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

Zhu, L.-C.

doi:10.1107/S1600536811045764

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1681-m1682

https://doi.org/10.1107/S1600536811045764

Open

access

Poly[[tetraaquabis(μ₃-imidazole-4,5-dicarboxylato)tetrakis(μ₂-imidazole-4,5-dicarboxylato)tricobalt(II)dilutetium(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 2 October 2011; accepted 31 October 2011; online 5 November 2011)

In the title compound, {[Co₃Lu₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O}_n, the Lu^III ions are 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. The Co^II ions are six-coordinated in a slightly distorted octahedral geometry and exhibit two types of coordination environments. One Co^II ion, located on an inversion center, is coordinated by two water O atoms as well as two O atoms and two N atoms from two imidazole-4,5-dicarboxylate ligands. The other 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 between 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

[Co₃Lu₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O
M_r = 1559.34
Triclinic, $[P \overline 1]$
a = 7.0332 (6) Å
b = 8.3468 (7) Å
c = 17.8510 (15) Å
α = 95.515 (1)°
β = 96.786 (1)°
γ = 97.195 (1)°
V = 1025.84 (15) Å³
Z = 1
Mo Kα radiation
μ = 6.08 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 = 0.308, T_max = 0.402
5351 measured reflections
3642 independent reflections
3280 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.069
S = 1.02
3642 reflections
376 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.38 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O5ⁱ	0.86 (4)	2.04 (4)	2.900 (6)	175 (5)
N2—H1⋯O6ⁱ	0.86 (4)	2.59 (5)	3.139 (6)	122 (4)
O1W—H1W⋯O8ⁱⁱ	0.80 (5)	2.04 (5)	2.806 (6)	161 (6)
N4—H2⋯O1Wⁱⁱⁱ	0.85 (4)	2.12 (3)	2.948 (6)	162 (5)
N4—H2⋯O10	0.85 (4)	2.57 (6)	3.016 (7)	114 (4)
O1W—H2W⋯O8^iv	0.81 (5)	1.94 (6)	2.748 (6)	174 (6)
O2W—H3W⋯O3W	0.81 (5)	1.89 (5)	2.693 (6)	172 (7)
N5—H4⋯O8^v	0.85 (4)	2.23 (4)	3.052 (6)	161 (5)
O2W—H4W⋯O10^vi	0.80 (6)	2.06 (6)	2.851 (7)	171 (6)
O3W—H5W⋯O11ⁱⁱⁱ	0.86 (5)	2.06 (6)	2.902 (6)	166 (5)
O3W—H6W⋯O4	0.86 (6)	2.10 (6)	2.928 (6)	163 (6)
C8—H8⋯O3	0.93	2.44	3.217 (7)	141
C8—H8⋯O9	0.93	2.39	3.190 (7)	144
C13—H13⋯O2W^vii	0.93	2.42	3.352 (7)	178
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y+1, z; (iii) x, y-1, z; (iv) -x, -y+1, -z; (v) -x, -y, -z; (vi) x+1, y, z; (vii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: https://doi.org/10.1107/S1600536811045764/pv2457sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045764/pv2457Isup2.hkl

checkCIF report

Comment top

In the past few years, interest in the lanthanide-transition metal heterometallic complexes with bridging multifunctionnal organic ligands has been increasing, not only because of their impressive topological structures, but also due to their versatile applications in ion exchange, magnetism, bimetallic catalysis and luminescent probe (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, has been determined which is presented in this artcle.

The asymmetric unit of the title compound (Fig. 1), contains one Lu^III ions, 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 Lu^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. One Co^II 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 other 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 (Fig. 2). The crystal structure is further stabilized by N—H···O, O—H···O, and C—H···O hydrogen-bonding interactions between water molecules, and imidazole-4,5-dicarboxylate ligands (Table 1).

Related literature top

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 top

A mixture of CoSO₄.7H₂O(0.141 g, 0.5 mmol), Lu₂O₃ (0.100 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 crystals suitable for X-ray analysis were obtained.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 showing the atomic-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: A: 1 - x, 2 - y, -z; B: 1 - x, 1 - y, 1 - z; C: x, -1 + y, z; D: 1 + x, 1 + y, z.
	Fig. 2. A view of the three-dimensional structure of the title compound, the hydrogen bonding interactions showed as broken lines.

