Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
Single crystals of a triclinic polymorphic form of mer-[mu]-oxalato-bis­[chloridotripyridine­cobalt(II)] pyridine disolvate, [Co2(C2O4)Cl2(C5H5N)6]·2C5H5N, have been prepared by solvothermal methods. The structure and geometric parameters strongly resemble those of the previously reported monoclinic polymorph [Bolte (2006). Acta Cryst. E62, m597-m598]. In both polymorphic forms, the dinuclear complex mol­ecules are located on a crystallographic centre of inversion, with the CoII 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 CoII 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...[pi] and [pi]-[pi] inter­actions link the dinuclear mol­ecules into a three-dimensional structure. Pyridine solvent mol­ecules are attached to this structure via weak inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011300499X/sk3477sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011300499X/sk3477Isup2.hkl
Contains datablock I

CCDC reference: 934594

Computing details top

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]·2C5H5NZ = 1
Mr = 909.58F(000) = 468
Triclinic, P1Dx = 1.495 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.6402 (7) ÅCell parameters from 6588 reflections
b = 9.9899 (7) Åθ = 1.9–31.5°
c = 10.7775 (7) ŵ = 1.01 mm1
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 tube3467 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
φ and ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.906, Tmax = 0.933k = 1212
10108 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-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 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = 0.28 e Å3
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
xyzUiso*/Ueq
Co10.86803 (3)0.17971 (3)0.32713 (3)0.01480 (9)
Cl10.74774 (6)0.15993 (6)0.15157 (6)0.02234 (14)
O10.99082 (16)0.17744 (15)0.47657 (15)0.0166 (3)
O21.10735 (16)0.03317 (15)0.61027 (15)0.0158 (3)
C11.0289 (2)0.0606 (2)0.5251 (2)0.0135 (5)
N11.0694 (2)0.17456 (19)0.20945 (18)0.0171 (4)
C111.0941 (3)0.0826 (2)0.1348 (2)0.0209 (5)
H111.01950.02880.12460.025*
C121.2233 (3)0.0632 (3)0.0723 (2)0.0259 (6)
H121.23550.00180.02090.031*
C131.3348 (3)0.1421 (3)0.0874 (2)0.0267 (6)
H131.42390.13030.04740.032*
C141.3114 (3)0.2389 (3)0.1629 (2)0.0237 (6)
H141.38410.29480.17350.028*
C151.1780 (2)0.2513 (2)0.2224 (2)0.0185 (5)
H151.16290.31600.27390.022*
N20.6780 (2)0.17402 (19)0.46278 (19)0.0183 (4)
C210.5513 (2)0.1812 (2)0.4217 (3)0.0221 (5)
H210.54710.19770.33430.027*
C220.4279 (3)0.1655 (2)0.5026 (3)0.0256 (6)
H220.34280.17250.46980.031*
C230.4311 (3)0.1393 (2)0.6321 (3)0.0259 (6)
H230.34900.12630.68860.031*
C240.5606 (3)0.1330 (3)0.6761 (3)0.0249 (6)
H240.56700.11680.76310.030*
