Poly[[tetra­aqua­bis­(μ3-1H-imidazole-4,5-dicarboxyl­ato)tetra­kis­(μ2-1H-imidazole-4,5-dicarboxyl­ato)tricobalt(II)diytterbium(III)] dihydrate]

Zhu, L.-C.

doi:10.1107/S1600536811028285

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1121-m1122

doi:10.1107/S1600536811028285

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Poly[[tetraaquabis(μ₃-1H-imidazole-4,5-dicarboxylato)tetrakis(μ₂-1H-imidazole-4,5-dicarboxylato)tricobalt(II)diytterbium(III)] dihydrate]

Li-Cai Zhu ^a ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: licaizhu1977@yahoo.com.cn

(Received 27 June 2011; accepted 14 July 2011; online 23 July 2011)

The asymmetric unit of the title compound, {[Co₃Yb₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O}_n, contains one Yb^III ion, two Co^II ions (one situated on an inversion centre), three imidazole-4,5-dicarboxylate ligands, two coordinated water molecules and one uncoordinated water molecule. The Yb^III ion is seven-coordinated, in a monocapped trigonal prismatic coordination geometry, by six O atoms from three imidazole-4,5-dicarboxylate ligands and one water O atom. Both Co^II ions are six-coordinated in a slightly distorted octahedral geometry. The Co^II ion that is located on an inversion center is coordinated by two O atoms from two water molecules, as well as two O atoms and two N atoms from two imidazole-4,5-dicarboxylate ligands. The second Co^II ion is bonded to four O atoms and two N atoms from four imidazole-4,5-dicarboxylate ligands. These metal coordination units are connected by bridging imidazole-4,5-dicarboxylate ligands, generating a three-dimensional network. The crystal structure is further stabilized by N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding interactions involving the water molecules and the imidazole-4,5-dicarboxylate ligands.

Related literature

For lanthanide–transition metal heterometallic complexes with bridging multifunctional organic ligands, see: Cheng et al. (2006 ); Kuang et al. (2007 ); Sun et al. (2006 ); Zhu et al. (2010 ).

Experimental

Crystal data

[Co₃Yb₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O
M_r = 1555.48
Triclinic, $[P \overline 1]$
a = 7.0413 (4) Å
b = 8.3538 (5) Å
c = 17.8755 (10) Å
α = 95.546 (1)°
β = 96.886 (1)°
γ = 97.177 (1)°
V = 1029.03 (10) Å³
Z = 1
Mo Kα radiation
μ = 5.81 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.325, T_max = 0.418
5347 measured reflections
3640 independent reflections
3350 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.04
3640 reflections
376 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O12ⁱ	0.87 (3)	2.18 (3)	3.036 (4)	172 (3)
O1W—H1W⋯O12ⁱⁱ	0.82 (4)	1.93 (4)	2.747 (4)	173 (4)
N4—H2⋯O9ⁱⁱⁱ	0.86 (3)	2.07 (3)	2.909 (4)	166 (5)
O1W—H2W⋯O12^iv	0.80 (3)	2.07 (4)	2.808 (4)	153 (5)
O2W—H3W⋯O3^v	0.80 (4)	2.08 (4)	2.870 (5)	168 (5)
N6—H4⋯O1W^vi	0.87 (3)	2.13 (3)	2.948 (5)	157 (4)
N6—H4⋯O3	0.87 (3)	2.53 (4)	3.026 (5)	117 (3)
O2W—H4W⋯O3W	0.81 (3)	1.91 (4)	2.686 (5)	159 (5)
O3W—H5W⋯O8	0.86 (4)	2.09 (4)	2.928 (4)	165 (5)
O3W—H6W⋯O2^vi	0.87 (4)	2.08 (5)	2.904 (4)	158 (4)
C3—H3⋯O2W^vii	0.93	2.43	3.365 (5)	178
C13—H13⋯O4	0.93	2.39	3.198 (5)	145
C13—H13⋯O7	0.93	2.46	3.232 (5)	141
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+2, -z; (iv) x, y-1, z; (v) x-1, y, z; (vi) x, y+1, z; (vii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028285/su2289sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028285/su2289Isup2.hkl

