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The title compound, [CoCl(C12H8N2)2(H2O)]Cl·[CoCl2(C12H8N2)2]·6H2O, is the first example of a new 1:1 cocrystal of the octa­hedral [CoCl2(phen)2] and [CoCl(phen)2(H2O)]+·Cl- complexes (phen is 1,10-phenanthroline). The latter form heterochiral dimers held by strong [pi]-[pi] stacking inter­actions via their phenathroline ligands, which confirms that [pi] stacking is an important and reliable synthon in supra­molecular design. In addition, the crystal structure is networked by H2O...H2O, H2O...Cl- and H2O...Cl hydrogen bonds, which inter­connect the different units of the cobalt complexes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107064803/sk3176sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107064803/sk3176Isup2.hkl
Contains datablock I

CCDC references: 1141976; 1150235

Comment top

We have been studying recently supramolecular chemistry based on ππ stacking interactions, involving aromatic units such as 1,10-phenanthroline (phen) and its larger derivatives with extended aromatic systems and ligating capacity and exploring their coordination chemistry with various transition metals (Bergman et al., 2002, 2004, 2005; Gut et al., 2002). We found, for example, that octahedral complexes of ruthenium and osmium with such ligands tend to dimerize via ππ stacking is solution as well as in the solid state. We noted also that metal complexes with phen or modified-phen ligands can be useful in diagnostic and therapeutic applications (Barton, 1986; Naing et al., 1995), which adds interest to studies of the structural chemistry of these materials. In the above context, only a small number of reports on the structural chemistry of CoII complexes with phen ligands have been published so far, justifying further studies in this area.

In the present work, we prepared crystals of [CoCl2(phen)2] dihydrate, (I) (green blocks), of the previously known structure (Ablov et al., 1966; Andersen & Josephsen, 1971) [CoCl(phen)2(H2O)], (II) (pink prisms), in good agreement with the literature (Zhao et al., 2003), and of a new 1:1 cocrystal of the two Co–phenanthroline complexes in a polyhydrated form, (III) (maroon cubes).

Compound (I) crystallized in an orthorhombic space group [Pbcn, with a = 12.619 (1) Å, b = 23.410 (1) Å and c = 176.034 (2) Å], but the analyzed crystals were of poor quality and its structure could not be analyzed with acceptable precision. The crystallographic refinement converged at R1 = 0.074, adequately low to identify unequivocally the molecular structure of the complex. It is noteworthy that (I) has unit-cell parameters quite different from those given for the monohydrate [Cambridge Structural Database (Allen, 2002) refcode QQQERJ; a = 12.270 Å, b = 13.500 Å, c = 15.330 Å and β = 99.40°; Andersen & Josephsen, 1971] and the trihydrate (refcode CPHCOC; a = 15.460 Å, b = 13.500 Å, c = 12.280 Å and β = 90.17°; Ablov et al., 1966). On the other hand, the crystal data for (I) are in good agreement with those published for [CrIII(phen)2Cl2]Cl·2H2O (QQQEQS; Andersen & Josephsen, 1971). Atomic coordinates are not available in either of the earlier reports, which may reflect the difficulty of obtaining good quality crystals of these species, probably as a result of the to instability of CoII and the tendency of its complexes to crystallize as solvates.

Compound (II) crystallized in a triclinic space group [P1, with a = 9.631 (1) Å, b = 11.340 (1) Å, c = 12.958 (1) Å, α = 64.083 (7), β = 83.358 (5) and γ = 78.199 (4)°], in good agreement with the previously reported structure (ESEQO1; Zhao et al., 2003).

Compound (III) is of particular interest as it represents a unique 1:1 cocrystal of the two species [CoCl2(phen)2] and [CoCl(phen)2(H2O)]Cl in a hexahydrated form, the structure of which has not been published before. It is the subject matter of the current report. This material was obtained by hydrothermal synthesis, which provides unique crystallization conditions to yield new products that are often inaccessible by standard techniques of crystal growth by evaporation and temperature control. Fig. 1 shows the molecular structure of (III) at 110 (2) K, as observed in this study. In this family of octahedral complexes, the two molecules of the bidentate 1,10-phenanthroline ligand are cis to one another, as are the two additional monodentate ligands Cl and H2O. All the observed cobalt–ligand bond lengths are in good agreement with the literature (Orpen et al., 1989).

The intermolecular interaction of the cobalt complexes via aryl–aryl stacking of the phenanthroline fragments of the two species is addressed first. Within the asymmetric unit there is partial overlap between the C1–C12/N25/N26 ring system and C44–C47/C54/N58 ring [please check; with original description it was not clear whether these referred to the whole phen system or just one or two rings within the system], with shortest interatomic distances near 3.7 Å. These two ring systems are not fully parallel to one another, the dihedral angle between their mean planes being 16.69 (5)°. An apparently more effective interaction occurs between the ring systems C13–C19/C23/C24/N27 of one complex and C32–C38/C42/C43/N56 of another complex at (-x + 1, y + 1/2, -z + 1/2). In this case, the two ring systems are quite parallel, the dihedral angle between them being only 1.88 (5)°, with an average distance of 3.26 Å between their mean planes. The overlapping systems are depicted in Fig. 2. These observations confirm that the cobalt complexes with phen are organized as distinct dimers in which the phen residues interact via ππ stacking interactions. Moreover, the two interacting complexes are of opposing Δ and Λ chirality, which are not related by inversion. This confirms that heterochiral dimer formation occurs not only in organometallic complexes with large aromatic ligands as reported earlier (Bergman et al., 2002, 2004, 2005; Gut et al., 2002), but also with the relatively small phen ligand. The crystal structure of (III) is stabilized also by an extended array of O—H···O, O—H···Cl and O—H···Cl- hydrogen bonds, through the aqua and Cl ligands as well as the water solvent molecules and chloride anions that interface the coordination complexes (Fig. 3). These interactions are in the normal range (Table 1). The hydrogen bonds link between species that are located in the crystal structure in layered zones centered at (x, 0, z) and (x, 1/2, z). The hydrogen-bonded layers are stacked along the b axis, with the phen residues of the two complexes lining the interface between them. Fig. 4 shows the projection of the crystal structure approximately down the c axis, illustrating the two perpendicular zones along a and along c occupied by columns of the phen fragments.

