Download citation
Download citation
link to html
In the title compound, [Co(C2H6N4O2)3]2(C2O4)(SO4)2­12H2O, the Co3+ ion adopts a distorted octa­hedral coordination involving six imino N atoms of three bidentate oxamide dioxime ligands. The oxalate ion is centrosymmetric. The bulk structure is consolidated by a network of O—H...O and N—H...O hydrogen bonds, inter­connecting the building blocks in such a manner that the framework delineates infinite channels parallel to [100]. The 12 water mol­ecules are lodged inside the channels, six of them being O—H...O and N—H...O bonded to the ionic species, whilst the other six, located along the central axis of the channel, form infinite cyclo­hexa­meric water tapes. Two of the water mol­ecules are disordered over two sites, in 0.786 (7):0.214 (7) and 0.637 (8):0.363 (8) ratios.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031169/hb2446sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031169/hb2446Isup2.hkl
Contains datablock I

CCDC reference: 648383

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in solvent or counterion
  • R factor = 0.062
  • wR factor = 0.158
  • Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... 2 PLAT245_ALERT_2_C U(iso) H7O Smaller than U(eq) O4 by ... 0.02 AngSq PLAT245_ALERT_2_C U(iso) H8O Smaller than U(eq) O4 by ... 0.02 AngSq PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 11.00 Perc. PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O5A PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O5B PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O6A PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O6B PLAT355_ALERT_3_C Long O-H Bond (0.82A) O4 - H7O ... 1.02 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C41 - C41_a ... 1.56 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H5O .. H8O .. 2.14 Ang. PLAT430_ALERT_2_C Short Inter D...A Contact O43 .. N31 .. 2.88 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O25 .. C41 .. 2.92 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O25 .. C41 .. 2.96 Ang.
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C14 H52 Co2 N24 O36 S2 Atom count from _chemical_formula_moiety:C14 H60 Co2 N24 O36 S2 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 18 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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

Comment top

Water clusters, encapsulated as crystal hydrates in various solid networks, were recently introduced as a new field of considerable scientific relevance, both in theoretical and in experimental studies (Ludwig, 2001; Infantes & Motherwell, 2002; Mascal et al., 2006). The point at stake relates to the need for a comprehensive analysis of hydrogen-bonded water clusters, (H2O)n, where n > 1. Infantes and Motherwell (2002) have selected the cluster patterns and sorted their structures into five broad classes designated D, R, C, T and L.

We describe here compound (I) as a salt of the rare complex cation, [Co(H2oxado)3]3+ (Bekaroglu et al., 1978; Bélombé et al., 1993; Nenwa, 2004). It is a transition metal complex system that crystallizes in a nanochannelled lattice encapsulating infinite tapes of cyclic water hexamers, and it provides, therefore, another well documented example to be added to category T of the aforementioned classification.

The constituent parts of (I) are depicted in Fig. 1. The pseudo-octahedral coordination in the complex cation is similar to the chiral geometries, and the bond lengths and angles compare within experimental error with those reported previously (Nenwa, 2004; Bekaroglu et al., 1978; Bélombé et al., 1993). The host lattice of the structure is realised by the ionic partners which are linked together via a three dimensional network of O–H···O and N–H···O hydrogen bonds. The ions of each kind pile up in an eclipsed sequence to generate the corresponding charged stacks. The electrically neutral scaffold thus constructed is characterized by infinite channels (ca 6.4 Å wide) oriented parallel to [100], and encapsulating twelve water molecules of crystallization per unit cell.

The projection of a unit cell of (I) in Fig. 2 shows the positioning of the water molecules within the channels, reminiscent of the structure of a silver salt reported recently (Bélombé et al., 2007). The oxalate ion is centrosymmetric. Thus, only one oxalate ion is present in the unit cell, the other species being represented twice. A short segment of a water tape in (I) viewed down [010] is shown in Fig. 3. One distinguishes, from the ellipsoid size, two types of water molecules per asymmetric unit. Those containing atoms O1, O2 and O3, positioned close to the periphery of the channels – due to their involvement in H-bonding to the ionic building blocks of the host lattice – may be dubbed "peripheral" waters. The reduced ellipsoid size of these O atoms reveals that they are well ordered. The water molecules with the atoms O4, O5A and O6A may be referred to as "central" waters, as they are located around the central axis of the channel. The ellipsoid extent of these O atoms indicates their high disorder, probably due to their increased mobility since they are less strongly bonded than their "peripheral" congeners.