checkCIF report

Comment top

In the past few years increasing interest has been shown in lanthanide-transition metal heterometallic complexs with bridging multifunctionnal organic ligands, not only because of their impressive topological structures, but also due to their versatile applications in ion exchange, magnetism, bimetallic catalysis and as luminescent probes (Cheng et al., 2006; Kuang et al., 2007; Sun et al., 2006; Zhu et al., 2010). As an extension of this research the structure of the title compound, a new heterometallic coordination polymer, is presented herein.

The asymmetric unit of the title compound (Fig. 1), contains one Yb^III ion, one and a half Co^II ions, three imidazole-4, 5-dicarboxylate ligands, two coordinated water molecules and one uncoordinated water molecule. The Yb^III ion is seven-coordinated in a monocapped trigonal prismatic coordination geometry by six O atoms from three imidazole-4,5-dicarboxylate ligands and one water O atom. Both Co^II ions are six-coordinated in a slightly distorted octahedral geometry. The Co1 ion lies on an inversion center and is coordinated with two O atoms from two coordinated water molecules as well as two O atoms and two N atoms from two imidazole-4, 5-dicarboxylate ligands. The Co2 ion is bonded to four O atoms and two N atoms from four imidazole-4,5-dicarboxylate ligands.

These metal coordination units are connected by bridging imidazole-4, 5-dicarboxylate ligands, generating a three-dimensional network (Fig. 2). The crystal structure is further stabilized by N—H···O, O—H···O, and C—H···O hydrogen-bonding interactions involving the water molecules, and the imidazole-4, 5-dicarboxylate ligands (Table 1).

Related literature top

For lanthanide–transition metal heterometallic complexs with bridging multifunctional organic ligands, see: Cheng et al. (2006); Kuang et al. (2007); Sun et al. (2006); Zhu et al. (2010).

Experimental top

A mixture of CoSO₄.7H₂O(0.028 g, 0.1 mmol), Yb₂O₃(0.099 g, 0.25 mmol), imidazole-4,5-dicarboxylic acid (0.156 g, 1 mmol), and H₂O(10 ml) was sealed in a 20 ml Teflon-lined reaction vessel at 443 K for 5 days then slowly cooled to room temperature. The product was collected by filtration, washed with water and air-dried. Red block-like crystals suitable for X-ray analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound showing the atomic-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (A) x, 1 + y, z; (B) 1 - x, 1 - y, -z; (C) 1 - x, -y, 1 - z; (D) -1 + x, -1 + y, z.
	Fig. 2. A view of the three-dimensional structure of the title compound. The hydrogen bonding interactions are shown as dashed lines (see Table 1 for details).

Poly[[tetraaquabis(µ₃-1H-imidazole-4,5-dicarboxylato)tetrakis(µ₂- 1H-imidazole-4,5-dicarboxylato)tricobalt(II)diytterbium(III)] dihydrate] top

Crystal data top

[Co₃Yb₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O	Z = 1
M_r = 1555.48	F(000) = 749
Triclinic, P1	D_x = 2.510 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0413 (4) Å	Cell parameters from 3204 reflections
b = 8.3538 (5) Å	θ = 2.5–28.0°
c = 17.8755 (10) Å	µ = 5.81 mm⁻¹
α = 95.546 (1)°	T = 296 K
β = 96.886 (1)°	Block, red
γ = 97.177 (1)°	0.20 × 0.18 × 0.15 mm
V = 1029.03 (10) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	3350 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.325, T_max = 0.418	k = −9→10
5347 measured reflections	l = −19→21

