Poly[[tetra­aqua­tetra­kis­[μ3-5-(pyridine-4-carboxamido)­isophthalato]cobalt(II)dierbium(III)] tetra­hydrate]

Deng, Y.-F.; Chen, M.-S.; Zhang, C.-H.; Tan, X.-W.

doi:10.1107/S1600536811039948

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1478-m1479

doi:10.1107/S1600536811039948

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Poly[[tetraaquatetrakis[μ₃-5-(pyridine-4-carboxamido)isophthalato]cobalt(II)dierbium(III)] tetrahydrate]

Yi-Fang Deng,^a Man-Sheng Chen,^a ^* Chun-Hua Zhang ^a ^* and Xiong-Wen Tan ^a

^aKey Laboratory of Functional Organometallic Materials, Hengyang Normal University, Department of Chemistry and Materials Science, Hengyang, Hunan 421008, People's Republic of China
^*Correspondence e-mail: cmsniu@163.com, zhangchunhua668@163.com

(Received 20 September 2011; accepted 28 September 2011; online 5 October 2011)

In the centrosymmetric polymeric title compound, {[CoEr₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O}_n, the Er^III cation has a coordination number of eight and is surrounded by seven carboxylate O atoms from four 5-(pyridine-4-carboxamido)isophthalate (L) ligands and one water molecule, forming a distorted square-antiprismatic arrangement. The Co^II cation is located on an inversion center and is coordinated by two pyridine N atoms, two carboxylate O atoms and two water molecules in a distorted octahedral geometry. The asymmetric unit contains two anionic L ligands. One bridges two Er^III cations and one Co^II cation through two carboxylate groups and one pyridine N atom, while the other bridges two Er^III cations and one Co^II cation through two carboxylate groups. Extensive O—H⋯O, O—H⋯N and N—H⋯O hydrogen-bonding interactions are present in the crystal, involving all uncoordinated water molecules and the uncoordinated pyridine N atom of one of the ligands bonded to an adjacent coordinated water molecule. The title compound is isotypic with the gadolinium analogue.

Related literature

For the isotypic structure of the gadolinium analogue, see: Deng et al. (2011 ). For related hetero-metallic complexes, see: Chen et al. (2011a ,b ); Gu & Xue (2006 ); Liang et al. (2000 ); Prasad et al. (2007 ); Zhao et al. (2003 , 2004 ).

Experimental

Crystal data

[CoEr₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M_r = 1674.47
Triclinic, $[P \overline 1]$
a = 10.0816 (9) Å
b = 10.7844 (10) Å
c = 13.7316 (12) Å
α = 79.174 (1)°
β = 78.771 (2)°
γ = 86.355 (2)°
V = 1437.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 3.28 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.560, T_max = 0.735
7172 measured reflections
4979 independent reflections
4649 reflections with I > 2σ(I)
R_int = 0.096

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.136
S = 1.02
4979 reflections
430 parameters
H-atom parameters constrained
Δρ_max = 3.52 e Å⁻³
Δρ_min = −2.99 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3Wⁱ	0.86	2.16	3.007 (8)	166
O1W—H1WB⋯O4Wⁱⁱ	0.85	2.05	2.769 (9)	142
O1W—H1WA⋯O8ⁱⁱⁱ	0.85	2.22	2.975 (8)	149
O2W—H2WB⋯O4W^iv	0.85	2.32	3.109 (10)	156
O2W—H2WC⋯N2^v	0.85	1.94	2.687 (8)	147
O3W—H3WA⋯O7^vi	0.85	2.30	3.041 (8)	147
O3W—H3WB⋯O9	0.85	2.30	3.042 (8)	147
O4W—H4WA⋯O3^vii	0.85	1.92	2.729 (8)	159
O4W—H4WB⋯O6^viii	0.85	1.95	2.762 (8)	159
Symmetry codes: (i) x-1, y, z; (ii) x-1, y, z+1; (iii) -x, -y+1, -z+2; (iv) x-1, y+1, z+1; (v) x, y, z+1; (vi) x+1, y, z; (vii) x+1, y, z-1; (viii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811039948/wm2536sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039948/wm2536Isup2.hkl

checkCIF report

Comment top

The rational design and synthesis of higher-dimensional transition-lanthanide metal heterometallic networks have attracted increasing attention, which is justified not only by the fascinating structural diversity of the resulting architectures but also by the potential applications of these complexes as important functional solid materials (Chen et al., 2011a,b; Gu & Xue, 2006; Liang et al., 2000; Prasad et al., 2007; Zhao et al., 2003, 2004). In this context, we have synthesized a new 3d-4f coordination polymer, [CoEr₂(C₁₄H₈O₅N₂)₄(H₂O)₄]^.4H₂O, or [CoEr₂(L)₄(H₂O)₄]^.4H₂O and report its crystal structure here.

The title compound is isotypic with the gadolinium analogue (Deng et al., 2011). The central Er^III ion is eight-coordinated by seven O atoms from four L^2- ligands and one water molecule, forming a distorted square antiprismatic arrangement around the metal (Fig. 1). The carboxyl groups of the two unique L^2- ligands exhibit different coordination modes: one coordinates to two Er^III and one Co^II atom (site symmetry 1) using its two carboxylate groups with bidentate-chelate and bis-monodentate coordination modes while the pyridyl group is free of coordination. The other ligand coordinates to two Er^III ions through the carboxylate groups with a bidentate-chelate coordination mode and to one Co^II via the pyridyl group. Based on the coordination modes of the carboxylate and pyridyl groups of the ligands, a three-dimensional network is formed (Fig. 2), which is similar to that of complexes of the type {[LnCo_0.5(INAIP)₂(H₂O)₂].2H₂O}_n (Chen, et al. 2011b). Extensive O—H···O and N—H···O hydrogen bonding interactions are present in the crystal structure (Table 1).

Related literature top

For the isotypic structure of the gadolinium analogue, see: Deng et al. (2011). For related hetero-metallic complexes, see: Chen et al. (2011a,b); Gu & Xue (2006); Liang et al. (2000); Prasad et al. (2007); Zhao et al. (2003, 2004).

Experimental top

A mixture of 0.05 mmol Er(NO₃)₃^.6H₂O (22.5 mg. 0.05 mmol), H₂L (28.6 mg, 0.1 mmol), Co(OAc)₂.4H₂O (13.2 mg, 0.05 mmol), NaOH (6.0 mg, 0.15 mmol), MeOH (4 ml) and H₂O (6 ml) was heated in a 16 mL capacity Teflon-lined reaction vessel at 433 K for 4 days. The reaction mixture was then cooled to room temperature over a period of 40 h. The product was collected by filtration, washed with water and air-dried.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The ORTEP drawing of the title compound (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -1 + x, y, 1 + z (ii) -x, 1 - y, 1 - z (iii) -1 - x, 1 - y, 2 - z (iv) x, 1 + y, z (v)-1 + x, y, z.]
	Fig. 2. Projectionn along [001] showing the three-dimensional structure of the compound. Colour code: Er (pink), Co (light blue), O (red), N (blue), C (grey).

Poly[[tetraaquatetrakis[µ₃-5-(pyridine-4- carboxamido)isophthalato]cobalt(II)dierbium(III)] tetrahydrate] top

Crystal data top

[CoEr₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O	Z = 1
M_r = 1674.47	F(000) = 827
Triclinic, P1	D_x = 1.934 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0816 (9) Å	Cell parameters from 5230 reflections
b = 10.7844 (10) Å	θ = 2.3–28.1°
c = 13.7316 (12) Å	µ = 3.28 mm⁻¹
α = 79.174 (1)°	T = 293 K
β = 78.771 (2)°	Block, pink
γ = 86.355 (2)°	0.20 × 0.18 × 0.10 mm
V = 1437.7 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4979 independent reflections
Radiation source: fine-focus sealed tube	4649 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.096
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→12
T_min = 0.560, T_max = 0.735	k = −12→12
7172 measured reflections	l = −15→16

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.1058P)²] where P = (F_o² + 2F_c²)/3
4979 reflections	(Δ/σ)_max = 0.001
430 parameters	Δρ_max = 3.52 e Å⁻³
0 restraints	Δρ_min = −2.99 e Å⁻³

Crystal data top

[CoEr₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O	γ = 86.355 (2)°
M_r = 1674.47	V = 1437.7 (2) Å³
Triclinic, P1	Z = 1
a = 10.0816 (9) Å	Mo Kα radiation
b = 10.7844 (10) Å	µ = 3.28 mm⁻¹
c = 13.7316 (12) Å	T = 293 K
α = 79.174 (1)°	0.20 × 0.18 × 0.10 mm
β = 78.771 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4979 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4649 reflections with I > 2σ(I)
T_min = 0.560, T_max = 0.735	R_int = 0.096
7172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.02	Δρ_max = 3.52 e Å⁻³
4979 reflections	Δρ_min = −2.99 e Å⁻³
430 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
Co1	−0.5000	0.5000	1.0000	0.0223 (3)
Er1	−0.18176 (2)	0.92224 (2)	0.796262 (18)	0.01355 (14)
C1	−0.2010 (6)	0.5274 (6)	0.7723 (5)	0.0162 (12)
C2	−0.1777 (7)	0.5835 (6)	0.6709 (5)	0.0203 (13)
H2A	−0.1712	0.6707	0.6528	0.024*
C3	−0.1640 (6)	0.5091 (6)	0.5959 (5)	0.0178 (13)
C4	−0.1655 (6)	0.3777 (6)	0.6249 (5)	0.0187 (13)
H4A	−0.1543	0.3266	0.5762	0.022*
C5	−0.1833 (6)	0.3243 (6)	0.7250 (5)	0.0165 (12)
C6	−0.2041 (6)	0.3972 (6)	0.8004 (5)	0.0187 (13)
H6A	−0.2197	0.3594	0.8682	0.022*
C7	−0.1869 (6)	0.1837 (6)	0.7518 (5)	0.0178 (13)
C8	−0.2318 (7)	0.6074 (6)	0.8526 (5)	0.0205 (14)
C9	−0.1651 (7)	0.5169 (7)	0.4170 (5)	0.0264 (15)
C10	−0.1506 (7)	0.6000 (7)	0.3142 (5)	0.0239 (15)
C11	−0.1432 (8)	0.5403 (8)	0.2318 (5)	0.0325 (17)
H11A	−0.1416	0.4526	0.2406	0.039*
C12	−0.1385 (9)	0.6116 (8)	0.1383 (5)	0.0356 (18)
H12A	−0.1338	0.5698	0.0843	0.043*
C13	−0.1448 (8)	0.7939 (8)	0.1996 (6)	0.0337 (17)
H13A	−0.1442	0.8816	0.1888	0.040*
C14	−0.1505 (8)	0.7294 (7)	0.2963 (5)	0.0284 (16)
H14A	−0.1543	0.7730	0.3491	0.034*
C15	0.2360 (7)	0.8871 (6)	0.6690 (5)	0.0198 (14)
C16	0.2649 (6)	0.8586 (6)	0.5711 (5)	0.0188 (13)
H16A	0.1946	0.8527	0.5375	0.023*
C17	0.3943 (6)	0.8397 (6)	0.5257 (5)	0.0182 (13)
C18	0.5006 (6)	0.8521 (6)	0.5738 (5)	0.0192 (13)
H18A	0.5896	0.8420	0.5413	0.023*
C19	0.4738 (6)	0.8796 (6)	0.6698 (5)	0.0191 (13)
C20	0.3414 (6)	0.8968 (6)	0.7185 (5)	0.0199 (13)
H20A	0.3237	0.9147	0.7835	0.024*
C21	0.0908 (6)	0.9019 (6)	0.7170 (5)	0.0195 (13)
C22	0.5927 (6)	0.8916 (6)	0.7177 (5)	0.0181 (13)
C23	0.5058 (6)	0.7065 (7)	0.4098 (5)	0.0211 (14)
C24	0.5094 (6)	0.6636 (7)	0.3100 (5)	0.0226 (14)
C25	0.5104 (7)	0.5355 (7)	0.3108 (5)	0.0258 (15)
H25A	0.5077	0.4783	0.3709	0.031*
C26	0.5155 (7)	0.4933 (7)	0.2211 (5)	0.0274 (15)
H26A	0.5150	0.4068	0.2225	0.033*
C27	0.5258 (8)	0.6949 (7)	0.1321 (5)	0.0300 (16)
H27A	0.5354	0.7497	0.0703	0.036*
C28	0.5172 (7)	0.7460 (7)	0.2184 (5)	0.0262 (15)
H28A	0.5167	0.8330	0.2151	0.031*
N1	−0.1457 (5)	0.5694 (5)	0.4954 (4)	0.0197 (11)
H1	−0.1199	0.6463	0.4819	0.024*
N2	−0.1400 (7)	0.7376 (7)	0.1191 (5)	0.0352 (15)
N3	0.4213 (5)	0.8043 (5)	0.4280 (4)	0.0199 (12)
H3	0.3831	0.8460	0.3806	0.024*
N4	0.5212 (6)	0.5710 (6)	0.1323 (4)	0.0243 (13)
O1	−0.3059 (5)	0.5656 (5)	0.9346 (3)	0.0292 (11)
O2	−0.1793 (5)	0.7147 (4)	0.8335 (4)	0.0280 (11)
O3	−0.1703 (6)	0.1271 (4)	0.8379 (3)	0.0325 (12)
O4	−0.2075 (6)	0.1200 (5)	0.6898 (4)	0.0331 (12)
O5	−0.1926 (8)	0.4070 (5)	0.4251 (4)	0.0521 (18)
O6	0.0561 (5)	0.9015 (5)	0.8108 (4)	0.0279 (12)
O7	0.0016 (5)	0.9159 (6)	0.6644 (3)	0.0356 (13)
O8	0.5758 (5)	0.9079 (5)	0.8090 (4)	0.0285 (12)
O9	0.7095 (4)	0.8844 (4)	0.6686 (3)	0.0214 (10)
O10	0.5752 (5)	0.6497 (6)	0.4668 (4)	0.0357 (13)
O1W	−0.4267 (6)	0.3145 (5)	1.0665 (4)	0.0339 (12)
H1WB	−0.3591	0.2868	1.0285	0.041*
H1WA	−0.4880	0.2603	1.0843	0.041*
O2W	−0.2229 (6)	0.9033 (5)	0.9693 (4)	0.0335 (12)
H2WB	−0.1908	0.9650	0.9863	0.040*
H2WC	−0.1880	0.8351	0.9967	0.040*
O3W	0.9154 (8)	0.8418 (6)	0.4834 (4)	0.0568 (19)
H3WA	0.9711	0.8601	0.5171	0.068*
H3WB	0.8369	0.8457	0.5189	0.068*
O4W	0.8025 (7)	0.1615 (8)	0.0328 (5)	0.066 (2)
H4WA	0.8294	0.1409	−0.0248	0.079*
H4WB	0.8595	0.1331	0.0702	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0270 (7)	0.0208 (7)	0.0212 (6)	−0.0031 (5)	−0.0058 (5)	−0.0071 (5)
Er1	0.0144 (2)	0.0097 (2)	0.0188 (2)	0.00035 (12)	−0.00753 (12)	−0.00390 (12)
C1	0.017 (3)	0.011 (3)	0.021 (3)	−0.001 (2)	−0.005 (2)	−0.004 (2)
C2	0.023 (3)	0.012 (3)	0.026 (3)	0.000 (3)	−0.004 (3)	−0.003 (3)
C3	0.016 (3)	0.015 (3)	0.023 (3)	0.001 (2)	−0.005 (2)	−0.003 (2)
C4	0.017 (3)	0.016 (3)	0.026 (3)	−0.002 (2)	−0.006 (3)	−0.007 (3)
C5	0.016 (3)	0.012 (3)	0.023 (3)	0.002 (2)	−0.007 (2)	−0.004 (2)
C6	0.017 (3)	0.016 (3)	0.023 (3)	−0.001 (3)	−0.007 (3)	−0.001 (3)
C7	0.014 (3)	0.018 (3)	0.021 (3)	0.000 (3)	−0.006 (2)	−0.002 (3)
C8	0.021 (3)	0.017 (3)	0.027 (3)	0.008 (3)	−0.013 (3)	−0.006 (3)
C9	0.031 (4)	0.024 (4)	0.026 (3)	0.000 (3)	−0.012 (3)	−0.005 (3)
C10	0.018 (3)	0.029 (4)	0.028 (4)	−0.001 (3)	−0.010 (3)	−0.006 (3)
C11	0.041 (4)	0.029 (4)	0.031 (4)	0.002 (3)	−0.011 (3)	−0.009 (3)
C12	0.045 (5)	0.042 (5)	0.022 (4)	0.001 (4)	−0.008 (3)	−0.011 (3)
C13	0.040 (4)	0.028 (4)	0.035 (4)	−0.007 (3)	−0.016 (3)	0.002 (3)
C14	0.032 (4)	0.030 (4)	0.026 (4)	−0.003 (3)	−0.014 (3)	−0.002 (3)
C15	0.017 (3)	0.016 (3)	0.028 (3)	0.001 (3)	−0.008 (3)	−0.006 (3)
C16	0.016 (3)	0.020 (3)	0.024 (3)	0.002 (3)	−0.012 (2)	−0.005 (3)
C17	0.022 (3)	0.014 (3)	0.022 (3)	0.000 (3)	−0.010 (3)	−0.006 (2)
C18	0.014 (3)	0.019 (3)	0.025 (3)	0.000 (2)	−0.007 (3)	−0.003 (3)
C19	0.013 (3)	0.019 (3)	0.027 (3)	−0.003 (3)	−0.008 (3)	−0.003 (3)
C20	0.022 (3)	0.023 (3)	0.019 (3)	0.002 (3)	−0.009 (3)	−0.011 (3)
C21	0.020 (3)	0.013 (3)	0.028 (3)	−0.003 (2)	−0.009 (3)	−0.006 (3)
C22	0.018 (3)	0.011 (3)	0.029 (3)	−0.006 (2)	−0.007 (3)	−0.008 (3)
C23	0.015 (3)	0.031 (4)	0.019 (3)	−0.001 (3)	−0.005 (3)	−0.006 (3)
C24	0.009 (3)	0.035 (4)	0.026 (3)	0.002 (3)	−0.003 (2)	−0.011 (3)
C25	0.031 (4)	0.030 (4)	0.020 (3)	0.002 (3)	−0.009 (3)	−0.009 (3)
C26	0.036 (4)	0.027 (4)	0.024 (3)	0.004 (3)	−0.012 (3)	−0.013 (3)
