6	119.6 (3)
N1—Co1—O1	95.83 (8)	C8—C7—H7	120.2
N2—Co1—O1	170.25 (7)	C6—C7—H7	120.2
C1—N1—C5	118.6 (2)	C9—C8—C7	119.3 (3)
C1—N1—Co1	125.54 (18)	C9—C8—H8	120.3
C5—N1—Co1	115.80 (17)	C7—C8—H8	120.3
C10—N2—C6	118.8 (2)	C8—C9—C10	118.6 (3)
C10—N2—Co1	125.67 (16)	C8—C9—H9	120.7
C6—N2—Co1	115.58 (17)	C10—C9—H9	120.7
C11—O1—Co1	112.63 (14)	N2—C10—C9	122.9 (3)
C11—O2—Co1^ii	113.30 (14)	N2—C10—H110	118.5
C12—O3—Co1	113.72 (14)	C9—C10—H110	118.5
C12—O4—Co1^ii	112.70 (15)	O1—C11—O2	126.4 (2)
N1—C1—C2	122.5 (3)	O1—C11—C12	116.67 (18)
N1—C1—H1	118.8	O2—C11—C12	116.88 (17)
C2—C1—H1	118.8	O3—C12—O4	125.7 (2)
C3—C2—C1	118.5 (3)	O3—C12—C11	117.35 (17)
C3—C2—H2	120.8	O4—C12—C11	116.98 (18)
C1—C2—H2	120.8
O3—Co1—N1—C1	86.2 (2)	C1—N1—C5—C6	−178.5 (2)
O2^i—Co1—N1—C1	−86.0 (2)	Co1—N1—C5—C6	4.1 (3)
N2—Co1—N1—C1	179.0 (2)	C3—C4—C5—N1	0.2 (4)
O1—Co1—N1—C1	6.0 (2)	C3—C4—C5—C6	179.3 (3)
O3—Co1—N1—C5	−96.68 (18)	C10—N2—C6—C7	−1.1 (4)
O2^i—Co1—N1—C5	91.16 (18)	Co1—N2—C6—C7	179.0 (2)
N2—Co1—N1—C5	−3.84 (18)	C10—N2—C6—C5	178.2 (2)
O1—Co1—N1—C5	−176.83 (18)	Co1—N2—C6—C5	−1.7 (3)
O3—Co1—N2—C10	−81.0 (2)	N1—C5—C6—N2	−1.6 (3)
O2^i—Co1—N2—C10	90.2 (2)	C4—C5—C6—N2	179.2 (3)
O4^i—Co1—N2—C10	9.8 (2)	N1—C5—C6—C7	177.7 (3)
N1—Co1—N2—C10	−177.0 (2)	C4—C5—C6—C7	−1.5 (4)
O3—Co1—N2—C6	98.92 (19)	N2—C6—C7—C8	0.4 (5)
O2^i—Co1—N2—C6	−89.91 (18)	C5—C6—C7—C8	−178.9 (2)
O4^i—Co1—N2—C6	−170.23 (18)	C6—C7—C8—C9	0.5 (5)
N1—Co1—N2—C6	2.91 (19)	C7—C8—C9—C10	−0.7 (5)
O3—Co1—O1—C11	0.09 (16)	C6—N2—C10—C9	0.9 (4)
O2^i—Co1—O1—C11	−169.87 (16)	Co1—N2—C10—C9	−179.2 (2)
O4^i—Co1—O1—C11	−90.06 (16)	C8—C9—C10—N2	0.0 (4)
N1—Co1—O1—C11	95.94 (17)	Co1—O1—C11—O2	−179.71 (19)
O2^i—Co1—O3—C12	47.6 (4)	Co1—O1—C11—C12	1.1 (2)
O4^i—Co1—O3—C12	89.55 (17)	Co1^ii—O2—C11—O1	177.06 (19)
N1—Co1—O3—C12	−96.27 (17)	Co1^ii—O2—C11—C12	−3.8 (2)
N2—Co1—O3—C12	−173.95 (17)	Co1—O3—C12—O4	−178.58 (19)
O1—Co1—O3—C12	−1.55 (16)	Co1—O3—C12—C11	2.6 (2)
C5—N1—C1—C2	−1.3 (4)	Co1^ii—O4—C12—O3	−174.00 (19)
Co1—N1—C1—C2	175.8 (2)	Co1^ii—O4—C12—C11	4.9 (2)
N1—C1—C2—C3	0.9 (5)	O1—C11—C12—O3	−2.6 (3)
C1—C2—C3—C4	0.0 (5)	O2—C11—C12—O3	178.2 (2)
C2—C3—C4—C5	−0.5 (5)	O1—C11—C12—O4	178.4 (2)
C1—N1—C5—C4	0.7 (4)	O2—C11—C12—O4	−0.8 (3)
Co1—N1—C5—C4	−176.7 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+3/2, z.