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

Crystal data top

[Co₃Lu₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O	Z = 1
M_r = 1559.34	F(000) = 751
Triclinic, P1	D_x = 2.524 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0332 (6) Å	Cell parameters from 2416 reflections
b = 8.3468 (7) Å	θ = 2.3–27.1°
c = 17.8510 (15) Å	µ = 6.08 mm⁻¹
α = 95.515 (1)°	T = 296 K
β = 96.786 (1)°	Block, red
γ = 97.195 (1)°	0.20 × 0.18 × 0.15 mm
V = 1025.84 (15) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3642 independent reflections
Radiation source: fine-focus sealed tube	3280 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scan	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→8
T_min = 0.308, T_max = 0.402	k = −10→8
5351 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0315P)² + 1.6377P] where P = (F_o² + 2F_c²)/3
3642 reflections	(Δ/σ)_max = 0.001
376 parameters	Δρ_max = 1.38 e Å⁻³
12 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

[Co₃Lu₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O	γ = 97.195 (1)°
M_r = 1559.34	V = 1025.84 (15) Å³
Triclinic, P1	Z = 1
a = 7.0332 (6) Å	Mo Kα radiation
b = 8.3468 (7) Å	µ = 6.08 mm⁻¹
c = 17.8510 (15) Å	T = 296 K
α = 95.515 (1)°	0.20 × 0.18 × 0.15 mm
β = 96.786 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3642 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3280 reflections with I > 2σ(I)
T_min = 0.308, T_max = 0.402	R_int = 0.023
5351 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	12 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 1.38 e Å⁻³
3642 reflections	Δρ_min = −1.34 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
Lu1	0.70112 (4)	0.58976 (3)	0.256536 (13)	0.01212 (9)
Co1	0.38269 (11)	0.06475 (9)	0.42418 (4)	0.01307 (17)
Co2	0.5000	1.0000	0.0000	0.0142 (2)
C1	0.6258 (8)	0.7760 (7)	0.4223 (3)	0.0133 (12)
C2	0.7053 (8)	0.6660 (7)	0.4742 (3)	0.0133 (12)
C3	0.8108 (9)	0.6042 (7)	0.5848 (4)	0.0220 (14)
H3	0.8561	0.6115	0.6362	0.026*
C4	0.7216 (8)	0.5032 (6)	0.4657 (3)	0.0103 (11)
C5	0.6582 (8)	0.3717 (7)	0.4028 (3)	0.0143 (12)
C6	0.1022 (8)	−0.2023 (7)	0.3429 (3)	0.0132 (12)
C7	0.1583 (8)	−0.1024 (6)	0.2827 (3)	0.0134 (12)
C8	0.3107 (9)	0.1157 (7)	0.2497 (3)	0.0195 (13)
H8	0.3898	0.2141	0.2508	0.023*
C9	0.1057 (8)	−0.1066 (7)	0.2054 (3)	0.0138 (12)
C10	−0.0137 (8)	−0.2248 (7)	0.1460 (3)	0.0149 (12)
C11	0.2968 (9)	0.4493 (7)	0.1376 (3)	0.0172 (13)
C12	0.3326 (8)	0.5562 (7)	0.0773 (3)	0.0138 (12)
C13	0.2892 (9)	0.6358 (7)	−0.0373 (3)	0.0189 (13)
H13	0.2474	0.6347	−0.0887	0.023*
C14	0.4316 (8)	0.7088 (7)	0.0769 (3)	0.0135 (12)
C15	0.5438 (8)	0.8341 (7)	0.1358 (3)	0.0140 (12)
