catena-Poly[[diaquaterbium(III)]-tetrakis(μ2-pyridine-4-carboxylato-κ2O:O′)-[diaquaterbium(III)]-bis(μ2-pyridine-4-carboxylato-κ2O:O′)]

Zhang, X.; Zhai, B.

doi:10.1107/S1600536811038487

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Pages m1439-m1440

https://doi.org/10.1107/S1600536811038487

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catena-Poly[[diaquaterbium(III)]-tetrakis(μ₂-pyridine-4-carboxylato-κ²O:O′)-[diaquaterbium(III)]-bis(μ₂-pyridine-4-carboxylato-κ²O:O′)]

Xiangfei Zhang ^a and Bin Zhai ^a ^*

^aDepartment of Chemistry, Shangqiu Normal University, Shangqiu 476000 Henan, People's Republic of China
^*Correspondence e-mail: zhaibin1978@163.com

(Received 10 August 2011; accepted 20 September 2011; online 30 September 2011)

The title complex, [Tb₂(C₆H₄NO₂)₆(H₂O)₄]_n, was isolated under hydrothermal conditions using the ligand pyridine-4-carboxylic acid (HL) and Tb₂O₃. The deprotonated L²⁻ ligands adopt bridging coordination modes. The central Tb^III atom is bridged by L²⁻ ligands, forming a polymeric chain parallel to the a axis. Supramolecular O—H⋯N interactions link the chains, building up a layer parallel to (010). O—H⋯O hydrogen bonds also occur. Two of the pyridine rings are disordered by rotation around the central C—N direction with occupancy ratios of 0.53 (1):0.47 (1).

Related literature

For the properties of metal-organic coordination polymers, see: Bradshaw et al. (2004 ); Singh & Roesky (2007 ); Rosi et al. (2002 ); Thirumurugan & Natarajan (2005 ); Thirumurugan et al. (2008 ); Forster & Cheetham (2002 ); Fan & Zhu (2007 ).

Experimental

Crystal data

[Tb₂(C₆H₄NO₂)₆(H₂O)₄]
M_r = 1122.52
Monoclinic, P 2₁ /c
a = 9.7008 (10) Å
b = 19.813 (2) Å
c = 11.6253 (12) Å
β = 112.009 (1)°
V = 2071.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.46 mm⁻¹
T = 293 K
0.26 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.466, T_max = 0.575
11208 measured reflections
4055 independent reflections
2998 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.105
S = 1.11
4055 reflections
259 parameters
148 restraints
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −1.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯N3ⁱ	0.84	1.96	2.787 (7)	168
O7—H72⋯N2ⁱⁱ	0.84	1.98	2.802 (5)	167
O8—H81⋯N1ⁱⁱⁱ	0.85	2.01	2.837 (7)	163
O8—H82⋯O7^iv	0.85	2.16	3.002 (5)	171
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038487/dn2711sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038487/dn2711Isup2.hkl

checkCIF report

Comment top

Nowadays the connection of metal-organic coordination polymers based on transition metals and multifunctional bridging ligands has proven to be a promising field due to their intriguing and beautiful topologies and potential functions in material chemistry (Singh & Roesky, 2007; Forster & Cheetham, 2002 ). Great effort has been devoted to prepare such materials (Rosi et al., 2002; Thirumurugan & Natarajan, 2005; Fan & Zhu, 2007; Bradshaw et al., 2004; Thirumurugan et al., 2008), for example, multidentate aromatic polycarboxylic acids including benzene-1,2-dicarboxylate, benzene-1,3-dicarboxylate, benzene-1,4-dicarboxylate, benzene-1,2,3-tricarboxylate, benzene-1,2,4-tricarboxylate, benzene-1,3,5- tricarboxylate and benzene-1,2,4,5-tetracarboxylate have been widely used for the syntheses of coordination polymers of transition metal ions, and the syntheses are mainly through the direct interaction between the metal ions and carboxylate groups to construct one-, two-, and three-dimensional networks in a variety of coordination modes. In general, carboxylate positions, functional groups and ligand conformations are important for syntheses of these hybrid materials. The ligand pyridine-4-carboxylic acid (H₂L) has proven to be a good building block for constructing functional coordination polymers. On the other hand, Tb³⁺ complex is strongly fluorescent, having a large fluorescence quantum yield and very long fluorescence lifetime.

In compound I, each Tb^III atom is bonded to six Oatoms from six different carboxylates (Tb–O = 2.424 (3)–2.491 (4) Å) and two water molecules (Tb–O_w = 2.531 (3)–2.559 (3) Å). The coordination geometry around Tb atom can also be described as a distorted square antiprism with O–Tb–O bond angles ranging from 70.52 (11) to 147.15 (11)°. Adjacent two Tb centers are connected together via four bridging carboxylates with the Tb···Tb distances of 4.349 Å, which are further extended by other two L^2-ligand to generate an infinite chain (Figure 1) which develop parallel to the a axis. All carboxylate groups in (I) adopt bridging modes and the potential N-donor coordination site still remains free.

O-H···N supramolecular interactions link the chain to form layers parallel to the (0 1 0) plane (Table 1, Fig. 2). There are also O-H···O intramolecular hydrogen bonds within the chains (Table 1).

Related literature top

For the properties of metal-organic coordination polymers, see: Bradshaw et al. (2004); Singh & Roesky (2007); Rosi et al. (2002); Thirumurugan & Natarajan (2005); Thirumurugan et al. (2008); Forster & Cheetham (2002); Fan & Zhu (2007).

Experimental top

Synthesis of [TbL₃(H₂O)₂]_n (I). A mixture of H₂L (0.3 mmol), Tb₂O₃(0.1 mmol) and H₂O (15 mL) were placed in a 25 mL Teflon-lined steel vessel and heated to 180 °C for 5 days, then cooled to room temperature. The resulting colorless block-shaped crystals of (I) were washed several times by water and diethyl ether. Elemental analysis calcd for (I) (%): C, 38.52; H, 2.87; N, 7.49. Found: C, 38.46; H, 2.94; N,7.45. Selected IR spectra for (I): ν (cm^-1) = 3449 s, 1632 s, 1401 m,745 m.

Structure description top

For the properties of metal-organic coordination polymers, see: Bradshaw et al. (2004); Singh & Roesky (2007); Rosi et al. (2002); Thirumurugan & Natarajan (2005); Thirumurugan et al. (2008); Forster & Cheetham (2002); Fan & Zhu (2007).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Partial view of the polymeric chain. Ellipsoids are drawn at the 30% probability level. H atoms and one component of the disordered pyridine rings have been omitted for clarity. [Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1]
	Fig. 2. Partial packing view showing the formation of layer through O-H···N hydrogen bonds. H atoms not involved in hydrogen bondings have been omitted for clarity.

catena-Poly[[diaquaterbium(III)]-tetrakis(µ₂-pyridine-4- carboxylato-κ²O:O')-[diaquaterbium(III)]-bis(µ₂- pyridine-4-carboxylato-κ²O:O')] top

Crystal data top

[Tb₂(C₆H₄NO₂)₆(H₂O)₄]	F(000) = 1096
M_r = 1122.52	D_x = 1.800 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5467 reflections
a = 9.7008 (10) Å	θ = 2.2–26.4°
b = 19.813 (2) Å	µ = 3.46 mm⁻¹
c = 11.6253 (12) Å	T = 293 K
β = 112.009 (1)°	Block, colourless
V = 2071.6 (4) Å³	0.26 × 0.20 × 0.18 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	4055 independent reflections
Radiation source: fine-focus sealed tube	2998 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −11→11
T_min = 0.466, T_max = 0.575	k = −10→24
11208 measured reflections	l = −14→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0526P)² + 5.420P] where P = (F_o² + 2F_c²)/3
4055 reflections	(Δ/σ)_max = 0.012
259 parameters	Δρ_max = 0.78 e Å⁻³
148 restraints	Δρ_min = −1.60 e Å⁻³

Crystal data top

[Tb₂(C₆H₄NO₂)₆(H₂O)₄]	V = 2071.6 (4) Å³
M_r = 1122.52	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7008 (10) Å	µ = 3.46 mm⁻¹
b = 19.813 (2) Å	T = 293 K
c = 11.6253 (12) Å	0.26 × 0.20 × 0.18 mm
β = 112.009 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4055 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	2998 reflections with I > 2σ(I)
T_min = 0.466, T_max = 0.575	R_int = 0.026
11208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	148 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.11	Δρ_max = 0.78 e Å⁻³
4055 reflections	Δρ_min = −1.60 e Å⁻³
259 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. The ISOR instruction are used for C16 C16' C17' C5 C5' C15 C15' C18' atoms to insolve their ADP alerts. The instructions of DFIX and DANG are used for H atoms on O7 and O8 water molecules, in order to place H atoms of water molecules in calculated positions as rigiding atoms. The SIMU and DELU instructions against C16 N3 C13 O6 C1 O2 atoms are used for insolveing their ADP alerts. In addition, the disordered C3 C4 C5 C6 and C3' C4' C5' C6' atoms are localized by the differece Fourier map, which are treated as disordered part with 0.5 occupancy. Whereas, the C15 C16 C17 C18 and C15' C16' C17' C18' atoms are treated as disordered part with free refinement.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Tb1	0.28030 (2)	0.499202 (11)	0.50935 (2)	0.01827 (11)
O1	0.3953 (4)	0.61276 (17)	0.5299 (3)	0.0248 (8)
O2	0.5886 (4)	0.60949 (17)	0.4690 (3)	0.0270 (8)
O3	0.3869 (4)	0.49073 (17)	0.3515 (3)	0.0253 (8)
O4	0.5557 (4)	0.49956 (19)	0.2667 (4)	0.0324 (10)
O5	0.0756 (4)	0.43450 (17)	0.3615 (3)	0.0235 (8)
O6	−0.1256 (4)	0.43637 (18)	0.4071 (3)	0.0274 (8)
O7	0.1132 (4)	0.57515 (17)	0.3392 (3)	0.0262 (8)
H71	0.1377	0.6148	0.3290	0.039*
H72	0.0602	0.5633	0.2667	0.039*
O8	0.1792 (4)	0.41684 (18)	0.6284 (3)	0.0267 (8)
H81	0.2344	0.3999	0.6975	0.040*
H82	0.0949	0.4233	0.6325	0.040*
N2	0.1002 (5)	0.4546 (3)	−0.1043 (4)	0.0355 (12)
C1	0.5085 (5)	0.6369 (2)	0.5182 (4)	0.0191 (10)
C2	0.5552 (6)	0.7071 (3)	0.5691 (5)	0.0263 (11)
C3	0.5412 (18)	0.7272 (6)	0.6767 (14)	0.065 (2)	0.53
H3	0.4991	0.6988	0.7183	0.078*	0.53
C4	0.5922 (18)	0.7922 (6)	0.7231 (14)	0.065 (2)	0.53
H4	0.5850	0.8049	0.7976	0.078*	0.53
N1	0.6468 (7)	0.8341 (3)	0.6704 (7)	0.0652 (19)
C5	0.6418 (18)	0.8184 (6)	0.5577 (13)	0.065 (2)	0.53
H5	0.6608	0.8519	0.5093	0.078*	0.53
C6	0.6088 (18)	0.7530 (6)	0.5098 (14)	0.065 (2)	0.53
H6	0.6236	0.7410	0.4379	0.078*	0.53
C3'	0.4669 (18)	0.7485 (7)	0.6043 (18)	0.065 (2)	0.47
H3'	0.3716	0.7349	0.5949	0.078*	0.47
C4'	0.5197 (17)	0.8116 (7)	0.6545 (18)	0.065 (2)	0.47
H4'	0.4566	0.8389	0.6778	0.078*	0.47
C5'	0.7305 (18)	0.7961 (7)	0.6254 (18)	0.065 (2)	0.47
H5'	0.8200	0.8139	0.6273	0.078*	0.47
C6'	0.6903 (17)	0.7308 (7)	0.5758 (18)	0.065 (2)	0.47
H6'	0.7527	0.7052	0.5490	0.078*	0.47
C7	0.4248 (6)	0.4912 (2)	0.2593 (5)	0.0205 (11)
C8	0.3085 (5)	0.4796 (3)	0.1332 (4)	0.0201 (10)
C9	0.3287 (7)	0.5057 (3)	0.0274 (5)	0.0286 (12)
H9A	0.4113	0.5317	0.0344	0.034*
C10	0.2195 (7)	0.4908 (3)	−0.0881 (5)	0.0353 (15)
H10A	0.2319	0.5076	−0.1583	0.042*
C11	0.0841 (6)	0.4311 (3)	−0.0041 (5)	0.0392 (15)
H11A	0.0013	0.4045	−0.0146	0.047*
C12	0.1823 (6)	0.4436 (3)	0.1157 (5)	0.0304 (12)
H12A	0.1626	0.4276	0.1832	0.037*
C13	−0.0423 (5)	0.4099 (2)	0.3623 (4)	0.0148 (9)
C14	−0.0838 (6)	0.3403 (3)	0.3060 (5)	0.0251 (11)
C15	−0.061 (2)	0.3205 (7)	0.2026 (15)	0.067 (2)	0.47
H15	−0.0141	0.3488	0.1647	0.080*	0.47
C16	−0.110 (2)	0.2552 (6)	0.1541 (16)	0.067 (2)	0.47
H16	−0.1138	0.2452	0.0748	0.080*	0.47
N3	−0.1491 (7)	0.2101 (3)	0.2112 (6)	0.0647 (19)
C17	−0.186 (2)	0.2304 (7)	0.3059 (16)	0.067 (2)	0.47
H17	−0.2300	0.1996	0.3416	0.080*	0.47
C18	−0.1591 (19)	0.2972 (7)	0.3543 (17)	0.067 (2)	0.47
H18	−0.1916	0.3112	0.4162	0.080*	0.47
C15'	0.0235 (16)	0.3043 (6)	0.2749 (17)	0.067 (2)	0.53
H15'	0.1159	0.3229	0.2870	0.080*	0.53
C16'	−0.0161 (15)	0.2386 (6)	0.2247 (17)	0.067 (2)	0.53
H16'	0.0504	0.2144	0.2003	0.080*	0.53
C17'	−0.2435 (15)	0.2459 (6)	0.2278 (17)	0.067 (2)	0.53
H17'	−0.3388	0.2285	0.2064	0.080*	0.53
C18'	−0.2165 (14)	0.3119 (6)	0.2774 (17)	0.067 (2)	0.53
H18'	−0.2923	0.3356	0.2901	0.080*	0.53

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.01824 (16)	0.01848 (16)	0.01805 (16)	−0.00263 (9)	0.00676 (11)	−0.00260 (9)
O1	0.0188 (17)	0.0176 (17)	0.040 (2)	−0.0057 (14)	0.0135 (16)	−0.0055 (15)
O2	0.029 (2)	0.0208 (18)	0.037 (2)	0.0011 (16)	0.0197 (17)	−0.0011 (16)
O3	0.034 (2)	0.031 (2)	0.0143 (17)	−0.0008 (15)	0.0121 (16)	−0.0015 (14)
O4	0.0171 (19)	0.060 (3)	0.0183 (19)	−0.0084 (17)	0.0044 (16)	−0.0052 (17)
O5	0.0218 (18)	0.0230 (18)	0.0260 (19)	−0.0100 (15)	0.0092 (15)	−0.0068 (15)
O6	0.0246 (18)	0.0276 (19)	0.035 (2)	0.0016 (16)	0.0164 (17)	−0.0087 (17)
O7	0.0292 (19)	0.0203 (18)	0.0194 (17)	−0.0051 (15)	−0.0019 (15)	0.0041 (14)
O8	0.0188 (17)	0.035 (2)	0.029 (2)	0.0054 (15)	0.0126 (15)	0.0136 (16)
N2	0.029 (3)	0.053 (3)	0.017 (2)	0.008 (2)	−0.001 (2)	−0.008 (2)
C1	0.019 (2)	0.013 (2)	0.023 (3)	−0.0017 (19)	0.004 (2)	0.0002 (18)
C2	0.021 (2)	0.023 (2)	0.032 (3)	−0.008 (2)	0.006 (2)	−0.007 (2)
C3	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C4	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
N1	0.069 (4)	0.037 (3)	0.097 (5)	−0.030 (3)	0.041 (4)	−0.040 (3)
C5	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C6	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C3'	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C4'	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C5'	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C6'	0.074 (5)	0.041 (3)	0.094 (5)	−0.032 (3)	0.050 (4)	−0.034 (3)
C7	0.022 (3)	0.026 (3)	0.011 (2)	0.000 (2)	0.004 (2)	−0.0010 (19)
C8	0.018 (2)	0.031 (3)	0.010 (2)	0.004 (2)	0.005 (2)	−0.001 (2)
C9	0.027 (3)	0.047 (3)	0.014 (2)	−0.001 (2)	0.010 (2)	−0.001 (2)
C10	0.036 (3)	0.056 (4)	0.012 (3)	0.012 (3)	0.007 (2)	0.001 (2)
C11	0.023 (3)	0.055 (4)	0.035 (3)	−0.010 (3)	0.005 (3)	−0.011 (3)
C12	0.025 (3)	0.046 (3)	0.019 (3)	−0.005 (3)	0.008 (2)	−0.003 (2)
C13	0.017 (2)	0.012 (2)	0.011 (2)	−0.0018 (18)	0.0005 (18)	−0.0014 (17)
C14	0.021 (2)	0.020 (2)	0.031 (3)	−0.003 (2)	0.006 (2)	−0.009 (2)
C15	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C16	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
N3	0.063 (4)	0.032 (3)	0.084 (5)	−0.016 (3)	0.011 (4)	−0.031 (3)
C17	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C18	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C15'	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C16'	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C17'	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)
C18'	0.061 (4)	0.039 (3)	0.108 (6)	−0.021 (3)	0.041 (4)	−0.043 (4)

Geometric parameters (Å, º) top

Tb1—O3	2.426 (4)	C6—H6	0.9300
Tb1—O6ⁱ	2.432 (3)	C3'—C4'	1.393 (14)
Tb1—O5	2.446 (3)	C3'—H3'	0.9300
Tb1—O2ⁱⁱ	2.466 (3)	C4'—H4'	0.9300
Tb1—O1	2.483 (3)	C5'—C6'	1.410 (14)
Tb1—O4ⁱⁱ	2.491 (4)	C5'—H5'	0.9300
Tb1—O7	2.530 (3)	C6'—H6'	0.9300
Tb1—O8	2.561 (3)	C7—C8	1.495 (7)
O1—C1	1.250 (6)	C8—C12	1.365 (7)
O2—C1	1.249 (5)	C8—C9	1.414 (7)
O2—Tb1ⁱⁱ	2.466 (3)	C9—C10	1.395 (8)
O3—C7	1.258 (6)	C9—H9A	0.9300
O4—C7	1.250 (7)	C10—H10A	0.9300
O4—Tb1ⁱⁱ	2.491 (4)	C11—C12	1.383 (7)
O5—C13	1.247 (6)	C11—H11A	0.9300
O6—C13	1.232 (6)	C12—H12A	0.9300
O6—Tb1ⁱ	2.432 (3)	C13—C14	1.513 (6)
O7—H71	0.8413	C14—C18'	1.329 (12)
O7—H72	0.8403	C14—C15	1.360 (13)
O8—H81	0.8508	C14—C18	1.374 (14)
O8—H82	0.8460	C14—C15'	1.415 (12)
N2—C10	1.314 (8)	C15—C16	1.421 (14)
N2—C11	1.316 (8)	C15—H15	0.9300
C1—C2	1.513 (7)	C16—N3	1.252 (14)
C2—C3'	1.356 (13)	C16—H16	0.9300
C2—C6	1.357 (12)	N3—C17'	1.230 (12)
C2—C6'	1.367 (13)	N3—C17	1.338 (14)
C2—C3	1.368 (12)	N3—C16'	1.362 (13)
C3—C4	1.411 (13)	C17—C18	1.423 (14)
C3—H3	0.9300	C17—H17	0.9300
C4—N1	1.261 (12)	C18—H18	0.9300
C4—H4	0.9300	C15'—C16'	1.419 (13)
N1—C4'	1.259 (13)	C15'—H15'	0.9300
N1—C5	1.331 (13)	C16'—H16'	0.9300
N1—C5'	1.349 (13)	C17'—C18'	1.412 (13)
C5—C6	1.401 (13)	C17'—H17'	0.9300
C5—H5	0.9300	C18'—H18'	0.9300

O3—Tb1—O6ⁱ	147.12 (12)	C2—C3'—H3'	120.1
O3—Tb1—O5	84.03 (12)	C4'—C3'—H3'	120.1
O6ⁱ—Tb1—O5	95.50 (12)	N1—C4'—C3'	124.5 (13)
O3—Tb1—O2ⁱⁱ	70.56 (12)	N1—C4'—H4'	117.8
O6ⁱ—Tb1—O2ⁱⁱ	142.13 (12)	C3'—C4'—H4'	117.8
O5—Tb1—O2ⁱⁱ	82.30 (12)	N1—C5'—C6'	123.8 (12)
O3—Tb1—O1	80.33 (11)	N1—C5'—H5'	118.1
O6ⁱ—Tb1—O1	78.94 (12)	C6'—C5'—H5'	118.1
O5—Tb1—O1	139.44 (12)	C2—C6'—C5'	116.9 (12)
O2ⁱⁱ—Tb1—O1	125.85 (13)	C2—C6'—H6'	121.6
O3—Tb1—O4ⁱⁱ	120.33 (13)	C5'—C6'—H6'	121.6
O6ⁱ—Tb1—O4ⁱⁱ	79.95 (13)	O4—C7—O3	123.8 (5)
O5—Tb1—O4ⁱⁱ	140.54 (12)	O4—C7—C8	117.5 (4)
O2ⁱⁱ—Tb1—O4ⁱⁱ	78.39 (12)	O3—C7—C8	118.7 (5)
O1—Tb1—O4ⁱⁱ	78.61 (12)	C12—C8—C9	118.1 (5)
O3—Tb1—O7	77.28 (12)	C12—C8—C7	122.1 (5)
O6ⁱ—Tb1—O7	71.90 (12)	C9—C8—C7	119.8 (5)
O5—Tb1—O7	69.43 (12)	C10—C9—C8	117.2 (6)
O2ⁱⁱ—Tb1—O7	138.97 (12)	C10—C9—H9A	121.4
O1—Tb1—O7	70.70 (11)	C8—C9—H9A	121.4
O4ⁱⁱ—Tb1—O7	141.47 (12)	N2—C10—C9	124.4 (5)
O3—Tb1—O8	136.28 (12)	N2—C10—H10A	117.8
O6ⁱ—Tb1—O8	72.55 (12)	C9—C10—H10A	117.8
O5—Tb1—O8	70.81 (12)	N2—C11—C12	124.2 (5)
O2ⁱⁱ—Tb1—O8	71.07 (11)	N2—C11—H11A	117.9
O1—Tb1—O8	140.79 (12)	C12—C11—H11A	117.9
O4ⁱⁱ—Tb1—O8	70.46 (12)	C8—C12—C11	118.9 (5)
O7—Tb1—O8	122.57 (11)	C8—C12—H12A	120.5
C1—O1—Tb1	135.8 (3)	C11—C12—H12A	120.5
C1—O2—Tb1ⁱⁱ	135.9 (3)	O6—C13—O5	125.9 (4)
C7—O3—Tb1	171.2 (4)	O6—C13—C14	117.5 (4)
C7—O4—Tb1ⁱⁱ	107.9 (3)	O5—C13—C14	116.7 (4)
C13—O5—Tb1	134.8 (3)	C18'—C14—C15	96.9 (10)
C13—O6—Tb1ⁱ	173.6 (3)	C18'—C14—C18	39.1 (10)
Tb1—O7—H71	122.2	C15—C14—C18	118.0 (9)
Tb1—O7—H72	126.1	C18'—C14—C15'	117.3 (8)
H71—O7—H72	102.6	C15—C14—C15'	41.4 (9)
Tb1—O8—H81	122.0	C18—C14—C15'	110.2 (9)
Tb1—O8—H82	120.6	C18'—C14—C13	124.7 (7)
H81—O8—H82	106.6	C15—C14—C13	122.8 (7)
C10—N2—C11	117.1 (5)	C18—C14—C13	119.0 (7)
O2—C1—O1	127.3 (5)	C15'—C14—C13	117.9 (6)
O2—C1—C2	115.6 (4)	C14—C15—C16	118.1 (13)
O1—C1—C2	117.1 (4)	C14—C15—H15	120.9
C3'—C2—C6	98.8 (10)	C16—C15—H15	120.9
C3'—C2—C6'	118.3 (8)	N3—C16—C15	124.2 (14)
C6—C2—C6'	42.0 (9)	N3—C16—H16	117.9
C3'—C2—C3	42.0 (9)	C15—C16—H16	117.9
C6—C2—C3	117.2 (8)	C17'—N3—C16	93.6 (12)
C6'—C2—C3	105.6 (10)	C17'—N3—C17	41.9 (11)
C3'—C2—C1	123.0 (7)	C16—N3—C17	116.6 (9)
C6—C2—C1	122.2 (7)	C17'—N3—C16'	118.1 (9)
C6'—C2—C1	118.7 (7)	C16—N3—C16'	46.0 (10)
C3—C2—C1	120.5 (6)	C17—N3—C16'	108.1 (10)
C2—C3—C4	118.3 (11)	N3—C17—C18	122.7 (13)
C2—C3—H3	120.8	N3—C17—H17	118.6
C4—C3—H3	120.8	C18—C17—H17	118.6
N1—C4—C3	124.6 (12)	C14—C18—C17	117.5 (12)
N1—C4—H4	117.7	C14—C18—H18	121.3
C3—C4—H4	117.7	C17—C18—H18	121.3
C4'—N1—C4	43.1 (10)	C14—C15'—C16'	117.1 (11)
C4'—N1—C5	95.7 (11)	C14—C15'—H15'	121.4
C4—N1—C5	117.2 (8)	C16'—C15'—H15'	121.4
C4'—N1—C5'	116.3 (9)	N3—C16'—C15'	121.7 (11)
C4—N1—C5'	104.1 (10)	N3—C16'—H16'	119.1
C5—N1—C5'	44.9 (10)	C15'—C16'—H16'	119.1
N1—C5—C6	121.8 (12)	N3—C17'—C18'	124.3 (12)
N1—C5—H5	119.1	N3—C17'—H17'	117.9
C6—C5—H5	119.1	C18'—C17'—H17'	117.9
C2—C6—C5	119.5 (11)	C14—C18'—C17'	120.6 (11)
C2—C6—H6	120.2	C14—C18'—H18'	119.7
C5—C6—H6	120.2	C17'—C18'—H18'	119.7
C2—C3'—C4'	119.7 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···N3ⁱⁱⁱ	0.84	1.96	2.787 (7)	168
O7—H72···N2^iv	0.84	1.98	2.802 (5)	167
O8—H81···N1^v	0.85	2.01	2.837 (7)	163
O8—H82···O7ⁱ	0.85	2.16	3.002 (5)	171

Symmetry codes: (i) −x, −y+1, −z+1; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z; (v) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Tb₂(C₆H₄NO₂)₆(H₂O)₄]
M_r	1122.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.7008 (10), 19.813 (2), 11.6253 (12)
β (°)	112.009 (1)
V (Å³)	2071.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.46
Crystal size (mm)	0.26 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.466, 0.575
No. of measured, independent and observed [I > 2σ(I)] reflections	11208, 4055, 2998
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.105, 1.11
No. of reflections	4055
No. of parameters	259
No. of restraints	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −1.60

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···N3ⁱ	0.84	1.96	2.787 (7)	167.8
O7—H72···N2ⁱⁱ	0.84	1.98	2.802 (5)	167.1
O8—H81···N1ⁱⁱⁱ	0.85	2.01	2.837 (7)	162.6
O8—H82···O7^iv	0.85	2.16	3.002 (5)	170.7

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x, −y+1, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21001071), the Natural Science Research Program of the Education Department of Henan Province (2010A150018) and the Youth Fund Program of Shangqiu Normal University.

References

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