C250.6795 (3)0.1509 (2)0.5891 (2)0.0217 (5)
H250.76570.14680.61980.026*
N30.87816 (19)0.39786 (19)0.28724 (18)0.0162 (4)
C310.8835 (2)0.4701 (2)0.1678 (2)0.0176 (5)
H310.88340.42320.10120.021*
C320.8891 (2)0.6108 (2)0.1394 (2)0.0217 (5)
H320.89270.65740.05550.026*
C330.8893 (2)0.6812 (2)0.2376 (3)0.0223 (5)
H330.89260.77610.22100.027*
C340.8846 (2)0.6085 (2)0.3607 (2)0.0205 (5)
H340.88510.65360.42850.025*
C350.8791 (2)0.4675 (2)0.3818 (2)0.0171 (5)
H350.87590.41900.46490.020*
N40.7342 (2)0.4453 (2)0.6847 (2)0.0249 (5)
C410.6138 (3)0.4893 (3)0.6445 (2)0.0234 (5)
H410.61450.52770.55860.028*
C420.4878 (3)0.4813 (3)0.7226 (2)0.0238 (6)
H420.40650.51370.68990.029*
C430.4852 (3)0.4247 (3)0.8496 (3)0.0250 (6)
H430.40210.41820.90460.030*
C440.6081 (3)0.3777 (3)0.8941 (2)0.0256 (6)
H440.60970.33900.97960.031*
C450.7283 (3)0.3893 (3)0.8091 (3)0.0255 (6)
H450.81050.35630.83960.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01578 (16)0.01368 (16)0.01546 (17)0.00052 (12)0.00472 (12)0.00236 (12)
Cl10.0256 (3)0.0230 (3)0.0210 (3)0.0016 (2)0.0104 (3)0.0060 (2)
O10.0199 (8)0.0124 (8)0.0176 (9)0.0004 (7)0.0039 (7)0.0025 (7)
O20.0143 (8)0.0148 (8)0.0188 (9)0.0000 (6)0.0052 (7)0.0028 (7)
C10.0102 (10)0.0177 (12)0.0126 (11)0.0026 (9)0.0012 (9)0.0042 (9)
N10.0210 (10)0.0130 (10)0.0172 (10)0.0017 (8)0.0031 (8)0.0025 (8)
C110.0266 (13)0.0176 (12)0.0184 (13)0.0004 (10)0.0038 (10)0.0031 (10)
C120.0331 (15)0.0229 (13)0.0221 (14)0.0057 (11)0.0020 (11)0.0065 (11)
C130.0240 (13)0.0282 (14)0.0249 (14)0.0038 (11)0.0030 (11)0.0017 (12)
C140.0185 (12)0.0249 (13)0.0255 (14)0.0046 (10)0.0014 (11)0.0001 (11)
C150.0212 (12)0.0165 (12)0.0177 (12)0.0007 (10)0.0026 (10)0.0028 (10)
N20.0182 (10)0.0138 (10)0.0228 (11)0.0002 (8)0.0026 (8)0.0034 (9)
C210.0210 (12)0.0155 (12)0.0298 (14)0.0008 (10)0.0057 (11)0.0026 (11)
C220.0158 (12)0.0196 (13)0.0410 (17)0.0009 (10)0.0043 (11)0.0045 (12)
C230.0203 (13)0.0165 (12)0.0383 (16)0.0004 (10)0.0057 (11)0.0048 (11)
C240.0278 (14)0.0211 (13)0.0244 (14)0.0009 (11)0.0031 (11)0.0046 (11)
C250.0185 (12)0.0197 (12)0.0272 (14)0.0006 (10)0.0030 (10)0.0054 (11)
N30.0132 (9)0.0179 (10)0.0179 (10)0.0014 (8)0.0027 (8)0.0037 (8)
C310.0166 (12)0.0181 (12)0.0183 (12)0.0022 (9)0.0032 (10)0.0033 (10)
C320.0178 (12)0.0196 (12)0.0242 (14)0.0005 (10)0.0016 (10)0.0036 (10)
C330.0155 (12)0.0132 (11)0.0374 (15)0.0002 (9)0.0018 (11)0.0040 (11)
C340.0152 (11)0.0202 (13)0.0290 (14)0.0012 (10)0.0047 (10)0.0109 (11)
C350.0126 (11)0.0207 (12)0.0180 (12)0.0022 (9)0.0026 (9)0.0040 (10)
N40.0189 (11)0.0290 (12)0.0265 (12)0.0018 (9)0.0003 (9)0.0066 (10)
C410.0249 (13)0.0232 (13)0.0219 (13)0.0012 (11)0.0031 (11)0.0036 (11)
C420.0192 (12)0.0268 (14)0.0262 (14)0.0022 (10)0.0065 (11)0.0049 (11)
