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

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

doi:10.1107/S1600536811042814

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1574-m1575

doi:10.1107/S1600536811042814

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

Yi-Fang Deng,^a Man-Sheng Chen,^a ^* Chun-Hua Zhang ^a and Xue Nie ^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

(Received 5 October 2011; accepted 15 October 2011; online 22 October 2011)

In the centrosymmetric polymeric title compound, {[CoHo₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O}_n, the Ho^III ion is coordinated by one water molecule and four 5-(pyridine-4-carboxamido)isophthalate (L) ligands in a distorted square-antiprismatic arrangement. The Co^II ion, located on an inversion center, is coordinated by two pyridine N atoms, two carboxylate O atoms and two water molecules in a distorted octahedral geometry. One L ligand bridges two Ho ions and one Co ion through two carboxylate groups and one pyridine N atom. The other L ligand bridges two Ho ions and one Co ion through two carboxylate groups, while the uncoordinated pyridine N atom accepts a hydrogen bond from an adjacent coordinated water molecule. Extensive O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonding is present in the crystal.

Related literature

For related hetero-metallic complexes, see: Chen et al. (2011 ); Deng et al. (2011 ); Gu & Xue (2006 ); Liang et al. (2000 ); Prasad et al. (2007 ); Zhao et al. (2003 , 2004 ).

Experimental

Crystal data

[CoHo₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M_r = 1669.81
Triclinic, $[P \overline 1]$
a = 10.0597 (9) Å
b = 10.7824 (10) Å
c = 13.7261 (13) Å
α = 79.141 (3)°
β = 78.801 (1)°
γ = 86.578 (3)°
V = 1433.9 (2) Å³
Z = 1
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 291 K
0.20 × 0.14 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.574, T_max = 0.746
7154 measured reflections
4968 independent reflections
4756 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.123
S = 1.06
4968 reflections
430 parameters
H-atom parameters constrained
Δρ_max = 2.89 e Å⁻³
Δρ_min = −1.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4Wⁱ	0.85	2.00	2.761 (8)	149
O1W—H1WB⋯O7ⁱⁱ	0.85	2.26	2.988 (7)	144
O2W—H2WB⋯N2ⁱⁱⁱ	0.85	1.96	2.699 (8)	145
O3W—H3WA⋯O6^iv	0.85	2.20	3.048 (8)	177
O3W—H3WB⋯O9^v	0.85	2.20	3.054 (8)	177
O4W—H4WA⋯O4ⁱ	0.85	1.90	2.732 (8)	164
O4W—H4WB⋯O8^vi	0.85	1.94	2.752 (8)	160
N1—H1⋯O3W	0.86	2.16	2.996 (7)	165
N3—H3⋯O3^vii	0.86	2.16	2.933 (7)	150
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+2, -z; (iii) x, y+1, z-1; (iv) x, y-1, z; (v) -x+2, -y+1, -z+1; (vi) x-1, y-1, z; (vii) -x+2, -y+2, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536811042814/hy2478sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042814/hy2478Isup2.hkl

checkCIF report

Comment top

The rational synthesis and investigation of 3d-4f or 4d-4f heterometallic complexes are challenge for chemists and have attracted increasing attention in last few years since the competitive reaction containing 3d-4f metal ions in conjunction with ligands often results in the formation of a mixture of homometallic assemblies rather than heterometallic analogous (Gu & Xue, 2006; Liang et al., 2000; Prasad et al., 2007; Zhao et al., 2003, 2004). We have recently prepared a new lanthanide(III)–transition metal(II) coordination polymer, the title compound, under hydrothermal conditions.

In the title compound, the Ho^III ion is eight-coordinated by seven O atoms from four pyridine-4-carboxamidoisophthalate (L) ligands and one water molecule, forming a distorted square-antiprismatic geometry (Fig. 1). It is interesting that the carboxylate groups of two unique L ligands exhibit different coordination modes: one coordinates to two Ho^III ions and one Co^II ion using its two carboxylate groups with µ₁-η¹:η¹-chelate and µ₂-η¹:η¹-bis-monodentate coordination modes while the pyridyl group is free of coordination, the other one coordinates to two Ho^III ions through the carboxylate groups with µ₁-η¹:η¹-chelate coordination mode and to one Co^II ion through the pyridyl group. Based on the coordination modes of the carboxylate and pyridyl groups, a complicated three-dimensional network is formed (Fig. 2), which is similar to the complex {[LnCo_0.5(INAIP)₂(H₂O)₂].2H₂O}_n (Chen et al. 2011) and a Gd analogue (Deng et al., 2011).

Related literature top

For related hetero-metallic complexes, see: Chen et al. (2011); Deng et al. (2011); Gu & Xue (2006); Liang et al. (2000); Prasad et al. (2007); Zhao et al. (2003, 2004). Supplementary Figure 2 is missing; please supply.

