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Single crystals of a triclinic polymorphic form of
mer-
-oxalato-bis[chloridotripyridinecobalt(II)] pyridine disolvate, [Co
2(C
2O
4)Cl
2(C
5H
5N)
6]·2C
5H
5N, have been prepared by solvothermal methods. The structure and geometric parameters strongly resemble those of the previously reported monoclinic polymorph [Bolte (2006).
Acta Cryst. E
62, m597-m598]. In both polymorphic forms, the dinuclear complex molecules are located on a crystallographic centre of inversion, with the Co
II cations in a distorted octahedral environment consisting of a chloride ligand, three pyridine ligands and a chelating bis-bidentate oxalate ligand. This last serves as a bridging ligand between two Co
II cations. The polymorphs differ in the mutual orientation of their pyridine ligands in the dinuclear molecules and in their intermolecular connectivity. In the triclinic polymorph, C-H
O, C-H
Cl, C-H
and
-
interactions link the dinuclear molecules into a three-dimensional structure. Pyridine solvent molecules are attached to this structure
via weak interactions.
Supporting information
CCDC reference: 934594
Data collection: SMART (Siemens, 1994); cell refinement: SMART (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury
(Macrae
et al., 2008).
mer-µ-Oxalato-bis[chloridotripyridinecobalt(II)] pyridine disolvate
top
Crystal data top
[Co2(C2O4)Cl2(C5H5N)6]·2C5H5N | Z = 1 |
Mr = 909.58 | F(000) = 468 |
Triclinic, P1 | Dx = 1.495 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6402 (7) Å | Cell parameters from 6588 reflections |
b = 9.9899 (7) Å | θ = 1.9–31.5° |
c = 10.7775 (7) Å | µ = 1.01 mm−1 |
α = 78.834 (1)° | T = 90 K |
β = 82.856 (1)° | Block, pink |
γ = 89.704 (1)° | 0.10 × 0.09 × 0.07 mm |
V = 1010.18 (12) Å3 | |
Data collection top
Siemens P4 diffractometer with a CCD area-detector | 4614 independent reflections |
Radiation source: fine-focus sealed tube | 3467 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.906, Tmax = 0.933 | k = −12→12 |
10108 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3 |
4614 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.86803 (3) | 0.17971 (3) | 0.32713 (3) | 0.01480 (9) | |
Cl1 | 0.74774 (6) | 0.15993 (6) | 0.15157 (6) | 0.02234 (14) | |
O1 | 0.99082 (16) | 0.17744 (15) | 0.47657 (15) | 0.0166 (3) | |
O2 | 1.10735 (16) | 0.03317 (15) | 0.61027 (15) | 0.0158 (3) | |
C1 | 1.0289 (2) | 0.0606 (2) | 0.5251 (2) | 0.0135 (5) | |
N1 | 1.0694 (2) | 0.17456 (19) | 0.20945 (18) | 0.0171 (4) | |
C11 | 1.0941 (3) | 0.0826 (2) | 0.1348 (2) | 0.0209 (5) | |