Table 2 summarizes the three categories of H-bonds that are effective in this structure. O–H···O and N–H···O bridges interconnect the ionic partners amongst themselves into the three dimensional host lattice. Note that these bridges represent the most efficient ones, with the shortest O···O separation of 2.584 (4)Å linking an oxamide dioxime to an oxalate O atom, viz. O15···O43x (see Table 2 for symmetry code). Then, O–H···O and N–H···O bridges of medium efficiency interlink the "peripheral" water molecules to the ionic partners. Finally, O–H···O bridges weakly interconnect water molecules amongst themselves within the nanochannels.

Related literature top

For related literature, see: Bélombé et al. (1993, 2007); Bailar & Jones (1939); Bekaroglu et al. (1978); Infantes & Motherwell (2002); Ludwig (2001); Mascal et al. (2006); Nenwa (2004).

Experimental top

Commercial CoSO4.7H2O, freshly prepared H2oxado (Nenwa, 2004), and K3[Co(C2O4)3].3H2O (Bailar & Jones, 1939), were mixed together in a ratio of 0.56 g (2 mmol):0.95 g (8 mmol):0.99 g (2 mmol) in water (120 ml) with stirring at room temperature. The resulting red-brown precipitate was discarded by filtration. Concentration of the filtrate by slow evaporation in the hood over three weeks yielded dark-red prisms of (I) that were filtered off and dried in air at room temperature.

Refinement top

The non-water H atoms were positioned geometrically (O—H = 0.84 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2 Ueq(N) or 1.5Ueq(O). All the water H atoms were first located in a difference Fourier map and then refined with distance restraints of O–H = 0.85 (3) Å and H···H = 1.39 (3) Å, and with equal Uiso(H). The highest peak and deepest hole in the final difference map are 0.55 Å from atom H6A and 0.29 Å from O5A, respectively.

Due to the disorder observed for the two oxygen sites (O5 and O6), no hydrogen atoms could be located for these O atoms.

Structure description top

Water clusters, encapsulated as crystal hydrates in various solid networks, were recently introduced as a new field of considerable scientific relevance, both in theoretical and in experimental studies (Ludwig, 2001; Infantes & Motherwell, 2002; Mascal et al., 2006). The point at stake relates to the need for a comprehensive analysis of hydrogen-bonded water clusters, (H2O)n, where n > 1. Infantes and Motherwell (2002) have selected the cluster patterns and sorted their structures into five broad classes designated D, R, C, T and L.

We describe here compound (I) as a salt of the rare complex cation, [Co(H2oxado)3]3+ (Bekaroglu et al., 1978; Bélombé et al., 1993; Nenwa, 2004). It is a transition metal complex system that crystallizes in a nanochannelled lattice encapsulating infinite tapes of cyclic water hexamers, and it provides, therefore, another well documented example to be added to category T of the aforementioned classification.

The constituent parts of (I) are depicted in Fig. 1. The pseudo-octahedral coordination in the complex cation is similar to the chiral geometries, and the bond lengths and angles compare within experimental error with those reported previously (Nenwa, 2004; Bekaroglu et al., 1978; Bélombé et al., 1993). The host lattice of the structure is realised by the ionic partners which are linked together via a three dimensional network of O–H···O and N–H···O hydrogen bonds. The ions of each kind pile up in an eclipsed sequence to generate the corresponding charged stacks. The electrically neutral scaffold thus constructed is characterized by infinite channels (ca 6.4 Å wide) oriented parallel to [100], and encapsulating twelve water molecules of crystallization per unit cell.