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.025P)² + 0.2573P] where P = (F_o² + 2F_c²)/3
3640 reflections	(Δ/σ)_max = 0.001
376 parameters	Δρ_max = 0.78 e Å⁻³
12 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Co₃Yb₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O	γ = 97.177 (1)°
M_r = 1555.48	V = 1029.03 (10) Å³
Triclinic, P1	Z = 1
a = 7.0413 (4) Å	Mo Kα radiation
b = 8.3538 (5) Å	µ = 5.81 mm⁻¹
c = 17.8755 (10) Å	T = 296 K
α = 95.546 (1)°	0.20 × 0.18 × 0.15 mm
β = 96.886 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3640 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3350 reflections with I > 2σ(I)
T_min = 0.325, T_max = 0.418	R_int = 0.019
5347 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	12 restraints
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.78 e Å⁻³
3640 reflections	Δρ_min = −0.78 e Å⁻³
376 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

	x	y	z	U_iso*/U_eq
Yb1	0.29829 (3)	0.41070 (2)	0.243626 (10)	0.01363 (7)
Co1	0.5000	0.0000	0.5000	0.01581 (18)
Co2	0.61668 (8)	0.93516 (6)	0.07597 (3)	0.01372 (13)
C1	0.4567 (6)	0.1646 (5)	0.3642 (2)	0.0139 (9)
C2	0.5695 (6)	0.2898 (5)	0.4232 (2)	0.0144 (9)
C3	0.7118 (6)	0.3644 (5)	0.5375 (2)	0.0200 (9)
H3	0.7531	0.3657	0.5890	0.024*
C4	0.6687 (6)	0.4428 (5)	0.4231 (2)	0.0149 (9)
C5	0.7011 (6)	0.5510 (5)	0.3626 (2)	0.0183 (9)
C6	0.3753 (6)	0.2247 (5)	0.0775 (2)	0.0147 (9)
C7	0.2950 (6)	0.3342 (5)	0.0250 (2)	0.0131 (8)
C8	0.1892 (6)	0.3962 (5)	−0.0851 (2)	0.0210 (10)
H8	0.1429	0.3890	−0.1365	0.025*
C9	0.2778 (6)	0.4982 (5)	0.0341 (2)	0.0142 (9)
C10	0.3400 (6)	0.6297 (5)	0.0970 (2)	0.0147 (9)
C11	0.8955 (6)	1.2012 (5)	0.1572 (2)	0.0155 (9)
C12	0.8402 (6)	1.1020 (5)	0.2173 (2)	0.0139 (8)
C13	0.6907 (6)	0.8844 (5)	0.2507 (2)	0.0222 (10)
H13	0.6135	0.7851	0.2494	0.027*
C14	0.8922 (6)	1.1069 (5)	0.2941 (2)	0.0132 (8)
C15	1.0131 (6)	1.2253 (5)	0.3539 (2)	0.0153 (9)
O1	0.4104 (4)	0.0283 (3)	0.38480 (16)	0.0192 (6)
O2	0.4150 (4)	0.1990 (3)	0.29715 (16)	0.0213 (7)
O3	0.8522 (4)	0.6467 (4)	0.37243 (18)	0.0270 (7)
O4	0.5683 (5)	0.5394 (4)	0.30733 (18)	0.0297 (8)