Experimental top

A mixture of Ho(NO₃)₃.6H₂O (22.5 mg, 0.05 mmol), H₂L (28.6 mg, 0.1 mmol), Co(OAc)₂.4H₂O (13.1 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 cooled to room temperature over a period of 40 h. The product was collected by filtration, washed with H₂O and air-dried.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 2-x, 2-y, 1-z; (ii) x, -1+y, -1+z; (iii) 2-x, 1-y, -z; (iv) x, 1+y, z; (v) -1+x, y, z.]
	Fig. 2. A view of the three-dimensional network of the title compound.

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

Crystal data top

[CoHo₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O	Z = 1
M_r = 1669.81	F(000) = 825
Triclinic, P1	D_x = 1.934 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0597 (9) Å	Cell parameters from 5442 reflections
b = 10.7824 (10) Å	θ = 2.7–28.1°
c = 13.7261 (13) Å	µ = 3.12 mm⁻¹
α = 79.141 (3)°	T = 291 K
β = 78.801 (1)°	Block, pink
γ = 86.578 (3)°	0.20 × 0.14 × 0.10 mm
V = 1433.9 (2) Å³

Data collection top

Bruker APEX CCD diffractometer	4968 independent reflections
Radiation source: fine-focus sealed tube	4756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.574, T_max = 0.746	k = −12→10
7154 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0881P)²] where P = (F_o² + 2F_c²)/3
4968 reflections	(Δ/σ)_max = 0.002
430 parameters	Δρ_max = 2.89 e Å⁻³
0 restraints	Δρ_min = −1.93 e Å⁻³

Crystal data top

[CoHo₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O	γ = 86.578 (3)°
M_r = 1669.81	V = 1433.9 (2) Å³
Triclinic, P1	Z = 1
a = 10.0597 (9) Å	Mo Kα radiation
b = 10.7824 (10) Å	µ = 3.12 mm⁻¹
c = 13.7261 (13) Å	T = 291 K
α = 79.141 (3)°	0.20 × 0.14 × 0.10 mm
β = 78.801 (1)°

Data collection top

Bruker APEX CCD diffractometer	4968 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4756 reflections with I > 2σ(I)
T_min = 0.574, T_max = 0.746	R_int = 0.070
7154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.06	Δρ_max = 2.89 e Å⁻³
4968 reflections	Δρ_min = −1.93 e Å⁻³
430 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	1.0000	0.5000	0.0000	0.0253 (3)
Ho1	0.68057 (2)	1.07784 (2)	0.204341 (17)	0.01470 (13)
C1	0.6994 (6)	0.4719 (5)	0.2279 (4)	0.0217 (12)
C2	0.7035 (6)	0.6032 (6)	0.1993 (5)	0.0236 (13)
H2	0.7193	0.6407	0.1315	0.028*
C3	0.6834 (6)	0.6770 (5)	0.2746 (4)	0.0221 (12)
C4	0.6647 (6)	0.6223 (6)	0.3756 (5)	0.0229 (12)
H4	0.6529	0.6730	0.4246	0.027*
C5	0.6636 (6)	0.4913 (6)	0.4041 (5)	0.0233 (12)
C6	0.6770 (6)	0.4169 (6)	0.3298 (5)	0.0240 (13)
H6	0.6709	0.3296	0.3485	0.029*
C7	0.6875 (6)	0.8177 (6)	0.2476 (5)	0.0236 (13)
C8	0.7308 (6)	0.3913 (6)	0.1481 (5)	0.0228 (13)
C9	0.6680 (7)	0.4839 (6)	0.5835 (5)	0.0289 (14)
C10	0.6509 (6)	0.4012 (6)	0.6856 (5)	0.0264 (13)
C11	0.6448 (8)	0.4618 (7)	0.7689 (5)	0.0363 (16)
H11	0.6452	0.5494	0.7600	0.044*
C12	0.6382 (8)	0.3898 (8)	0.8632 (6)	0.0425 (18)
H12	0.6334	0.4310	0.9176	0.051*
C13	0.6446 (7)	0.2083 (7)	0.8032 (5)	0.0366 (16)
H13	0.6453	0.1205	0.8150	0.044*
C14	0.6503 (7)	0.2708 (7)	0.7046 (5)	0.0325 (15)
H14	0.6536	0.2260	0.6525	0.039*
C15	0.9066 (6)	1.1082 (6)	0.2811 (5)	0.0229 (13)
C16	1.0260 (6)	1.1190 (6)	0.3296 (5)	0.0238 (13)
C17	1.1593 (6)	1.1035 (6)	0.2809 (5)	0.0248 (13)
H17	1.1774	1.0870	0.2154	0.030*
C18	1.2633 (6)	1.1125 (6)	0.3300 (5)	0.0228 (13)
C19	1.2362 (6)	1.1400 (6)	0.4285 (5)	0.0252 (13)
H19	1.3070	1.1440	0.4623	0.030*
C20	1.1051 (6)	1.1606 (6)	0.4744 (4)	0.0231 (12)
C21	0.9979 (6)	1.1474 (6)	0.4250 (5)	0.0234 (13)
H21	0.9086	1.1579	0.4568	0.028*
C22	1.4092 (6)	1.0971 (5)	0.2832 (5)	0.0229 (13)
C23	0.9939 (6)	1.2942 (6)	0.5906 (5)	0.0257 (13)
C24	0.9915 (6)	1.3357 (6)	0.6897 (5)	0.0264 (13)
C25	0.9898 (7)	1.4651 (7)	0.6893 (5)	0.0302 (15)
H25	0.9920	1.5228	0.6294	0.036*
C26	0.9847 (7)	1.5063 (6)	0.7794 (5)	0.0294 (14)
H26	0.9852	1.5929	0.7780	0.035*
C27	0.9748 (7)	1.3039 (6)	0.8680 (5)	0.0313 (15)
H27	0.9658	1.2485	0.9295	0.038*
C28	0.9831 (7)	1.2549 (6)	0.7813 (5)	0.0306 (14)
H28	0.9831	1.1679	0.7844	0.037*
N1	0.6462 (5)	0.4309 (5)	0.5055 (4)	0.0259 (11)
H1	0.6196	0.3541	0.5196	0.031*
N2	0.6383 (6)	0.2642 (6)	0.8813 (5)	0.0399 (14)
N3	1.0799 (5)	1.1948 (5)	0.5708 (4)	0.0260 (11)
H3	1.1190	1.1529	0.6176	0.031*
N4	0.9792 (5)	1.4296 (5)	0.8675 (4)	0.0269 (12)
O1	0.8061 (5)	0.4321 (4)	0.0666 (3)	0.0333 (11)
O2	0.6754 (5)	0.2834 (4)	0.1695 (4)	0.0331 (11)
O3	0.7064 (6)	0.8823 (4)	0.3105 (4)	0.0398 (13)
O4	0.6712 (6)	0.8746 (4)	0.1615 (4)	0.0411 (13)
O5	0.6942 (7)	0.5942 (5)	0.5749 (4)	0.0603 (18)
O6	0.7902 (4)	1.1165 (4)	0.3309 (3)	0.0270 (9)
O7	0.9238 (5)	1.0921 (5)	0.1893 (3)	0.0320 (11)
O8	1.4436 (5)	1.0967 (5)	0.1889 (4)	0.0333 (11)
O9	1.4993 (5)	1.0839 (5)	0.3355 (3)	0.0405 (12)
O10	0.9226 (5)	1.3484 (5)	0.5328 (4)	0.0421 (13)
O1W	0.9246 (5)	0.6839 (4)	−0.0658 (3)	0.0366 (11)
H1WA	0.8426	0.7036	−0.0440	0.044*
H1WB	0.9828	0.7414	−0.0764	0.044*
O2W	0.7208 (5)	1.0991 (5)	0.0330 (3)	0.0399 (12)
H2WA	0.8039	1.0888	0.0078	0.048*
H2WB	0.6856	1.1678	0.0062	0.048*
O3W	0.5839 (8)	0.1598 (5)	0.5164 (4)	0.0640 (19)
H3WA	0.6415	0.1444	0.4657	0.077*
H3WB	0.5633	0.0901	0.5562	0.077*
O4W	0.3038 (7)	0.1634 (8)	0.0325 (5)	0.084 (3)
H4WA	0.3255	0.1440	−0.0260	0.101*
H4WB	0.3604	0.1340	0.0701	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0279 (7)	0.0260 (6)	0.0239 (6)	−0.0029 (5)	−0.0040 (5)	−0.0097 (5)
Ho1	0.01438 (18)	0.01247 (18)	0.01903 (18)	0.00036 (11)	−0.00550 (11)	−0.00507 (11)
C1	0.021 (3)	0.019 (3)	0.027 (3)	0.002 (2)	−0.008 (2)	−0.008 (2)
C2	0.019 (3)	0.022 (3)	0.028 (3)	−0.001 (2)	−0.001 (2)	−0.002 (2)
C3	0.025 (3)	0.018 (3)	0.026 (3)	0.001 (2)	−0.008 (2)	−0.007 (2)
C4	0.020 (3)	0.021 (3)	0.029 (3)	0.002 (2)	−0.006 (2)	−0.006 (2)
C5	0.015 (3)	0.024 (3)	0.029 (3)	0.003 (2)	−0.002 (2)	−0.005 (2)
C6	0.027 (3)	0.018 (3)	0.026 (3)	0.000 (2)	−0.003 (3)	−0.006 (2)
C7	0.024 (3)	0.023 (3)	0.024 (3)	0.006 (2)	−0.007 (2)	−0.002 (3)
C8	0.017 (3)	0.024 (3)	0.029 (3)	0.000 (2)	−0.008 (2)	−0.005 (3)
C9	0.036 (4)	0.026 (3)	0.029 (3)	−0.005 (3)	−0.013 (3)	−0.005 (3)
C10	0.022 (3)	0.028 (3)	0.030 (3)	0.004 (2)	−0.010 (3)	−0.003 (3)
C11	0.044 (4)	0.036 (4)	0.032 (4)	0.003 (3)	−0.008 (3)	−0.011 (3)
C12	0.046 (5)	0.055 (5)	0.030 (4)	0.000 (4)	−0.008 (3)	−0.016 (4)
C13	0.037 (4)	0.037 (4)	0.037 (4)	−0.007 (3)	−0.017 (3)	0.000 (3)
C14	0.032 (4)	0.039 (4)	0.029 (3)	−0.007 (3)	−0.011 (3)	−0.005 (3)
C15	0.018 (3)	0.022 (3)	0.031 (3)	−0.003 (2)	−0.005 (3)	−0.010 (3)
C16	0.020 (3)	0.023 (3)	0.031 (3)	0.000 (2)	−0.008 (3)	−0.008 (3)
C17	0.023 (3)	0.027 (3)	0.025 (3)	0.002 (2)	−0.005 (2)	−0.005 (2)
C18	0.020 (3)	0.022 (3)	0.028 (3)	−0.001 (2)	−0.005 (2)	−0.007 (2)
C19	0.019 (3)	0.030 (3)	0.030 (3)	0.002 (2)	−0.013 (3)	−0.007 (3)
C20	0.023 (3)	0.024 (3)	0.026 (3)	0.005 (2)	−0.010 (2)	−0.011 (2)
C21	0.016 (3)	0.029 (3)	0.028 (3)	−0.001 (2)	−0.006 (2)	−0.010 (3)
C22	0.021 (3)	0.019 (3)	0.028 (3)	0.000 (2)	−0.003 (3)	−0.003 (2)
C23	0.019 (3)	0.034 (3)	0.026 (3)	0.001 (3)	−0.006 (3)	−0.011 (3)
C24	0.018 (3)	0.039 (4)	0.026 (3)	0.003 (3)	−0.007 (2)	−0.015 (3)
C25	0.029 (4)	0.038 (4)	0.025 (3)	0.000 (3)	−0.008 (3)	−0.008 (3)
C26	0.030 (4)	0.029 (3)	0.031 (3)	−0.001 (3)	−0.004 (3)	−0.013 (3)
C27	0.033 (4)	0.030 (4)	0.032 (4)	−0.005 (3)	−0.008 (3)	−0.004 (3)
C28	0.032 (4)	0.030 (3)	0.032 (3)	−0.006 (3)	−0.005 (3)	−0.014 (3)
N1	0.034 (3)	0.018 (3)	0.025 (3)	0.001 (2)	−0.006 (2)	0.001 (2)
N2	0.041 (4)	0.046 (4)	0.033 (3)	−0.002 (3)	−0.011 (3)	−0.002 (3)
N3	0.023 (3)	0.030 (3)	0.026 (3)	0.000 (2)	−0.004 (2)	−0.010 (2)
N4	0.024 (3)	0.032 (3)	0.028 (3)	−0.004 (2)	−0.005 (2)	−0.014 (2)
O1	0.033 (3)	0.039 (3)	0.029 (2)	−0.011 (2)	0.001 (2)	−0.011 (2)
O2	0.044 (3)	0.021 (2)	0.038 (3)	−0.004 (2)	−0.010 (2)	−0.009 (2)
O3	0.073 (4)	0.019 (2)	0.036 (3)	0.003 (2)	−0.031 (3)	−0.008 (2)
O4	0.074 (4)	0.021 (2)	0.032 (3)	0.001 (2)	−0.021 (3)	−0.003 (2)
O5	0.113 (6)	0.034 (3)	0.040 (3)	−0.025 (3)	−0.026 (3)	−0.001 (2)
O6	0.018 (2)	0.035 (2)	0.033 (2)	−0.0004 (18)	−0.0057 (18)	−0.0164 (19)
O7	0.026 (2)	0.048 (3)	0.027 (2)	−0.002 (2)	−0.0062 (19)	−0.020 (2)
O8	0.022 (2)	0.049 (3)	0.033 (3)	0.003 (2)	−0.007 (2)	−0.019 (2)
O9	0.018 (2)	0.074 (4)	0.032 (3)	0.006 (2)	−0.009 (2)	−0.013 (2)
O10	0.040 (3)	0.054 (3)	0.043 (3)	0.019 (2)	−0.022 (2)	−0.027 (2)
O1W	0.038 (3)	0.034 (3)	0.036 (3)	0.005 (2)	−0.005 (2)	−0.004 (2)
O2W	0.053 (3)	0.034 (3)	0.031 (3)	0.002 (2)	−0.008 (2)	−0.001 (2)
O3W	0.120 (6)	0.037 (3)	0.035 (3)	−0.023 (3)	−0.009 (3)	−0.008 (2)
O4W	0.059 (4)	0.155 (8)	0.039 (3)	0.029 (4)	−0.018 (3)	−0.022 (4)

Geometric parameters (Å, º) top

Co1—O1	2.098 (4)	C13—H13	0.9300
Co1—O1ⁱ	2.098 (4)	C14—H14	0.9300
Co1—N4ⁱⁱ	2.148 (5)	C15—O6	1.243 (7)
Co1—N4ⁱⁱⁱ	2.148 (5)	C15—O7	1.282 (7)
Co1—O1Wⁱ	2.176 (5)	C15—C16	1.502 (8)
Co1—O1W	2.176 (5)	C16—C21	1.373 (8)
Ho1—O2^iv	2.177 (4)	C16—C17	1.393 (9)
Ho1—O2W	2.278 (5)	C17—C18	1.367 (9)
Ho1—O9^v	2.307 (5)	C17—H17	0.9300
Ho1—O6	2.341 (4)	C18—C19	1.411 (8)
Ho1—O3	2.358 (4)	C18—C22	1.496 (8)
Ho1—O4	2.385 (4)	C19—C20	1.371 (9)
Ho1—O8^v	2.427 (5)	C19—H19	0.9300
Ho1—O7	2.426 (5)	C20—C21	1.408 (8)
Ho1—C22^v	2.745 (6)	C20—N3	1.412 (7)
C1—C6	1.393 (8)	C21—H21	0.9300
C1—C2	1.397 (8)	C22—O9	1.248 (7)
C1—C8	1.499 (8)	C22—O8	1.274 (8)
C2—C3	1.397 (8)	C23—O10	1.217 (8)
C2—H2	0.9300	C23—N3	1.370 (8)
C3—C4	1.381 (9)	C23—C24	1.506 (8)
C3—C7	1.494 (8)	C24—C28	1.379 (9)
C4—C5	1.393 (8)	C24—C25	1.394 (10)
C4—H4	0.9300	C25—C26	1.382 (9)
C5—C6	1.394 (8)	C25—H25	0.9300
C5—N1	1.403 (8)	C26—N4	1.324 (9)
C6—H6	0.9300	C26—H26	0.9300
C7—O3	1.254 (8)	C27—N4	1.358 (9)
C7—O4	1.261 (8)	C27—C28	1.377 (9)
C8—O1	1.242 (7)	C27—H27	0.9300
C8—O2	1.279 (7)	C28—H28	0.9300
C9—O5	1.212 (8)	N1—H1	0.8600
C9—N1	1.363 (8)	N3—H3	0.8600
C9—C10	1.498 (9)	O1W—H1WA	0.8500
C10—C14	1.382 (10)	O1W—H1WB	0.8510
C10—C11	1.409 (9)	O2W—H2WA	0.8500
C11—C12	1.370 (10)	O2W—H2WB	0.8520
C11—H11	0.9300	O3W—H3WA	0.8503
C12—N2	1.331 (10)	O3W—H3WB	0.8522
C12—H12	0.9300	O4W—H4WA	0.8514
C13—N2	1.315 (9)	O4W—H4WB	0.8504
C13—C14	1.385 (10)

O1—Co1—O1ⁱ	180.0 (2)	C12—C11—H11	120.4
O1—Co1—N4ⁱⁱ	92.16 (19)	C10—C11—H11	120.4
O1ⁱ—Co1—N4ⁱⁱ	87.84 (19)	N2—C12—C11	123.6 (7)
O1—Co1—N4ⁱⁱⁱ	87.84 (19)	N2—C12—H12	118.2
O1ⁱ—Co1—N4ⁱⁱⁱ	92.16 (19)	C11—C12—H12	118.2
N4ⁱⁱ—Co1—N4ⁱⁱⁱ	180.0 (3)	N2—C13—C14	124.7 (7)
O1—Co1—O1Wⁱ	85.97 (19)	N2—C13—H13	117.6
O1ⁱ—Co1—O1Wⁱ	94.03 (19)	C14—C13—H13	117.6
N4ⁱⁱ—Co1—O1Wⁱ	89.3 (2)	C10—C14—C13	118.4 (6)
N4ⁱⁱⁱ—Co1—O1Wⁱ	90.7 (2)	C10—C14—H14	120.8
O1—Co1—O1W	94.03 (19)	C13—C14—H14	120.8
O1ⁱ—Co1—O1W	85.97 (19)	O6—C15—O7	120.1 (5)
N4ⁱⁱ—Co1—O1W	90.7 (2)	O6—C15—C16	119.1 (5)
N4ⁱⁱⁱ—Co1—O1W	89.3 (2)	O7—C15—C16	120.8 (5)
O1Wⁱ—Co1—O1W	180.0 (2)	C21—C16—C17	120.8 (6)
O2^iv—Ho1—O2W	82.48 (17)	C21—C16—C15	116.6 (5)
O2^iv—Ho1—O9^v	89.62 (19)	C17—C16—C15	122.6 (5)
O2W—Ho1—O9^v	138.85 (17)	C18—C17—C16	119.6 (6)
O2^iv—Ho1—O6	81.57 (16)	C18—C17—H17	120.2
O2W—Ho1—O6	138.55 (17)	C16—C17—H17	120.2
O9^v—Ho1—O6	78.95 (15)	C17—C18—C19	120.3 (6)
O2^iv—Ho1—O3	153.22 (17)	C17—C18—C22	123.0 (6)
O2W—Ho1—O3	122.18 (16)	C19—C18—C22	116.7 (5)
O9^v—Ho1—O3	78.12 (19)	C20—C19—C18	119.9 (6)
O6—Ho1—O3	72.81 (15)	C20—C19—H19	120.1
O2^iv—Ho1—O4	152.59 (18)	C18—C19—H19	120.1
O2W—Ho1—O4	71.43 (17)	C19—C20—C21	119.7 (5)
O9^v—Ho1—O4	104.37 (19)	C19—C20—N3	119.3 (5)
O6—Ho1—O4	123.81 (16)	C21—C20—N3	121.0 (5)
O3—Ho1—O4	54.16 (15)	C16—C21—C20	119.6 (6)
O2^iv—Ho1—O8^v	84.81 (18)	C16—C21—H21	120.2
O2W—Ho1—O8^v	84.52 (17)	C20—C21—H21	120.2
O9^v—Ho1—O8^v	54.48 (15)	O9—C22—O8	118.7 (6)
O6—Ho1—O8^v	131.43 (15)	O9—C22—C18	120.9 (5)
O3—Ho1—O8^v	106.24 (18)	O8—C22—C18	120.4 (5)
O4—Ho1—O8^v	84.49 (17)	O9—C22—Ho1^vi	56.6 (3)
O2^iv—Ho1—O7	86.64 (18)	O8—C22—Ho1^vi	62.1 (3)
O2W—Ho1—O7	86.51 (17)	C18—C22—Ho1^vi	176.7 (4)
O9^v—Ho1—O7	133.46 (15)	O10—C23—N3	123.5 (6)
O6—Ho1—O7	54.60 (14)	O10—C23—C24	120.2 (6)
O3—Ho1—O7	84.87 (18)	N3—C23—C24	116.3 (5)
O4—Ho1—O7	99.70 (18)	C28—C24—C25	118.0 (6)
O8^v—Ho1—O7	168.33 (16)	C28—C24—C23	124.5 (6)
O2^iv—Ho1—C22^v	86.17 (18)	C25—C24—C23	117.5 (6)
O2W—Ho1—C22^v	112.05 (19)	C26—C25—C24	118.8 (6)
O9^v—Ho1—C22^v	26.84 (16)	C26—C25—H25	120.6
O6—Ho1—C22^v	104.75 (16)	C24—C25—H25	120.6
O3—Ho1—C22^v	92.79 (19)	N4—C26—C25	123.8 (6)
O4—Ho1—C22^v	95.75 (18)	N4—C26—H26	118.1
O8^v—Ho1—C22^v	27.66 (17)	C25—C26—H26	118.1
O7—Ho1—C22^v	158.98 (17)	N4—C27—C28	122.8 (6)
C6—C1—C2	120.0 (5)	N4—C27—H27	118.6
C6—C1—C8	120.6 (5)	C28—C27—H27	118.6
C2—C1—C8	119.2 (5)	C27—C28—C24	119.5 (6)
C3—C2—C1	118.7 (6)	C27—C28—H28	120.3
C3—C2—H2	120.6	C24—C28—H28	120.3
C1—C2—H2	120.6	C9—N1—C5	125.3 (5)
C4—C3—C2	121.3 (6)	C9—N1—H1	117.4
C4—C3—C7	118.1 (5)	C5—N1—H1	117.4
C2—C3—C7	120.6 (5)	C13—N2—C12	116.9 (6)
C3—C4—C5	120.0 (6)	C23—N3—C20	120.8 (5)
C3—C4—H4	120.0	C23—N3—H3	119.6
C5—C4—H4	120.0	C20—N3—H3	119.6
C4—C5—C6	119.2 (6)	C26—N4—C27	117.0 (6)
C4—C5—N1	122.4 (5)	C26—N4—Co1^vii	121.1 (4)
C6—C5—N1	118.4 (5)	C27—N4—Co1^vii	121.5 (4)
C1—C6—C5	120.7 (6)	C8—O1—Co1	144.4 (4)
C1—C6—H6	119.6	C8—O2—Ho1^viii	153.1 (4)
C5—C6—H6	119.6	C7—O3—Ho1	94.4 (4)
O3—C7—O4	118.3 (6)	C7—O4—Ho1	93.0 (4)
O3—C7—C3	120.6 (5)	C15—O6—Ho1	95.1 (3)
O4—C7—C3	121.0 (6)	C15—O7—Ho1	90.1 (4)
O1—C8—O2	124.3 (6)	C22—O8—Ho1^vi	90.2 (4)
O1—C8—C1	119.4 (5)	C22—O9—Ho1^vi	96.5 (4)
O2—C8—C1	116.3 (5)	Co1—O1W—H1WA	117.2
O5—C9—N1	123.5 (6)	Co1—O1W—H1WB	112.7
O5—C9—C10	119.3 (6)	H1WA—O1W—H1WB	117.3
N1—C9—C10	117.1 (5)	Ho1—O2W—H2WA	113.0
C14—C10—C11	117.2 (6)	Ho1—O2W—H2WB	110.9
C14—C10—C9	125.8 (6)	H2WA—O2W—H2WB	113.5
C11—C10—C9	116.9 (6)	H3WA—O3W—H3WB	108.4
C12—C11—C10	119.1 (7)	H4WA—O4W—H4WB	112.3