O1	0.5982 (6)	0.7412 (5)	0.3519 (2)	0.0215 (10)
O2	0.5862 (6)	0.9071 (4)	0.4555 (2)	0.0147 (8)
O3	0.6263 (6)	0.4072 (5)	0.3362 (2)	0.0195 (9)
O4	0.6378 (6)	0.2288 (4)	0.4209 (2)	0.0192 (9)
O5	0.1840 (6)	−0.1529 (5)	0.4094 (2)	0.0200 (9)
O6	−0.0193 (6)	−0.3287 (5)	0.3281 (2)	0.0221 (10)
O7	−0.1116 (6)	−0.3469 (5)	0.1661 (2)	0.0194 (9)
O8	−0.0117 (6)	−0.2004 (5)	0.0777 (2)	0.0191 (9)
O9	0.4324 (6)	0.4605 (5)	0.1932 (2)	0.0264 (10)
O10	0.1470 (6)	0.3533 (5)	0.1285 (2)	0.0256 (10)
O11	0.5857 (6)	0.8010 (5)	0.2037 (2)	0.0184 (9)
O12	0.5894 (6)	0.9710 (5)	0.1153 (2)	0.0178 (9)
N1	0.7588 (7)	0.7273 (6)	0.5495 (3)	0.0176 (11)
N2	0.7899 (7)	0.4672 (6)	0.5366 (3)	0.0164 (11)
N3	0.2873 (7)	0.0359 (5)	0.3091 (3)	0.0158 (11)
N4	0.2033 (8)	0.0336 (6)	0.1876 (3)	0.0204 (11)
N5	0.2432 (7)	0.5151 (6)	0.0041 (3)	0.0173 (11)
N6	0.4021 (7)	0.7565 (5)	0.0052 (3)	0.0139 (10)
H1	0.801 (9)	0.372 (4)	0.550 (3)	0.021*
H2	0.209 (9)	0.060 (7)	0.1428 (17)	0.021*
H4	0.181 (8)	0.420 (4)	−0.008 (3)	0.021*
O1W	0.2273 (6)	1.0469 (5)	0.0245 (2)	0.0223 (10)
H1W	0.160 (8)	0.965 (5)	0.030 (4)	0.033*
H2W	0.168 (8)	1.090 (7)	−0.008 (3)	0.033*
O2W	0.8496 (7)	0.3654 (5)	0.2236 (3)	0.0252 (10)
H3W	0.826 (10)	0.284 (5)	0.244 (4)	0.038*
H4W	0.931 (8)	0.351 (7)	0.197 (3)	0.038*
O3W	0.8053 (7)	0.0904 (5)	0.2910 (3)	0.0314 (11)
H5W	0.734 (8)	0.016 (7)	0.260 (3)	0.047*
H6W	0.741 (9)	0.111 (8)	0.328 (3)	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Lu1	0.01755 (14)	0.00981 (13)	0.00769 (13)	−0.00126 (9)	−0.00124 (9)	0.00199 (9)
Co1	0.0202 (4)	0.0086 (4)	0.0091 (4)	0.0011 (3)	−0.0020 (3)	0.0002 (3)
Co2	0.0174 (6)	0.0130 (5)	0.0121 (6)	0.0005 (4)	0.0001 (5)	0.0060 (4)
C1	0.016 (3)	0.014 (3)	0.010 (3)	−0.001 (2)	0.003 (2)	0.006 (2)
C2	0.015 (3)	0.015 (3)	0.011 (3)	0.005 (2)	0.006 (2)	−0.001 (2)
C3	0.030 (4)	0.018 (3)	0.017 (3)	0.007 (3)	−0.004 (3)	−0.001 (3)
C4	0.011 (3)	0.010 (3)	0.010 (3)	0.003 (2)	−0.002 (2)	0.004 (2)
C5	0.015 (3)	0.013 (3)	0.016 (3)	0.002 (2)	0.004 (2)	0.003 (2)
C6	0.015 (3)	0.014 (3)	0.011 (3)	0.003 (2)	0.002 (2)	0.003 (2)
C7	0.014 (3)	0.010 (3)	0.016 (3)	0.000 (2)	0.000 (2)	0.003 (2)
C8	0.029 (4)	0.013 (3)	0.014 (3)	−0.003 (3)	−0.004 (3)	0.004 (2)
C9	0.017 (3)	0.015 (3)	0.009 (3)	0.002 (2)	0.000 (2)	0.004 (2)
C10	0.013 (3)	0.018 (3)	0.015 (3)	0.006 (2)	0.001 (2)	0.003 (2)
C11	0.022 (3)	0.010 (3)	0.020 (3)	0.003 (2)	0.002 (3)	0.005 (2)
C12	0.012 (3)	0.015 (3)	0.013 (3)	0.001 (2)	−0.002 (2)	0.001 (2)
C13	0.022 (3)	0.021 (3)	0.012 (3)	0.003 (3)	−0.007 (3)	0.002 (2)
C14	0.011 (3)	0.015 (3)	0.014 (3)	0.003 (2)	−0.001 (2)	0.001 (2)
C15	0.019 (3)	0.013 (3)	0.009 (3)	0.000 (2)	0.000 (2)	0.002 (2)
O1	0.035 (3)	0.021 (2)	0.009 (2)	0.011 (2)	−0.0023 (18)	0.0024 (17)
O2	0.025 (2)	0.0101 (19)	0.0083 (19)	0.0051 (17)	−0.0017 (17)	−0.0002 (16)
O3	0.031 (2)	0.015 (2)	0.011 (2)	−0.0016 (18)	−0.0005 (18)	0.0032 (17)
O4	0.023 (2)	0.011 (2)	0.022 (2)	−0.0015 (17)	−0.0008 (19)	0.0044 (17)
O5	0.028 (2)	0.018 (2)	0.011 (2)	−0.0003 (18)	−0.0064 (18)	0.0051 (17)
O6	0.027 (2)	0.018 (2)	0.017 (2)	−0.0079 (19)	−0.0043 (19)	0.0075 (18)
O7	0.025 (2)	0.015 (2)	0.015 (2)	−0.0040 (18)	0.0003 (18)	−0.0023 (17)
O8	0.024 (2)	0.022 (2)	0.009 (2)	−0.0009 (18)	−0.0021 (18)	0.0035 (17)
O9	0.031 (3)	0.020 (2)	0.023 (2)	−0.0083 (19)	−0.012 (2)	0.0112 (19)
O10	0.021 (2)	0.027 (2)	0.026 (2)	−0.006 (2)	−0.003 (2)	0.011 (2)
O11	0.033 (2)	0.013 (2)	0.009 (2)	0.0025 (18)	−0.0006 (18)	0.0029 (16)
O12	0.025 (2)	0.013 (2)	0.015 (2)	−0.0015 (17)	−0.0017 (18)	0.0090 (17)
N1	0.025 (3)	0.017 (3)	0.011 (2)	0.003 (2)	−0.001 (2)	0.002 (2)
N2	0.024 (3)	0.012 (2)	0.014 (3)	0.008 (2)	−0.002 (2)	0.007 (2)
N3	0.021 (3)	0.012 (2)	0.012 (2)	−0.003 (2)	−0.001 (2)	0.000 (2)
N4	0.026 (3)	0.024 (3)	0.013 (3)	0.001 (2)	0.005 (2)	0.011 (2)
N5	0.022 (3)	0.013 (2)	0.012 (3)	−0.004 (2)	−0.005 (2)	−0.004 (2)
N6	0.017 (3)	0.016 (3)	0.008 (2)	0.001 (2)	0.002 (2)	0.003 (2)
O1W	0.020 (2)	0.027 (3)	0.023 (2)	0.0045 (19)	0.0031 (19)	0.014 (2)
O2W	0.035 (3)	0.018 (2)	0.026 (3)	0.007 (2)	0.013 (2)	0.006 (2)
O3W	0.042 (3)	0.020 (2)	0.032 (3)	0.001 (2)	0.014 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Lu1—O9	2.183 (4)	C7—N3	1.382 (7)
Lu1—O6ⁱ	2.206 (4)	C8—N3	1.320 (7)
Lu1—O3	2.238 (4)	C8—N4	1.340 (8)
Lu1—O7ⁱ	2.261 (4)	C8—H8	0.9300
Lu1—O1	2.264 (4)	C9—N4	1.366 (7)
Lu1—O11	2.270 (4)	C9—C10	1.477 (8)
Lu1—O2W	2.317 (4)	C10—O8	1.257 (7)
Co1—N3	2.066 (5)	C10—O7	1.263 (7)
Co1—O2ⁱⁱ	2.121 (4)	C11—O10	1.226 (7)
Co1—O5	2.123 (4)	C11—O9	1.281 (7)
Co1—O2ⁱⁱⁱ	2.125 (4)	C11—C12	1.486 (8)
Co1—O4	2.126 (4)	C12—C14	1.374 (8)
Co1—N1ⁱⁱ	2.147 (5)	C12—N5	1.374 (7)
Co2—N6	2.077 (4)	C13—N6	1.316 (7)
Co2—N6^iv	2.077 (4)	C13—N5	1.335 (8)
Co2—O1W^iv	2.092 (4)	C13—H13	0.9300
Co2—O1W	2.092 (4)	C14—N6	1.377 (7)
Co2—O12^iv	2.126 (4)	C14—C15	1.486 (7)
Co2—O12	2.126 (4)	C15—O12	1.249 (6)
C1—O1	1.249 (6)	C15—O11	1.278 (6)
C1—O2	1.272 (6)	O2—Co1ⁱⁱ	2.121 (4)
C1—C2	1.478 (8)	O2—Co1^v	2.125 (4)
C2—C4	1.374 (7)	O6—Lu1^vi	2.206 (4)
C2—N1	1.383 (7)	O7—Lu1^vi	2.261 (4)
C3—N1	1.323 (8)	N1—Co1ⁱⁱ	2.147 (5)
C3—N2	1.344 (7)	N2—H1	0.87 (2)
C3—H3	0.9300	N4—H2	0.85 (2)
C4—N2	1.374 (7)	N5—H4	0.85 (2)
C4—C5	1.479 (7)	O1W—H1W	0.80 (5)
C5—O3	1.256 (7)	O1W—H2W	0.81 (5)
C5—O4	1.260 (7)	O2W—H3W	0.81 (5)
C6—O6	1.258 (7)	O2W—H4W	0.80 (6)
C6—O5	1.262 (6)	O3W—H5W	0.86 (5)
C6—C7	1.481 (7)	O3W—H6W	0.86 (6)
C7—C9	1.382 (8)