O5	0.4029 (5)	0.2590 (3)	0.14763 (16)	0.0240 (7)
O6	0.4133 (4)	0.0941 (3)	0.04421 (15)	0.0155 (6)
O7	0.3723 (4)	0.5930 (3)	0.16348 (16)	0.0205 (7)
O8	0.3603 (4)	0.7716 (3)	0.07878 (15)	0.0185 (6)
O9	0.8149 (4)	1.1523 (3)	0.09059 (15)	0.0190 (6)
O10	1.0184 (4)	1.3279 (3)	0.17219 (16)	0.0235 (7)
O11	1.1107 (4)	1.3474 (3)	0.33394 (16)	0.0205 (7)
O12	1.0107 (4)	1.2009 (3)	0.42250 (16)	0.0203 (7)
N1	0.5995 (5)	0.2438 (4)	0.49534 (19)	0.0155 (7)
N2	0.7592 (5)	0.4862 (4)	0.4960 (2)	0.0175 (8)
N3	0.2427 (5)	0.2739 (4)	−0.05004 (19)	0.0180 (8)
N4	0.2106 (5)	0.5326 (4)	−0.0366 (2)	0.0184 (8)
N5	0.7125 (5)	0.9638 (4)	0.19128 (19)	0.0168 (8)
N6	0.7947 (5)	0.9664 (4)	0.3127 (2)	0.0195 (8)
H1	0.824 (6)	0.579 (3)	0.515 (2)	0.029*
H2	0.190 (7)	0.628 (3)	−0.047 (3)	0.029*
H4	0.801 (7)	0.937 (5)	0.3580 (15)	0.029*
O1W	0.7736 (4)	−0.0471 (4)	0.47573 (18)	0.0246 (7)
H1W	0.830 (6)	−0.099 (5)	0.506 (2)	0.037*
H2W	0.842 (6)	0.037 (3)	0.475 (3)	0.037*
O2W	0.1488 (5)	0.6362 (4)	0.2758 (2)	0.0290 (8)
H3W	0.055 (5)	0.640 (5)	0.297 (3)	0.044*
H4W	0.181 (7)	0.728 (3)	0.266 (3)	0.044*
O3W	0.1955 (5)	0.9104 (4)	0.2090 (2)	0.0338 (8)
H5W	0.250 (7)	0.888 (6)	0.1694 (19)	0.051*
H6W	0.281 (6)	0.978 (6)	0.240 (2)	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Yb1	0.01749 (11)	0.01215 (10)	0.00990 (10)	−0.00135 (7)	−0.00088 (7)	0.00222 (7)
Co1	0.0187 (4)	0.0159 (4)	0.0130 (4)	0.0003 (3)	0.0010 (3)	0.0064 (3)
Co2	0.0201 (3)	0.0096 (3)	0.0100 (3)	0.0011 (2)	−0.0023 (2)	0.0004 (2)
C1	0.013 (2)	0.015 (2)	0.014 (2)	0.0057 (17)	0.0015 (17)	−0.0011 (17)
C2	0.017 (2)	0.014 (2)	0.012 (2)	0.0024 (17)	0.0014 (17)	0.0046 (17)
C3	0.027 (3)	0.020 (2)	0.012 (2)	0.0045 (19)	−0.0026 (18)	0.0021 (18)
C4	0.012 (2)	0.017 (2)	0.016 (2)	0.0047 (17)	0.0015 (17)	0.0040 (17)
C5	0.023 (2)	0.013 (2)	0.019 (2)	0.0018 (18)	−0.0009 (19)	0.0052 (18)
C6	0.014 (2)	0.017 (2)	0.013 (2)	0.0027 (17)	0.0016 (17)	0.0026 (17)
C7	0.015 (2)	0.013 (2)	0.010 (2)	0.0000 (17)	0.0013 (16)	−0.0002 (16)
C8	0.029 (3)	0.023 (2)	0.011 (2)	0.007 (2)	−0.0036 (18)	0.0017 (18)
C9	0.018 (2)	0.015 (2)	0.009 (2)	0.0014 (17)	−0.0010 (17)	0.0022 (16)
C10	0.014 (2)	0.019 (2)	0.013 (2)	0.0029 (17)	0.0020 (16)	0.0061 (17)
C11	0.017 (2)	0.016 (2)	0.014 (2)	0.0041 (18)	−0.0013 (17)	0.0034 (17)
C12	0.014 (2)	0.011 (2)	0.016 (2)	0.0025 (16)	−0.0012 (17)	0.0008 (17)
C13	0.025 (3)	0.019 (2)	0.019 (2)	−0.0059 (19)	−0.0009 (19)	0.0025 (19)
C14	0.014 (2)	0.014 (2)	0.012 (2)	0.0029 (17)	−0.0001 (16)	0.0033 (17)
C15	0.015 (2)	0.017 (2)	0.015 (2)	0.0079 (18)	0.0012 (17)	0.0022 (18)
O1	0.0273 (17)	0.0132 (15)	0.0150 (16)	−0.0028 (13)	−0.0022 (13)	0.0040 (12)
O2	0.0328 (18)	0.0164 (15)	0.0131 (16)	0.0015 (13)	−0.0028 (13)	0.0036 (12)
O3	0.0205 (17)	0.0268 (17)	0.0309 (19)	−0.0070 (14)	−0.0046 (14)	0.0122 (15)
O4	0.0334 (19)	0.0232 (17)	0.0273 (18)	−0.0096 (15)	−0.0108 (15)	0.0125 (15)
O5	0.042 (2)	0.0211 (16)	0.0106 (16)	0.0132 (15)	0.0020 (14)	0.0009 (13)
O6	0.0248 (16)	0.0087 (14)	0.0128 (15)	0.0046 (12)	0.0008 (12)	−0.0012 (12)
O7	0.0355 (19)	0.0133 (14)	0.0113 (15)	−0.0018 (13)	0.0013 (13)	0.0026 (12)
O8	0.0272 (17)	0.0119 (14)	0.0156 (15)	−0.0011 (13)	0.0001 (13)	0.0059 (12)
O9	0.0251 (17)	0.0167 (15)	0.0115 (15)	−0.0068 (13)	−0.0031 (13)	0.0029 (12)
O10	0.0255 (17)	0.0207 (16)	0.0194 (17)	−0.0112 (14)	−0.0052 (13)	0.0063 (13)
O11	0.0247 (17)	0.0195 (16)	0.0146 (16)	−0.0056 (13)	0.0011 (13)	0.0006 (13)
O12	0.0239 (17)	0.0230 (16)	0.0138 (16)	0.0018 (13)	0.0027 (13)	0.0028 (13)
N1	0.0207 (19)	0.0152 (18)	0.0110 (18)	0.0034 (15)	0.0008 (14)	0.0039 (14)
N2	0.021 (2)	0.0134 (18)	0.0153 (19)	−0.0031 (15)	−0.0032 (15)	0.0006 (15)
N3	0.023 (2)	0.0166 (18)	0.0128 (18)	0.0017 (15)	−0.0025 (15)	−0.0007 (15)
N4	0.027 (2)	0.0142 (18)	0.0155 (19)	0.0071 (16)	0.0000 (16)	0.0045 (15)
N5	0.023 (2)	0.0114 (17)	0.0144 (18)	−0.0020 (15)	−0.0007 (15)	0.0023 (14)
N6	0.028 (2)	0.0189 (19)	0.0108 (19)	−0.0012 (16)	−0.0019 (16)	0.0080 (16)
O1W	0.0204 (18)	0.0289 (18)	0.0264 (18)	0.0038 (14)	0.0031 (14)	0.0127 (15)
O2W	0.036 (2)	0.0202 (17)	0.035 (2)	0.0044 (16)	0.0169 (16)	0.0079 (15)
O3W	0.041 (2)	0.0250 (19)	0.035 (2)	0.0032 (16)	0.0108 (17)	−0.0038 (16)