C6—C1—C2—C3	−0.6 (9)	C6—C5—N1—C9	161.2 (6)
C8—C1—C2—C3	−175.6 (5)	C14—C13—N2—C12	−0.4 (11)
C1—C2—C3—C4	2.4 (9)	C11—C12—N2—C13	−0.3 (12)
C1—C2—C3—C7	179.7 (6)	O10—C23—N3—C20	9.1 (10)
C2—C3—C4—C5	−1.0 (9)	C24—C23—N3—C20	−170.5 (5)
C7—C3—C4—C5	−178.4 (5)	C19—C20—N3—C23	132.3 (6)
C3—C4—C5—C6	−2.1 (9)	C21—C20—N3—C23	−47.7 (8)
C3—C4—C5—N1	179.5 (6)	C25—C26—N4—C27	−1.8 (10)
C2—C1—C6—C5	−2.5 (9)	C25—C26—N4—Co1^vii	171.2 (5)
C8—C1—C6—C5	172.4 (5)	C28—C27—N4—C26	3.5 (10)
C4—C5—C6—C1	3.9 (9)	C28—C27—N4—Co1^vii	−169.4 (5)
N1—C5—C6—C1	−177.7 (5)	O2—C8—O1—Co1	−122.1 (7)
C4—C3—C7—O3	16.9 (9)	C1—C8—O1—Co1	58.6 (10)
C2—C3—C7—O3	−160.6 (6)	N4ⁱⁱ—Co1—O1—C8	−28.2 (8)
C4—C3—C7—O4	−162.6 (6)	N4ⁱⁱⁱ—Co1—O1—C8	151.8 (8)
C2—C3—C7—O4	20.0 (9)	O1Wⁱ—Co1—O1—C8	60.9 (7)
C6—C1—C8—O1	−148.0 (6)	O1W—Co1—O1—C8	−119.1 (7)
C2—C1—C8—O1	26.9 (8)	O1—C8—O2—Ho1^viii	69.4 (12)
C6—C1—C8—O2	32.6 (8)	C1—C8—O2—Ho1^viii	−111.3 (9)
C2—C1—C8—O2	−152.5 (6)	O4—C7—O3—Ho1	3.2 (7)
O5—C9—C10—C14	−165.1 (7)	C3—C7—O3—Ho1	−176.3 (5)
N1—C9—C10—C14	18.0 (10)	O2^iv—Ho1—O3—C7	−179.7 (4)
O5—C9—C10—C11	10.0 (10)	O2W—Ho1—O3—C7	−25.1 (5)
N1—C9—C10—C11	−166.8 (6)	O9^v—Ho1—O3—C7	115.9 (4)
C14—C10—C11—C12	−0.2 (10)	O6—Ho1—O3—C7	−162.2 (4)
C9—C10—C11—C12	−175.8 (7)	O4—Ho1—O3—C7	−1.8 (4)
C10—C11—C12—N2	0.6 (12)	O8^v—Ho1—O3—C7	68.7 (4)
C11—C10—C14—C13	−0.4 (10)	O7—Ho1—O3—C7	−107.7 (4)
C9—C10—C14—C13	174.7 (6)	C22^v—Ho1—O3—C7	93.3 (4)
N2—C13—C14—C10	0.7 (11)	O3—C7—O4—Ho1	−3.1 (7)
O6—C15—C16—C21	−4.9 (9)	C3—C7—O4—Ho1	176.3 (5)
O7—C15—C16—C21	174.4 (6)	O2^iv—Ho1—O4—C7	179.8 (4)
O6—C15—C16—C17	176.2 (6)	O2W—Ho1—O4—C7	161.2 (5)
O7—C15—C16—C17	−4.6 (9)	O9^v—Ho1—O4—C7	−61.6 (4)
C21—C16—C17—C18	2.2 (9)	O6—Ho1—O4—C7	24.6 (5)
C15—C16—C17—C18	−179.0 (6)	O3—Ho1—O4—C7	1.8 (4)
C16—C17—C18—C19	−1.3 (9)	O8^v—Ho1—O4—C7	−112.8 (4)
C16—C17—C18—C22	180.0 (6)	O7—Ho1—O4—C7	78.2 (4)
C17—C18—C19—C20	−1.6 (9)	C22^v—Ho1—O4—C7	−87.5 (4)
C22—C18—C19—C20	177.2 (6)	O7—C15—O6—Ho1	4.0 (6)
C18—C19—C20—C21	3.5 (9)	C16—C15—O6—Ho1	−176.8 (5)
C18—C19—C20—N3	−176.5 (6)	O2^iv—Ho1—O6—C15	−94.1 (4)
C17—C16—C21—C20	−0.2 (9)	O2W—Ho1—O6—C15	−25.7 (5)
C15—C16—C21—C20	−179.2 (5)	O9^v—Ho1—O6—C15	174.6 (4)
C19—C20—C21—C16	−2.6 (9)	O3—Ho1—O6—C15	93.8 (4)
N3—C20—C21—C16	177.4 (6)	O4—Ho1—O6—C15	74.6 (4)
C17—C18—C22—O9	−167.3 (6)	O8^v—Ho1—O6—C15	−169.5 (3)
C19—C18—C22—O9	13.9 (9)	O7—Ho1—O6—C15	−2.2 (3)
C17—C18—C22—O8	12.4 (9)	C22^v—Ho1—O6—C15	−177.9 (4)
C19—C18—C22—O8	−166.4 (6)	O6—C15—O7—Ho1	−3.8 (6)
O10—C23—C24—C28	133.8 (7)	C16—C15—O7—Ho1	176.9 (5)
N3—C23—C24—C28	−46.7 (9)	O2^iv—Ho1—O7—C15	84.2 (4)
O10—C23—C24—C25	−42.3 (9)	O2W—Ho1—O7—C15	166.9 (4)
N3—C23—C24—C25	137.2 (6)	O9^v—Ho1—O7—C15	−2.1 (5)
C28—C24—C25—C26	2.3 (9)	O6—Ho1—O7—C15	2.2 (3)
C23—C24—C25—C26	178.6 (6)	O3—Ho1—O7—C15	−70.4 (4)
C24—C25—C26—N4	−1.1 (10)	O4—Ho1—O7—C15	−122.7 (4)
N4—C27—C28—C24	−2.4 (10)	O8^v—Ho1—O7—C15	127.1 (7)
C25—C24—C28—C27	−0.6 (10)	C22^v—Ho1—O7—C15	14.0 (7)
C23—C24—C28—C27	−176.7 (6)	O9—C22—O8—Ho1^vi	−2.7 (6)
O5—C9—N1—C5	6.6 (11)	C18—C22—O8—Ho1^vi	177.6 (5)
C10—C9—N1—C5	−176.7 (6)	O8—C22—O9—Ho1^vi	2.9 (6)
C4—C5—N1—C9	−20.3 (9)	C18—C22—O9—Ho1^vi	−177.4 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4W^ix	0.85	2.00	2.761 (8)	149
O1W—H1WB···O7^x	0.85	2.26	2.988 (7)	144
O2W—H2WB···N2^xi	0.85	1.96	2.699 (8)	145
O3W—H3WA···O6^viii	0.85	2.20	3.048 (8)	177
O3W—H3WB···O9^xii	0.85	2.20	3.054 (8)	177
O4W—H4WA···O4^ix	0.85	1.90	2.732 (8)	164
O4W—H4WB···O8^xiii	0.85	1.94	2.752 (8)	160
N1—H1···O3W	0.86	2.16	2.996 (7)	165
N3—H3···O3ⁱⁱ	0.86	2.16	2.933 (7)	150

