Poly[[tetra­aqua­(μ4-imidazole-4,5-dicarboxyl­ato)(μ3-imidazole-4,5-dicarboxyl­ato)-μ3-sulfato-μ2-sulfato-cobalt(II)digadolinium(III)] monohydrate]

Zhu, L.-C.

doi:10.1107/S160053681104726X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1741-m1742

https://doi.org/10.1107/S160053681104726X

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Poly[[tetraaqua(μ₄-imidazole-4,5-dicarboxylato)(μ₃-imidazole-4,5-dicarboxylato)-μ₃-sulfato-μ₂-sulfato-cobalt(II)digadolinium(III)] monohydrate]

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 29 October 2011; accepted 8 November 2011; online 12 November 2011)

The asymmetric unit of the title compound, {[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O}_n, contains one Co^II ion, two Gd^III ions, two imidazole-4,5-dicarboxylate ligands, two SO₄²⁻ anions, four coordinated water molecules and one uncoordinated water molecule. The Co^II ion is six-coordinated by 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, giving a slightly distorted octahedral geometry. Both Gd^III ions are eight-coordinated in a distorted bicapped trigonal–prismatic geometry. One Gd^III ion is coordinated by four O atoms from two imidazole-4,5-dicarboxylate ligands, three O atoms from three SO₄²⁻ anions and a water O atom; the other Gd^III ion is bonded to five O atoms from three imidazole-4,5-dicarboxylate ligands, two O atoms from two SO₄²⁻ anions as well as a water O atom. These metal coordination units are connected by bridging imidazole-4,5-dicarboxylate and sulfate ligands, generating a heterometallic layer parallel to the ac plane. The layers are stacked along the b axis via N—H⋯O, O—H⋯O, and C—H⋯O hydrogen-bonding interactions, generating a three-dimensional framework.

Related literature

For applications of 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

[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O
M_r = 963.82
Triclinic, $[P \overline 1]$
a = 9.0916 (5) Å
b = 10.7714 (6) Å
c = 12.9736 (7) Å
α = 93.119 (1)°
β = 96.416 (1)°
γ = 108.840 (1)°
V = 1189.35 (11) Å³
Z = 2
Mo Kα radiation
μ = 6.48 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 = 0.284, T_max = 0.378
6174 measured reflections
4208 independent reflections
3790 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.054
S = 1.02
4208 reflections
397 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (4)	1.96 (4)	2.820 (5)	172 (5)
O1W—H1W⋯O5Wⁱⁱ	0.81 (4)	1.95 (3)	2.745 (5)	169 (6)
N3—H2⋯O14ⁱⁱⁱ	0.87 (3)	1.93 (3)	2.787 (4)	169 (4)
O2W—H3W⋯O1ⁱ	0.80 (3)	2.09 (4)	2.878 (5)	171 (5)
O2W—H4W⋯O14ⁱ	0.81 (4)	2.04 (4)	2.842 (5)	172 (5)
O2W—H4W⋯O15ⁱ	0.81 (4)	2.52 (4)	3.035 (5)	123 (4)
O3W—H5W⋯O12^iv	0.82 (3)	1.95 (4)	2.734 (4)	162 (5)
O3W—H6W⋯O14^v	0.83 (3)	2.41 (4)	2.919 (4)	120 (3)
O4W—H7W⋯O3^vi	0.82 (3)	2.49 (3)	3.306 (6)	174 (6)
O4W—H8W⋯O5Wⁱⁱⁱ	0.82 (5)	1.89 (5)	2.700 (6)	175 (6)
O5W—H9W⋯O12^v	0.85 (4)	1.99 (4)	2.797 (6)	161 (5)
O5W—H10W⋯O1ⁱ	0.85 (5)	1.93 (5)	2.728 (5)	157 (6)
C3—H3⋯O3^vii	0.93	2.44	3.193 (5)	138
Symmetry codes: (i) x-1, y, z; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) -x+1, -y+2, -z; (v) -x+1, -y+1, -z; (vi) -x+1, -y+1, -z+1; (vii) -x+1, -y, -z+1.

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/S160053681104726X/hp2018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104726X/hp2018Isup2.hkl

checkCIF report

Comment top

In the past few years, lanthanide-transition metal heterometallic complexs with bridging multifunctionnal organic ligands are of increasing interest, 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, (I), has been determined which is presented in this artcle.