H11 | 1.0195 | 0.0288 | 0.1246 | 0.025* | |
C12 | 1.2233 (3) | 0.0632 (3) | 0.0723 (2) | 0.0259 (6) | |
H12 | 1.2355 | −0.0018 | 0.0209 | 0.031* | |
C13 | 1.3348 (3) | 0.1421 (3) | 0.0874 (2) | 0.0267 (6) | |
H13 | 1.4239 | 0.1303 | 0.0474 | 0.032* | |
C14 | 1.3114 (3) | 0.2389 (3) | 0.1629 (2) | 0.0237 (6) | |
H14 | 1.3841 | 0.2948 | 0.1735 | 0.028* | |
C15 | 1.1780 (2) | 0.2513 (2) | 0.2224 (2) | 0.0185 (5) | |
H15 | 1.1629 | 0.3160 | 0.2739 | 0.022* | |
N2 | 0.6780 (2) | 0.17402 (19) | 0.46278 (19) | 0.0183 (4) | |
C21 | 0.5513 (2) | 0.1812 (2) | 0.4217 (3) | 0.0221 (5) | |
H21 | 0.5471 | 0.1977 | 0.3343 | 0.027* | |
C22 | 0.4279 (3) | 0.1655 (2) | 0.5026 (3) | 0.0256 (6) | |
H22 | 0.3428 | 0.1725 | 0.4698 | 0.031* | |
C23 | 0.4311 (3) | 0.1393 (2) | 0.6321 (3) | 0.0259 (6) | |
H23 | 0.3490 | 0.1263 | 0.6886 | 0.031* | |
C24 | 0.5606 (3) | 0.1330 (3) | 0.6761 (3) | 0.0249 (6) | |
H24 | 0.5670 | 0.1168 | 0.7631 | 0.030* | |
C25 | 0.6795 (3) | 0.1509 (2) | 0.5891 (2) | 0.0217 (5) | |
H25 | 0.7657 | 0.1468 | 0.6198 | 0.026* | |
N3 | 0.87816 (19) | 0.39786 (19) | 0.28724 (18) | 0.0162 (4) | |
C31 | 0.8835 (2) | 0.4701 (2) | 0.1678 (2) | 0.0176 (5) | |
H31 | 0.8834 | 0.4232 | 0.1012 | 0.021* | |
C32 | 0.8891 (2) | 0.6108 (2) | 0.1394 (2) | 0.0217 (5) | |
H32 | 0.8927 | 0.6574 | 0.0555 | 0.026* | |
C33 | 0.8893 (2) | 0.6812 (2) | 0.2376 (3) | 0.0223 (5) | |
H33 | 0.8926 | 0.7761 | 0.2210 | 0.027* | |
C34 | 0.8846 (2) | 0.6085 (2) | 0.3607 (2) | 0.0205 (5) | |
H34 | 0.8851 | 0.6536 | 0.4285 | 0.025* | |
C35 | 0.8791 (2) | 0.4675 (2) | 0.3818 (2) | 0.0171 (5) | |
H35 | 0.8759 | 0.4190 | 0.4649 | 0.020* | |
N4 | 0.7342 (2) | 0.4453 (2) | 0.6847 (2) | 0.0249 (5) | |
C41 | 0.6138 (3) | 0.4893 (3) | 0.6445 (2) | 0.0234 (5) | |
H41 | 0.6145 | 0.5277 | 0.5586 | 0.028* | |
C42 | 0.4878 (3) | 0.4813 (3) | 0.7226 (2) | 0.0238 (6) | |
H42 | 0.4065 | 0.5137 | 0.6899 | 0.029* | |
C43 | 0.4852 (3) | 0.4247 (3) | 0.8496 (3) | 0.0250 (6) | |
H43 | 0.4021 | 0.4182 | 0.9046 | 0.030* | |
C44 | 0.6081 (3) | 0.3777 (3) | 0.8941 (2) | 0.0256 (6) | |
H44 | 0.6097 | 0.3390 | 0.9796 | 0.031* | |
C45 | 0.7283 (3) | 0.3893 (3) | 0.8091 (3) | 0.0255 (6) | |
H45 | 0.8105 | 0.3563 | 0.8396 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01578 (16) | 0.01368 (16) | 0.01546 (17) | 0.00052 (12) | −0.00472 (12) | −0.00236 (12) |
Cl1 | 0.0256 (3) | 0.0230 (3) | 0.0210 (3) | 0.0016 (2) | −0.0104 (3) | −0.0060 (2) |
O1 | 0.0199 (8) | 0.0124 (8) | 0.0176 (9) | −0.0004 (7) | −0.0039 (7) | −0.0025 (7) |
O2 | 0.0143 (8) | 0.0148 (8) | 0.0188 (9) | 0.0000 (6) | −0.0052 (7) | −0.0028 (7) |