The projection of a unit cell of (I) in Fig. 2 shows the positioning of the water molecules within the channels, reminiscent of the structure of a silver salt reported recently (Bélombé et al., 2007). The oxalate ion is centrosymmetric. Thus, only one oxalate ion is present in the unit cell, the other species being represented twice. A short segment of a water tape in (I) viewed down [010] is shown in Fig. 3. One distinguishes, from the ellipsoid size, two types of water molecules per asymmetric unit. Those containing atoms O1, O2 and O3, positioned close to the periphery of the channels – due to their involvement in H-bonding to the ionic building blocks of the host lattice – may be dubbed "peripheral" waters. The reduced ellipsoid size of these O atoms reveals that they are well ordered. The water molecules with the atoms O4, O5A and O6A may be referred to as "central" waters, as they are located around the central axis of the channel. The ellipsoid extent of these O atoms indicates their high disorder, probably due to their increased mobility since they are less strongly bonded than their "peripheral" congeners.

Table 2 summarizes the three categories of H-bonds that are effective in this structure. O–H···O and N–H···O bridges interconnect the ionic partners amongst themselves into the three dimensional host lattice. Note that these bridges represent the most efficient ones, with the shortest O···O separation of 2.584 (4)Å linking an oxamide dioxime to an oxalate O atom, viz. O15···O43x (see Table 2 for symmetry code). Then, O–H···O and N–H···O bridges of medium efficiency interlink the "peripheral" water molecules to the ionic partners. Finally, O–H···O bridges weakly interconnect water molecules amongst themselves within the nanochannels.