The asymmetric unite of the title compound (Fig. 1), contains one Co^II ion, two Gd^III ions, two imidazole-4, 5-dicarboxylate ligands, two SO₄^2- anions, four coordinated water molecules and one uncoordinated water molecule. The Co^II ion is six-coordinated with two O atoms from two coordinated water molecules, two O atoms and two N atoms from two imidazole-4, 5-dicarboxylate ligands, giving a slightly distorted octahedral geometry. Both Gd^III ions are eight-coordinated in a bicapped trigonal prismatic coordination geometry. One Gd^III ion is coordinated by four O atoms from two imidazole-4,5-dicarboxylate ligands, three O atoms from three SO₄^2- anions and one water molecule; the other Gd^III ion is bonded to five O atoms from three imidazole-4, 5-dicarboxylate ligands, two O atoms from two SO₄^2- anions as well as one coordinated water molecule. These metal coordination units are connected by bridging imidazole-4, 5-dicarboxylate and sulfate ligands, generating a two-dimensional heterometallic layer. The two-dimensional layers are stacked along b axis via N—H···O, O—H···O, and C—H···O hydrogen-bonding interactions to generate the three-dimensional framework(Table 1 and Fig. 2).

Related literature top

For applications of 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), Gd₂O₃(0.09 g, 0.25 mmol), imidazole-4,5-dicarboxylic acid (0.156 g, 1 mmol), and H₂O(7 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 applications of 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 molecular structure showing the atomic-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (A) 2 - x, 1 - y, 1 - z; (B) 1 - x, 1 - y, 1 - z; (C) 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[[tetraaqua(µ₄-imidazole-4,5-dicarboxylato)(µ₃-imidazole-4,5- dicarboxylato)-µ₃-sulfato-µ₂-sulfato-cobalt(II)digadolinium(III)] monohydrate] top

Crystal data top

[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O	Z = 2
M_r = 963.82	F(000) = 914
Triclinic, P1	D_x = 2.691 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0916 (5) Å	Cell parameters from 4033 reflections
b = 10.7714 (6) Å	θ = 2.4–27.9°
c = 12.9736 (7) Å	µ = 6.48 mm⁻¹
α = 93.119 (1)°	T = 296 K
β = 96.416 (1)°	Block, red
γ = 108.840 (1)°	0.20 × 0.18 × 0.15 mm
V = 1189.35 (11) Å³

Data collection top

Bruker APEXII area-detector diffractometer	4208 independent reflections
Radiation source: fine-focus sealed tube	3790 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
φ and ω scan	θ_max = 25.2°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
T_min = 0.284, T_max = 0.378	k = −9→12
6174 measured reflections	l = −14→15