C430.0160 (12)0.0300 (14)0.0269 (14)0.0023 (11)0.0002 (10)0.0020 (12)
C440.0275 (14)0.0258 (14)0.0212 (14)0.0001 (11)0.0055 (11)0.0024 (11)
C450.0184 (12)0.0293 (14)0.0296 (15)0.0004 (11)0.0069 (11)0.0056 (12)
Geometric parameters (Å, º) top
Co1—O12.1107 (16)C23—C241.385 (4)
Co1—O2i2.1244 (15)C23—H230.9300
Co1—N32.1383 (19)C24—C251.377 (3)
Co1—N12.189 (2)C24—H240.9300
Co1—N22.191 (2)C25—H250.9300
Co1—Cl12.3785 (7)N3—C351.341 (3)
O1—C11.256 (3)N3—C311.344 (3)
O2—C11.250 (3)C31—C321.379 (3)
O2—Co1i2.1245 (15)C31—H310.9300
C1—C1i1.551 (4)C32—C331.380 (3)
N1—C111.335 (3)C32—H320.9300
N1—C151.338 (3)C33—C341.379 (4)
C11—C121.372 (3)C33—H330.9300
C11—H110.9300C34—C351.383 (3)
C12—C131.380 (4)C34—H340.9300
C12—H120.9300C35—H350.9300
C13—C141.381 (4)N4—C411.332 (3)
C13—H130.9300N4—C451.343 (3)
C14—C151.379 (3)C41—C421.382 (3)
C14—H140.9300C41—H410.9300
C15—H150.9300C42—C431.373 (4)
N2—C251.338 (3)C42—H420.9300
N2—C211.347 (3)C43—C441.379 (3)
C21—C221.375 (3)C43—H430.9300
C21—H210.9300C44—C451.375 (3)
C22—C231.374 (4)C44—H440.9300
C22—H220.9300C45—H450.9300
O1—Co1—O2i78.64 (6)C23—C22—H22120.2
O1—Co1—N389.69 (7)C21—C22—H22120.2
O2i—Co1—N3167.95 (7)C22—C23—C24118.0 (2)
O1—Co1—N184.44 (7)C22—C23—H23121.0
O2i—Co1—N185.88 (6)C24—C23—H23121.0
N3—Co1—N190.07 (7)C25—C24—C23119.1 (2)
O1—Co1—N289.86 (7)C25—C24—H24120.5
O2i—Co1—N290.34 (7)C23—C24—H24120.5
N3—Co1—N292.63 (7)N2—C25—C24123.6 (2)
N1—Co1—N2173.69 (7)N2—C25—H25118.2
O1—Co1—Cl1172.80 (5)C24—C25—H25118.2
O2i—Co1—Cl195.89 (5)C35—N3—C31117.6 (2)
N3—Co1—Cl195.49 (5)C35—N3—Co1120.69 (16)
N1—Co1—Cl190.55 (5)C31—N3—Co1121.74 (15)
N2—Co1—Cl194.88 (5)N3—C31—C32123.0 (2)
C1—O1—Co1114.05 (14)N3—C31—H31118.5
C1—O2—Co1i113.27 (14)C32—C31—H31118.5
O2—C1—O1126.2 (2)C31—C32—C33118.9 (2)
O2—C1—C1i117.4 (2)C31—C32—H32120.6
O1—C1—C1i116.4 (2)C33—C32—H32120.6
C11—N1—C15117.2 (2)C34—C33—C32118.9 (2)
C11—N1—Co1121.38 (16)C34—C33—H33120.6
C15—N1—Co1120.87 (16)C32—C33—H33120.6
N1—C11—C12123.7 (2)C33—C34—C35119.0 (2)
N1—C11—H11118.2C33—C34—H34120.5
C12—C11—H11118.2C35—C34—H34120.5
C11—C12—C13118.6 (2)N3—C35—C34122.8 (2)
C11—C12—H12120.7N3—C35—H35118.6
C13—C12—H12120.7C34—C35—H35118.6
C12—C13—C14118.7 (2)C41—N4—C45116.1 (2)
C12—C13—H13120.6N4—C41—C42124.0 (2)
C14—C13—H13120.6N4—C41—H41118.0
C15—C14—C13118.8 (2)C42—C41—H41118.0
C15—C14—H14120.6C43—C42—C41118.6 (2)
C13—C14—H14120.6C43—C42—H42120.7
N1—C15—C14123.1 (2)C41—C42—H42120.7
N1—C15—H15118.5C42—C43—C44118.8 (2)
C14—C15—H15118.5C42—C43—H43120.6
C25—N2—C21116.5 (2)C44—C43—H43120.6
C25—N2—Co1122.86 (16)C45—C44—C43118.5 (2)
C21—N2—Co1120.32 (17)C45—C44—H44120.8
N2—C21—C22123.2 (2)C43—C44—H44120.8
N2—C21—H21118.4N4—C45—C44124.0 (2)
C22—C21—H21118.4N4—C45—H45118.0
C23—C22—C21119.6 (2)C44—C45—H45118.0
Symmetry code: (i) x+2, y, z+1.