C1 | 0.0102 (10) | 0.0177 (12) | 0.0126 (11) | −0.0026 (9) | 0.0012 (9) | −0.0042 (9) |
N1 | 0.0210 (10) | 0.0130 (10) | 0.0172 (10) | 0.0017 (8) | −0.0031 (8) | −0.0025 (8) |
C11 | 0.0266 (13) | 0.0176 (12) | 0.0184 (13) | −0.0004 (10) | −0.0038 (10) | −0.0031 (10) |
C12 | 0.0331 (15) | 0.0229 (13) | 0.0221 (14) | 0.0057 (11) | −0.0020 (11) | −0.0065 (11) |
C13 | 0.0240 (13) | 0.0282 (14) | 0.0249 (14) | 0.0038 (11) | 0.0030 (11) | −0.0017 (12) |
C14 | 0.0185 (12) | 0.0249 (13) | 0.0255 (14) | −0.0046 (10) | −0.0014 (11) | −0.0001 (11) |
C15 | 0.0212 (12) | 0.0165 (12) | 0.0177 (12) | −0.0007 (10) | −0.0026 (10) | −0.0028 (10) |
N2 | 0.0182 (10) | 0.0138 (10) | 0.0228 (11) | 0.0002 (8) | −0.0026 (8) | −0.0034 (9) |
C21 | 0.0210 (12) | 0.0155 (12) | 0.0298 (14) | 0.0008 (10) | −0.0057 (11) | −0.0026 (11) |
C22 | 0.0158 (12) | 0.0196 (13) | 0.0410 (17) | 0.0009 (10) | −0.0043 (11) | −0.0045 (12) |
C23 | 0.0203 (13) | 0.0165 (12) | 0.0383 (16) | −0.0004 (10) | 0.0057 (11) | −0.0048 (11) |
C24 | 0.0278 (14) | 0.0211 (13) | 0.0244 (14) | 0.0009 (11) | 0.0031 (11) | −0.0046 (11) |
C25 | 0.0185 (12) | 0.0197 (12) | 0.0272 (14) | −0.0006 (10) | −0.0030 (10) | −0.0054 (11) |
N3 | 0.0132 (9) | 0.0179 (10) | 0.0179 (10) | 0.0014 (8) | −0.0027 (8) | −0.0037 (8) |
C31 | 0.0166 (12) | 0.0181 (12) | 0.0183 (12) | 0.0022 (9) | −0.0032 (10) | −0.0033 (10) |
C32 | 0.0178 (12) | 0.0196 (12) | 0.0242 (14) | 0.0005 (10) | −0.0016 (10) | 0.0036 (10) |
C33 | 0.0155 (12) | 0.0132 (11) | 0.0374 (15) | −0.0002 (9) | −0.0018 (11) | −0.0040 (11) |
C34 | 0.0152 (11) | 0.0202 (13) | 0.0290 (14) | 0.0012 (10) | −0.0047 (10) | −0.0109 (11) |
C35 | 0.0126 (11) | 0.0207 (12) | 0.0180 (12) | 0.0022 (9) | −0.0026 (9) | −0.0040 (10) |
N4 | 0.0189 (11) | 0.0290 (12) | 0.0265 (12) | −0.0018 (9) | 0.0003 (9) | −0.0066 (10) |
C41 | 0.0249 (13) | 0.0232 (13) | 0.0219 (13) | −0.0012 (11) | −0.0031 (11) | −0.0036 (11) |
C42 | 0.0192 (12) | 0.0268 (14) | 0.0262 (14) | 0.0022 (10) | −0.0065 (11) | −0.0049 (11) |
C43 | 0.0160 (12) | 0.0300 (14) | 0.0269 (14) | −0.0023 (11) | 0.0002 (10) | −0.0020 (12) |
C44 | 0.0275 (14) | 0.0258 (14) | 0.0212 (14) | 0.0001 (11) | −0.0055 (11) | 0.0024 (11) |
C45 | 0.0184 (12) | 0.0293 (14) | 0.0296 (15) | 0.0004 (11) | −0.0069 (11) | −0.0056 (12) |
Geometric parameters (Å, º) top
Co1—O1 | 2.1107 (16) | C23—C24 | 1.385 (4) |
Co1—O2i | 2.1244 (15) | C23—H23 | 0.9300 |
Co1—N3 | 2.1383 (19) | C24—C25 | 1.377 (3) |
Co1—N1 | 2.189 (2) | C24—H24 | 0.9300 |
Co1—N2 | 2.191 (2) | C25—H25 | 0.9300 |
Co1—Cl1 | 2.3785 (7) | N3—C35 | 1.341 (3) |
O1—C1 | 1.256 (3) | N3—C31 | 1.344 (3) |
O2—C1 | 1.250 (3) | C31—C32 | 1.379 (3) |
