catena-Poly[[[aqua­formato(1,10-phenanthroline)cobalt(II)]-μ-formato] mono­hydrate]

In the polymeric title compound, {[Co(CHO₂)₂(C₁₂H₈N₂)(H₂O)]·H₂O}_n, the cobalt ion is coordinated by two N atoms from one chelating 1,10-phenanthroline ligand, three formate O atoms and one water O atom, giving a cis-CoN₂O₄ octa­hedral geometry. Pairs of formate anions bridge the metal atoms into a chain. A network of O—H...O hydrogen bonds helps to establish the packing.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.043
• wR factor = 0.100
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.03

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           25.02
           From the CIF: _reflns_number_total               2562
           Count of symmetry unique reflns         1410
           Completeness (_total/calc)            181.70%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1152
           Fraction of Friedel pairs measured     0.817
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (9)       1.67
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          7

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 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
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Recently, formate complexes have received attention in terms of their structure, magnetism and biological activity (Peng et al., 2006; Cui et al., 2007).

We report here the structure (Fig. 1) of the polymeric title compound, (I), in which two formate anions are bridging between Co centres. The cobalt coordinaion is completed by a monodentate-O terminal formate ion, an N,N-bidentate 1,10-phenanthroline molecule and a water molecule. This results in a distorted cis-CoN₂O₄ octahedral coordination gemoetry (Table 1).

The bridging formate anions lead to a one-dimensional polymeric chain. The packing for (I) is consolidated by a network of O—H···O hydrogen bonds (Table 2).

Related literature

For background, see: Peng et al. (2006); Cui et al. (2007).

S2. Experimental

The title compound was prepared by adding 5 ml of aqueous solution of cobalt nitrate (0.146 g, 0.5 mmol), to 10 ml of ethanol solution of 1,10-phenanthroline (0.099 g, 0.5 mmol), after which sodium formate (0.232 g, 4 mmol) was added and was refluexed for 2 h. The resulting solution was filtrated and the filtrate was kept at room temperature and orange blocks of (I) appeared after a week.

S3. Refinement

The H atoms were positioned geometrically (C—H = 0.96–0.97 Å, O—H = 0.85 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. A view of a fragemnt of the polymeric structure of (I). Displacement ellopsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radius. Atoms with a suffix A are at the symmetry position (1 - x, 1 - y, z - 1/2).

catena-Poly[[[aquaformato(1,10-phenanthroline)cobalt(II)]-µ-formato] monohydrate]

Crystal data

[Co(CHO2)2(C12H8N2)(H2O)]·H2O	Dx = 1.677 Mg m^−3
Mr = 365.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 3127 reflections
a = 18.908 (4) Å	θ = 2.0–27.9°
b = 12.014 (2) Å	µ = 1.22 mm^−1
c = 6.3685 (13) Å	T = 113 K
V = 1446.7 (5) Å^3	Block, orange
Z = 4	0.20 × 0.18 × 0.08 mm
F(000) = 748

Data collection

Rigaku Saturn diffractometer	2562 independent reflections
Radiation source: rotating anode	2153 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.085
ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −22→22
Tmin = 0.792, Tmax = 0.909	k = −11→14
8676 measured reflections	l = −7→7