For related literature, see: Bélombé et al. (1993, 2007); Bailar & Jones (1939); Bekaroglu et al. (1978); Infantes & Motherwell (2002); Ludwig (2001); Mascal et al. (2006); Nenwa (2004).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Structures of the ions [Co(H2oxado)3]3+, C2O42– and SO42– in (I) with ellipsoids drawn at 50% probability. Symmetry code: (i) 1 - x, 2 - y, 2 - z.
[Figure 2] Fig. 2. Projection down [100] of the unit cell of (I) showing the positioning of water molecules in the channels, and the extended network of O–H···O and N–H···O bridgings (dashed lines).
[Figure 3] Fig. 3. View down [010] of a segment (encompassing two adjacent unit cells) of a water tape in (I), brought about by O–H···O bridgings within the nanochannel, with O atom numbering and ellipsoids drawn at 50% probability. Symmetry code: (iii) 1 - x, 1 - y, -z
Bis[tris(oxamide dioxime-κ2N,N')cobalt(III)] oxalate bis(sulfate) dodecahydrate top
Crystal data top
[Co(C2H6N4O2)3]2(C2O4)(SO4)2·12H2OZ = 1
Mr = 1314.78F(000) = 678
Triclinic, P1Dx = 1.698 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.4298 (10) ÅCell parameters from 20047 reflections
b = 11.7820 (12) Åθ = 1.8–30.0°
c = 12.8118 (13) ŵ = 0.85 mm1
α = 65.494 (2)°T = 193 K
β = 83.088 (2)°Prism, red
γ = 86.735 (2)°0.25 × 0.15 × 0.10 mm
V = 1285.7 (2) Å3
Data collection top
Bruker APEX CCD
diffractometer
7453 independent reflections
Radiation source: fine-focus sealed tube5173 reflections with I > 2s(I)
Graphite monochromatorRint = 0.056
ω scansθmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1313
Tmin = 0.816, Tmax = 0.919k = 1616
20047 measured reflectionsl = 1818
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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0654P)2 + 0.8468P]
where P = (Fo2 + 2Fc2)/3
7453 reflections(Δ/σ)max < 0.001
381 parametersΔρmax = 0.91 e Å3
12 restraintsΔρmin = 0.53 e Å3
Crystal data top
[Co(C2H6N4O2)3]2(C2O4)(SO4)2·12H2Oγ = 86.735 (2)°
Mr = 1314.78V = 1285.7 (2) Å3
Triclinic, P1Z = 1
a = 9.4298 (10) ÅMo Kα radiation
b = 11.7820 (12) ŵ = 0.85 mm1
c = 12.8118 (13) ÅT = 193 K
α = 65.494 (2)°0.25 × 0.15 × 0.10 mm
β = 83.088 (2)°
Data collection top
Bruker APEX CCD
diffractometer
7453 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
5173 reflections with I > 2s(I)
Tmin = 0.816, Tmax = 0.919Rint = 0.056
20047 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06212 restraints
wR(F2) = 0.158H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.91 e Å3
7453 reflectionsΔρmin = 0.53 e Å3
381 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co0.72701 (5)0.84049 (4)0.30836 (4)0.01529 (12)
N240.6030 (3)0.8386 (3)0.4406 (2)0.0171 (6)
N310.5850 (3)0.7379 (3)0.2960 (3)0.0189 (6)
N140.8825 (3)0.9315 (3)0.3172 (2)0.0178 (6)
N110.8492 (3)0.8491 (3)0.1742 (2)0.0189 (6)
N340.8108 (3)0.6788 (3)0.3867 (3)0.0202 (6)
N210.6281 (3)0.9941 (3)0.2389 (2)0.0189 (6)
C230.4943 (3)0.9156 (3)0.4158 (3)0.0174 (6)
C120.9796 (3)0.8860 (3)0.1652 (3)0.0181 (7)
C220.5210 (3)1.0192 (3)0.2997 (3)0.0191 (7)
C130.9951 (3)0.9473 (3)0.2431 (3)0.0180 (7)
C320.6064 (4)0.6183 (3)0.3411 (3)0.0207 (7)
C330.7511 (4)0.5856 (3)0.3794 (3)0.0215 (7)