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0292P)² + 0.3497P] where P = (F_o² + 2F_c²)/3
4208 reflections	(Δ/σ)_max = 0.002
397 parameters	Δρ_max = 0.79 e Å⁻³
17 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O	γ = 108.840 (1)°
M_r = 963.82	V = 1189.35 (11) Å³
Triclinic, P1	Z = 2
a = 9.0916 (5) Å	Mo Kα radiation
b = 10.7714 (6) Å	µ = 6.48 mm⁻¹
c = 12.9736 (7) Å	T = 296 K
α = 93.119 (1)°	0.20 × 0.18 × 0.15 mm
β = 96.416 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	4208 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3790 reflections with I > 2σ(I)
T_min = 0.284, T_max = 0.378	R_int = 0.016
6174 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	17 restraints
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.79 e Å⁻³
4208 reflections	Δρ_min = −0.81 e Å⁻³
397 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
Gd1	0.90952 (2)	0.549083 (19)	0.364770 (14)	0.01526 (7)
Gd2	0.37043 (2)	0.410578 (19)	0.108204 (14)	0.01441 (7)
Co1	0.35411 (7)	0.78823 (6)	0.27426 (4)	0.01829 (13)
S1	0.92233 (13)	0.22231 (10)	0.40357 (8)	0.0196 (2)
S2	0.77447 (12)	0.42234 (10)	0.09511 (7)	0.0157 (2)
C1	0.7564 (5)	0.3980 (4)	0.5774 (3)	0.0152 (9)
C2	0.5906 (5)	0.3349 (4)	0.5377 (3)	0.0175 (9)
C3	0.3614 (5)	0.1987 (4)	0.5498 (3)	0.0224 (10)
H3	0.2790	0.1358	0.5738	0.027*
C4	0.4925 (5)	0.3440 (4)	0.4526 (3)	0.0176 (9)
C5	0.5166 (5)	0.4170 (4)	0.3574 (3)	0.0179 (9)
C6	0.5196 (5)	0.6976 (4)	0.1215 (3)	0.0183 (9)
C7	0.5717 (5)	0.8417 (4)	0.1198 (3)	0.0198 (9)
C8	0.5810 (6)	1.0356 (4)	0.1824 (3)	0.0262 (11)
H8	0.5656	1.1038	0.2221	0.031*
C9	0.6687 (5)	0.9312 (4)	0.0646 (3)	0.0212 (10)
C10	0.7527 (5)	0.9224 (4)	−0.0265 (3)	0.0253 (10)
N1	0.3480 (4)	0.2571 (4)	0.4626 (3)	0.0219 (8)
N2	0.5066 (4)	0.2422 (3)	0.5971 (3)	0.0188 (8)
N3	0.6720 (5)	1.0523 (3)	0.1057 (3)	0.0251 (9)
N4	0.5169 (4)	0.9092 (3)	0.1936 (3)	0.0209 (8)
O1	1.0507 (4)	0.2115 (3)	0.3471 (2)	0.0307 (8)
O2	0.9891 (4)	0.2677 (3)	0.5141 (2)	0.0260 (7)
O3	0.7976 (4)	0.0979 (3)	0.3993 (3)	0.0429 (10)
O4	0.8622 (4)	0.3220 (3)	0.3559 (2)	0.0236 (7)
O5	0.8508 (3)	0.4831 (3)	0.5314 (2)	0.0191 (6)
O6	0.8087 (3)	0.3626 (3)	0.6615 (2)	0.0195 (6)
O7	0.6446 (3)	0.5035 (3)	0.3536 (2)	0.0227 (7)
O8	0.4026 (4)	0.3819 (3)	0.2864 (2)	0.0291 (8)
O9	0.4237 (4)	0.6481 (3)	0.1835 (2)	0.0216 (7)
O10	0.5663 (3)	0.6222 (3)	0.0648 (2)	0.0201 (7)
O11	0.7322 (4)	0.8084 (3)	−0.0689 (3)	0.0373 (9)
O12	0.8336 (4)	1.0256 (3)	−0.0559 (3)	0.0371 (9)
O13	0.7800 (4)	0.5049 (3)	0.0081 (2)	0.0261 (7)
O14	0.8239 (4)	0.3108 (3)	0.0655 (2)	0.0302 (8)
O15	0.8852 (4)	0.5027 (3)	0.1839 (2)	0.0315 (8)
O16	0.6158 (4)	0.3748 (3)	0.1261 (2)	0.0296 (8)
H1	0.260 (4)	0.251 (5)	0.426 (3)	0.044*
H2	0.725 (5)	1.128 (3)	0.087 (4)	0.044*
O1W	0.8720 (5)	0.7325 (3)	0.2745 (3)	0.0411 (9)
H1W	0.931 (6)	0.807 (3)	0.275 (4)	0.062*
H2W	0.843 (7)	0.703 (5)	0.216 (2)	0.062*
O2W	0.1300 (4)	0.3676 (4)	0.1756 (3)	0.0301 (8)
H3W	0.115 (5)	0.331 (5)	0.227 (2)	0.045*
H4W	0.046 (4)	0.359 (5)	0.143 (3)	0.045*
O3W	0.1637 (4)	0.7554 (3)	0.1538 (2)	0.0305 (8)
H5W	0.166 (7)	0.811 (3)	0.113 (3)	0.046*
H6W	0.131 (6)	0.686 (3)	0.114 (3)	0.046*
O4W	0.2924 (5)	0.9293 (4)	0.3611 (3)	0.0402 (9)