In summary, a new cocrystal of two different octahedral complexes of CoII has been determined. The observed results confirm the tendency of such octahedral complexes to aggregate in heterochiral dimers via ππ stacking interactions, in agreement with our earlier findings with other aromatic components (Bergman et al., 2002, 2004, 2005; Gut et al., 2002). They indicate also that such chiral recognition is well expressed, not only in chemical systems held solely by π-stacking, but also in the presence of other supramolecular interactions, such as hydrogen bonding, thus providing a reliable synthon for supramolecular design of new materials. Similar stacking features characterize the crystal structure of (II) (Zhao et al., 2003).

Related literature top

For related literature, see: Ablov et al. (1966); Andersen & Josephsen (1971); Barton (1986); Bergman et al. (2002, 2004, 2005); Gut et al. (2002); Naing et al. (1995); Orpen et al. (1989); Zhao et al. (2003).

Experimental top

Cobalt chloride hexahydrate and 1,10-phenanthroline (phen) were supplied by Aldrich and used without any further purification. All solvents used were of AR grade.

For the preparation of (I), CoCl2·6H2O (0.0020 g), pyridine hydrochloride (0.0064 g) and phen (0.0037 g) were dissolved in ca 5 ml of EtOH by gentle heating and continuous stirring for 1 h. The solution was then allowed to stand sealed with perforated parafilm under ambient conditions. After three weeks, several dark-green blocks suitable for X-ray diffraction were observed alongside the pink prisms of (II) (see below). FT–IR: 738 (s), 876(s), 1396 (s), 1456 (m), 1609 (m), 3020 (w), 3340 (b).

For the preparation of (II), isonicotinic acid (0.056 g) and phen (0.0035 g) were dissolved in 5 ml of EtOH and crystallized as above. FT–IR: 735 (s), 874 (s), 1395 (w), 1453 (w), 1604 (w), 3018 (w), 3339 (s).

For the preparation of (III), CoCl2·6H2O (0.162 g) and phen (0.242 g) were dissolved in 1M HCl and heated under solvothermal conditions for a total of 177 h (24 h at 423 K peak). Cubic crystals of maroon color were found in the reaction vessel at the end of this period. FT–IR: 737 (s), 875 (m), 1398 (s), 1456 (m), 1604 (m), 3021 (w), 3334(vs). Addition of excess of ammonium chloride improved the quality of the crystals.

Refinement top

The asymmetric unit contains one molecule of each Co complex species and six molecules of water. The isolated chloride anion is disordered between two equally populated positions (Cl70 and Cl71). Another water molecule is disordered between the same two sites (O68 and O69) in an alternating manner with the chloride anions. The actual water content was assessed by best fit of the structural model to the diffraction data. It is consistent with the results of thermal gravimetric (TGA) measurements, though the latter indicate a slightly higher content of seven water molecules (the additional molecule may represent some solvent absorbed on the crystal surface). H atoms bound to C atoms were located in calculated positions and were constrained to ride on their parent atoms with C—H distances of 0.95 Å and with Uiso(H) values of 1.2Ueq(C). Those bound to O atoms were located in fixed calculated positions at O—H distances within 0.88–095 Å, so as to optimize the hydrogen-bonding pattern in the crystal structure. They were also assigned Uiso(H) values of 1.2Ueq(O). H atoms of the disordered water molecule at O67, O68 and O69 were not included in the structural model but they were included in the structural formula, density and F(000) calculations. Water molecules O66 and O67 exhibit large-amplitude displacement parameters, a possible indication of their partial disorder as well.