Geometric parameters (Å, º) top

Yb1—O4	2.191 (3)	C7—C9	1.386 (5)
Yb1—O10ⁱ	2.209 (3)	C8—N3	1.320 (5)
Yb1—O7	2.246 (3)	C8—N4	1.344 (5)
Yb1—O11ⁱ	2.266 (3)	C8—H8	0.9300
Yb1—O5	2.282 (3)	C9—N4	1.366 (5)
Yb1—O2	2.285 (3)	C9—C10	1.479 (6)
Yb1—O2W	2.328 (3)	C10—O8	1.254 (5)
Co1—N1ⁱⁱ	2.082 (3)	C10—O7	1.257 (5)
Co1—N1	2.082 (3)	C11—O9	1.262 (5)
Co1—O1W	2.100 (3)	C11—O10	1.265 (5)
Co1—O1Wⁱⁱ	2.100 (3)	C11—C12	1.478 (5)
Co1—O1ⁱⁱ	2.125 (3)	C12—C14	1.374 (5)
Co1—O1	2.125 (3)	C12—N5	1.376 (5)
Co2—N5	2.072 (3)	C13—N5	1.320 (5)
Co2—O9	2.120 (3)	C13—N6	1.330 (6)
Co2—O6ⁱⁱⁱ	2.120 (3)	C13—H13	0.9300
Co2—O8	2.132 (3)	C14—N6	1.374 (5)
Co2—O6^iv	2.136 (3)	C14—C15	1.487 (6)
Co2—N3ⁱⁱⁱ	2.152 (3)	C15—O11	1.262 (5)
C1—O1	1.247 (5)	C15—O12	1.264 (5)
C1—O2	1.268 (5)	O6—Co2ⁱⁱⁱ	2.120 (3)
C1—C2	1.489 (5)	O6—Co2^v	2.136 (3)
C2—C4	1.378 (6)	O10—Yb1^vi	2.209 (3)
C2—N1	1.380 (5)	O11—Yb1^vi	2.266 (3)
C3—N1	1.312 (5)	N2—H1	0.867 (19)
C3—N2	1.347 (5)	N3—Co2ⁱⁱⁱ	2.152 (3)
C3—H3	0.9300	N4—H2	0.863 (19)
C4—N2	1.374 (5)	N6—H4	0.865 (19)
C4—C5	1.496 (5)	O1W—H1W	0.82 (4)
C5—O3	1.232 (5)	O1W—H2W	0.804 (19)
C5—O4	1.264 (5)	O2W—H3W	0.80 (4)
C6—O5	1.245 (5)	O2W—H4W	0.811 (19)
C6—O6	1.265 (5)	O3W—H5W	0.86 (4)
C6—C7	1.484 (5)	O3W—H6W	0.87 (4)
C7—N3	1.376 (5)