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)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0651P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.86	(Δ/σ)max = 0.001
2562 reflections	Δρmax = 0.33 e Å^−3
209 parameters	Δρmin = −0.42 e Å^−3
7 restraints	Absolute structure: Flack (1983), 1152 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (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. 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	0.58489 (2)	0.37977 (4)	0.81148 (10)	0.01363 (16)
O1	0.57437 (16)	0.2373 (2)	0.6343 (5)	0.0212 (8)
O2	0.56006 (18)	0.0562 (2)	0.5806 (6)	0.0273 (8)
O3	0.59367 (14)	0.5412 (2)	0.9471 (5)	0.0177 (7)
O4	0.49223 (15)	0.5437 (2)	1.1272 (5)	0.0186 (7)
O5	0.50825 (16)	0.3308 (2)	1.0273 (5)	0.0209 (8)
H5A	0.5086	0.2784	1.1163	0.025*
H5B	0.4983	0.3956	1.0733	0.025*
N1	0.66885 (18)	0.4293 (3)	0.6150 (6)	0.0136 (8)
N2	0.67416 (19)	0.3116 (3)	0.9751 (6)	0.0173 (8)
C1	0.6659 (3)	0.4838 (4)	0.4355 (7)	0.0208 (10)
H1	0.6218	0.5067	0.3880	0.025*
C2	0.7245 (2)	0.5094 (3)	0.3127 (10)	0.0240 (9)
H2	0.7193	0.5481	0.1871	0.029*
C3	0.7901 (2)	0.4762 (4)	0.3807 (8)	0.0253 (12)
H3	0.8301	0.4913	0.3007	0.030*
C4	0.7962 (2)	0.4191 (4)	0.5731 (8)	0.0214 (11)
C5	0.8627 (3)	0.3794 (4)	0.6570 (9)	0.0323 (13)
H5	0.9045	0.3951	0.5862	0.039*
C6	0.8646 (2)	0.3205 (4)	0.8352 (10)	0.0319 (13)
H6	0.9080	0.2957	0.8852	0.038*
C7	0.8015 (2)	0.2944 (4)	0.9519 (8)	0.0235 (11)
C8	0.8010 (3)	0.2328 (4)	1.1383 (8)	0.0268 (12)
H8	0.8432	0.2066	1.1942	0.032*
C9	0.7387 (3)	0.2112 (4)	1.2382 (8)	0.0292 (13)
H9	0.7382	0.1696	1.3614	0.035*
C10	0.6751 (2)	0.2524 (3)	1.1525 (8)	0.0226 (11)
H10	0.6327	0.2380	1.2214	0.027*
C11	0.7362 (2)	0.3326 (4)	0.8765 (7)	0.0181 (10)
C12	0.7338 (2)	0.3958 (4)	0.6843 (8)	0.0183 (11)
C13	0.5675 (2)	0.1395 (4)	0.6949 (8)	0.0225 (11)
H13	0.5679	0.1275	0.8391	0.027*
C14	0.5454 (2)	0.5899 (4)	1.0437 (7)	0.0169 (10)
H14	0.5488	0.6669	1.0554	0.020*
O6	0.49393 (19)	0.1397 (2)	0.2288 (6)	0.0332 (9)
H6A	0.4752	0.0902	0.1500	0.040*
H6B	0.5149	0.1157	0.3384	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0135 (3)	0.0126 (3)	0.0147 (3)	0.0009 (2)	−0.0011 (3)	0.0004 (3)
O1	0.0298 (19)	0.0150 (18)	0.0187 (19)	0.0002 (13)	−0.0043 (14)	0.0023 (15)
O2	0.044 (2)	0.0148 (17)	0.0235 (18)	−0.0011 (15)	−0.0075 (16)	−0.0029 (16)
O3	0.0163 (16)	0.0160 (17)	0.0207 (18)	0.0009 (12)	0.0034 (13)	0.0012 (15)
O4	0.0172 (16)	0.0181 (16)	0.0203 (18)	−0.0024 (13)	0.0056 (14)	0.0011 (14)
O5	0.0251 (17)	0.0109 (16)	0.027 (2)	0.0023 (12)	0.0103 (15)	0.0023 (14)
N1	0.016 (2)	0.0094 (18)	0.016 (2)	0.0001 (14)	−0.0008 (16)	−0.0020 (17)
N2	0.018 (2)	0.0143 (19)	0.020 (2)	0.0029 (15)	−0.0013 (16)	−0.0040 (18)
C1	0.029 (3)	0.018 (2)	0.016 (2)	0.0018 (19)	0.002 (2)	−0.002 (2)
C2	0.035 (2)	0.017 (2)	0.020 (2)	−0.0100 (17)	0.005 (3)	−0.003 (3)
C3	0.029 (3)	0.017 (3)	0.030 (3)	−0.008 (2)	0.014 (2)	−0.011 (2)
C4	0.019 (3)	0.018 (2)	0.027 (3)	−0.0049 (18)	0.006 (2)	−0.008 (2)
C5	0.011 (3)	0.046 (3)	0.041 (3)	−0.002 (2)	0.005 (2)	−0.020 (3)
C6	0.018 (2)	0.038 (3)	0.039 (4)	0.0110 (19)	−0.012 (3)	−0.021 (3)
C7	0.022 (3)	0.023 (3)	0.026 (3)	0.005 (2)	−0.007 (2)	−0.009 (2)
C8	0.032 (3)	0.019 (3)	0.030 (3)	0.009 (2)	−0.014 (2)	−0.011 (2)
C9	0.039 (3)	0.030 (3)	0.019 (2)	0.005 (2)	−0.014 (2)	−0.006 (2)
C10	0.032 (3)	0.012 (2)	0.024 (3)	0.0009 (19)	−0.006 (2)	0.000 (2)
C11	0.021 (2)	0.014 (2)	0.019 (3)	0.0056 (18)	−0.0033 (18)	−0.0070 (19)
C12	0.016 (2)	0.016 (2)	0.023 (3)	0.0020 (18)	0.000 (2)	−0.009 (2)
C13	0.022 (3)	0.025 (3)	0.020 (3)	0.005 (2)	0.002 (2)	0.000 (2)
C14	0.015 (2)	0.015 (2)	0.021 (3)	0.0028 (18)	−0.0028 (19)	−0.001 (2)
O6	0.052 (2)	0.0204 (18)	0.027 (2)	−0.0118 (15)	−0.0135 (17)	0.0055 (16)