Computing details top

Data collection: Collect (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labeling scheme. The atom ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. H atoms have been omitted.
[Figure 2] Fig. 2. An illustration of the ππ stacking interaction between the two cobalt complexes in (III). Selected atomic labels identify the two interacting components of the dimer.
[Figure 3] Fig. 3. A view of the hydrogen-bonding pattern in (III), denoted by dashed lines. The Co, Cl and O atoms are shown as small spheres. The various atom types that take part in the hydrogen-bonding scheme are labeled. Atoms Co62, O61 and Cl60 are related by (-x, -y + 1, -z + 1) to those in Fig. 1. Labels X and Y represent the disordered chloride anions and water molecule. X represents in an alternating manner (i.e. with 50% occupancy each) atomic positions O68 and Cl70, while Y represents similarly atomic positions O69 and Cl71. H atoms have been omitted for clarity.
[Figure 4] Fig. 4. A projection of the crystal structure approximately down the c axis, showing the stacking of the aromatic residues along two perpendicular directions a and c. The water solvent molecules, chloride anions and H atoms have been omitted.
aquachloridobis(1,10-phenanthroline)cobalt(II) chloride dichloridobis(1,10-phenanthroline)cobalt(II) hexahydrate top
Crystal data top
[CoCl(C12H8N2)2(H2O)]Cl·[CoCl2(C12H8N2)2]·6H2OF(000) = 2272
Mr = 1106.59Dx = 1.549 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.0905 (2) ÅCell parameters from 9880 reflections
b = 23.9088 (3) Åθ = 2.4–27.9°
c = 14.2504 (2) ŵ = 0.99 mm1
β = 98.7921 (7)°T = 110 K
V = 4744.36 (11) Å3Cubes, red
Z = 40.25 × 0.20 × 0.20 mm
Data collection top
Nonius KappaCCD
diffractometer
11176 independent reflections
Radiation source: fine-focus sealed tube6868 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
Detector resolution: 12.8 pixels mm-1θmax = 27.9°, θmin = 2.4°
1 deg. ϕ scansh = 018
Absorption correction: multi-scan
(Blessing, 1995)
k = 030
Tmin = 0.791, Tmax = 0.827l = 1818
33988 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycleSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0884P)2 + 3.9707P]
where P = (Fo2 + 2Fc2)/3
11176 reflections(Δ/σ)max = 0.043
641 parametersΔρmax = 1.34 e Å3
0 restraintsΔρmin = 1.14 e Å3
Crystal data top
[CoCl(C12H8N2)2(H2O)]Cl·[CoCl2(C12H8N2)2]·6H2OV = 4744.36 (11) Å3
Mr = 1106.59Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.0905 (2) ŵ = 0.99 mm1
b = 23.9088 (3) ÅT = 110 K
c = 14.2504 (2) Å0.25 × 0.20 × 0.20 mm
β = 98.7921 (7)°
Data collection top
Nonius KappaCCD
diffractometer
11176 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
6868 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.827Rint = 0.071
33988 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.179H-atom parameters constrained
S = 1.02Δρmax = 1.34 e Å3
11176 reflectionsΔρmin = 1.14 e Å3
641 parameters
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. The chloride anion is disordered between two equally populated positions represented by Cl70 and Cl71. One molecule of water is disordered between two similar positions (O68 and O69). Water solvent molecules O66 and O67 also reveal partial disorder. The H-atoms of O67, O68 and O69 couldn't be located; those of O66 couldn't be positioned precisely either.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.4003 (3)0.55556 (16)0.2711 (3)0.0277 (9)