Symmetry codes: (ii) −x+2, −y+2, −z+1; (viii) x, y−1, z; (ix) −x+1, −y+1, −z; (x) −x+2, −y+2, −z; (xi) x, y+1, z−1; (xii) −x+2, −y+1, −z+1; (xiii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	[CoHo₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M_r	1669.81
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	10.0597 (9), 10.7824 (10), 13.7261 (13)
α, β, γ (°)	79.141 (3), 78.801 (1), 86.578 (3)
V (Å³)	1433.9 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.20 × 0.14 × 0.10

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.574, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7154, 4968, 4756
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.123, 1.06
No. of reflections	4968
No. of parameters	430
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.89, −1.93

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
O1W—H1WA···O4Wⁱ	0.85	2.00	2.761 (8)	149
O1W—H1WB···O7ⁱⁱ	0.85	2.26	2.988 (7)	144
O2W—H2WB···N2ⁱⁱⁱ	0.85	1.96	2.699 (8)	145
O3W—H3WA···O6^iv	0.85	2.20	3.048 (8)	177
O3W—H3WB···O9^v	0.85	2.20	3.054 (8)	177
O4W—H4WA···O4ⁱ	0.85	1.90	2.732 (8)	164
O4W—H4WB···O8^vi	0.85	1.94	2.752 (8)	160
N1—H1···O3W	0.86	2.16	2.996 (7)	165
N3—H3···O3^vii	0.86	2.16	2.933 (7)	150

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

Acknowledgements

This work was supported by the Open Fund Project of Key Laboratories in Hunan Universities (grant No. 11 K009) and the Science Foundation of Hengyang Normal University of China (grant No. 10B67).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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