C27	0.037 (4)	0.031 (4)	0.022 (3)	−0.007 (3)	−0.006 (3)	−0.002 (3)
C28	0.026 (4)	0.029 (4)	0.028 (3)	−0.003 (3)	−0.006 (3)	−0.013 (3)
N1	0.025 (3)	0.013 (3)	0.022 (3)	0.001 (2)	−0.009 (2)	0.000 (2)
N2	0.040 (4)	0.040 (4)	0.027 (3)	−0.004 (3)	−0.016 (3)	0.001 (3)
N3	0.022 (3)	0.026 (3)	0.015 (3)	0.002 (2)	−0.010 (2)	−0.006 (2)
N4	0.021 (3)	0.029 (3)	0.026 (3)	−0.003 (2)	−0.003 (2)	−0.013 (3)
O1	0.030 (3)	0.032 (3)	0.025 (2)	−0.009 (2)	0.001 (2)	−0.009 (2)
O2	0.043 (3)	0.009 (2)	0.033 (3)	−0.005 (2)	−0.010 (2)	−0.0046 (19)
O3	0.069 (4)	0.011 (2)	0.023 (2)	−0.004 (2)	−0.020 (2)	−0.0013 (19)
O4	0.062 (4)	0.017 (3)	0.029 (3)	−0.002 (2)	−0.025 (2)	−0.007 (2)
O5	0.106 (6)	0.021 (3)	0.035 (3)	−0.020 (3)	−0.028 (3)	0.002 (2)
O6	0.019 (2)	0.045 (3)	0.024 (2)	−0.001 (2)	−0.0048 (19)	−0.015 (2)
O7	0.017 (2)	0.066 (4)	0.024 (2)	0.005 (2)	−0.007 (2)	−0.005 (2)
O8	0.022 (3)	0.046 (3)	0.025 (2)	−0.002 (2)	−0.009 (2)	−0.017 (2)
O9	0.012 (2)	0.026 (3)	0.029 (2)	0.0022 (18)	−0.0079 (18)	−0.010 (2)
O10	0.034 (3)	0.046 (3)	0.035 (3)	0.018 (3)	−0.021 (2)	−0.020 (2)
O1W	0.040 (3)	0.029 (3)	0.033 (3)	0.000 (2)	−0.007 (2)	−0.007 (2)
O2W	0.054 (3)	0.021 (3)	0.026 (2)	0.002 (2)	−0.016 (2)	0.000 (2)
O3W	0.104 (6)	0.038 (4)	0.032 (3)	−0.018 (4)	−0.013 (3)	−0.012 (3)
O4W	0.053 (4)	0.111 (7)	0.034 (3)	0.023 (4)	−0.015 (3)	−0.014 (4)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.095 (5)	C15—C16	1.406 (9)
Co1—O1	2.095 (5)	C15—C21	1.495 (9)
Co1—N4ⁱⁱ	2.152 (5)	C16—C17	1.353 (9)
Co1—N4ⁱⁱⁱ	2.152 (5)	C16—H16A	0.9300
Co1—O1W	2.184 (5)	C17—C18	1.390 (9)
Co1—O1Wⁱ	2.184 (5)	C17—N3	1.434 (8)
Er1—O2	2.200 (5)	C18—C19	1.377 (9)
Er1—O2W	2.303 (5)	C18—H18A	0.9300
Er1—O7	2.330 (5)	C19—C20	1.389 (9)
Er1—O9^iv	2.348 (4)	C19—C22	1.498 (9)
Er1—O4^v	2.379 (5)	C20—H20A	0.9300
Er1—O3^v	2.398 (5)	C21—O7	1.245 (8)
Er1—O8^iv	2.429 (5)	C21—O6	1.266 (8)
Er1—O6	2.438 (5)	C22—O9	1.243 (8)
C1—C6	1.385 (9)	C22—O8	1.277 (8)
C1—C2	1.390 (9)	C23—O10	1.207 (8)
C1—C8	1.500 (8)	C23—N3	1.342 (9)
C2—C3	1.402 (9)	C23—C24	1.521 (9)
C2—H2A	0.9300	C24—C25	1.379 (10)
C3—C4	1.398 (9)	C24—C28	1.389 (10)
C3—N1	1.393 (8)	C25—C26	1.382 (9)
C4—C5	1.368 (9)	C25—H25A	0.9300
C4—H4A	0.9300	C26—N4	1.336 (10)
C5—C6	1.392 (9)	C26—H26A	0.9300
C5—C7	1.492 (9)	C27—N4	1.339 (10)
C6—H6A	0.9300	C27—C28	1.384 (10)
C7—O4	1.244 (8)	C27—H27A	0.9300
C7—O3	1.261 (8)	C28—H28A	0.9300
C8—O1	1.247 (8)	N1—H1	0.8600
C8—O2	1.263 (8)	N3—H3	0.8600
C9—O5	1.214 (9)	N4—Co1^vi	2.152 (5)
C9—N1	1.358 (8)	O3—Er1^vii	2.398 (5)
C9—C10	1.509 (10)	O4—Er1^vii	2.379 (5)
C10—C14	1.371 (11)	O8—Er1^viii	2.429 (5)
C10—C11	1.391 (10)	O9—Er1^viii	2.348 (4)
C11—C12	1.362 (11)	O1W—H1WB	0.8488
C11—H11A	0.9300	O1W—H1WA	0.8469
C12—N2	1.334 (11)	O2W—H2WB	0.8474
C12—H12A	0.9300	O2W—H2WC	0.8489
C13—N2	1.349 (10)	O3W—H3WA	0.8477
C13—C14	1.370 (10)	O3W—H3WB	0.8482
C13—H13A	0.9300	O4W—H4WA	0.8494
C14—H14A	0.9300	O4W—H4WB	0.8487
C15—C20	1.387 (9)

O1ⁱ—Co1—O1	180.0	O5—C9—C10	118.5 (6)
O1ⁱ—Co1—N4ⁱⁱ	87.4 (2)	N1—C9—C10	117.9 (6)
O1—Co1—N4ⁱⁱ	92.6 (2)	C14—C10—C11	117.6 (7)
O1ⁱ—Co1—N4ⁱⁱⁱ	92.6 (2)	C14—C10—C9	125.2 (6)
O1—Co1—N4ⁱⁱⁱ	87.4 (2)	C11—C10—C9	117.1 (7)
N4ⁱⁱ—Co1—N4ⁱⁱⁱ	180.000 (1)	C12—C11—C10	119.3 (7)
O1ⁱ—Co1—O1W	85.9 (2)	C12—C11—H11A	120.4
O1—Co1—O1W	94.1 (2)	C10—C11—H11A	120.4
N4ⁱⁱ—Co1—O1W	90.5 (2)	N2—C12—C11	124.2 (7)
N4ⁱⁱⁱ—Co1—O1W	89.5 (2)	N2—C12—H12A	117.9
O1ⁱ—Co1—O1Wⁱ	94.1 (2)	C11—C12—H12A	117.9
O1—Co1—O1Wⁱ	85.9 (2)	N2—C13—C14	123.9 (7)
N4ⁱⁱ—Co1—O1Wⁱ	89.5 (2)	N2—C13—H13A	118.1
N4ⁱⁱⁱ—Co1—O1Wⁱ	90.5 (2)	C14—C13—H13A	118.1
O1W—Co1—O1Wⁱ	180.000 (1)	C13—C14—C10	119.3 (7)
O2—Er1—O2W	82.38 (18)	C13—C14—H14A	120.3
O2—Er1—O7	90.7 (2)	C10—C14—H14A	120.3
O2W—Er1—O7	138.81 (18)	C20—C15—C16	119.5 (6)
O2—Er1—O9^iv	81.92 (18)	C20—C15—C21	122.5 (6)
O2W—Er1—O9^iv	139.01 (18)	C16—C15—C21	118.0 (6)
O7—Er1—O9^iv	78.93 (16)	C17—C16—C15	120.4 (6)
O2—Er1—O4^v	153.92 (18)	C17—C16—H16A	119.8
O2W—Er1—O4^v	121.33 (17)	C15—C16—H16A	119.8
O7—Er1—O4^v	78.2 (2)	C16—C17—C18	120.4 (6)
O9^iv—Er1—O4^v	72.87 (16)	C16—C17—N3	119.6 (6)
O2—Er1—O3^v	152.42 (18)	C18—C17—N3	120.0 (6)
O2W—Er1—O3^v	71.32 (17)	C19—C18—C17	119.7 (6)
O7—Er1—O3^v	103.5 (2)	C19—C18—H18A	120.1
O9^iv—Er1—O3^v	123.62 (17)	C17—C18—H18A	120.1
O4^v—Er1—O3^v	53.59 (16)	C18—C19—C20	120.6 (6)
O2—Er1—O8^iv	85.79 (19)	C18—C19—C22	117.2 (6)
O2W—Er1—O8^iv	87.16 (18)	C20—C19—C22	122.2 (6)
O7—Er1—O8^iv	132.96 (16)	C19—C20—C15	119.3 (6)
O9^iv—Er1—O8^iv	54.11 (15)	C19—C20—H20A	120.4
O4^v—Er1—O8^iv	84.85 (19)	C15—C20—H20A	120.4
O3^v—Er1—O8^iv	100.68 (19)	O7—C21—O6	118.8 (6)
O2—Er1—O6	85.14 (19)	O7—C21—C15	119.9 (6)
O2W—Er1—O6	85.04 (18)	O6—C21—C15	121.3 (6)
O7—Er1—O6	53.86 (16)	O9—C22—O8	119.3 (6)
O9^iv—Er1—O6	130.75 (15)	O9—C22—C19	120.0 (6)
O4^v—Er1—O6	106.15 (19)	O8—C22—C19	120.8 (6)
O3^v—Er1—O6	84.49 (19)	O9—C22—Er1^viii	57.8 (3)
O8^iv—Er1—O6	168.74 (18)	O8—C22—Er1^viii	61.5 (3)
O2—Er1—C22^iv	83.91 (19)	C19—C22—Er1^viii	176.9 (4)
O2W—Er1—C22^iv	113.99 (19)	O10—C23—N3	125.3 (6)
O7—Er1—C22^iv	105.45 (18)	O10—C23—C24	118.6 (6)
O9^iv—Er1—C22^iv	26.61 (17)	N3—C23—C24	116.1 (6)
O4^v—Er1—C22^iv	76.62 (18)	C25—C24—C28	118.8 (6)
O3^v—Er1—C22^iv	113.96 (19)	C25—C24—C23	117.6 (6)
O8^iv—Er1—C22^iv	27.52 (17)	C28—C24—C23	123.5 (6)
O6—Er1—C22^iv	156.44 (18)	C26—C25—C24	119.1 (7)
O2—Er1—C7^v	179.27 (18)	C26—C25—H25A	120.4
O2W—Er1—C7^v	96.94 (18)	C24—C25—H25A	120.4
O7—Er1—C7^v	90.0 (2)	N4—C26—C25	123.0 (7)
O9^iv—Er1—C7^v	98.43 (17)	N4—C26—H26A	118.5
O4^v—Er1—C7^v	26.59 (17)	C25—C26—H26A	118.5
O3^v—Er1—C7^v	27.03 (17)	N4—C27—C28	123.8 (7)
O8^iv—Er1—C7^v	93.89 (19)	N4—C27—H27A	118.1
O6—Er1—C7^v	95.10 (19)	C28—C27—H27A	118.1
C22^iv—Er1—C7^v	96.11 (18)	C24—C28—C27	118.0 (7)
C6—C1—C2	120.6 (6)	C24—C28—H28A	121.0
C6—C1—C8	119.0 (6)	C27—C28—H28A	121.0
C2—C1—C8	120.3 (6)	C9—N1—C3	125.4 (6)
C1—C2—C3	120.3 (6)	C9—N1—H1	117.3
C1—C2—H2A	119.9	C3—N1—H1	117.3
C3—C2—H2A	119.9	C12—N2—C13	115.7 (6)
C4—C3—N1	122.8 (6)	C23—N3—C17	120.5 (5)
C4—C3—C2	118.7 (6)	C23—N3—H3	119.7
N1—C3—C2	118.4 (6)	C17—N3—H3	119.7
C5—C4—C3	120.0 (6)	C26—N4—C27	117.2 (6)
C5—C4—H4A	120.0	C26—N4—Co1^vi	120.6 (5)
C3—C4—H4A	120.0	C27—N4—Co1^vi	121.8 (5)
C4—C5—C6	121.9 (6)	C8—O1—Co1	143.4 (4)
C4—C5—C7	117.8 (6)	C8—O2—Er1	154.6 (5)
C6—C5—C7	120.3 (6)	C7—O3—Er1^vii	93.2 (4)
C1—C6—C5	118.4 (6)	C7—O4—Er1^vii	94.6 (4)
C1—C6—H6A	120.8	C21—O6—Er1	90.8 (4)
C5—C6—H6A	120.8	C21—O7—Er1	96.5 (4)
O4—C7—O3	118.6 (6)	C22—O8—Er1^viii	90.9 (4)
O4—C7—C5	120.5 (6)	C22—O9—Er1^viii	95.6 (4)
O3—C7—C5	120.9 (6)	Co1—O1W—H1WB	112.7
O4—C7—Er1^vii	58.9 (3)	Co1—O1W—H1WA	112.9
O3—C7—Er1^vii	59.8 (3)	H1WB—O1W—H1WA	110.2
C5—C7—Er1^vii	177.4 (5)	Er1—O2W—H2WB	110.5
O1—C8—O2	123.2 (6)	Er1—O2W—H2WC	111.1
O1—C8—C1	119.2 (6)	H2WB—O2W—H2WC	109.0
O2—C8—C1	117.6 (6)	H3WA—O3W—H3WB	107.4
O5—C9—N1	123.6 (6)	H4WA—O4W—H4WB	108.9