N270.3745 (3)0.9059 (3)0.4837 (3)0.0241 (7)
H27B0.36290.84340.55220.029*
H27A0.30620.96200.46040.029*
N161.0876 (3)0.8716 (3)0.0946 (3)0.0262 (7)
H16A1.07360.83480.04940.031*
H16B1.17310.89890.09310.031*
N171.1079 (3)1.0139 (3)0.2339 (3)0.0261 (7)
H17B1.11071.05190.28000.031*
H17A1.18031.02030.18150.031*
N360.5106 (4)0.5328 (3)0.3572 (3)0.0321 (8)
H36A0.42420.55580.33660.039*
H36B0.53340.45310.38860.039*
N260.4420 (3)1.1219 (3)0.2664 (3)0.0265 (7)
H26A0.46041.18140.19690.032*
H26B0.37111.13070.31390.032*
N370.8072 (4)0.4730 (3)0.4041 (3)0.0344 (8)
H37B0.89270.45560.42800.041*
H37A0.75890.41550.39670.041*
O280.5724 (3)0.7321 (2)0.5422 (2)0.0207 (5)
H280.64440.71160.57900.031*
O350.4425 (2)0.7706 (2)0.2803 (2)0.0227 (5)
H350.43730.82820.21450.034*
O150.8358 (3)0.7791 (3)0.1115 (2)0.0252 (6)
H150.75320.78850.09080.038*
O380.9540 (3)0.6557 (3)0.4085 (2)0.0253 (6)
H380.97320.69060.45040.038*
O180.8796 (3)1.0069 (2)0.3777 (2)0.0227 (5)
H180.87340.96180.44880.034*
O250.6574 (3)1.0865 (2)0.1272 (2)0.0235 (5)
H250.72871.12760.12440.035*
S0.09424 (9)0.24928 (9)0.35902 (8)0.0222 (2)
O540.1647 (3)0.1248 (2)0.3908 (2)0.0251 (6)
O530.0244 (3)0.2839 (3)0.2537 (2)0.0303 (6)
O510.2052 (3)0.3409 (3)0.3414 (3)0.0377 (7)
O520.0110 (3)0.2428 (3)0.4557 (3)0.0329 (7)
C410.5668 (3)0.9661 (4)0.9842 (3)0.0222 (7)
O420.6460 (3)1.0302 (3)0.8951 (2)0.0261 (6)
O430.5845 (3)0.8550 (3)1.0492 (2)0.0274 (6)
O10.8832 (3)0.2297 (3)0.0879 (3)0.0339 (7)
O20.7212 (3)0.3062 (3)0.3112 (2)0.0296 (6)
O30.2201 (4)0.5849 (4)0.2797 (4)0.0605 (11)
O40.4136 (7)0.6487 (6)0.0773 (5)0.110 (2)
O5A0.8644 (7)0.4954 (6)0.0420 (6)0.0863 (19)*0.786 (7)
O5B0.989 (3)0.449 (2)0.092 (2)0.0863 (19)*0.214 (7)
O6A0.5585 (8)0.3823 (8)0.1243 (6)0.0709 (17)*0.637 (8)
O6B0.6096 (14)0.4563 (13)0.1069 (11)0.0709 (17)*0.363 (8)
H1O0.874 (7)0.299 (3)0.042 (4)0.094 (9)*
H2O0.936 (6)0.227 (6)0.133 (4)0.094 (9)*
H3O0.804 (3)0.289 (6)0.292 (5)0.094 (9)*
H4O0.685 (6)0.334 (6)0.247 (4)0.094 (9)*
H5O0.234 (8)0.616 (5)0.207 (2)0.094 (9)*
H6O0.191 (7)0.513 (3)0.296 (5)0.094 (9)*
H7O0.480 (6)0.657 (6)0.006 (4)0.094 (9)*
H8O0.366 (6)0.594 (5)0.069 (6)0.094 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0097 (2)0.0186 (2)0.0200 (2)0.00156 (16)0.00084 (16)0.01075 (18)
N240.0145 (13)0.0192 (14)0.0173 (14)0.0002 (11)0.0005 (11)0.0076 (11)
N310.0127 (13)0.0198 (15)0.0249 (15)0.0013 (11)0.0013 (11)0.0103 (12)
N140.0132 (13)0.0215 (15)0.0239 (15)0.0004 (11)0.0001 (11)0.0152 (13)
N110.0162 (13)0.0250 (15)0.0209 (15)0.0005 (11)0.0022 (11)0.0147 (13)
N340.0161 (14)0.0233 (15)0.0242 (15)0.0058 (11)0.0059 (11)0.0123 (13)
N210.0152 (13)0.0212 (15)0.0187 (14)0.0010 (11)0.0010 (11)0.0068 (12)
C230.0133 (15)0.0219 (17)0.0209 (17)0.0023 (12)0.0022 (12)0.0127 (14)
C120.0144 (15)0.0211 (17)0.0202 (16)0.0016 (12)0.0018 (12)0.0102 (14)
C220.0134 (15)0.0216 (17)0.0245 (18)0.0003 (12)0.0044 (13)0.0111 (14)
C130.0136 (15)0.0207 (17)0.0219 (17)0.0040 (12)0.0035 (12)0.0110 (14)
C320.0203 (17)0.0244 (18)0.0188 (17)0.0002 (13)0.0007 (13)0.0107 (14)
C330.0201 (17)0.0228 (18)0.0250 (18)0.0050 (13)0.0061 (14)0.0128 (15)
N270.0159 (14)0.0283 (17)0.0256 (16)0.0050 (12)0.0021 (12)0.0105 (13)