H10.40430.57600.32870.033*
C20.4053 (3)0.49726 (17)0.2752 (3)0.0292 (9)
H20.41240.47870.33480.035*
C30.3999 (3)0.46692 (16)0.1930 (3)0.0288 (9)
H30.40310.42720.19540.035*
C40.3895 (3)0.49485 (16)0.1050 (3)0.0244 (8)
C50.3824 (3)0.46726 (15)0.0149 (3)0.0259 (9)
H50.38370.42760.01280.031*
C60.3739 (3)0.49658 (16)0.0674 (3)0.0261 (9)
H60.36810.47710.12620.031*
C70.3735 (3)0.55655 (16)0.0669 (3)0.0243 (8)
C80.3682 (3)0.58944 (17)0.1502 (3)0.0270 (9)
H80.36450.57220.21070.032*
C90.3686 (3)0.64690 (17)0.1421 (3)0.0295 (9)
H90.36550.66970.19700.035*
C100.3736 (3)0.67137 (16)0.0525 (3)0.0261 (9)
H100.37360.71100.04830.031*
C110.3859 (3)0.55395 (16)0.1075 (3)0.0230 (8)
C120.3786 (3)0.58509 (16)0.0202 (3)0.0237 (8)
C130.6006 (3)0.64456 (16)0.1951 (3)0.0268 (9)
H130.58270.60720.20700.032*
C140.6974 (3)0.65613 (16)0.1976 (3)0.0289 (9)
H140.74370.62710.20900.035*
C150.7256 (3)0.71033 (16)0.1833 (3)0.0275 (9)
H150.79160.71910.18540.033*
C160.6553 (3)0.75235 (16)0.1657 (3)0.0231 (8)
C170.6778 (3)0.81001 (16)0.1512 (3)0.0275 (9)
H170.74300.82130.15580.033*
C180.6066 (3)0.84865 (17)0.1310 (3)0.0286 (9)
H180.62280.88650.12110.034*
C190.5075 (3)0.83299 (16)0.1243 (3)0.0253 (9)
C200.4308 (3)0.87144 (17)0.1018 (3)0.0307 (9)
H200.44340.90960.08990.037*
C210.3379 (3)0.85285 (17)0.0974 (3)0.0310 (9)
H210.28570.87810.08290.037*
C220.3209 (3)0.79655 (16)0.1145 (3)0.0272 (9)
H220.25640.78430.11180.033*
C230.5588 (3)0.73647 (16)0.1613 (3)0.0228 (8)
C240.4826 (3)0.77701 (15)0.1398 (3)0.0229 (8)
N250.3900 (2)0.58349 (13)0.1893 (2)0.0238 (7)
N260.3785 (2)0.64207 (13)0.0272 (2)0.0224 (7)
N270.5316 (2)0.68246 (13)0.1770 (2)0.0242 (7)
N280.3907 (2)0.75939 (13)0.1342 (2)0.0240 (7)
Cl290.38626 (8)0.69405 (4)0.33589 (7)0.0321 (2)
Cl300.20582 (9)0.67114 (5)0.13647 (8)0.0395 (3)
Co310.37999 (4)0.67221 (2)0.16867 (4)0.02126 (14)
C320.2773 (3)0.32646 (17)0.1056 (3)0.0300 (9)
H320.27080.36530.11670.036*
C330.3690 (3)0.30521 (19)0.1058 (3)0.0343 (10)
H330.42320.32930.11450.041*
C340.3801 (3)0.24854 (19)0.0931 (3)0.0339 (10)
H340.44240.23290.09500.041*
C350.2984 (3)0.21428 (17)0.0774 (3)0.0296 (9)
C360.3031 (4)0.15465 (18)0.0642 (3)0.0343 (10)
H360.36390.13690.06800.041*
C370.2222 (4)0.12382 (18)0.0465 (3)0.0378 (11)
H370.22710.08450.03850.045*
C380.1286 (4)0.14898 (17)0.0394 (3)0.0341 (10)
C390.0427 (4)0.11885 (18)0.0175 (3)0.0398 (11)
H390.04380.07980.00570.048*
C400.0435 (4)0.14684 (19)0.0135 (3)0.0416 (12)
H400.10250.12720.00120.050*
C410.0432 (3)0.20445 (18)0.0312 (3)0.0345 (10)
H410.10310.22310.02860.041*
C420.2085 (3)0.23969 (16)0.0747 (3)0.0274 (9)
C430.1220 (3)0.20720 (16)0.0546 (3)0.0268 (9)
C440.1078 (3)0.42893 (17)0.2111 (3)0.0318 (10)
H440.10030.40700.26500.038*
C450.1374 (3)0.48476 (18)0.2251 (3)0.0369 (11)
H450.15080.49990.28730.044*
C460.1465 (3)0.51722 (17)0.1472 (3)0.0349 (10)
H460.16570.55520.15510.042*
C470.1272 (3)0.49367 (16)0.0553 (3)0.0310 (10)
C480.1335 (3)0.52386 (17)0.0295 (4)0.0360 (11)
H480.15150.56220.02520.043*
C490.1147 (3)0.49968 (18)0.1154 (3)0.0362 (11)
H490.12030.52110.17050.043*
C500.0860 (3)0.44150 (17)0.1258 (3)0.0288 (9)
C510.0635 (3)0.41416 (19)0.2135 (3)0.0348 (10)
H510.06660.43360.27100.042*
C520.0371 (3)0.35911 (19)0.2150 (3)0.0328 (10)
H520.02270.33980.27360.039*
C530.0314 (3)0.33136 (17)0.1291 (3)0.0280 (9)
H530.01200.29330.13130.034*
C540.0992 (3)0.43698 (16)0.0486 (3)0.0263 (9)