O2—Co1i | 2.1245 (15) | C31—H31 | 0.9300 |
C1—C1i | 1.551 (4) | C32—C33 | 1.380 (3) |
N1—C11 | 1.335 (3) | C32—H32 | 0.9300 |
N1—C15 | 1.338 (3) | C33—C34 | 1.379 (4) |
C11—C12 | 1.372 (3) | C33—H33 | 0.9300 |
C11—H11 | 0.9300 | C34—C35 | 1.383 (3) |
C12—C13 | 1.380 (4) | C34—H34 | 0.9300 |
C12—H12 | 0.9300 | C35—H35 | 0.9300 |
C13—C14 | 1.381 (4) | N4—C41 | 1.332 (3) |
C13—H13 | 0.9300 | N4—C45 | 1.343 (3) |
C14—C15 | 1.379 (3) | C41—C42 | 1.382 (3) |
C14—H14 | 0.9300 | C41—H41 | 0.9300 |
C15—H15 | 0.9300 | C42—C43 | 1.373 (4) |
N2—C25 | 1.338 (3) | C42—H42 | 0.9300 |
N2—C21 | 1.347 (3) | C43—C44 | 1.379 (3) |
C21—C22 | 1.375 (3) | C43—H43 | 0.9300 |
C21—H21 | 0.9300 | C44—C45 | 1.375 (3) |
C22—C23 | 1.374 (4) | C44—H44 | 0.9300 |
C22—H22 | 0.9300 | C45—H45 | 0.9300 |
| | | |
O1—Co1—O2i | 78.64 (6) | C23—C22—H22 | 120.2 |
O1—Co1—N3 | 89.69 (7) | C21—C22—H22 | 120.2 |
O2i—Co1—N3 | 167.95 (7) | C22—C23—C24 | 118.0 (2) |
O1—Co1—N1 | 84.44 (7) | C22—C23—H23 | 121.0 |
O2i—Co1—N1 | 85.88 (6) | C24—C23—H23 | 121.0 |
N3—Co1—N1 | 90.07 (7) | C25—C24—C23 | 119.1 (2) |
O1—Co1—N2 | 89.86 (7) | C25—C24—H24 | 120.5 |
O2i—Co1—N2 | 90.34 (7) | C23—C24—H24 | 120.5 |
N3—Co1—N2 | 92.63 (7) | N2—C25—C24 | 123.6 (2) |
N1—Co1—N2 | 173.69 (7) | N2—C25—H25 | 118.2 |
O1—Co1—Cl1 | 172.80 (5) | C24—C25—H25 | 118.2 |
O2i—Co1—Cl1 | 95.89 (5) | C35—N3—C31 | 117.6 (2) |
N3—Co1—Cl1 | 95.49 (5) | C35—N3—Co1 | 120.69 (16) |
N1—Co1—Cl1 | 90.55 (5) | C31—N3—Co1 | 121.74 (15) |
N2—Co1—Cl1 | 94.88 (5) | N3—C31—C32 | 123.0 (2) |
C1—O1—Co1 | 114.05 (14) | N3—C31—H31 | 118.5 |
C1—O2—Co1i | 113.27 (14) | C32—C31—H31 | 118.5 |
O2—C1—O1 | 126.2 (2) | C31—C32—C33 | 118.9 (2) |
O2—C1—C1i | 117.4 (2) | C31—C32—H32 | 120.6 |
O1—C1—C1i | 116.4 (2) | C33—C32—H32 | 120.6 |
C11—N1—C15 | 117.2 (2) | C34—C33—C32 | 118.9 (2) |
C11—N1—Co1 | 121.38 (16) | C34—C33—H33 | 120.6 |
C15—N1—Co1 | 120.87 (16) | C32—C33—H33 | 120.6 |
N1—C11—C12 | 123.7 (2) | C33—C34—C35 | 119.0 (2) |
N1—C11—H11 | 118.2 | C33—C34—H34 | 120.5 |
C12—C11—H11 | 118.2 | C35—C34—H34 | 120.5 |
C11—C12—C13 | 118.6 (2) | N3—C35—C34 | 122.8 (2) |
C11—C12—H12 | 120.7 | N3—C35—H35 | 118.6 |
C13—C12—H12 | 120.7 | C34—C35—H35 | 118.6 |
C12—C13—C14 | 118.7 (2) | C41—N4—C45 | 116.1 (2) |
C12—C13—H13 | 120.6 | N4—C41—C42 | 124.0 (2) |
C14—C13—H13 | 120.6 | N4—C41—H41 | 118.0 |
C15—C14—C13 | 118.8 (2) | C42—C41—H41 | 118.0 |
C15—C14—H14 | 120.6 | C43—C42—C41 | 118.6 (2) |
C13—C14—H14 | 120.6 | C43—C42—H42 | 120.7 |
N1—C15—C14 | 123.1 (2) | C41—C42—H42 | 120.7 |
N1—C15—H15 | 118.5 | C42—C43—C44 | 118.8 (2) |
C14—C15—H15 | 118.5 | C42—C43—H43 | 120.6 |