C6—C1—C2—C3	3.3 (10)	O5—C9—N1—C3	−5.1 (12)
C8—C1—C2—C3	−172.9 (6)	C10—C9—N1—C3	175.4 (6)
C1—C2—C3—C4	−4.1 (9)	C4—C3—N1—C9	19.7 (10)
C1—C2—C3—N1	177.7 (6)	C2—C3—N1—C9	−162.1 (6)
N1—C3—C4—C5	179.7 (6)	C11—C12—N2—C13	0.9 (12)
C2—C3—C4—C5	1.6 (9)	C14—C13—N2—C12	−1.2 (12)
C3—C4—C5—C6	1.8 (10)	O10—C23—N3—C17	−8.0 (11)
C3—C4—C5—C7	178.8 (6)	C24—C23—N3—C17	170.3 (6)
C2—C1—C6—C5	0.0 (9)	C16—C17—N3—C23	−131.1 (7)
C8—C1—C6—C5	176.2 (6)	C18—C17—N3—C23	47.8 (9)
C4—C5—C6—C1	−2.6 (10)	C25—C26—N4—C27	1.9 (11)
C7—C5—C6—C1	−179.5 (6)	C25—C26—N4—Co1^vi	−171.1 (6)
C4—C5—C7—O4	−17.8 (9)	C28—C27—N4—C26	−3.9 (11)
C6—C5—C7—O4	159.2 (6)	C28—C27—N4—Co1^vi	169.1 (6)
C4—C5—C7—O3	162.8 (6)	O2—C8—O1—Co1	120.6 (7)
C6—C5—C7—O3	−20.2 (10)	C1—C8—O1—Co1	−60.1 (10)
C6—C1—C8—O1	−26.8 (9)	N4ⁱⁱ—Co1—O1—C8	29.9 (8)
C2—C1—C8—O1	149.4 (6)	N4ⁱⁱⁱ—Co1—O1—C8	−150.1 (8)
C6—C1—C8—O2	152.5 (6)	O1W—Co1—O1—C8	120.6 (8)
C2—C1—C8—O2	−31.2 (9)	O1Wⁱ—Co1—O1—C8	−59.4 (8)
O5—C9—C10—C14	164.4 (8)	O1—C8—O2—Er1	−74.1 (13)
N1—C9—C10—C14	−16.0 (11)	C1—C8—O2—Er1	106.6 (10)
O5—C9—C10—C11	−12.4 (11)	O2W—Er1—O2—C8	91.1 (11)
N1—C9—C10—C11	167.2 (6)	O7—Er1—O2—C8	−129.7 (11)
C14—C10—C11—C12	−1.0 (11)	O9^iv—Er1—O2—C8	−51.0 (11)
C9—C10—C11—C12	176.0 (7)	O4^v—Er1—O2—C8	−65.8 (12)
C10—C11—C12—N2	0.2 (13)	O3^v—Er1—O2—C8	108.5 (11)
N2—C13—C14—C10	0.4 (12)	O8^iv—Er1—O2—C8	3.4 (11)
C11—C10—C14—C13	0.7 (11)	O6—Er1—O2—C8	176.7 (11)
C9—C10—C14—C13	−176.0 (7)	C22^iv—Er1—O2—C8	−24.2 (11)
C20—C15—C16—C17	0.6 (10)	O4—C7—O3—Er1^vii	3.6 (7)
C21—C15—C16—C17	−177.6 (6)	C5—C7—O3—Er1^vii	−177.1 (5)
C15—C16—C17—C18	−2.1 (10)	O3—C7—O4—Er1^vii	−3.6 (7)
C15—C16—C17—N3	176.8 (6)	C5—C7—O4—Er1^vii	177.0 (5)
C16—C17—C18—C19	2.3 (10)	O7—C21—O6—Er1	2.5 (7)
N3—C17—C18—C19	−176.6 (6)	C15—C21—O6—Er1	−178.0 (6)
C17—C18—C19—C20	−1.0 (10)	O2—Er1—O6—C21	92.9 (4)
C17—C18—C19—C22	179.9 (6)	O2W—Er1—O6—C21	175.7 (4)
C18—C19—C20—C15	−0.5 (10)	O7—Er1—O6—C21	−1.5 (4)
C22—C19—C20—C15	178.6 (6)	O9^iv—Er1—O6—C21	17.9 (5)
C16—C15—C20—C19	0.7 (10)	O4^v—Er1—O6—C21	−63.1 (4)
C21—C15—C20—C19	178.8 (6)	O3^v—Er1—O6—C21	−112.7 (4)
C20—C15—C21—O7	166.6 (6)	O8^iv—Er1—O6—C21	129.4 (7)
C16—C15—C21—O7	−15.3 (10)	C22^iv—Er1—O6—C21	30.4 (7)
C20—C15—C21—O6	−12.9 (10)	C7^v—Er1—O6—C21	−87.8 (4)
C16—C15—C21—O6	165.2 (6)	O6—C21—O7—Er1	−2.7 (7)
C18—C19—C22—O9	4.3 (9)	C15—C21—O7—Er1	177.8 (5)
C20—C19—C22—O9	−174.8 (6)	O2—Er1—O7—C21	−82.0 (4)
C18—C19—C22—O8	−174.9 (6)	O2W—Er1—O7—C21	−2.8 (6)
C20—C19—C22—O8	6.0 (10)	O9^iv—Er1—O7—C21	−163.6 (5)
O10—C23—C24—C25	41.6 (9)	O4^v—Er1—O7—C21	121.8 (4)
N3—C23—C24—C25	−136.8 (7)	O3^v—Er1—O7—C21	74.1 (4)
O10—C23—C24—C28	−135.7 (7)	O8^iv—Er1—O7—C21	−166.9 (4)
N3—C23—C24—C28	45.9 (9)	O6—Er1—O7—C21	1.5 (4)
C28—C24—C25—C26	−1.7 (10)	C22^iv—Er1—O7—C21	−165.9 (4)
C23—C24—C25—C26	−179.1 (6)	C7^v—Er1—O7—C21	97.8 (4)
C24—C25—C26—N4	0.8 (11)	O9—C22—O8—Er1^viii	3.2 (6)
C25—C24—C28—C27	−0.1 (10)	C19—C22—O8—Er1^viii	−177.6 (5)
C23—C24—C28—C27	177.2 (6)	O8—C22—O9—Er1^viii	−3.3 (7)
N4—C27—C28—C24	3.0 (11)	C19—C22—O9—Er1^viii	177.4 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3W^iv	0.86	2.16	3.007 (8)	166
O1W—H1WB···O4Wⁱⁱⁱ	0.85	2.05	2.769 (9)	142
O1W—H1WA···O8^ix	0.85	2.22	2.975 (8)	149
O2W—H2WB···O4W^x	0.85	2.32	3.109 (10)	156
O2W—H2WC···N2^xi	0.85	1.94	2.687 (8)	147
O3W—H3WA···O7^viii	0.85	2.30	3.041 (8)	147
O3W—H3WB···O9	0.85	2.30	3.042 (8)	147
O4W—H4WA···O3^vi	0.85	1.92	2.729 (8)	159
O4W—H4WB···O6^xii	0.85	1.95	2.762 (8)	159