H7W	0.267 (6)	0.916 (6)	0.419 (2)	0.060*
H8W	0.221 (5)	0.949 (6)	0.330 (4)	0.060*
O5W	0.0564 (5)	−0.0166 (4)	0.2481 (3)	0.0440 (10)
H9W	0.079 (7)	−0.006 (5)	0.187 (2)	0.066*
H10W	0.028 (7)	0.046 (4)	0.271 (4)	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Gd1	0.01463 (12)	0.01957 (12)	0.01160 (11)	0.00505 (9)	0.00226 (8)	0.00460 (8)
Gd2	0.01453 (12)	0.01764 (12)	0.01186 (11)	0.00550 (9)	0.00300 (8)	0.00492 (8)
Co1	0.0212 (3)	0.0206 (3)	0.0141 (3)	0.0069 (2)	0.0050 (2)	0.0054 (2)
S1	0.0214 (6)	0.0180 (5)	0.0181 (5)	0.0053 (4)	0.0011 (4)	0.0022 (4)
S2	0.0164 (5)	0.0211 (5)	0.0111 (5)	0.0077 (4)	0.0024 (4)	0.0041 (4)
C1	0.020 (2)	0.017 (2)	0.0083 (19)	0.0053 (18)	0.0044 (17)	0.0013 (16)
C2	0.022 (2)	0.021 (2)	0.0102 (19)	0.0082 (18)	0.0032 (17)	0.0004 (17)
C3	0.021 (2)	0.024 (2)	0.020 (2)	0.0035 (19)	0.0038 (19)	0.0055 (18)
C4	0.018 (2)	0.021 (2)	0.013 (2)	0.0056 (18)	0.0011 (17)	0.0031 (17)
C5	0.017 (2)	0.029 (2)	0.010 (2)	0.0095 (19)	0.0058 (17)	0.0057 (17)
C6	0.018 (2)	0.020 (2)	0.015 (2)	0.0039 (18)	−0.0011 (18)	0.0041 (18)
C7	0.023 (2)	0.018 (2)	0.018 (2)	0.0057 (18)	0.0050 (18)	0.0017 (17)
C8	0.038 (3)	0.017 (2)	0.025 (2)	0.009 (2)	0.012 (2)	0.0031 (19)
C9	0.026 (3)	0.014 (2)	0.021 (2)	0.0034 (18)	0.0045 (19)	0.0031 (18)
C10	0.027 (3)	0.024 (3)	0.023 (2)	0.003 (2)	0.010 (2)	0.005 (2)
N1	0.016 (2)	0.031 (2)	0.0177 (19)	0.0067 (17)	0.0005 (15)	0.0044 (16)
N2	0.020 (2)	0.0204 (19)	0.0142 (17)	0.0039 (15)	0.0035 (15)	0.0047 (14)
N3	0.035 (2)	0.0154 (19)	0.025 (2)	0.0043 (17)	0.0127 (18)	0.0081 (16)
N4	0.024 (2)	0.0188 (19)	0.0185 (18)	0.0050 (16)	0.0045 (16)	0.0011 (15)
O1	0.033 (2)	0.046 (2)	0.0184 (16)	0.0199 (16)	0.0057 (14)	0.0000 (15)
O2	0.037 (2)	0.0269 (17)	0.0154 (15)	0.0120 (15)	0.0022 (14)	0.0038 (13)
O3	0.031 (2)	0.0262 (19)	0.057 (2)	−0.0065 (15)	−0.0102 (18)	0.0148 (17)
O4	0.0266 (18)	0.0222 (16)	0.0229 (16)	0.0107 (14)	−0.0012 (14)	0.0020 (13)
O5	0.0160 (16)	0.0252 (16)	0.0149 (14)	0.0041 (13)	0.0030 (12)	0.0064 (12)
O6	0.0167 (16)	0.0296 (17)	0.0125 (14)	0.0070 (13)	0.0029 (12)	0.0074 (12)
O7	0.0161 (16)	0.0295 (17)	0.0225 (16)	0.0057 (13)	0.0029 (13)	0.0122 (13)
O8	0.0191 (17)	0.048 (2)	0.0167 (16)	0.0052 (15)	0.0010 (13)	0.0133 (15)
O9	0.0276 (18)	0.0182 (15)	0.0193 (15)	0.0049 (13)	0.0105 (13)	0.0067 (12)
O10	0.0246 (17)	0.0149 (15)	0.0209 (15)	0.0048 (13)	0.0084 (13)	0.0036 (12)
O11	0.053 (2)	0.0187 (18)	0.037 (2)	0.0021 (16)	0.0258 (18)	0.0011 (15)
O12	0.050 (2)	0.0236 (18)	0.039 (2)	0.0061 (16)	0.0248 (18)	0.0103 (15)
O13	0.0230 (18)	0.042 (2)	0.0184 (16)	0.0142 (15)	0.0053 (13)	0.0170 (14)
O14	0.039 (2)	0.0200 (17)	0.0346 (18)	0.0095 (15)	0.0187 (16)	0.0038 (14)
O15	0.035 (2)	0.0346 (19)	0.0158 (16)	0.0001 (15)	0.0002 (14)	−0.0013 (14)
O16	0.0236 (18)	0.045 (2)	0.0275 (17)	0.0164 (15)	0.0122 (14)	0.0208 (15)
O1W	0.053 (3)	0.029 (2)	0.035 (2)	0.0081 (18)	−0.0066 (19)	0.0089 (16)
O2W	0.0199 (18)	0.049 (2)	0.0271 (18)	0.0154 (16)	0.0092 (14)	0.0182 (16)
O3W	0.035 (2)	0.0295 (18)	0.0251 (17)	0.0100 (16)	−0.0016 (15)	0.0045 (14)
O4W	0.055 (3)	0.041 (2)	0.032 (2)	0.0265 (19)	0.0098 (18)	0.0015 (18)
O5W	0.063 (3)	0.040 (2)	0.043 (2)	0.028 (2)	0.026 (2)	0.0114 (18)

Geometric parameters (Å, º) top

Gd1—O7	2.283 (3)	C3—N2	1.314 (5)
Gd1—O2ⁱ	2.319 (3)	C3—N1	1.336 (5)
Gd1—O4	2.337 (3)	C3—H3	0.9300
Gd1—O15	2.343 (3)	C4—N1	1.370 (5)
Gd1—O5	2.375 (3)	C4—C5	1.498 (5)
Gd1—O1W	2.447 (3)	C5—O7	1.242 (5)
Gd1—O6ⁱ	2.498 (3)	C5—O8	1.249 (5)
Gd1—O5ⁱ	2.562 (3)	C6—O9	1.263 (5)
Gd1—C1ⁱ	2.905 (4)	C6—O10	1.268 (5)
Gd1—Gd1ⁱ	4.0465 (4)	C6—C7	1.471 (6)
Gd2—O11ⁱⁱ	2.244 (3)	C7—C9	1.373 (6)
Gd2—O13ⁱⁱ	2.338 (3)	C7—N4	1.399 (5)
Gd2—O8	2.348 (3)	C8—N4	1.320 (5)
Gd2—O2W	2.361 (3)	C8—N3	1.347 (6)
Gd2—O16	2.373 (3)	C8—H8	0.9300
Gd2—O10ⁱⁱ	2.414 (3)	C9—N3	1.372 (5)
Gd2—O10	2.535 (3)	C9—C10	1.493 (6)
Gd2—O9	2.561 (3)	C10—O12	1.226 (5)
Gd2—C6	2.934 (4)	C10—O11	1.265 (5)
Gd2—Gd2ⁱⁱ	4.0349 (4)	N1—H1	0.87 (4)
Co1—N4	2.058 (4)	N2—Co1ⁱⁱⁱ	2.086 (3)
Co1—N2ⁱⁱⁱ	2.086 (3)	N3—H2	0.87 (3)
Co1—O6ⁱⁱⁱ	2.096 (3)	O2—Gd1ⁱ	2.319 (3)
Co1—O4W	2.097 (4)	O5—Gd1ⁱ	2.562 (3)
Co1—O3W	2.122 (3)	O6—Co1ⁱⁱⁱ	2.096 (3)
Co1—O9	2.157 (3)	O6—Gd1ⁱ	2.498 (3)
S1—O3	1.443 (3)	O10—Gd2ⁱⁱ	2.414 (3)
S1—O1	1.478 (3)	O11—Gd2ⁱⁱ	2.244 (3)
S1—O2	1.483 (3)	O13—Gd2ⁱⁱ	2.338 (3)
S1—O4	1.486 (3)	O1W—H1W	0.81 (4)
S2—O14	1.459 (3)	O1W—H2W	0.789 (19)
S2—O15	1.469 (3)	O2W—H3W	0.80 (3)
S2—O13	1.470 (3)	O2W—H4W	0.81 (4)
S2—O16	1.476 (3)	O3W—H5W	0.82 (3)
C1—O5	1.264 (5)	O3W—H6W	0.83 (3)
C1—O6	1.269 (5)	O4W—H7W	0.82 (3)
C1—C2	1.458 (6)	O4W—H8W	0.82 (5)
C1—Gd1ⁱ	2.905 (4)	O5W—H9W	0.85 (4)
C2—C4	1.369 (6)	O5W—H10W	0.85 (5)
C2—N2	1.377 (5)

O7—Gd1—O2ⁱ	103.56 (11)	O4W—Co1—O3W	93.45 (14)
O7—Gd1—O4	87.61 (10)	N4—Co1—O9	78.00 (12)
O2ⁱ—Gd1—O4	139.04 (10)	N2ⁱⁱⁱ—Co1—O9	87.71 (13)
O7—Gd1—O15	90.06 (11)	O6ⁱⁱⁱ—Co1—O9	91.82 (11)
O2ⁱ—Gd1—O15	137.61 (11)	O4W—Co1—O9	178.18 (14)
O4—Gd1—O15	80.42 (11)	O3W—Co1—O9	87.04 (13)
O7—Gd1—O5	76.05 (10)	O3—S1—O1	112.2 (2)
O2ⁱ—Gd1—O5	71.43 (10)	O3—S1—O2	108.8 (2)
O4—Gd1—O5	73.46 (10)	O1—S1—O2	107.78 (19)
O15—Gd1—O5	150.71 (11)	O3—S1—O4	110.53 (19)
O7—Gd1—O1W	77.94 (12)	O1—S1—O4	107.51 (18)
O2ⁱ—Gd1—O1W	74.57 (11)	O2—S1—O4	110.02 (17)
O4—Gd1—O1W	146.18 (11)	O14—S2—O15	108.6 (2)
O15—Gd1—O1W	69.33 (12)	O14—S2—O13	109.56 (18)
O5—Gd1—O1W	130.26 (12)	O15—S2—O13	107.94 (19)
O7—Gd1—O6ⁱ	164.37 (9)	O14—S2—O16	110.07 (19)
O2ⁱ—Gd1—O6ⁱ	76.75 (10)	O15—S2—O16	109.10 (19)
O4—Gd1—O6ⁱ	102.43 (10)	O13—S2—O16	111.47 (17)
O15—Gd1—O6ⁱ	80.01 (10)	O5—C1—O6	118.6 (4)
O5—Gd1—O6ⁱ	118.09 (9)	O5—C1—C2	123.7 (3)
O1W—Gd1—O6ⁱ	87.23 (12)	O6—C1—C2	117.7 (3)
O7—Gd1—O5ⁱ	144.56 (9)	O5—C1—Gd1ⁱ	61.8 (2)
O2ⁱ—Gd1—O5ⁱ	75.17 (10)	O6—C1—Gd1ⁱ	58.9 (2)
O4—Gd1—O5ⁱ	73.51 (10)	C2—C1—Gd1ⁱ	163.6 (3)
O15—Gd1—O5ⁱ	115.09 (11)	C4—C2—N2	109.0 (4)
O5—Gd1—O5ⁱ	69.99 (11)	C4—C2—C1	135.5 (4)
O1W—Gd1—O5ⁱ	132.85 (11)	N2—C2—C1	115.5 (3)
O6ⁱ—Gd1—O5ⁱ	50.97 (9)	N2—C3—N1	110.9 (4)
O7—Gd1—C1ⁱ	168.66 (10)	N2—C3—H3	124.5
O2ⁱ—Gd1—C1ⁱ	70.40 (11)	N1—C3—H3	124.5
O4—Gd1—C1ⁱ	91.09 (11)	C2—C4—N1	105.5 (3)
O15—Gd1—C1ⁱ	100.83 (11)	C2—C4—C5	133.9 (4)
O5—Gd1—C1ⁱ	92.78 (10)	N1—C4—C5	120.4 (4)
O1W—Gd1—C1ⁱ	108.73 (12)	O7—C5—O8	125.4 (4)
O6ⁱ—Gd1—C1ⁱ	25.79 (9)	O7—C5—C4	119.5 (4)
O5ⁱ—Gd1—C1ⁱ	25.77 (10)	O8—C5—C4	115.1 (4)
O7—Gd1—Gd1ⁱ	111.99 (7)	O9—C6—O10	119.1 (4)
O2ⁱ—Gd1—Gd1ⁱ	69.58 (7)	O9—C6—C7	117.3 (4)
O4—Gd1—Gd1ⁱ	69.70 (7)	O10—C6—C7	123.6 (4)
O15—Gd1—Gd1ⁱ	141.31 (9)	O9—C6—Gd2	60.5 (2)
O5—Gd1—Gd1ⁱ	36.51 (7)	O10—C6—Gd2	59.4 (2)
O1W—Gd1—Gd1ⁱ	144.09 (9)	C7—C6—Gd2	171.4 (3)
O6ⁱ—Gd1—Gd1ⁱ	82.97 (6)	C9—C7—N4	109.2 (4)
O5ⁱ—Gd1—Gd1ⁱ	33.48 (6)	C9—C7—C6	135.5 (4)
C1ⁱ—Gd1—Gd1ⁱ	57.20 (7)	N4—C7—C6	115.3 (4)
O11ⁱⁱ—Gd2—O13ⁱⁱ	104.05 (12)	N4—C8—N3	110.6 (4)
O11ⁱⁱ—Gd2—O8	90.51 (12)	N4—C8—H8	124.7
O13ⁱⁱ—Gd2—O8	138.78 (11)	N3—C8—H8	124.7
O11ⁱⁱ—Gd2—O2W	79.70 (13)	N3—C9—C7	105.2 (4)
O13ⁱⁱ—Gd2—O2W	75.63 (11)	N3—C9—C10	119.4 (4)
O8—Gd2—O2W	69.29 (11)	C7—C9—C10	135.2 (4)
O11ⁱⁱ—Gd2—O16	85.00 (13)	O12—C10—O11	125.0 (4)
O13ⁱⁱ—Gd2—O16	139.36 (10)	O12—C10—C9	117.9 (4)
O8—Gd2—O16	79.29 (11)	O11—C10—C9	117.1 (4)
O2W—Gd2—O16	144.68 (10)	C3—N1—C4	108.3 (3)
O11ⁱⁱ—Gd2—O10ⁱⁱ	76.41 (10)	C3—N1—H1	125 (4)
O13ⁱⁱ—Gd2—O10ⁱⁱ	71.52 (10)	C4—N1—H1	126 (4)
O8—Gd2—O10ⁱⁱ	149.64 (11)	C3—N2—C2	106.3 (3)
O2W—Gd2—O10ⁱⁱ	132.68 (11)	C3—N2—Co1ⁱⁱⁱ	140.8 (3)
O16—Gd2—O10ⁱⁱ	72.45 (10)	C2—N2—Co1ⁱⁱⁱ	112.8 (3)
O11ⁱⁱ—Gd2—O10	145.26 (11)	C8—N3—C9	109.0 (4)
O13ⁱⁱ—Gd2—O10	76.33 (10)	C8—N3—H2	125 (4)
O8—Gd2—O10	112.31 (10)	C9—N3—H2	126 (4)
O2W—Gd2—O10	131.93 (11)	C8—N4—C7	106.0 (4)
O16—Gd2—O10	74.61 (10)	C8—N4—Co1	139.7 (3)
O10ⁱⁱ—Gd2—O10	70.80 (11)	C7—N4—Co1	114.0 (3)
O11ⁱⁱ—Gd2—O9	163.85 (11)	S1—O2—Gd1ⁱ	144.35 (18)
O13ⁱⁱ—Gd2—O9	74.78 (10)	S1—O4—Gd1	141.43 (18)
O8—Gd2—O9	80.86 (10)	C1—O5—Gd1	143.6 (3)
O2W—Gd2—O9	84.47 (11)	C1—O5—Gd1ⁱ	92.4 (2)
O16—Gd2—O9	106.54 (11)	Gd1—O5—Gd1ⁱ	110.01 (11)
O10ⁱⁱ—Gd2—O9	117.44 (9)	C1—O6—Co1ⁱⁱⁱ	115.4 (3)
O10—Gd2—O9	50.71 (9)	C1—O6—Gd1ⁱ	95.3 (2)
O11ⁱⁱ—Gd2—C6	169.70 (11)	Co1ⁱⁱⁱ—O6—Gd1ⁱ	143.17 (13)
O13ⁱⁱ—Gd2—C6	71.59 (11)	C5—O7—Gd1	145.3 (3)
O8—Gd2—C6	98.84 (11)	C5—O8—Gd2	134.4 (3)
O2W—Gd2—C6	107.59 (12)	C6—O9—Co1	115.0 (3)
O16—Gd2—C6	92.46 (12)	C6—O9—Gd2	94.1 (2)
O10ⁱⁱ—Gd2—C6	93.30 (11)	Co1—O9—Gd2	149.36 (13)
O10—Gd2—C6	25.50 (10)	C6—O10—Gd2ⁱⁱ	142.3 (3)
O9—Gd2—C6	25.43 (10)	C6—O10—Gd2	95.1 (2)
O11ⁱⁱ—Gd2—Gd2ⁱⁱ	112.07 (8)	Gd2ⁱⁱ—O10—Gd2	109.20 (11)
O13ⁱⁱ—Gd2—Gd2ⁱⁱ	70.24 (7)	C10—O11—Gd2ⁱⁱ	159.9 (3)
O8—Gd2—Gd2ⁱⁱ	139.01 (7)	S2—O13—Gd2ⁱⁱ	144.17 (19)
O2W—Gd2—Gd2ⁱⁱ	145.64 (8)	S2—O15—Gd1	141.6 (2)
O16—Gd2—Gd2ⁱⁱ	69.68 (7)	S2—O16—Gd2	142.69 (18)
O10ⁱⁱ—Gd2—Gd2ⁱⁱ	36.40 (6)	Gd1—O1W—H1W	130 (4)
O10—Gd2—Gd2ⁱⁱ	34.41 (6)	Gd1—O1W—H2W	104 (4)
O9—Gd2—Gd2ⁱⁱ	82.98 (6)	H1W—O1W—H2W	108 (3)
C6—Gd2—Gd2ⁱⁱ	57.82 (8)	Gd2—O2W—H3W	122 (4)
N4—Co1—N2ⁱⁱⁱ	102.68 (14)	Gd2—O2W—H4W	127 (3)
N4—Co1—O6ⁱⁱⁱ	169.67 (13)	H3W—O2W—H4W	108 (3)
N2ⁱⁱⁱ—Co1—O6ⁱⁱⁱ	78.43 (12)	Co1—O3W—H5W	120 (4)
N4—Co1—O4W	100.20 (15)	Co1—O3W—H6W	121 (4)
N2ⁱⁱⁱ—Co1—O4W	92.40 (14)	H5W—O3W—H6W	102 (3)
O6ⁱⁱⁱ—Co1—O4W	89.98 (14)	Co1—O4W—H7W	121 (4)
N4—Co1—O3W	94.51 (14)	Co1—O4W—H8W	113 (4)
N2ⁱⁱⁱ—Co1—O3W	160.56 (13)	H7W—O4W—H8W	104 (3)
O6ⁱⁱⁱ—Co1—O3W	83.04 (12)	H9W—O5W—H10W	110 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^iv	0.87 (4)	1.96 (4)	2.820 (5)	172 (5)
O1W—H1W···O5W^v	0.81 (4)	1.95 (3)	2.745 (5)	169 (6)
N3—H2···O14^vi	0.87 (3)	1.93 (3)	2.787 (4)	169 (4)
O2W—H3W···O1^iv	0.80 (3)	2.09 (4)	2.878 (5)	171 (5)
O2W—H4W···O14^iv	0.81 (4)	2.04 (4)	2.842 (5)	172 (5)
O2W—H4W···O15^iv	0.81 (4)	2.52 (4)	3.035 (5)	123 (4)
O3W—H5W···O12^vii	0.82 (3)	1.95 (4)	2.734 (4)	162 (5)
O3W—H6W···O14ⁱⁱ	0.83 (3)	2.41 (4)	2.919 (4)	120 (3)
O4W—H7W···O3ⁱⁱⁱ	0.82 (3)	2.49 (3)	3.306 (6)	174 (6)
O4W—H8W···O5W^vi	0.82 (5)	1.89 (5)	2.700 (6)	175 (6)
O5W—H9W···O12ⁱⁱ	0.85 (4)	1.99 (4)	2.797 (6)	161 (5)
O5W—H10W···O1^iv	0.85 (5)	1.93 (5)	2.728 (5)	157 (6)
C3—H3···O3^viii	0.93	2.44	3.193 (5)	138