N160.0123 (13)0.043 (2)0.0336 (18)0.0032 (13)0.0039 (12)0.0273 (16)
N170.0149 (14)0.0404 (19)0.0333 (18)0.0059 (13)0.0038 (12)0.0264 (16)
N360.0270 (17)0.0210 (16)0.047 (2)0.0032 (13)0.0104 (15)0.0103 (15)
N260.0236 (16)0.0239 (16)0.0265 (17)0.0089 (13)0.0015 (13)0.0064 (13)
N370.0310 (18)0.0237 (17)0.054 (2)0.0104 (14)0.0170 (17)0.0198 (17)
O280.0161 (11)0.0223 (13)0.0199 (12)0.0009 (10)0.0023 (9)0.0049 (10)
O350.0122 (11)0.0242 (13)0.0287 (14)0.0004 (9)0.0037 (10)0.0074 (11)
O150.0138 (11)0.0390 (16)0.0359 (15)0.0017 (11)0.0035 (11)0.0285 (13)
O380.0155 (12)0.0331 (15)0.0365 (15)0.0089 (10)0.0098 (11)0.0227 (13)
O180.0224 (12)0.0263 (13)0.0261 (13)0.0015 (10)0.0020 (11)0.0184 (11)
O250.0217 (13)0.0248 (13)0.0194 (13)0.0037 (10)0.0016 (10)0.0040 (10)
S0.0178 (4)0.0249 (5)0.0301 (5)0.0048 (3)0.0093 (3)0.0163 (4)
O540.0202 (12)0.0260 (14)0.0330 (15)0.0061 (10)0.0061 (11)0.0158 (12)
O530.0246 (14)0.0374 (16)0.0311 (15)0.0051 (12)0.0116 (11)0.0147 (13)
O510.0317 (16)0.0261 (15)0.055 (2)0.0019 (12)0.0212 (14)0.0120 (14)
O520.0243 (14)0.0493 (18)0.0365 (16)0.0101 (13)0.0081 (12)0.0290 (15)
C410.0110 (15)0.038 (2)0.0225 (18)0.0025 (14)0.0052 (13)0.0156 (16)
O420.0152 (12)0.0383 (16)0.0249 (14)0.0030 (11)0.0046 (10)0.0143 (12)
O430.0189 (13)0.0346 (15)0.0282 (14)0.0003 (11)0.0052 (11)0.0118 (12)
O10.0319 (16)0.0387 (17)0.0354 (17)0.0066 (13)0.0050 (13)0.0183 (14)
O20.0196 (13)0.0339 (16)0.0347 (16)0.0010 (11)0.0004 (11)0.0147 (13)
O30.047 (2)0.038 (2)0.098 (3)0.0035 (17)0.010 (2)0.029 (2)
O40.139 (5)0.105 (5)0.084 (4)0.056 (4)0.030 (4)0.024 (3)
Geometric parameters (Å, º) top
Co—N211.900 (3)N17—H17B0.8800
Co—N141.906 (3)N17—H17A0.8800
Co—N311.917 (3)N36—H36A0.8800
Co—N111.920 (3)N36—H36B0.8800
Co—N341.922 (3)N26—H26A0.8800
Co—N241.932 (3)N26—H26B0.8800
N24—C231.307 (4)N37—H37B0.8800
N24—O281.396 (4)N37—H37A0.8800
N31—C321.297 (4)O28—H280.8400
N31—O351.391 (3)O35—H350.8400
N14—C131.302 (4)O15—H150.8400
N14—O181.398 (3)O38—H380.8400
N11—C121.303 (4)O18—H180.8400
N11—O151.388 (4)O25—H250.8400
N34—C331.303 (4)S—O531.465 (3)
N34—O381.400 (3)S—O521.469 (3)
N21—C221.297 (4)S—O511.477 (3)
N21—O251.398 (4)S—O541.489 (3)
C23—N271.319 (4)C41—O431.241 (5)
C23—C221.485 (5)C41—O421.255 (4)
C12—N161.330 (4)C41—C41i1.555 (7)
C12—C131.478 (5)O1—H1O0.79 (3)
C22—N261.321 (4)O1—H2O0.80 (3)
C13—N171.323 (4)O2—H3O0.83 (3)
C32—N361.327 (5)O2—H4O0.85 (3)
C32—C331.482 (5)O3—H5O0.84 (3)
C33—N371.324 (5)O3—H6O0.84 (3)
N27—H27B0.8800O4—H7O1.01 (3)
N27—H27A0.8800O4—H8O0.85 (3)
N16—H16A0.8800O5A—O5B1.45 (2)
N16—H16B0.8800O6A—O6B0.950 (13)
N21—Co—N1488.61 (12)N17—C13—C12123.1 (3)
N21—Co—N3196.04 (12)N31—C32—N36125.4 (3)
N14—Co—N31174.13 (12)N31—C32—C33111.9 (3)
N21—Co—N1197.98 (12)N36—C32—C33122.6 (3)
N14—Co—N1179.99 (12)N34—C33—N37126.2 (3)
N31—Co—N1195.78 (12)N34—C33—C32111.9 (3)
N21—Co—N34174.77 (12)N37—C33—C32121.9 (3)
N14—Co—N3495.29 (12)C23—N27—H27B120.0
N31—Co—N3480.29 (12)C23—N27—H27A120.0
N11—Co—N3486.15 (13)H27B—N27—H27A120.0
N21—Co—N2479.98 (12)C12—N16—H16A120.0
N14—Co—N2499.14 (12)C12—N16—H16B120.0
N31—Co—N2485.24 (12)H16A—N16—H16B120.0
N11—Co—N24177.82 (13)C13—N17—H17B120.0
N34—Co—N2495.93 (12)C13—N17—H17A120.0
C23—N24—O28112.3 (3)H17B—N17—H17A120.0