C550.0785 (3)0.41121 (16)0.0434 (3)0.0271 (9)
N560.1981 (2)0.29568 (13)0.0907 (2)0.0260 (7)
N570.0369 (2)0.23429 (14)0.0514 (2)0.0286 (8)
N580.0898 (2)0.40538 (13)0.1257 (2)0.0264 (7)
N590.0520 (2)0.35603 (14)0.0453 (2)0.0279 (8)
Cl600.05511 (8)0.29552 (4)0.25788 (7)0.0326 (2)
O610.1083 (2)0.33240 (10)0.07215 (17)0.0281 (7)
H61A0.13710.33140.01060.034*
H61B0.13700.31030.11080.034*
Co620.05181 (4)0.32047 (2)0.09281 (4)0.02421 (15)
O630.2033 (3)0.62453 (18)0.3507 (3)0.0658 (11)
H63A0.25750.64440.34700.079*
H63B0.20850.59170.38560.079*
O640.2185 (3)0.52729 (16)0.4533 (3)0.0661 (11)
H64A0.19270.52600.50920.079*
H64B0.27670.51120.47490.079*
O650.3321 (3)0.47836 (14)0.7064 (2)0.0585 (11)
H65A0.27000.48460.69720.070*
H65B0.36150.47830.65070.070*
O660.1333 (4)0.6334 (3)0.7175 (4)0.110 (2)
H66A0.07890.65320.72300.132*
H66B0.13300.59820.69050.132*
O670.1886 (5)0.7330 (3)0.8100 (5)0.147 (3)
O680.3928 (6)0.4721 (4)0.5183 (6)0.066 (2)0.50
O690.1356 (8)0.5197 (4)0.6388 (5)0.080 (3)0.50
Cl700.41358 (16)0.47596 (9)0.52169 (14)0.0335 (5)0.50
Cl710.13496 (19)0.52574 (10)0.63260 (19)0.0503 (6)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.032 (2)0.028 (2)0.023 (2)0.0028 (17)0.0037 (17)0.0019 (17)
C20.031 (2)0.029 (2)0.026 (2)0.0034 (17)0.0008 (18)0.0066 (17)
C30.028 (2)0.024 (2)0.033 (2)0.0019 (16)0.0015 (18)0.0040 (18)
C40.024 (2)0.0221 (19)0.026 (2)0.0015 (15)0.0013 (16)0.0001 (16)
C50.026 (2)0.0175 (18)0.034 (2)0.0008 (15)0.0044 (18)0.0044 (17)
C60.028 (2)0.027 (2)0.024 (2)0.0001 (16)0.0063 (17)0.0085 (17)
C70.020 (2)0.029 (2)0.0233 (19)0.0006 (15)0.0041 (16)0.0006 (16)
C80.028 (2)0.036 (2)0.0169 (18)0.0024 (17)0.0030 (16)0.0032 (16)
C90.033 (2)0.032 (2)0.023 (2)0.0019 (18)0.0034 (18)0.0049 (17)
C100.031 (2)0.0211 (19)0.027 (2)0.0003 (16)0.0068 (17)0.0037 (17)
C110.020 (2)0.0254 (19)0.0236 (19)0.0007 (15)0.0019 (16)0.0013 (16)
C120.019 (2)0.027 (2)0.025 (2)0.0010 (15)0.0037 (16)0.0007 (16)
C130.029 (2)0.0220 (19)0.030 (2)0.0000 (16)0.0056 (17)0.0003 (17)
C140.027 (2)0.026 (2)0.034 (2)0.0045 (16)0.0042 (18)0.0020 (18)
C150.026 (2)0.031 (2)0.026 (2)0.0015 (17)0.0051 (17)0.0035 (17)
C160.026 (2)0.0242 (19)0.0195 (19)0.0033 (16)0.0040 (16)0.0043 (16)
C170.029 (2)0.027 (2)0.028 (2)0.0063 (17)0.0079 (18)0.0015 (17)
C180.036 (3)0.024 (2)0.027 (2)0.0027 (17)0.0089 (18)0.0005 (17)
C190.035 (2)0.0222 (19)0.0187 (18)0.0018 (16)0.0034 (17)0.0046 (15)
C200.039 (3)0.025 (2)0.028 (2)0.0001 (18)0.0049 (19)0.0008 (17)
C210.037 (3)0.027 (2)0.027 (2)0.0087 (18)0.0006 (18)0.0016 (18)
C220.030 (2)0.026 (2)0.026 (2)0.0023 (17)0.0043 (17)0.0005 (17)
C230.028 (2)0.0242 (19)0.0162 (18)0.0014 (16)0.0023 (16)0.0013 (15)
C240.029 (2)0.0231 (19)0.0161 (18)0.0004 (16)0.0027 (16)0.0014 (15)
N250.0222 (18)0.0271 (17)0.0224 (17)0.0028 (13)0.0042 (14)0.0007 (14)
N260.0217 (18)0.0211 (16)0.0245 (17)0.0014 (13)0.0043 (13)0.0013 (13)
N270.0276 (19)0.0224 (16)0.0228 (17)0.0009 (13)0.0051 (14)0.0007 (13)
N280.0268 (19)0.0216 (16)0.0225 (16)0.0005 (13)0.0000 (14)0.0024 (13)
Cl290.0364 (6)0.0346 (5)0.0250 (5)0.0008 (4)0.0040 (4)0.0059 (4)
Cl300.0362 (6)0.0416 (6)0.0401 (6)0.0046 (5)0.0036 (5)0.0008 (5)
Co310.0218 (3)0.0206 (3)0.0213 (3)0.0008 (2)0.0029 (2)0.0015 (2)
C320.028 (2)0.029 (2)0.033 (2)0.0009 (17)0.0026 (18)0.0016 (18)
C330.026 (2)0.043 (3)0.033 (2)0.0005 (19)0.0026 (19)0.002 (2)
C340.029 (2)0.049 (3)0.024 (2)0.008 (2)0.0034 (18)0.0016 (19)