O9—Lu1—O6ⁱ	168.24 (15)	O6—C6—C7	121.6 (5)
O9—Lu1—O3	80.23 (15)	O5—C6—C7	116.0 (5)
O6ⁱ—Lu1—O3	89.91 (15)	C9—C7—N3	109.7 (5)
O9—Lu1—O7ⁱ	104.39 (15)	C9—C7—C6	136.0 (5)
O6ⁱ—Lu1—O7ⁱ	80.05 (14)	N3—C7—C6	114.2 (5)
O3—Lu1—O7ⁱ	144.82 (15)	N3—C8—N4	109.9 (5)
O9—Lu1—O1	103.10 (16)	N3—C8—H8	125.1
O6ⁱ—Lu1—O1	80.68 (15)	N4—C8—H8	125.1
O3—Lu1—O1	77.20 (14)	N4—C9—C7	103.9 (5)
O7ⁱ—Lu1—O1	132.94 (14)	N4—C9—C10	121.1 (5)
O9—Lu1—O11	80.95 (15)	C7—C9—C10	134.9 (5)
O6ⁱ—Lu1—O11	110.81 (14)	O8—C10—O7	122.9 (5)
O3—Lu1—O11	140.82 (15)	O8—C10—C9	118.6 (5)
O7ⁱ—Lu1—O11	73.48 (15)	O7—C10—C9	118.5 (5)
O1—Lu1—O11	74.08 (14)	O10—C11—O9	125.5 (5)
O9—Lu1—O2W	88.27 (17)	O10—C11—C12	118.2 (5)
O6ⁱ—Lu1—O2W	82.72 (17)	O9—C11—C12	116.1 (5)
O3—Lu1—O2W	73.16 (15)	C14—C12—N5	104.4 (5)
O7ⁱ—Lu1—O2W	72.16 (15)	C14—C12—C11	134.2 (5)
O1—Lu1—O2W	145.87 (15)	N5—C12—C11	121.2 (5)
O11—Lu1—O2W	139.98 (15)	N6—C13—N5	110.3 (5)
N3—Co1—O2ⁱⁱ	167.15 (17)	N6—C13—H13	124.8
N3—Co1—O5	76.85 (16)	N5—C13—H13	124.8
O2ⁱⁱ—Co1—O5	95.95 (15)	C12—C14—N6	109.5 (5)
N3—Co1—O2ⁱⁱⁱ	112.98 (17)	C12—C14—C15	135.0 (5)
O2ⁱⁱ—Co1—O2ⁱⁱⁱ	76.14 (16)	N6—C14—C15	115.2 (5)
O5—Co1—O2ⁱⁱⁱ	83.14 (15)	O12—C15—O11	123.1 (5)
N3—Co1—O4	97.10 (17)	O12—C15—C14	116.4 (5)
O2ⁱⁱ—Co1—O4	93.03 (15)	O11—C15—C14	120.5 (5)
O5—Co1—O4	160.66 (16)	C1—O1—Lu1	142.1 (4)
O2ⁱⁱⁱ—Co1—O4	82.44 (15)	C1—O2—Co1ⁱⁱ	117.9 (3)
N3—Co1—N1ⁱⁱ	95.80 (18)	C1—O2—Co1^v	132.2 (4)
O2ⁱⁱ—Co1—N1ⁱⁱ	76.66 (16)	Co1ⁱⁱ—O2—Co1^v	103.86 (16)
O5—Co1—N1ⁱⁱ	111.04 (17)	C5—O3—Lu1	144.9 (4)
O2ⁱⁱⁱ—Co1—N1ⁱⁱ	150.45 (16)	C5—O4—Co1	130.4 (4)
O4—Co1—N1ⁱⁱ	87.67 (17)	C6—O5—Co1	117.4 (4)
N6—Co2—N6^iv	180.0 (2)	C6—O6—Lu1^vi	138.2 (4)
N6—Co2—O1W^iv	93.28 (18)	C10—O7—Lu1^vi	139.6 (4)
N6^iv—Co2—O1W^iv	86.72 (18)	C11—O9—Lu1	149.6 (4)
N6—Co2—O1W	86.72 (18)	C15—O11—Lu1	134.8 (4)
N6^iv—Co2—O1W	93.28 (18)	C15—O12—Co2	116.7 (4)
O1W^iv—Co2—O1W	180.0	C3—N1—C2	105.8 (5)
N6—Co2—O12^iv	102.48 (16)	C3—N1—Co1ⁱⁱ	136.7 (4)
N6^iv—Co2—O12^iv	77.52 (16)	C2—N1—Co1ⁱⁱ	110.0 (4)
O1W^iv—Co2—O12^iv	91.60 (16)	C3—N2—C4	107.8 (5)
O1W—Co2—O12^iv	88.40 (16)	C3—N2—H1	124 (4)
N6—Co2—O12	77.52 (16)	C4—N2—H1	127 (4)
N6^iv—Co2—O12	102.48 (16)	C8—N3—C7	106.3 (5)
O1W^iv—Co2—O12	88.40 (16)	C8—N3—Co1	138.1 (4)
O1W—Co2—O12	91.60 (16)	C7—N3—Co1	115.6 (4)
O12^iv—Co2—O12	180.0 (2)	C8—N4—C9	110.2 (5)
O1—C1—O2	123.3 (5)	C8—N4—H2	124 (4)
O1—C1—C2	122.4 (5)	C9—N4—H2	126 (4)
O2—C1—C2	114.3 (5)	C13—N5—C12	109.3 (5)
C4—C2—N1	109.3 (5)	C13—N5—H4	133 (4)
C4—C2—C1	133.0 (5)	C12—N5—H4	118 (4)
N1—C2—C1	117.3 (5)	C13—N6—C14	106.5 (5)
N1—C3—N2	111.4 (5)	C13—N6—Co2	138.4 (4)
N1—C3—H3	124.3	C14—N6—Co2	113.9 (3)
N2—C3—H3	124.3	Co2—O1W—H1W	111 (5)
C2—C4—N2	105.7 (5)	Co2—O1W—H2W	114 (5)
C2—C4—C5	133.4 (5)	H1W—O1W—H2W	107 (3)
N2—C4—C5	120.3 (5)	Lu1—O2W—H3W	119 (4)
O3—C5—O4	124.3 (5)	Lu1—O2W—H4W	133 (4)
O3—C5—C4	119.3 (5)	H3W—O2W—H4W	108 (3)
O4—C5—C4	116.4 (5)	H5W—O3W—H6W	107 (3)
O6—C6—O5	122.4 (5)

Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+2, −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···O5^vii	0.86 (4)	2.04 (4)	2.900 (6)	175 (5)
N2—H1···O6^vii	0.86 (4)	2.59 (5)	3.139 (6)	122 (4)
O1W—H1W···O8^v	0.80 (5)	2.04 (5)	2.806 (6)	161 (6)
N4—H2···O1Wⁱⁱⁱ	0.85 (4)	2.12 (3)	2.948 (6)	162 (5)
N4—H2···O10	0.85 (4)	2.57 (6)	3.016 (7)	114 (4)
O1W—H2W···O8^viii	0.81 (5)	1.94 (6)	2.748 (6)	174 (6)
O2W—H3W···O3W	0.81 (5)	1.89 (5)	2.693 (6)	172 (7)
N5—H4···O8^ix	0.85 (4)	2.23 (4)	3.052 (6)	161 (5)
O2W—H4W···O10^x	0.80 (6)	2.06 (6)	2.851 (7)	171 (6)
O3W—H5W···O11ⁱⁱⁱ	0.86 (5)	2.06 (6)	2.902 (6)	166 (5)
O3W—H6W···O4	0.86 (6)	2.10 (6)	2.928 (6)	163 (6)
C8—H8···O3	0.93	2.44	3.217 (7)	141
C8—H8···O9	0.93	2.39	3.190 (7)	144
C13—H13···O2W^xi	0.93	2.42	3.352 (7)	178