C23—N24—Co114.8 (2)C32—N36—H36A120.0
O28—N24—Co124.3 (2)C32—N36—H36B120.0
C32—N31—O35113.0 (3)H36A—N36—H36B120.0
C32—N31—Co117.3 (2)C22—N26—H26A120.0
O35—N31—Co125.9 (2)C22—N26—H26B120.0
C13—N14—O18113.8 (3)H26A—N26—H26B120.0
C13—N14—Co117.9 (2)C33—N37—H37B120.0
O18—N14—Co126.8 (2)C33—N37—H37A120.0
C12—N11—O15112.9 (3)H37B—N37—H37A120.0
C12—N11—Co116.3 (2)N24—O28—H28109.5
O15—N11—Co126.0 (2)N31—O35—H35109.5
C33—N34—O38113.0 (3)N11—O15—H15109.5
C33—N34—Co116.2 (2)N34—O38—H38109.5
O38—N34—Co125.5 (2)N14—O18—H18109.5
C22—N21—O25114.6 (3)N21—O25—H25109.5
C22—N21—Co118.1 (2)O53—S—O52110.50 (16)
O25—N21—Co127.3 (2)O53—S—O51110.43 (18)
N24—C23—N27125.7 (3)O52—S—O51109.38 (18)
N24—C23—C22111.6 (3)O53—S—O54110.55 (16)
N27—C23—C22122.7 (3)O52—S—O54108.07 (17)
N11—C12—N16124.9 (3)O51—S—O54107.84 (16)
N11—C12—C13112.0 (3)O43—C41—O42126.7 (3)
N16—C12—C13123.0 (3)O43—C41—C41i117.1 (4)
N21—C22—N26126.4 (3)O42—C41—C41i116.2 (4)
N21—C22—C23111.4 (3)H1O—O1—H2O111 (4)
N26—C22—C23122.2 (3)H3O—O2—H4O101 (4)
N14—C13—N17125.2 (3)H5O—O3—H6O103 (4)
N14—C13—C12111.7 (3)H7O—O4—H8O90 (3)
Symmetry code: (i) x+1, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N16—H16B···O42ii0.881.992.864 (4)172
N17—H17B···O54iii0.882.062.926 (4)167
N17—H17A···O42ii0.882.002.835 (4)159
N27—H27A···O54iv0.882.203.069 (4)170
N26—H26B···O54iv0.882.062.900 (4)158
N36—H36B···O28v0.882.232.952 (4)139
N37—H37B···O52vi0.882.512.998 (4)115
N37—H37B···O38vii0.882.543.321 (4)149
O15—H15···O43viii0.841.772.584 (4)162
O18—H18···O54v0.841.882.709 (4)172
O18—H18···O52v0.842.563.124 (4)125
O28—H28···O51v0.841.782.617 (4)177
O35—H35···O42ix0.841.882.667 (4)155
O35—H35···O43viii0.842.302.881 (4)127
O38—H38···O52v0.841.762.602 (4)177
N16—H16A···O1x0.882.183.016 (4)159
N27—H27B···O2v0.882.022.865 (4)162
N36—H36A···O30.882.102.971 (5)170
N37—H37A···O20.882.072.879 (5)152
O25—H25···O1iv0.841.832.662 (4)169
O1—H2O···O53vi0.80 (3)2.19 (4)2.931 (4)156 (6)
O2—H3O···O53vi0.83 (3)2.08 (3)2.890 (4)165 (6)
O3—H6O···O510.84 (3)1.87 (4)2.653 (5)157 (7)
O1—H1O···O5A0.79 (3)2.11 (3)2.879 (7)164 (6)
O2—H4O···O6A0.85 (3)1.96 (3)2.799 (8)166 (6)
O3—H5O···O40.84 (3)2.16 (6)2.831 (8)137 (7)
O4—H7O···O6Axi1.01 (3)1.99 (6)2.736 (9)128 (5)
O4—H8O···O5Axi0.85 (3)2.59 (4)3.375 (8)153 (6)
Symmetry codes: (ii) x+2, y+2, z+1; (iii) x+1, y+1, z; (iv) x, y+1, z; (v) x+1, y+1, z+1; (vi) x+1, y, z; (vii) x+2, y+1, z+1; (viii) x, y, z1; (ix) x+1, y+2, z+1; (x) x+2, y+1, z; (xi) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Co(C2H6N4O2)3]2(C2O4)(SO4)2·12H2O
Mr1314.78
Crystal system, space groupTriclinic, P1
Temperature (K)193
a, b, c (Å)9.4298 (10), 11.7820 (12), 12.8118 (13)
α, β, γ (°)65.494 (2), 83.088 (2), 86.735 (2)
V3)1285.7 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.85
Crystal size (mm)0.25 × 0.15 × 0.10
Data collection
DiffractometerBruker APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.816, 0.919
No. of measured, independent and
observed [I > 2s(I)] reflections
20047, 7453, 5173
Rint0.056
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.158, 1.10
No. of reflections7453
No. of parameters381
No. of restraints12
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.91, 0.53