C350.036 (3)0.032 (2)0.021 (2)0.0089 (18)0.0043 (18)0.0051 (17)
C360.046 (3)0.032 (2)0.027 (2)0.014 (2)0.013 (2)0.0041 (18)
C370.054 (3)0.026 (2)0.036 (2)0.011 (2)0.015 (2)0.0034 (19)
C380.055 (3)0.025 (2)0.024 (2)0.002 (2)0.013 (2)0.0034 (17)
C390.057 (3)0.022 (2)0.043 (3)0.006 (2)0.013 (2)0.0049 (19)
C400.046 (3)0.037 (2)0.043 (3)0.015 (2)0.008 (2)0.007 (2)
C410.034 (3)0.034 (2)0.036 (2)0.0053 (19)0.006 (2)0.0031 (19)
C420.033 (2)0.027 (2)0.0225 (19)0.0014 (17)0.0052 (17)0.0036 (17)
C430.036 (3)0.025 (2)0.0200 (19)0.0002 (17)0.0054 (17)0.0007 (16)
C440.033 (3)0.030 (2)0.030 (2)0.0017 (18)0.0015 (19)0.0015 (18)
C450.034 (3)0.031 (2)0.043 (3)0.0003 (19)0.004 (2)0.010 (2)
C460.023 (2)0.026 (2)0.054 (3)0.0022 (17)0.001 (2)0.009 (2)
C470.023 (2)0.022 (2)0.047 (3)0.0032 (16)0.003 (2)0.0008 (19)
C480.025 (2)0.026 (2)0.059 (3)0.0021 (17)0.010 (2)0.007 (2)
C490.028 (2)0.034 (2)0.048 (3)0.0052 (18)0.011 (2)0.015 (2)
C500.020 (2)0.034 (2)0.033 (2)0.0038 (17)0.0077 (17)0.0060 (18)
C510.028 (2)0.043 (3)0.035 (2)0.0075 (19)0.0102 (19)0.010 (2)
C520.030 (2)0.045 (3)0.024 (2)0.0068 (19)0.0065 (18)0.0045 (19)
C530.025 (2)0.033 (2)0.026 (2)0.0029 (17)0.0034 (17)0.0055 (17)
C540.023 (2)0.023 (2)0.033 (2)0.0039 (16)0.0039 (17)0.0013 (17)
C550.021 (2)0.027 (2)0.034 (2)0.0037 (16)0.0059 (17)0.0038 (18)
N560.027 (2)0.0246 (17)0.0257 (17)0.0038 (14)0.0025 (15)0.0025 (14)
N570.028 (2)0.0289 (18)0.0283 (18)0.0022 (14)0.0022 (15)0.0009 (15)
N580.0246 (19)0.0247 (17)0.0294 (18)0.0005 (14)0.0027 (15)0.0011 (14)
N590.0238 (19)0.0307 (18)0.0289 (18)0.0013 (14)0.0032 (15)0.0009 (15)
Cl600.0389 (6)0.0300 (5)0.0286 (5)0.0047 (4)0.0046 (5)0.0049 (4)
O610.059 (2)0.0162 (13)0.0103 (12)0.0070 (12)0.0077 (12)0.0051 (10)
Co620.0252 (3)0.0215 (3)0.0255 (3)0.0012 (2)0.0022 (2)0.0001 (2)
O630.048 (2)0.076 (3)0.075 (3)0.010 (2)0.016 (2)0.019 (2)
O640.084 (3)0.063 (3)0.045 (2)0.007 (2)0.008 (2)0.0013 (19)
O650.095 (3)0.041 (2)0.0360 (19)0.0110 (19)0.001 (2)0.0031 (15)
O660.062 (3)0.155 (5)0.122 (5)0.044 (3)0.041 (3)0.016 (4)
O670.114 (5)0.181 (7)0.152 (6)0.054 (5)0.042 (5)0.021 (5)
O680.044 (5)0.092 (6)0.070 (5)0.024 (4)0.031 (4)0.032 (5)
O690.128 (9)0.077 (6)0.041 (5)0.008 (6)0.031 (5)0.005 (4)
Cl700.0355 (12)0.0381 (11)0.0271 (10)0.0052 (9)0.0050 (9)0.0021 (9)
Cl710.0491 (16)0.0495 (14)0.0548 (15)0.0151 (11)0.0154 (12)0.0187 (12)
Geometric parameters (Å, º) top
C1—N251.332 (5)C34—C351.403 (6)
C1—C21.397 (6)C34—H340.9500
C1—H10.9500C35—C421.400 (6)
C2—C31.369 (6)C35—C361.441 (6)
C2—H20.9500C36—C371.349 (7)
C3—C41.409 (5)C36—H360.9500
C3—H30.9500C37—C381.438 (7)
C4—C111.415 (5)C37—H370.9500
C4—C51.434 (5)C38—C391.402 (7)
C5—C61.356 (6)C38—C431.414 (6)
C5—H50.9500C39—C401.380 (7)
C6—C71.434 (5)C39—H390.9500
C6—H60.9500C40—C411.400 (6)
C7—C121.409 (5)C40—H400.9500
C7—C81.416 (5)C41—N571.329 (5)
C8—C91.379 (6)C41—H410.9500
C8—H80.9500C42—N561.370 (5)
C9—C101.396 (6)C42—C431.436 (6)
C9—H90.9500C43—N571.358 (5)
C10—N261.327 (5)C44—N581.329 (5)
C10—H100.9500C44—C451.403 (6)
C11—N251.356 (5)C44—H440.9500
C11—C121.440 (5)C45—C461.376 (6)
C12—N261.366 (5)C45—H450.9500
C13—N271.325 (5)C46—C471.413 (6)
C13—C141.387 (6)C46—H460.9500
C13—H130.9500C47—C541.411 (5)
C14—C151.379 (6)C47—C481.421 (6)
C14—H140.9500C48—C491.344 (7)
C15—C161.406 (6)C48—H480.9500
C15—H150.9500C49—C501.450 (6)
C16—C231.405 (6)C49—H490.9500
C16—C171.436 (5)C50—C551.397 (6)