Geometric parameters (Å, º)

Co1—O1	2.060 (3)	C3—C4	1.409 (7)
Co1—O5	2.082 (3)	C3—H3	0.9300
Co1—O4^i	2.086 (3)	C4—C12	1.404 (6)
Co1—N1	2.107 (4)	C4—C5	1.446 (7)
Co1—O3	2.129 (3)	C5—C6	1.338 (8)
Co1—N2	2.146 (4)	C5—H5	0.9300
O1—C13	1.244 (5)	C6—C7	1.440 (7)
O2—C13	1.245 (5)	C6—H6	0.9300
O3—C14	1.246 (5)	C7—C8	1.398 (7)
O4—C14	1.266 (5)	C7—C11	1.402 (6)
O4—Co1^ii	2.086 (3)	C8—C9	1.363 (7)
O5—H5A	0.8473	C8—H8	0.9300
O5—H5B	0.8533	C9—C10	1.411 (6)
N1—C1	1.319 (6)	C9—H9	0.9300
N1—C12	1.366 (6)	C10—H10	0.9300
N2—C10	1.335 (6)	C11—C12	1.441 (7)
N2—C11	1.355 (6)	C13—H13	0.9300
C1—C2	1.389 (6)	C14—H14	0.9300
C1—H1	0.9300	O6—H6A	0.8544
C2—C3	1.375 (6)	O6—H6B	0.8532
C2—H2	0.9300
O1—Co1—O5	93.42 (12)	C4—C3—H3	120.4
O1—Co1—O4^i	89.45 (11)	C12—C4—C3	117.9 (4)
O5—Co1—O4^i	90.54 (12)	C12—C4—C5	118.5 (5)
O1—Co1—N1	88.97 (13)	C3—C4—C5	123.5 (4)
O5—Co1—N1	174.97 (14)	C6—C5—C4	120.7 (5)
O4^i—Co1—N1	93.91 (13)	C6—C5—H5	119.6
O1—Co1—O3	170.57 (13)	C4—C5—H5	119.6
O5—Co1—O3	92.52 (12)	C5—C6—C7	122.1 (4)
O4^i—Co1—O3	83.18 (11)	C5—C6—H6	119.0
N1—Co1—O3	85.70 (12)	C7—C6—H6	119.0
O1—Co1—N2	91.42 (13)	C8—C7—C11	117.2 (4)
O5—Co1—N2	96.83 (14)	C8—C7—C6	124.0 (4)
O4^i—Co1—N2	172.51 (14)	C11—C7—C6	118.7 (5)
N1—Co1—N2	78.67 (13)	C9—C8—C7	120.2 (4)
O3—Co1—N2	95.14 (13)	C9—C8—H8	119.9
C13—O1—Co1	128.7 (3)	C7—C8—H8	119.9
C14—O3—Co1	124.8 (3)	C8—C9—C10	119.3 (5)
C14—O4—Co1^ii	126.8 (3)	C8—C9—H9	120.4
Co1—O5—H5A	130.2	C10—C9—H9	120.4
Co1—O5—H5B	97.0	N2—C10—C9	121.7 (5)
H5A—O5—H5B	116.8	N2—C10—H10	119.1
C1—N1—C12	117.6 (4)	C9—C10—H10	119.1
C1—N1—Co1	128.6 (3)	N2—C11—C7	122.9 (4)
C12—N1—Co1	113.7 (3)	N2—C11—C12	117.7 (4)
C10—N2—C11	118.7 (4)	C7—C11—C12	119.4 (4)
C10—N2—Co1	128.7 (3)	N1—C12—C4	122.3 (5)
C11—N2—Co1	112.7 (3)	N1—C12—C11	117.2 (4)
N1—C1—C2	124.4 (5)	C4—C12—C11	120.5 (4)
N1—C1—H1	117.8	O1—C13—O2	126.1 (5)
C2—C1—H1	117.8	O1—C13—H13	116.9
C3—C2—C1	118.5 (5)	O2—C13—H13	116.9