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

Experimental details

Crystal data
Chemical formula	[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O
M_r	963.82
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.0916 (5), 10.7714 (6), 12.9736 (7)
α, β, γ (°)	93.119 (1), 96.416 (1), 108.840 (1)
V (Å³)	1189.35 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.48
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	0.284, 0.378
No. of measured, independent and observed [I > 2σ(I)] reflections	6174, 4208, 3790
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.054, 1.02
No. of reflections	4208
No. of parameters	397
No. of restraints	17
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.81

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
N1—H1···O1ⁱ	0.87 (4)	1.96 (4)	2.820 (5)	172 (5)
O1W—H1W···O5Wⁱⁱ	0.81 (4)	1.95 (3)	2.745 (5)	169 (6)
N3—H2···O14ⁱⁱⁱ	0.87 (3)	1.93 (3)	2.787 (4)	169 (4)
O2W—H3W···O1ⁱ	0.80 (3)	2.09 (4)	2.878 (5)	171 (5)
O2W—H4W···O14ⁱ	0.81 (4)	2.04 (4)	2.842 (5)	172 (5)
O2W—H4W···O15ⁱ	0.81 (4)	2.52 (4)	3.035 (5)	123 (4)
O3W—H5W···O12^iv	0.82 (3)	1.95 (4)	2.734 (4)	162 (5)
O3W—H6W···O14^v	0.83 (3)	2.41 (4)	2.919 (4)	120 (3)
O4W—H7W···O3^vi	0.82 (3)	2.49 (3)	3.306 (6)	174 (6)
O4W—H8W···O5Wⁱⁱⁱ	0.82 (5)	1.89 (5)	2.700 (6)	175 (6)
O5W—H9W···O12^v	0.85 (4)	1.99 (4)	2.797 (6)	161 (5)
O5W—H10W···O1ⁱ	0.85 (5)	1.93 (5)	2.728 (5)	157 (6)
C3—H3···O3^vii	0.9300	2.4400	3.193 (5)	138.00

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

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

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