C17—C181.361 (6)C50—C511.403 (6)
C17—H170.9500C51—C521.367 (6)
C18—C191.435 (6)C51—H510.9500
C18—H180.9500C52—C531.405 (6)
C19—C241.409 (5)C52—H520.9500
C19—C201.418 (6)C53—N591.324 (5)
C20—C211.374 (6)C53—H530.9500
C20—H200.9500C54—N581.357 (5)
C21—C221.395 (6)C54—C551.437 (6)
C21—H210.9500C55—N591.370 (5)
C22—N281.324 (5)N56—Co622.150 (3)
C22—H220.9500N57—Co622.145 (3)
C23—N271.375 (5)N58—Co622.133 (3)
C23—C241.443 (5)N59—Co622.144 (3)
C24—N281.352 (5)Cl60—Co622.4204 (11)
N25—Co312.143 (3)O61—Co622.249 (3)
N26—Co312.138 (3)O61—H61A0.9089
N27—Co312.136 (3)O61—H61B0.9027
N28—Co312.152 (3)O63—H63A0.9084
Cl29—Co312.4279 (11)O63—H63B0.9251
Cl30—Co312.4269 (13)O64—H64A0.9254
C32—N561.326 (5)O64—H64B0.9145
C32—C331.388 (6)O65—H65A0.8780
C32—H320.9500O65—H65B0.9492
C33—C341.379 (6)O66—H66A0.9152
C33—H330.9500O66—H66B0.9243
N25—C1—C2122.4 (4)C34—C33—H33120.5
N25—C1—H1118.8C32—C33—H33120.5
C2—C1—H1118.8C33—C34—C35119.2 (4)
C3—C2—C1119.8 (4)C33—C34—H34120.4
C3—C2—H2120.1C35—C34—H34120.4
C1—C2—H2120.1C42—C35—C34117.9 (4)
C2—C3—C4119.7 (4)C42—C35—C36119.0 (4)
C2—C3—H3120.2C34—C35—C36123.0 (4)
C4—C3—H3120.2C37—C36—C35120.7 (4)
C3—C4—C11116.8 (3)C37—C36—H36119.7
C3—C4—C5124.3 (3)C35—C36—H36119.7
C11—C4—C5119.0 (3)C36—C37—C38121.6 (4)
C6—C5—C4121.5 (3)C36—C37—H37119.2
C6—C5—H5119.3C38—C37—H37119.2
C4—C5—H5119.3C39—C38—C43117.7 (4)
C5—C6—C7120.8 (3)C39—C38—C37123.5 (4)
C5—C6—H6119.6C43—C38—C37118.8 (4)
C7—C6—H6119.6C40—C39—C38119.0 (4)
C12—C7—C8117.3 (4)C40—C39—H39120.5
C12—C7—C6119.3 (3)C38—C39—H39120.5
C8—C7—C6123.4 (3)C39—C40—C41119.4 (4)
C9—C8—C7119.0 (4)C39—C40—H40120.3
C9—C8—H8120.5C41—C40—H40120.3
C7—C8—H8120.5N57—C41—C40123.1 (4)
C8—C9—C10119.5 (4)N57—C41—H41118.5
C8—C9—H9120.2C40—C41—H41118.5
C10—C9—H9120.2N56—C42—C35122.6 (4)
N26—C10—C9123.4 (4)N56—C42—C43116.9 (4)
N26—C10—H10118.3C35—C42—C43120.5 (4)
C9—C10—H10118.3N57—C43—C38122.9 (4)
N25—C11—C4123.0 (3)N57—C43—C42117.8 (4)
N25—C11—C12117.4 (3)C38—C43—C42119.3 (4)
C4—C11—C12119.5 (3)N58—C44—C45122.9 (4)
N26—C12—C7123.1 (3)N58—C44—H44118.5
N26—C12—C11117.0 (3)C45—C44—H44118.5
C7—C12—C11119.9 (3)C46—C45—C44119.0 (4)
N27—C13—C14123.9 (4)C46—C45—H45120.5
N27—C13—H13118.0C44—C45—H45120.5
C14—C13—H13118.0C45—C46—C47119.6 (4)
C15—C14—C13119.2 (4)C45—C46—H46120.2
C15—C14—H14120.4C47—C46—H46120.2
C13—C14—H14120.4C54—C47—C46117.3 (4)
C14—C15—C16119.2 (4)C54—C47—C48118.9 (4)
C14—C15—H15120.4C46—C47—C48123.8 (4)
C16—C15—H15120.4C49—C48—C47121.8 (4)
C23—C16—C15117.7 (3)C49—C48—H48119.1
C23—C16—C17119.1 (4)C47—C48—H48119.1
C15—C16—C17123.2 (4)C48—C49—C50121.2 (4)
C18—C17—C16120.7 (4)C48—C49—H49119.4
C18—C17—H17119.6C50—C49—H49119.4
C16—C17—H17119.6C55—C50—C51118.1 (4)
C17—C18—C19121.0 (4)C55—C50—C49117.9 (4)
C17—C18—H18119.5C51—C50—C49124.0 (4)
C19—C18—H18119.5C52—C51—C50119.1 (4)
C24—C19—C20116.9 (4)C52—C51—H51120.5
C24—C19—C18120.0 (4)C50—C51—H51120.5
C20—C19—C18123.1 (4)C51—C52—C53119.5 (4)
C21—C20—C19119.2 (4)C51—C52—H52120.2
C21—C20—H20120.4C53—C52—H52120.2
C19—C20—H20120.4N59—C53—C52122.8 (4)
C20—C21—C22119.5 (4)N59—C53—H53118.6
C20—C21—H21120.3C52—C53—H53118.6
C22—C21—H21120.3N58—C54—C47122.7 (4)
N28—C22—C21122.9 (4)N58—C54—C55117.9 (3)
N28—C22—H22118.6C47—C54—C55119.3 (4)
C21—C22—H22118.6N59—C55—C50122.5 (4)
N27—C23—C16122.6 (4)N59—C55—C54116.6 (3)
N27—C23—C24116.7 (3)C50—C55—C54120.9 (4)
C16—C23—C24120.8 (3)C32—N56—C42117.4 (4)
N28—C24—C19123.0 (4)C32—N56—Co62129.0 (3)