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Co—N211.900 (3)Co—N111.920 (3)
Co—N141.906 (3)Co—N341.922 (3)
Co—N311.917 (3)Co—N241.932 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N16—H16B···O42i0.881.992.864 (4)172
N17—H17B···O54ii0.882.062.926 (4)167
N17—H17A···O42i0.882.002.835 (4)159
N27—H27A···O54iii0.882.203.069 (4)170
N26—H26B···O54iii0.882.062.900 (4)158
N36—H36B···O28iv0.882.232.952 (4)139
N37—H37B···O52v0.882.512.998 (4)115
N37—H37B···O38vi0.882.543.321 (4)149
O15—H15···O43vii0.841.772.584 (4)162
O18—H18···O54iv0.841.882.709 (4)172
O18—H18···O52iv0.842.563.124 (4)125
O28—H28···O51iv0.841.782.617 (4)177
O35—H35···O42viii0.841.882.667 (4)155
O35—H35···O43vii0.842.302.881 (4)127
O38—H38···O52iv0.841.762.602 (4)177
N16—H16A···O1ix0.882.183.016 (4)159
N27—H27B···O2iv0.882.022.865 (4)162
N36—H36A···O30.882.102.971 (5)170
N37—H37A···O20.882.072.879 (5)152
O25—H25···O1iii0.841.832.662 (4)169
O1—H2O···O53v0.80 (3)2.19 (4)2.931 (4)156 (6)
O2—H3O···O53v0.83 (3)2.08 (3)2.890 (4)165 (6)
O3—H6O···O510.84 (3)1.87 (4)2.653 (5)157 (7)
O1—H1O···O5A0.79 (3)2.11 (3)2.879 (7)164 (6)
O2—H4O···O6A0.85 (3)1.96 (3)2.799 (8)166 (6)
O3—H5O···O40.84 (3)2.16 (6)2.831 (8)137 (7)
O4—H7O···O6Ax1.01 (3)1.99 (6)2.736 (9)128 (5)
O4—H8O···O5Ax0.85 (3)2.59 (4)3.375 (8)153 (6)
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) x+1, y+1, z+1; (v) x+1, y, z; (vi) x+2, y+1, z+1; (vii) x, y, z1; (viii) x+1, y+2, z+1; (ix) x+2, y+1, z; (x) x+1, y+1, z.
 

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