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

Experimental details

Crystal data
Chemical formula	[Co₃Lu₂(C₅H₂N₂O₄)₆(H₂O)₄]·2H₂O
M_r	1559.34
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.0332 (6), 8.3468 (7), 17.8510 (15)
α, β, γ (°)	95.515 (1), 96.786 (1), 97.195 (1)
V (Å³)	1025.84 (15)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	6.08
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.308, 0.402
No. of measured, independent and observed [I > 2σ(I)] reflections	5351, 3642, 3280
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.069, 1.02
No. of reflections	3642
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)	1.38, −1.34

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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···O5ⁱ	0.86 (4)	2.04 (4)	2.900 (6)	175 (5)
N2—H1···O6ⁱ	0.86 (4)	2.59 (5)	3.139 (6)	122 (4)
O1W—H1W···O8ⁱⁱ	0.80 (5)	2.04 (5)	2.806 (6)	161 (6)
N4—H2···O1Wⁱⁱⁱ	0.85 (4)	2.12 (3)	2.948 (6)	162 (5)
N4—H2···O10	0.85 (4)	2.57 (6)	3.016 (7)	114 (4)
O1W—H2W···O8^iv	0.81 (5)	1.94 (6)	2.748 (6)	174 (6)
O2W—H3W···O3W	0.81 (5)	1.89 (5)	2.693 (6)	172 (7)
N5—H4···O8^v	0.85 (4)	2.23 (4)	3.052 (6)	161 (5)
O2W—H4W···O10^vi	0.80 (6)	2.06 (6)	2.851 (7)	171 (6)
O3W—H5W···O11ⁱⁱⁱ	0.86 (5)	2.06 (6)	2.902 (6)	166 (5)
O3W—H6W···O4	0.86 (6)	2.10 (6)	2.928 (6)	163 (6)
C8—H8···O3	0.9300	2.4400	3.217 (7)	141.00
C8—H8···O9	0.9300	2.3900	3.190 (7)	144.00
C13—H13···O2W^vii	0.9300	2.4200	3.352 (7)	178.00

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

Acknowledgements

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

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Cheng, J.-W., Zhang, J., Zheng, S.-T., Zhang, M.-B. & Yang, G.-Y. (2006). Angew. Chem. Int. Ed. 45, 73–77. Web of Science CSD CrossRef CAS Google Scholar
Kuang, D.-Z., Feng, Y.-L., Peng, Y.-L. & Deng, Y.-F. (2007). Acta Cryst. E63, m2526–m2527. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y.-Q., Zhang, J. & Yang, G.-Y. (2006). Chem. Commun. pp. 4700–4702. Web of Science CSD CrossRef Google Scholar
Zhu, L.-C., Zhao, Y., Yu, S.-J. & Zhao, M.-M. (2010). Inorg. Chem. Commun. 13, 1299–1303. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.