C3—C2—H2	120.7	O3—C14—O4	125.7 (4)
C1—C2—H2	120.7	O3—C14—H14	117.2
C2—C3—C4	119.3 (5)	O4—C14—H14	117.2
C2—C3—H3	120.4	H6A—O6—H6B	116.0
O5—Co1—O1—C13	−41.7 (4)	C4—C5—C6—C7	−0.3 (7)
O4^i—Co1—O1—C13	−132.2 (4)	C5—C6—C7—C8	179.8 (5)
N1—Co1—O1—C13	133.9 (4)	C5—C6—C7—C11	−0.4 (7)
N2—Co1—O1—C13	55.3 (4)	C11—C7—C8—C9	0.6 (7)
O5—Co1—O3—C14	−27.5 (3)	C6—C7—C8—C9	−179.6 (4)
O4^i—Co1—O3—C14	62.8 (3)	C7—C8—C9—C10	−0.6 (7)
N1—Co1—O3—C14	157.2 (4)	C11—N2—C10—C9	−0.3 (6)
N2—Co1—O3—C14	−124.6 (3)	Co1—N2—C10—C9	178.6 (3)
O1—Co1—N1—C1	86.0 (4)	C8—C9—C10—N2	0.5 (7)
O4^i—Co1—N1—C1	−3.4 (4)	C10—N2—C11—C7	0.4 (6)
O3—Co1—N1—C1	−86.2 (4)	Co1—N2—C11—C7	−178.7 (3)
N2—Co1—N1—C1	177.6 (4)	C10—N2—C11—C12	179.5 (4)
O1—Co1—N1—C12	−91.7 (3)	Co1—N2—C11—C12	0.4 (5)
O4^i—Co1—N1—C12	179.0 (3)	C8—C7—C11—N2	−0.5 (7)
O3—Co1—N1—C12	96.1 (3)	C6—C7—C11—N2	179.7 (4)
N2—Co1—N1—C12	0.0 (3)	C8—C7—C11—C12	−179.6 (4)
O1—Co1—N2—C10	−90.5 (4)	C6—C7—C11—C12	0.6 (6)
O5—Co1—N2—C10	3.1 (4)	C1—N1—C12—C4	1.0 (6)
N1—Co1—N2—C10	−179.2 (4)	Co1—N1—C12—C4	178.9 (3)
O3—Co1—N2—C10	96.2 (4)	C1—N1—C12—C11	−177.7 (4)
O1—Co1—N2—C11	88.4 (3)	Co1—N1—C12—C11	0.2 (5)
O5—Co1—N2—C11	−178.0 (3)	C3—C4—C12—N1	−1.9 (6)
N1—Co1—N2—C11	−0.2 (3)	C5—C4—C12—N1	−179.4 (4)
O3—Co1—N2—C11	−84.8 (3)	C3—C4—C12—C11	176.8 (4)
C12—N1—C1—C2	0.0 (6)	C5—C4—C12—C11	−0.7 (6)
Co1—N1—C1—C2	−177.6 (3)	N2—C11—C12—N1	−0.4 (6)
N1—C1—C2—C3	0.0 (7)	C7—C11—C12—N1	178.7 (4)
C1—C2—C3—C4	−0.9 (7)	N2—C11—C12—C4	−179.2 (4)
C2—C3—C4—C12	1.8 (6)	C7—C11—C12—C4	0.0 (7)
C2—C3—C4—C5	179.2 (4)	Co1—O1—C13—O2	178.7 (3)
C12—C4—C5—C6	0.9 (7)	Co1—O3—C14—O4	20.8 (6)
C3—C4—C5—C6	−176.4 (5)	Co1^ii—O4—C14—O3	174.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6^iii	0.85	1.83	2.644 (4)	159
O6—H6A···O2^iv	0.85	1.93	2.734 (4)	156
O5—H5B···O4	0.85	1.82	2.653 (4)	167
O6—H6B···O2	0.85	1.90	2.755 (5)	178

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