O4—Yb1—O10ⁱ	168.77 (11)	O5—C6—C7	122.9 (4)
O4—Yb1—O7	80.61 (11)	O6—C6—C7	113.7 (3)
O10ⁱ—Yb1—O7	89.98 (10)	N3—C7—C9	109.4 (3)
O4—Yb1—O11ⁱ	104.42 (11)	N3—C7—C6	117.8 (3)
O10ⁱ—Yb1—O11ⁱ	79.80 (11)	C9—C7—C6	132.4 (4)
O7—Yb1—O11ⁱ	144.82 (11)	N3—C8—N4	110.9 (4)
O4—Yb1—O5	102.77 (12)	N3—C8—H8	124.6
O10ⁱ—Yb1—O5	80.83 (11)	N4—C8—H8	124.6
O7—Yb1—O5	76.85 (10)	N4—C9—C7	104.8 (3)
O11ⁱ—Yb1—O5	133.18 (10)	N4—C9—C10	120.7 (3)
O4—Yb1—O2	80.51 (11)	C7—C9—C10	133.8 (4)
O10ⁱ—Yb1—O2	110.72 (10)	O8—C10—O7	124.9 (4)
O7—Yb1—O2	140.86 (11)	O8—C10—C9	116.2 (3)
O11ⁱ—Yb1—O2	73.46 (11)	O7—C10—C9	118.9 (3)
O5—Yb1—O2	74.36 (10)	O9—C11—O10	122.2 (4)
O4—Yb1—O2W	88.67 (13)	O9—C11—C12	116.5 (4)
O10ⁱ—Yb1—O2W	82.67 (12)	O10—C11—C12	121.3 (4)
O7—Yb1—O2W	72.93 (11)	C14—C12—N5	109.5 (3)
O11ⁱ—Yb1—O2W	72.42 (11)	C14—C12—C11	136.1 (4)
O5—Yb1—O2W	145.39 (11)	N5—C12—C11	114.2 (3)
O2—Yb1—O2W	140.19 (11)	N5—C13—N6	110.4 (4)
N1ⁱⁱ—Co1—N1	180.000 (1)	N5—C13—H13	124.8
N1ⁱⁱ—Co1—O1W	93.48 (13)	N6—C13—H13	124.8
N1—Co1—O1W	86.52 (13)	N6—C14—C12	104.4 (3)
N1ⁱⁱ—Co1—O1Wⁱⁱ	86.52 (13)	N6—C14—C15	120.5 (3)
N1—Co1—O1Wⁱⁱ	93.48 (13)	C12—C14—C15	135.1 (4)
O1W—Co1—O1Wⁱⁱ	180.000 (1)	O11—C15—O12	122.9 (4)
N1ⁱⁱ—Co1—O1ⁱⁱ	77.93 (12)	O11—C15—C14	118.5 (4)
N1—Co1—O1ⁱⁱ	102.07 (12)	O12—C15—C14	118.6 (4)
O1W—Co1—O1ⁱⁱ	88.35 (12)	C1—O1—Co1	116.7 (3)
O1Wⁱⁱ—Co1—O1ⁱⁱ	91.65 (12)	C1—O2—Yb1	135.6 (3)
N1ⁱⁱ—Co1—O1	102.07 (12)	C5—O4—Yb1	149.7 (3)
N1—Co1—O1	77.93 (12)	C6—O5—Yb1	141.9 (3)
O1W—Co1—O1	91.65 (12)	C6—O6—Co2ⁱⁱⁱ	118.5 (2)
O1Wⁱⁱ—Co1—O1	88.35 (12)	C6—O6—Co2^v	131.8 (3)
O1ⁱⁱ—Co1—O1	180.0	Co2ⁱⁱⁱ—O6—Co2^v	103.63 (11)
N5—Co2—O9	77.03 (12)	C10—O7—Yb1	145.5 (3)
N5—Co2—O6ⁱⁱⁱ	166.83 (12)	C10—O8—Co2	130.1 (3)
O9—Co2—O6ⁱⁱⁱ	95.87 (10)	C11—O9—Co2	116.9 (3)
N5—Co2—O8	97.27 (12)	C11—O10—Yb1^vi	138.7 (3)
O9—Co2—O8	160.59 (11)	C15—O11—Yb1^vi	139.5 (3)
O6ⁱⁱⁱ—Co2—O8	92.93 (11)	C3—N1—C2	106.8 (3)
N5—Co2—O6^iv	113.16 (12)	C3—N1—Co1	138.9 (3)
O9—Co2—O6^iv	82.90 (11)	C2—N1—Co1	113.1 (3)
O6ⁱⁱⁱ—Co2—O6^iv	76.37 (11)	C3—N2—C4	108.2 (3)
O8—Co2—O6^iv	82.41 (11)	C3—N2—H1	124 (3)
N5—Co2—N3ⁱⁱⁱ	95.60 (13)	C4—N2—H1	127 (3)
O9—Co2—N3ⁱⁱⁱ	111.27 (12)	C8—N3—C7	106.1 (3)
O6ⁱⁱⁱ—Co2—N3ⁱⁱⁱ	76.47 (11)	C8—N3—Co2ⁱⁱⁱ	137.1 (3)
O8—Co2—N3ⁱⁱⁱ	87.60 (12)	C7—N3—Co2ⁱⁱⁱ	109.9 (3)
O6^iv—Co2—N3ⁱⁱⁱ	150.46 (12)	C8—N4—C9	108.7 (3)
O1—C1—O2	123.8 (4)	C8—N4—H2	127 (3)
O1—C1—C2	116.2 (3)	C9—N4—H2	124 (3)
O2—C1—C2	120.0 (3)	C13—N5—C12	106.3 (3)
C4—C2—N1	108.8 (4)	C13—N5—Co2	138.5 (3)
C4—C2—C1	135.1 (4)	C12—N5—Co2	115.2 (3)
N1—C2—C1	115.9 (3)	C13—N6—C14	109.4 (4)
N1—C3—N2	110.7 (4)	C13—N6—H4	126 (3)
N1—C3—H3	124.6	C14—N6—H4	125 (3)
N2—C3—H3	124.6	Co1—O1W—H1W	115 (4)
N2—C4—C2	105.4 (4)	Co1—O1W—H2W	110 (4)
N2—C4—C5	120.7 (4)	H1W—O1W—H2W	107 (3)
C2—C4—C5	133.8 (4)	Yb1—O2W—H3W	128 (3)
O3—C5—O4	126.0 (4)	Yb1—O2W—H4W	126 (3)
O3—C5—C4	116.9 (4)	H3W—O2W—H4W	106 (3)
O4—C5—C4	117.0 (4)	H5W—O3W—H6W	106 (3)
O5—C6—O6	123.4 (4)

Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z; (iv) x, y+1, z; (v) x, y−1, z; (vi) x+1, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O12^vii	0.87 (3)	2.18 (3)	3.036 (4)	172 (3)
O1W—H1W···O12^viii	0.82 (4)	1.93 (4)	2.747 (4)	173 (4)
N4—H2···O9^ix	0.86 (3)	2.07 (3)	2.909 (4)	166 (5)
O1W—H2W···O12^v	0.80 (3)	2.07 (4)	2.808 (4)	153 (5)
O2W—H3W···O3^x	0.80 (4)	2.08 (4)	2.870 (5)	168 (5)
N6—H4···O1W^iv	0.87 (3)	2.13 (3)	2.948 (5)	157 (4)
N6—H4···O3	0.87 (3)	2.53 (4)	3.026 (5)	117 (3)
O2W—H4W···O3W	0.81 (3)	1.91 (4)	2.686 (5)	159 (5)
O3W—H5W···O8	0.86 (4)	2.09 (4)	2.928 (4)	165 (5)
O3W—H6W···O2^iv	0.87 (4)	2.08 (5)	2.904 (4)	158 (4)
C3—H3···O2W^xi	0.93	2.43	3.365 (5)	178
C13—H13···O4	0.93	2.39	3.198 (5)	145
C13—H13···O7	0.93	2.46	3.232 (5)	141

Symmetry codes: (iv) x, y+1, z; (v) x, y−1, z; (vii) −x+2, −y+2, −z+1; (viii) −x+2, −y+1, −z+1; (ix) −x+1, −y+2, −z; (x) x−1, y, z; (xi) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Co₃Yb₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O
M_r	1555.48
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.0413 (4), 8.3538 (5), 17.8755 (10)
α, β, γ (°)	95.546 (1), 96.886 (1), 97.177 (1)
V (Å³)	1029.03 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	5.81
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.325, 0.418
No. of measured, independent and observed [I > 2σ(I)] reflections	5347, 3640, 3350
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.04
No. of reflections	3640
No. of parameters	376
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.78

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O12ⁱ	0.87 (3)	2.18 (3)	3.036 (4)	172 (3)
O1W—H1W···O12ⁱⁱ	0.82 (4)	1.93 (4)	2.747 (4)	173 (4)
N4—H2···O9ⁱⁱⁱ	0.86 (3)	2.07 (3)	2.909 (4)	166 (5)
O1W—H2W···O12^iv	0.80 (3)	2.07 (4)	2.808 (4)	153 (5)
O2W—H3W···O3^v	0.80 (4)	2.08 (4)	2.870 (5)	168 (5)
N6—H4···O1W^vi	0.87 (3)	2.13 (3)	2.948 (5)	157 (4)
N6—H4···O3	0.87 (3)	2.53 (4)	3.026 (5)	117 (3)
O2W—H4W···O3W	0.81 (3)	1.91 (4)	2.686 (5)	159 (5)
O3W—H5W···O8	0.86 (4)	2.09 (4)	2.928 (4)	165 (5)
O3W—H6W···O2^vi	0.87 (4)	2.08 (5)	2.904 (4)	158 (4)
C3—H3···O2W^vii	0.93	2.43	3.365 (5)	178
C13—H13···O4	0.93	2.39	3.198 (5)	145
C13—H13···O7	0.93	2.46	3.232 (5)	141

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+2, −z; (iv) x, y−1, z; (v) x−1, y, z; (vi) x, y+1, z; (vii) −x+1, −y+1, −z+1.

Acknowledgements

The author acknowledges South China Normal University for supporting this work.

References

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