N28—C24—C23118.5 (3)C42—N56—Co62113.5 (3)
C19—C24—C23118.5 (4)C41—N57—C43117.9 (4)
C1—N25—C11118.4 (3)C41—N57—Co62128.3 (3)
C1—N25—Co31127.8 (3)C43—N57—Co62113.6 (3)
C11—N25—Co31113.9 (2)C44—N58—C54118.5 (3)
C10—N26—C12117.7 (3)C44—N58—Co62127.7 (3)
C10—N26—Co31128.4 (3)C54—N58—Co62113.8 (3)
C12—N26—Co31113.9 (2)C53—N59—C55117.9 (3)
C13—N27—C23117.4 (3)C53—N59—Co62128.4 (3)
C13—N27—Co31129.1 (3)C55—N59—Co62113.7 (3)
C23—N27—Co31113.5 (3)Co62—O61—H61A114.4
C22—N28—C24118.5 (3)Co62—O61—H61B112.3
C22—N28—Co31128.5 (3)H61A—O61—H61B113.5
C24—N28—Co31112.8 (2)N58—Co62—N5977.83 (13)
N27—Co31—N2687.52 (12)N58—Co62—N57170.22 (13)
N27—Co31—N2593.52 (12)N59—Co62—N5798.17 (13)
N26—Co31—N2577.68 (12)N58—Co62—N5693.24 (13)
N27—Co31—N2878.28 (12)N59—Co62—N5687.77 (13)
N26—Co31—N2895.85 (12)N57—Co62—N5677.60 (13)
N25—Co31—N28169.87 (13)N58—Co62—O6196.96 (11)
N27—Co31—Cl30170.35 (9)N59—Co62—O6188.36 (11)
N26—Co31—Cl3087.39 (9)N57—Co62—O6191.80 (11)
N25—Co31—Cl3093.39 (9)N56—Co62—O61168.08 (11)
N28—Co31—Cl3094.10 (9)N58—Co62—Cl6093.09 (9)
N27—Co31—Cl2991.98 (9)N59—Co62—Cl60170.85 (10)
N26—Co31—Cl29172.58 (9)N57—Co62—Cl6090.98 (9)
N25—Co31—Cl2994.97 (9)N56—Co62—Cl6093.99 (9)
N28—Co31—Cl2991.29 (9)O61—Co62—Cl6091.62 (7)
Cl30—Co31—Cl2994.12 (4)H63A—O63—H63B118.4
N56—C32—C33123.9 (4)H64A—O64—H64B98.3
N56—C32—H32118.1H65A—O65—H65B115.3
C33—C32—H32118.1H66A—O66—H66B123.7
C34—C33—C32118.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O61—H61A···Cl30i0.912.173.080 (3)180
O61—H61B···O67ii0.901.772.670 (7)178
O63—H63A···Cl290.912.193.102 (4)178
O63—H63B···O640.931.812.737 (6)180
O64—H64A···O690.932.133.055 (9)178
O64—H64A···Cl710.932.052.973 (4)178
O64—H64B···O680.911.902.816 (10)175
O64—H64B···Cl700.912.123.032 (4)178
O65—H65A···O690.882.122.959 (11)159
O65—H65A···Cl710.882.213.035 (4)156
O65—H65B···O680.952.012.939 (8)166
O65—H65B···Cl700.952.083.028 (4)175
O66—H66A···Cl60ii0.922.303.217 (5)178
O66—H66B···O690.922.022.943 (11)177
O66—H66B···Cl710.921.922.845 (6)178
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[CoCl(C12H8N2)2(H2O)]Cl·[CoCl2(C12H8N2)2]·6H2O
Mr1106.59
Crystal system, space groupMonoclinic, P21/c
Temperature (K)110
a, b, c (Å)14.0905 (2), 23.9088 (3), 14.2504 (2)
β (°) 98.7921 (7)
V3)4744.36 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.99
Crystal size (mm)0.25 × 0.20 × 0.20
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.791, 0.827
No. of measured, independent and
observed [I > 2σ(I)] reflections
33988, 11176, 6868
Rint0.071
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.179, 1.02
No. of reflections11176
No. of parameters641
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.34, 1.14

Computer programs: Collect (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O61—H61A···Cl30i0.912.173.080 (3)180
O61—H61B···O67ii0.901.772.670 (7)178
O63—H63A···Cl290.912.193.102 (4)178
O63—H63B···O640.931.812.737 (6)180
O64—H64A···O690.932.133.055 (9)178
O64—H64A···Cl710.932.052.973 (4)178
O64—H64B···O680.911.902.816 (10)175
O64—H64B···Cl700.912.123.032 (4)178
O65—H65A···O690.882.122.959 (11)159
O65—H65A···Cl710.882.213.035 (4)156
O65—H65B···O680.952.012.939 (8)166
O65—H65B···Cl700.952.083.028 (4)175
O66—H66A···Cl60ii0.922.303.217 (5)178
O66—H66B···O690.922.022.943 (11)177
O66—H66B···Cl710.921.922.845 (6)178
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1.
 

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