C25—N2—C21 | 116.5 (2) | C44—C43—H43 | 120.6 |
C25—N2—Co1 | 122.86 (16) | C45—C44—C43 | 118.5 (2) |
C21—N2—Co1 | 120.32 (17) | C45—C44—H44 | 120.8 |
N2—C21—C22 | 123.2 (2) | C43—C44—H44 | 120.8 |
N2—C21—H21 | 118.4 | N4—C45—C44 | 124.0 (2) |
C22—C21—H21 | 118.4 | N4—C45—H45 | 118.0 |
C23—C22—C21 | 119.6 (2) | C44—C45—H45 | 118.0 |
Symmetry code: (i) −x+2, −y, −z+1. |
Crystal data for polymorphs A (Bolte, 2006a) and B
(this work) top | Polymorph A | Polymorph B |
Crystal system | Monoclinic | Triclinic |
Space group | P21/n | P1 |
a (Å) | 9.5335 (19) | 9.6402 (7) |
b (Å) | 10.518 (2) | 9.9899 (7) |
c (Å) | 21.205 (4) | 10.7775 (7) |
α (°) | 90 | 78.8340 (10) |
β (°) | 91.78 (2) | 82.8560 (10) |
γ (°) | 90 | 89.7040 (10) |
V (Å3) | 2125.3 (7) | 1010.18 (12) |
Dcalc (Mg m-3) | 1.421 | 1.495 |
T (K) | 173 (2) | 90 (2) |
Selected bond lengths (Å) and angles (°) in polymorphs A (Bolte,
2006a) and B (this work) topPolymorph A | | Polymorph B | |
Co1—O1 | 2.123 (3) | Co1—O1 | 2.1107 (16) |
Co1—O2i | 2.121 (3) | Co1—O2ii | 2.1244 (15) |
Co1—Cl1 | 2.4224 (17) | Co1—Cl1 | 2.3785 (7) |
Co1—N11 | 2.191 (4) | Co1—N1 | 2.189 (2) |
Co1—N21 | 2.193 (4) | Co1—N2 | 2.191 (2) |
Co1—N31 | 2.157 (4) | Co1—N3 | 2.1383 (19) |
| | | |
N11—Co1—N21 | 174.52 (15) | N1—Co1—N2 | 173.69 (7) |
Cl1—Co1—O1 | 172.21 (10) | Cl1—Co1—O1 | 172.80 (5) |
N31—Co1—O2i | 168.52 (13) | N3—Co1—O2ii | 167.95 (7) |
N11—Co1—O1 | 85.89 (13) | N1—Co1—O1 | 84.44 (7) |
N11—Co1—O2i | 85.61 (15) | N1—Co1—O2ii | 85.88 (6) |
N11—Co1—Cl1 | 92.58 (11) | N1—Co1—Cl1 | 90.55 (5) |
N11—Co1—N31 | 91.75 (16) | N1—Co1—N3 | 90.07 (7) |
N21—Co1—O1 | 89.04 (13) | N2—Co1—O1 | 89.86 (7) |
N21—Co1—O2i | 91.37 (14) | N2—Co1—O2ii | 90.34 (7) |
N21—Co1—Cl1 | 92.17 (11) | N2—Co1—Cl1 | 94.88 (5) |
N21—Co1—N31 | 90.31 (15) | N2—Co1—N3 | 92.63 (7) |
N31—Co1—O1 | 90.00 (14) | N3—Co1—O1 | 89.69 (7) |
O1—Co1—O2i | 78.68 (12) | O1—Co1—O2ii | 78.64 (6) |
O2i—Co1—Cl1 | 93.60 (9) | O2ii—Co1—Cl1 | 95.89 (5) |
Cl1—Co1—N31 | 97.68 (12) | Cl1—Co1—N3 | 95.49 (5) |
Symmetry codes: (i) -x + 1, -y + 1, -z + 2; (ii) -x
+ 2, -y, -z + 1. |
C—H···π interactions (Å, °) in polymorph B topCg3 and Cg5 are the centroids of pyridine rings N1/C11–C15 and
N3/C31–C35, respectively, andCg6 is the centroid of solvent pyridine
ring N4/C41–C45. |
D–H···Cg | D–H | H···Cg | D···Cg | D–H···Cg |
C32—H32···Cg3ii | 0.93 | 2.82 | 3.684 (2) | 155 |
C42—H42···Cg5 | 0.93 | 2.82 | 3.573 (3) | 139 |
C14—H14···Cg6vi | 0.93 | 2.90 | 3.592 (3) | 132 |
Symmetry codes: (ii) -x + 2, -y, -z + 1; (vi) x +
1, y, z. |
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