Crystal data for polymorphs A (Bolte, 2006a) and B (this work) top
Polymorph APolymorph B
Crystal systemMonoclinicTriclinic
Space groupP21/nP1
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 (°)9078.8340 (10)
β (°)91.78 (2)82.8560 (10)
γ (°)9089.7040 (10)
V3)2125.3 (7)1010.18 (12)
Dcalc (Mg m-3)1.4211.495
T (K)173 (2)90 (2)
Selected bond lengths (Å) and angles (°) in polymorphs A (Bolte, 2006a) and B (this work) top
Polymorph APolymorph B
Co1—O12.123 (3)Co1—O12.1107 (16)
Co1—O2i2.121 (3)Co1—O2ii2.1244 (15)
Co1—Cl12.4224 (17)Co1—Cl12.3785 (7)
Co1—N112.191 (4)Co1—N12.189 (2)
Co1—N212.193 (4)Co1—N22.191 (2)
Co1—N312.157 (4)Co1—N32.1383 (19)
N11—Co1—N21174.52 (15)N1—Co1—N2173.69 (7)
Cl1—Co1—O1172.21 (10)Cl1—Co1—O1172.80 (5)
N31—Co1—O2i168.52 (13)N3—Co1—O2ii167.95 (7)
N11—Co1—O185.89 (13)N1—Co1—O184.44 (7)
N11—Co1—O2i85.61 (15)N1—Co1—O2ii85.88 (6)
N11—Co1—Cl192.58 (11)N1—Co1—Cl190.55 (5)
N11—Co1—N3191.75 (16)N1—Co1—N390.07 (7)
N21—Co1—O189.04 (13)N2—Co1—O189.86 (7)
N21—Co1—O2i91.37 (14)N2—Co1—O2ii90.34 (7)
N21—Co1—Cl192.17 (11)N2—Co1—Cl194.88 (5)
N21—Co1—N3190.31 (15)N2—Co1—N392.63 (7)
N31—Co1—O190.00 (14)N3—Co1—O189.69 (7)
O1—Co1—O2i78.68 (12)O1—Co1—O2ii78.64 (6)
O2i—Co1—Cl193.60 (9)O2ii—Co1—Cl195.89 (5)
Cl1—Co1—N3197.68 (12)Cl1—Co1—N395.49 (5)
Symmetry codes: (i) -x + 1, -y + 1, -z + 2; (ii) -x + 2, -y, -z + 1.
C—H···π interactions (Å, °) in polymorph B top
Cg3 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···CgD–HH···CgD···CgD–H···Cg
C32—H32···Cg3ii0.932.823.684 (2)155
C42—H42···Cg50.932.823.573 (3)139
C14—H14···Cg6vi0.932.903.592 (3)132
Symmetry codes: (ii) -x + 2, -y, -z + 1; (vi) x + 1, y, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds