Poly[[penta­aqua­(μ4-pyridine-2,4,6-tri­carboxyl­ato)(μ3-pyridine-2,4,6-tri­carboxyl­ato)diterbium(III)] mono­hydrate]

Yu, X.-K.; Zhu, H.-L.

doi:10.1107/S1600536812032898

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1133-m1134

https://doi.org/10.1107/S1600536812032898

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Poly[[pentaaqua(μ₄-pyridine-2,4,6-tricarboxylato)(μ₃-pyridine-2,4,6-tricarboxylato)diterbium(III)] monohydrate]

Xiao-Ke Yu ^a and Hong-Lin Zhu ^a ^*

^aCenter of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: zhuhonglin1@nbu.edu.cn

(Received 23 May 2012; accepted 20 July 2012; online 28 July 2012)

The three-dimensional title coordination polymer, {[Tb₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O}_n, was hydrothermally synthesized by reacting the corresponding rare-earth salt with pyridine-2,4,6-tricarboxylic acid (H₃ptc). There are two independent Tb^III atoms in the structure, one of which is nine-coordinated, forming a monocapped NO₈ square-antiprism and the other is eight-coordinated exhibiting a 4,4-bicapped NO₇ trigonal–prismatic environment. The complex units are interconnected through the ptc³⁻ anions acting in different coordination modes, resulting in a three-dimensional coordination polymer. The crystal structure features extensive O—H⋯O hydrogen bonds.

Related literature

For general background to the design and synthesis of metal organic frameworks (MOFs) with lanthanides, see: Wang et al. (2007 ); Fu & Xu (2008 ); Das et al. (2009 ). For related structures, see: Lin et al. (2011 ).

Experimental

Crystal data

[Tb₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O
M_r = 842.15
Monoclinic, P 2₁ /n
a = 18.426 (4) Å
b = 6.9082 (14) Å
c = 18.583 (4) Å
β = 111.98 (3)°
V = 2193.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 6.50 mm⁻¹
T = 293 K
0.38 × 0.34 × 0.31 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.101, T_max = 0.128
20352 measured reflections
4912 independent reflections
4764 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.045
S = 1.20
4912 reflections
344 parameters
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Tb1—O1ⁱ	2.508 (2)
Tb1—O2	2.400 (2)
Tb1—O6	2.378 (2)
Tb1—O7	2.426 (2)
Tb1—O8	2.406 (2)
Tb1—O9	2.431 (2)
Tb1—O12	2.590 (2)
Tb1—O13	2.489 (2)
Tb1—N1	2.534 (2)
Tb2—O3ⁱⁱ	2.365 (2)
Tb2—O4ⁱⁱⁱ	2.387 (2)
Tb2—O10^iv	2.336 (2)
Tb2—O11	2.403 (2)
Tb2—O15	2.384 (2)
Tb2—O16	2.430 (2)
Tb2—O17	2.358 (2)
Tb2—N2	2.507 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) -x+1, -y+1, -z+1; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O14^v	0.84	1.86	2.700 (3)	174.4
O7—H7B⋯O2ⁱ	0.87	1.80	2.651 (3)	164.8
O8—H8A⋯O12ⁱⁱⁱ	0.85	1.89	2.741 (3)	176.0
O8—H8B⋯O9^vi	0.86	2.39	2.844 (3)	113.0
O9—H9A⋯O5^v	0.85	2.56	3.057 (3)	119.0
O9—H9A⋯O6^v	0.85	1.86	2.711 (3)	176.0
O9—H9B⋯O5^v	0.85	2.56	3.057 (3)	118.0
O16—H16A⋯O4^v	0.85	2.30	3.101 (3)	156.2
O16—H16B⋯O15^vii	0.81	1.96	2.766 (3)	171.0
O17—H17A⋯O18^iv	0.87	1.84	2.705 (4)	173.9
O17—H17B⋯O5^viii	0.82	1.95	2.759 (3)	163.6
O18—H18A⋯O14^ix	0.87	2.04	2.911 (4)	175.7
O18—H18B⋯O13	0.83	1.92	2.745 (4)	167.1
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+1, -y, -z+1; (vi) x, y+1, z; (vii) -x+1, -y, -z+2; (viii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ix) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812032898/bg2463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032898/bg2463Isup2.hkl

checkCIF report

Comment top

In recent years, the design and synthesis of metal organic frameworks (MOFs) with lanthanide have become an fascinating field due to their potential applications in luminescent materials, magnetic, catalyst and gas absorption (Wang et al., 2007). Multicarboxylic acids were widely used as organic linkers in the syntheses of MOFs such as phthalic acid, trimesic acid and pyromellitic acid. In addition, pyridine-2,4,6-tricarboxylato(H₃ptc) is a good building unit for constructing MFOs due to the existence of both N and O atoms in the ligands (Fu et al., 2008). Another reason for choosing H₃ptc is the inherent negative charge associated with them that helps in the charge compensation of the metal ion in the framework (Das et al., 2009). At the same time, Lanthanide complexes with aromatic carboxylic acids show higher thermal or luminescence stabilities for practical application than other lanthanide complex systems. Thus we design and synthesis the title compound prepared from Tb₄O₇ and pyridine-2, 4, 6-tricarboxylic acid.

The asymmetric unit of [Tb₂(H₂O)₅(ptc)₂]_n.nH₂O consists of two Tb³⁺ ions (Tb1,Tb2), two ptc^3- ions, five aqua ligands, and a lattice water as illustrated in Fig. 1. Its worth to mention,The Tb1 atoms is nine-coordinated fashion by three aqua ligands (O7, O8 and O9) as well as three ptc ligands to generate a distorted monocapped squarean-tiprismatic DyNO8 chromophore with d(Tb1—N1) = 2.517 (2) Å and d(Tb1—O) = 2.366–2.566 Å, and Tb2 is eight-coordinated fashion by two aqua ligands (O4 and O9) as well as three ptc ligands texhibit a 4,4-bicapped trigonal prismatic TbNO7 chromophore with d(Tb2—N2) = 2.486 (2) Å and d(Tb2—O) = 2.320–2.415 Å, respectively (Lin et al., 2011). Interestingly, the C7—O14 distance in pyridine-2, 4, 6-tricarboxylic acid is significantly shorter than that of corresponding C—O distance due to the the adjacent molecular's close packing. The three-dimensional polymer is constructed by the Tb₂ building units through ptc^3- anions in different coordination modes.

Related literature top

For general background to the design and synthesis of metal organic frameworks (MOFs) with lanthanides, see: Wang et al., (2007); Fu et al. (2008); Das et al. (2009). For related structures, see: Lin et al. (2011)

Experimental top

Pale green powder of TbCl₃.nH₂O was obtained by slow evaporation of a solution of Tb₄O₇(0.25 mmol, 0.185 g) dissolved in 10 ml HCl(1 M) under water boiling condition. The freshly prepared TbCl₃.nH₂O, H₃ptc(0.054 g, 0.25 mmol), malonic acid(0.026 g, 0.25 mmol),15 ml H₂O and 1 ml NaOH(1 M) were sealed in a 23 ml Teflon-lined stainless autoclave, which was heated at 453 K for three days and thereafter cooled slowly to room temperature, and Pale green crystals were seperated by filtering and washing.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top

	Fig. 1. ORTEP view of the title compound, The dispalcement ellipsoids are drawn at 45% probability dispalcement ellipsoids. Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) x, y, z + 1; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1/2, y - 1/2, -z + 3/2.
	Fig. 2. the three-dimensional structure of title complex.

Poly[[pentaaqua(µ₄-pyridine-2,4,6-tricarboxylato)(µ₃-pyridine- 2,4,6-tricarboxylato)diterbium(III)] monohydrate] top

Crystal data top

[Tb₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O	Z = 4
M_r = 842.15	F(000) = 1600
Monoclinic, P2₁/n	D_x = 2.550 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 18.426 (4) Å	θ = 3.2–27.5°
b = 6.9082 (14) Å	µ = 6.50 mm⁻¹
c = 18.583 (4) Å	T = 293 K
β = 111.98 (3)°	Block, colorless
V = 2193.6 (8) Å³	0.38 × 0.34 × 0.31 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	4912 independent reflections
Radiation source: fine-focus sealed tube	4764 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 27.3°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→23
T_min = 0.101, T_max = 0.128	k = −8→8
20352 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.020	H-atom parameters constrained
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.P)² + 4.3115P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max = 0.002
4912 reflections	Δρ_max = 1.07 e Å⁻³
344 parameters	Δρ_min = −1.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00271 (8)

Crystal data top

[Tb₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O	V = 2193.6 (8) Å³
M_r = 842.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 18.426 (4) Å	µ = 6.50 mm⁻¹
b = 6.9082 (14) Å	T = 293 K
c = 18.583 (4) Å	0.38 × 0.34 × 0.31 mm
β = 111.98 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	4912 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4764 reflections with I > 2σ(I)
T_min = 0.101, T_max = 0.128	R_int = 0.041
20352 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.20	Δρ_max = 1.07 e Å⁻³
4912 reflections	Δρ_min = −1.33 e Å⁻³
344 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
Tb1	0.373479 (7)	0.223057 (19)	0.377229 (7)	0.00937 (5)
Tb2	0.375301 (8)	0.251927 (17)	0.896094 (8)	0.00979 (5)
N1	0.42976 (13)	0.3322 (3)	0.27869 (13)	0.0120 (4)
C1	0.38349 (15)	0.4121 (4)	0.21132 (16)	0.0114 (5)
C2	0.40676 (16)	0.4340 (4)	0.14843 (16)	0.0133 (5)
H2A	0.3734	0.4880	0.1020	0.016*
C3	0.48211 (16)	0.3717 (4)	0.15760 (16)	0.0118 (5)
C4	0.53247 (16)	0.3018 (4)	0.22990 (16)	0.0124 (5)
H4A	0.5838	0.2683	0.2381	0.015*
C5	0.50402 (16)	0.2835 (4)	0.28911 (17)	0.0117 (5)
C6	0.30262 (16)	0.4654 (4)	0.20976 (16)	0.0129 (5)
O1	0.25948 (12)	0.5738 (3)	0.15823 (12)	0.0172 (4)
O2	0.28622 (12)	0.3911 (3)	0.26523 (12)	0.0199 (5)
C7	0.50831 (16)	0.3728 (4)	0.08905 (15)	0.0118 (5)
O3	0.45963 (13)	0.3158 (3)	0.02548 (12)	0.0209 (4)
O4	0.57796 (12)	0.4253 (3)	0.10240 (12)	0.0161 (4)
C8	0.55027 (16)	0.2057 (4)	0.36969 (16)	0.0128 (5)
O5	0.62146 (12)	0.1821 (4)	0.39036 (13)	0.0265 (5)
O6	0.50974 (12)	0.1686 (3)	0.41138 (12)	0.0177 (4)
O7	0.36674 (12)	−0.0446 (3)	0.29048 (12)	0.0209 (5)
H7B	0.3178	−0.0743	0.2654	0.025*
H7A	0.3876	−0.0504	0.2574	0.025*
O8	0.40741 (13)	0.5604 (3)	0.39763 (14)	0.0258 (5)
H8A	0.4527	0.6096	0.4200	0.031*
H8B	0.3682	0.5986	0.4083	0.031*
O9	0.37823 (13)	−0.0719 (3)	0.45020 (12)	0.0213 (5)
H9A	0.4149	−0.0984	0.4934	0.026*
H9B	0.3420	−0.1105	0.4649	0.026*
N2	0.38187 (14)	0.2851 (3)	0.76431 (14)	0.0118 (5)
C9	0.31950 (16)	0.3532 (4)	0.70517 (16)	0.0127 (5)
C10	0.31708 (17)	0.3629 (4)	0.62886 (16)	0.0148 (6)
H10A	0.2727	0.4069	0.5885	0.018*
C11	0.38337 (16)	0.3044 (4)	0.61552 (16)	0.0134 (5)
C12	0.44858 (17)	0.2370 (4)	0.67751 (17)	0.0124 (6)
H12A	0.4938	0.2006	0.6699	0.015*
C13	0.44498 (17)	0.2250 (4)	0.75132 (17)	0.0122 (5)
C14	0.25274 (16)	0.4193 (4)	0.72878 (16)	0.0138 (5)
O10	0.19299 (12)	0.4879 (3)	0.67646 (12)	0.0202 (4)
O11	0.26267 (12)	0.3988 (3)	0.79939 (12)	0.0215 (5)
C15	0.38344 (17)	0.3049 (4)	0.53373 (16)	0.0144 (5)
O12	0.44733 (13)	0.2845 (3)	0.52418 (13)	0.0209 (5)
O13	0.31908 (12)	0.3159 (3)	0.47642 (12)	0.0194 (4)
C16	0.50943 (16)	0.1457 (4)	0.82340 (16)	0.0121 (5)
O14	0.57132 (12)	0.0860 (3)	0.81932 (12)	0.0194 (4)
O15	0.49393 (12)	0.1463 (3)	0.88514 (11)	0.0184 (4)
O16	0.39547 (13)	−0.0436 (3)	0.97204 (12)	0.0226 (5)
H16B	0.4251	−0.0676	1.0162	0.027*
H16A	0.3898	−0.1570	0.9529	0.027*
O17	0.28287 (12)	0.3108 (4)	0.95346 (13)	0.0257 (5)
H17B	0.2358	0.3132	0.9261	0.031*
H17A	0.2806	0.2465	0.9929	0.031*
O18	0.21272 (15)	0.6101 (4)	0.42001 (15)	0.0346 (6)
H18B	0.2389	0.5106	0.4367	0.041*
H18A	0.1688	0.5550	0.3908	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.00889 (8)	0.01244 (7)	0.00678 (8)	0.00037 (4)	0.00293 (6)	0.00027 (4)
Tb2	0.00709 (8)	0.01571 (8)	0.00572 (8)	−0.00047 (4)	0.00141 (6)	0.00003 (4)
N1	0.0092 (11)	0.0155 (12)	0.0108 (11)	0.0008 (9)	0.0032 (10)	0.0015 (9)
C1	0.0086 (13)	0.0135 (13)	0.0111 (13)	0.0009 (10)	0.0023 (11)	0.0012 (10)
C2	0.0116 (13)	0.0156 (14)	0.0097 (13)	0.0002 (10)	0.0005 (11)	0.0028 (10)
C3	0.0130 (13)	0.0123 (13)	0.0105 (13)	−0.0037 (10)	0.0050 (11)	−0.0019 (9)
C4	0.0102 (13)	0.0136 (13)	0.0129 (14)	−0.0026 (10)	0.0040 (11)	−0.0009 (10)
C5	0.0099 (13)	0.0134 (13)	0.0105 (14)	−0.0017 (10)	0.0025 (12)	−0.0005 (10)
C6	0.0095 (13)	0.0166 (14)	0.0106 (13)	0.0004 (10)	0.0016 (11)	−0.0001 (10)
O1	0.0122 (10)	0.0235 (11)	0.0148 (10)	0.0044 (8)	0.0038 (9)	0.0062 (8)
O2	0.0130 (10)	0.0310 (12)	0.0174 (11)	0.0059 (8)	0.0076 (9)	0.0106 (9)
C7	0.0139 (13)	0.0121 (13)	0.0093 (13)	0.0016 (10)	0.0044 (11)	0.0018 (9)
O3	0.0208 (11)	0.0298 (12)	0.0091 (10)	−0.0040 (9)	0.0022 (9)	−0.0026 (9)
O4	0.0141 (10)	0.0208 (11)	0.0154 (10)	−0.0023 (8)	0.0080 (9)	0.0000 (8)
C8	0.0106 (13)	0.0146 (13)	0.0114 (13)	0.0002 (10)	0.0021 (12)	−0.0003 (10)
O5	0.0103 (11)	0.0439 (15)	0.0230 (13)	0.0050 (9)	0.0037 (10)	0.0105 (10)
O6	0.0130 (10)	0.0271 (12)	0.0133 (10)	0.0051 (8)	0.0051 (9)	0.0060 (8)
O7	0.0140 (10)	0.0330 (12)	0.0176 (11)	−0.0037 (9)	0.0081 (9)	−0.0103 (9)
O8	0.0238 (12)	0.0199 (12)	0.0321 (13)	−0.0043 (9)	0.0086 (11)	−0.0055 (9)
O9	0.0241 (12)	0.0237 (11)	0.0151 (11)	0.0032 (9)	0.0063 (10)	0.0067 (8)
N2	0.0100 (11)	0.0143 (11)	0.0097 (12)	−0.0011 (9)	0.0022 (10)	−0.0004 (9)
C9	0.0130 (13)	0.0137 (13)	0.0104 (13)	0.0008 (10)	0.0033 (11)	0.0008 (10)
C10	0.0136 (14)	0.0191 (14)	0.0092 (13)	0.0036 (10)	0.0013 (12)	0.0026 (10)
C11	0.0159 (14)	0.0146 (13)	0.0095 (14)	−0.0004 (11)	0.0043 (12)	−0.0023 (10)
C12	0.0125 (14)	0.0157 (14)	0.0096 (14)	0.0016 (9)	0.0049 (12)	−0.0007 (9)
C13	0.0114 (14)	0.0120 (13)	0.0128 (14)	0.0002 (10)	0.0039 (12)	−0.0005 (10)
C14	0.0130 (13)	0.0150 (13)	0.0127 (13)	0.0021 (10)	0.0038 (12)	−0.0001 (10)
O10	0.0159 (10)	0.0283 (12)	0.0122 (10)	0.0099 (9)	0.0006 (9)	0.0038 (8)
O11	0.0154 (11)	0.0391 (13)	0.0102 (10)	0.0086 (9)	0.0052 (9)	0.0039 (9)
C15	0.0191 (15)	0.0151 (14)	0.0095 (13)	0.0016 (11)	0.0060 (12)	−0.0002 (10)
O12	0.0166 (11)	0.0344 (12)	0.0119 (11)	0.0012 (9)	0.0056 (10)	−0.0019 (9)
O13	0.0169 (11)	0.0307 (12)	0.0095 (10)	0.0043 (9)	0.0036 (9)	−0.0018 (9)
C16	0.0107 (13)	0.0140 (13)	0.0099 (13)	−0.0010 (10)	0.0021 (11)	−0.0005 (10)
O14	0.0131 (10)	0.0293 (12)	0.0167 (11)	0.0063 (8)	0.0067 (9)	0.0022 (8)
O15	0.0125 (10)	0.0332 (12)	0.0091 (10)	0.0071 (8)	0.0035 (9)	0.0043 (8)
O16	0.0265 (12)	0.0206 (11)	0.0132 (11)	0.0038 (9)	−0.0011 (10)	0.0027 (8)
O17	0.0107 (10)	0.0488 (15)	0.0182 (12)	0.0049 (10)	0.0060 (10)	0.0052 (10)
O18	0.0298 (14)	0.0369 (15)	0.0294 (14)	0.0125 (11)	0.0023 (12)	−0.0028 (11)

Geometric parameters (Å, º) top

Tb1—O1ⁱ	2.508 (2)	O4—Tb2ⁱⁱⁱ	2.387 (2)
Tb1—O2	2.400 (2)	C8—O5	1.232 (3)
Tb1—O6	2.378 (2)	C8—O6	1.287 (3)
Tb1—O7	2.426 (2)	O7—H7B	0.8706
Tb1—O8	2.406 (2)	O7—H7A	0.8392
Tb1—O9	2.431 (2)	O8—H8A	0.8514
Tb1—O12	2.590 (2)	O8—H8B	0.8583
Tb1—O13	2.489 (2)	O9—H9A	0.8538
Tb1—N1	2.534 (2)	O9—H9B	0.8526
Tb2—O3ⁱⁱ	2.365 (2)	N2—C13	1.339 (4)
Tb2—O4ⁱⁱⁱ	2.387 (2)	N2—C9	1.343 (4)
Tb2—O10^iv	2.336 (2)	C9—C10	1.404 (4)
Tb2—O11	2.403 (2)	C9—C14	1.523 (4)
Tb2—O15	2.384 (2)	C10—C11	1.394 (4)
Tb2—O16	2.430 (2)	C10—H10A	0.9300
Tb2—O17	2.358 (2)	C11—C12	1.397 (4)
Tb2—N2	2.507 (2)	C11—C15	1.520 (4)
N1—C1	1.342 (3)	C12—C13	1.400 (4)
N1—C5	1.351 (4)	C12—H12A	0.9300
C1—C2	1.396 (4)	C13—C16	1.521 (4)
C1—C6	1.525 (4)	C14—O10	1.257 (3)
C2—C3	1.402 (4)	C14—O11	1.263 (3)
C2—H2A	0.9300	O10—Tb2^vii	2.336 (2)
C3—C4	1.402 (4)	C15—O12	1.262 (4)
C3—C7	1.522 (4)	C15—O13	1.265 (4)
C4—C5	1.390 (4)	C16—O14	1.241 (3)
C4—H4A	0.9300	C16—O15	1.282 (3)
C5—C8	1.517 (4)	O16—H16B	0.8149
C6—O1	1.241 (3)	O16—H16A	0.8500
C6—O2	1.285 (3)	O17—H17B	0.8253
O1—Tb1^v	2.508 (2)	O17—H17A	0.8714
C7—O3	1.250 (3)	O18—H18B	0.8298
C7—O4	1.266 (3)	O18—H18A	0.8749
O3—Tb2^vi	2.365 (2)

O6—Tb1—O2	127.28 (7)	C2—C1—C6	124.2 (2)
O6—Tb1—O8	85.70 (8)	C1—C2—C3	117.8 (2)
O2—Tb1—O8	73.64 (8)	C1—C2—H2A	121.1
O6—Tb1—O7	80.97 (7)	C3—C2—H2A	121.1
O2—Tb1—O7	86.64 (8)	C2—C3—C4	119.5 (2)
O8—Tb1—O7	142.08 (8)	C2—C3—C7	120.4 (2)
O6—Tb1—O9	84.53 (7)	C4—C3—C7	120.0 (2)
O2—Tb1—O9	139.62 (7)	C5—C4—C3	118.6 (3)
O8—Tb1—O9	140.44 (8)	C5—C4—H4A	120.7
O7—Tb1—O9	73.38 (8)	C3—C4—H4A	120.7
O6—Tb1—O13	121.38 (7)	N1—C5—C4	121.7 (3)
O2—Tb1—O13	101.12 (7)	N1—C5—C8	113.2 (2)
O8—Tb1—O13	77.68 (8)	C4—C5—C8	125.1 (3)
O7—Tb1—O13	138.92 (7)	O1—C6—O2	125.8 (3)
O9—Tb1—O13	75.12 (7)	O1—C6—C1	120.0 (2)
O6—Tb1—O1ⁱ	146.61 (7)	O2—C6—C1	114.2 (2)
O2—Tb1—O1ⁱ	72.52 (7)	C6—O1—Tb1^v	137.01 (18)
O8—Tb1—O1ⁱ	127.62 (7)	C6—O2—Tb1	127.35 (17)
O7—Tb1—O1ⁱ	73.14 (7)	O3—C7—O4	126.3 (3)
O9—Tb1—O1ⁱ	68.26 (8)	O3—C7—C3	116.7 (2)
O13—Tb1—O1ⁱ	71.10 (7)	O4—C7—C3	117.0 (2)
O6—Tb1—N1	64.09 (7)	C7—O3—Tb2^vi	170.3 (2)
O2—Tb1—N1	63.37 (7)	C7—O4—Tb2ⁱⁱⁱ	127.23 (17)
O8—Tb1—N1	70.91 (8)	O5—C8—O6	125.2 (3)
O7—Tb1—N1	71.31 (7)	O5—C8—C5	119.6 (3)
O9—Tb1—N1	135.54 (7)	O6—C8—C5	115.2 (2)
O13—Tb1—N1	147.75 (8)	C8—O6—Tb1	126.89 (18)
O1ⁱ—Tb1—N1	123.80 (7)	Tb1—O7—H7B	108.7
O6—Tb1—O12	70.06 (7)	Tb1—O7—H7A	126.8
O2—Tb1—O12	138.79 (8)	H7B—O7—H7A	105.2
O8—Tb1—O12	70.86 (8)	Tb1—O8—H8A	127.8
O7—Tb1—O12	134.56 (7)	Tb1—O8—H8B	98.2
O9—Tb1—O12	69.76 (7)	H8A—O8—H8B	121.3
O13—Tb1—O12	51.34 (7)	Tb1—O9—H9A	123.7
O1ⁱ—Tb1—O12	114.86 (7)	Tb1—O9—H9B	124.9
N1—Tb1—O12	121.18 (7)	H9A—O9—H9B	94.1
O6—Tb1—C15	95.68 (8)	C13—N2—C9	119.7 (2)
O2—Tb1—C15	123.08 (8)	C13—N2—Tb2	120.68 (19)
O8—Tb1—C15	74.82 (8)	C9—N2—Tb2	119.46 (18)
O7—Tb1—C15	141.56 (8)	N2—C9—C10	122.5 (2)
O9—Tb1—C15	68.18 (8)	N2—C9—C14	113.9 (2)
O13—Tb1—C15	25.73 (8)	C10—C9—C14	123.6 (2)
O1ⁱ—Tb1—C15	91.86 (8)	C11—C10—C9	117.8 (3)
N1—Tb1—C15	141.02 (8)	C11—C10—H10A	121.1
O12—Tb1—C15	25.80 (8)	C9—C10—H10A	121.1
O10^iv—Tb2—O17	94.09 (8)	C10—C11—C12	119.4 (2)
O10^iv—Tb2—O3ⁱⁱ	137.68 (8)	C10—C11—C15	120.4 (2)
O17—Tb2—O3ⁱⁱ	79.58 (8)	C12—C11—C15	120.2 (2)
O10^iv—Tb2—O15	91.41 (8)	C11—C12—C13	119.1 (3)
O17—Tb2—O15	158.69 (7)	C11—C12—H12A	120.5
O3ⁱⁱ—Tb2—O15	82.50 (8)	C13—C12—H12A	120.5
O10^iv—Tb2—O4ⁱⁱⁱ	148.23 (7)	N2—C13—C12	121.4 (3)
O17—Tb2—O4ⁱⁱⁱ	98.76 (8)	N2—C13—C16	113.4 (2)
O3ⁱⁱ—Tb2—O4ⁱⁱⁱ	73.56 (7)	C12—C13—C16	125.2 (2)
O15—Tb2—O4ⁱⁱⁱ	87.06 (7)	O10—C14—O11	126.2 (3)
O10^iv—Tb2—O11	76.71 (8)	O10—C14—C9	117.3 (2)
O17—Tb2—O11	72.40 (7)	O11—C14—C9	116.6 (2)
O3ⁱⁱ—Tb2—O11	137.43 (8)	C14—O10—Tb2^vii	150.1 (2)
O15—Tb2—O11	128.91 (7)	C14—O11—Tb2	124.96 (18)
O4ⁱⁱⁱ—Tb2—O11	79.69 (8)	O12—C15—O13	121.2 (3)
O10^iv—Tb2—O16	67.14 (8)	O12—C15—C11	119.3 (3)
O17—Tb2—O16	82.04 (8)	O13—C15—C11	119.4 (2)
O3ⁱⁱ—Tb2—O16	70.54 (8)	O12—C15—Tb1	63.24 (15)
O15—Tb2—O16	81.17 (8)	O13—C15—Tb1	58.67 (14)
O4ⁱⁱⁱ—Tb2—O16	143.32 (7)	C11—C15—Tb1	168.1 (2)
O11—Tb2—O16	133.68 (8)	C15—O12—Tb1	90.96 (18)
O10^iv—Tb2—N2	73.74 (7)	C15—O13—Tb1	95.60 (16)
O17—Tb2—N2	137.12 (8)	O14—C16—O15	125.0 (3)
O3ⁱⁱ—Tb2—N2	136.26 (8)	O14—C16—C13	119.9 (2)
O15—Tb2—N2	64.13 (8)	O15—C16—C13	115.2 (2)
O4ⁱⁱⁱ—Tb2—N2	77.11 (7)	C16—O15—Tb2	126.57 (18)
O11—Tb2—N2	64.84 (7)	Tb2—O16—H16B	130.9
O16—Tb2—N2	126.24 (8)	Tb2—O16—H16A	124.3
C1—N1—C5	119.5 (2)	H16B—O16—H16A	99.5
C1—N1—Tb1	120.52 (17)	Tb2—O17—H17B	119.8
C5—N1—Tb1	119.27 (18)	Tb2—O17—H17A	124.3
N1—C1—C2	122.6 (2)	H17B—O17—H17A	99.1
N1—C1—C6	113.1 (2)	H18B—O18—H18A	98.3

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O14^viii	0.84	1.86	2.700 (3)	174.4
O7—H7B···O2ⁱ	0.87	1.80	2.651 (3)	164.8
O8—H8A···O12ⁱⁱⁱ	0.85	1.89	2.741 (3)	176.0
O8—H8B···O9^ix	0.86	2.39	2.844 (3)	113.0
O9—H9A···O5^viii	0.85	2.56	3.057 (3)	119.0
O9—H9A···O6^viii	0.85	1.86	2.711 (3)	176.0
O9—H9B···O5^viii	0.85	2.56	3.057 (3)	118.0
O16—H16A···O4^viii	0.85	2.30	3.101 (3)	156.2
O16—H16B···O15^x	0.81	1.96	2.766 (3)	171.0
O17—H17A···O18^iv	0.87	1.84	2.705 (4)	173.9
O17—H17B···O5^xi	0.82	1.95	2.759 (3)	163.6
O18—H18A···O14^xii	0.87	2.04	2.911 (4)	175.7
O18—H18B···O13	0.83	1.92	2.745 (4)	167.1

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

Experimental details

Crystal data
Chemical formula	[Tb₂(C₈H₂NO₆)₂(H₂O)₅]·H₂O
M_r	842.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	18.426 (4), 6.9082 (14), 18.583 (4)
β (°)	111.98 (3)
V (Å³)	2193.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.50
Crystal size (mm)	0.38 × 0.34 × 0.31

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.101, 0.128
No. of measured, independent and observed [I > 2σ(I)] reflections	20352, 4912, 4764
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.646

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.045, 1.20
No. of reflections	4912
No. of parameters	344
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −1.33

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.

Selected bond lengths (Å) top

Tb1—O1ⁱ	2.508 (2)	Tb2—O3ⁱⁱ	2.365 (2)
Tb1—O2	2.400 (2)	Tb2—O4ⁱⁱⁱ	2.387 (2)
Tb1—O6	2.378 (2)	Tb2—O10^iv	2.336 (2)
Tb1—O7	2.426 (2)	Tb2—O11	2.403 (2)
Tb1—O8	2.406 (2)	Tb2—O15	2.384 (2)
Tb1—O9	2.431 (2)	Tb2—O16	2.430 (2)
Tb1—O12	2.590 (2)	Tb2—O17	2.358 (2)
Tb1—O13	2.489 (2)	Tb2—N2	2.507 (2)
Tb1—N1	2.534 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O14^v	0.84	1.86	2.700 (3)	174.4
O7—H7B···O2ⁱ	0.87	1.80	2.651 (3)	164.8
O8—H8A···O12ⁱⁱⁱ	0.85	1.89	2.741 (3)	176.0
O8—H8B···O9^vi	0.86	2.39	2.844 (3)	113.0
O9—H9A···O5^v	0.85	2.56	3.057 (3)	119.0
O9—H9A···O6^v	0.85	1.86	2.711 (3)	176.0
O9—H9B···O5^v	0.85	2.56	3.057 (3)	118.0
O16—H16A···O4^v	0.85	2.30	3.101 (3)	156.2
O16—H16B···O15^vii	0.81	1.96	2.766 (3)	171.0
O17—H17A···O18^iv	0.87	1.84	2.705 (4)	173.9
O17—H17B···O5^viii	0.82	1.95	2.759 (3)	163.6
O18—H18A···O14^ix	0.87	2.04	2.911 (4)	175.7
O18—H18B···O13	0.83	1.92	2.745 (4)	167.1

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

Acknowledgements

This project was supported by the K. C. Wong Magna Fund in Ningbo University.

References

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