Symmetry codes: (iii) x−1, y, z+1; (iv) x−1, y, z; (vi) x+1, y, z−1; (viii) x+1, y, z; (ix) −x, −y+1, −z+2; (x) x−1, y+1, z+1; (xi) x, y, z+1; (xii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[CoEr₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M_r	1674.47
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.0816 (9), 10.7844 (10), 13.7316 (12)
α, β, γ (°)	79.174 (1), 78.771 (2), 86.355 (2)
V (Å³)	1437.7 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.28
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.560, 0.735
No. of measured, independent and observed [I > 2σ(I)] reflections	7172, 4979, 4649
R_int	0.096
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.136, 1.02
No. of reflections	4979
No. of parameters	430
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.52, −2.99

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3Wⁱ	0.86	2.16	3.007 (8)	166.1
O1W—H1WB···O4Wⁱⁱ	0.85	2.05	2.769 (9)	141.6
O1W—H1WA···O8ⁱⁱⁱ	0.85	2.22	2.975 (8)	148.8
O2W—H2WB···O4W^iv	0.85	2.32	3.109 (10)	155.6
O2W—H2WC···N2^v	0.85	1.94	2.687 (8)	146.6
O3W—H3WA···O7^vi	0.85	2.30	3.041 (8)	146.8
O3W—H3WB···O9	0.85	2.30	3.042 (8)	146.7
O4W—H4WA···O3^vii	0.85	1.92	2.729 (8)	159.1
O4W—H4WB···O6^viii	0.85	1.95	2.762 (8)	159.4

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

Acknowledgements

This work was supported by the Open Fund Project of Key Laboratory in Hunan Universities (11 K009) and the Science Foundation of Hengyang Normal University of China (10B67).

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