catena-Poly[[[diaqua­terbium(III)]-tri-μ2-isonicotinato-κ6O:O′] tris(perchlorate) monohydrate]

Huang, X.-H.; Pan, W.-B.; Xu, X.-H.; Zeng, R.-H.

doi:10.1107/S1600536808023623

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages m1098-m1099

doi:10.1107/S1600536808023623

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catena-Poly[[[diaquaterbium(III)]-tri-μ₂-isonicotinato-κ⁶O:O′] tris(perchlorate) monohydrate]

Xiao-Hui Huang,^a Wei-Bo Pan,^a Xiao-Hong Xu ^a and Rong-Hua Zeng ^a,^b ^*

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bSouth China Normal University, Key Laboratory of the Technology of Electrochemical Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zrh321@yahoo.com.cn

(Received 17 July 2008; accepted 26 July 2008; online 31 July 2008)

In the title complex, {[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O}_n, the Tb^III ion is coordinated by six O atoms from six isonicotinate (inic) ligands and two water molecules, displaying a bicapped trigonal-prismatic geometry. The inic ligands, which are protonated at the pyridine N atom, link the metal centres, forming a polymeric chain running parallel to the a axis. The chains are further assembled via intra- and intermolecular O—H⋯O and N—H⋯O hydrogen-bonding interactions into a three-dimensional supramolecular network involving the inic ligands, the water molecules and the perchlorate anions. One of the perchlorate ions is disordered over two sites with occupancies of 0.561 (17) and 0.439 (17).

Related literature

For related literature, see: Eddaoudi et al. (2001 ); Rizk et al. (2005 ).

Experimental

Crystal data

[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O
M_r = 880.65
Triclinic, $[P \overline 1]$
a = 9.5270 (4) Å
b = 10.9508 (4) Å
c = 15.1309 (6) Å
α = 104.402 (2)°
β = 91.480 (2)°
γ = 111.159 (2)°
V = 1414.17 (10) Å³
Z = 2
Mo Kα radiation
μ = 2.88 mm⁻¹
T = 296 (2) K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS, Sheldrick, 1996 ) T_min = 0.566, T_max = 0.645
19700 measured reflections
6605 independent reflections
6206 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.048
S = 1.04
6605 reflections
452 parameters
77 restraints
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.86	2.15	2.949 (4)	154
N2—H2⋯O1Wⁱⁱ	0.86	1.91	2.756 (3)	166
N3—H3A⋯O5ⁱⁱⁱ	0.86	2.07	2.902 (3)	162
O1W—H1W⋯O4	0.84	2.48	3.054 (4)	127
O1W—H2W⋯O13	0.84	2.26	3.030 (3)	152
O2W—H4W⋯O3W^iv	0.84	2.20	2.920 (3)	145
O2W—H4W⋯O17	0.84	2.53	3.164 (2)	133
O2W—H3W⋯O11^v	0.83	2.23	2.959 (9)	147
O3W—H5W⋯O12	0.84	2.20	2.934 (9)	146
O3W—H6W⋯O11^vi	0.83	2.14	2.843 (9)	142
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z+1; (iii) -x, -y, -z; (iv) -x, -y+1, -z+1; (v) x, y+1, z; (vi) -x, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023623/rz2238sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023623/rz2238Isup2.hkl

checkCIF report

Comment top

The design, synthesis, characterization, and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centres are of great interest (Rizk et al., 2005; Eddaoudi et al., 2001). As a building block, isonicotinic acid is an excellent candidate for the construction of supramolecular complexes. Recently, we obtained the title new coordination polymer, whise structure is reported here.

In the title compound, each Tb^III centre is coordinated by six oxygen donors of six inic ligands and two water molecules (Fig. 1), and exhibits a bicapped trigonal prismatic coordination geometry. The Tb^III ions are linked by inic ligands to form a polymeric chain in the a axis direction. The Tb···Tb separations between adjacent metal atoms are 4.318 (4) and 5.259 (5) Å. Intra- and intermolecular O—H···O and N—H···O hydrogen bonding interaction (Table 1) involving the inic ligands, the water molecules and the perchlorate ions assemble neighboring chains into a three-dimensional supramolecular network (Fig. 2).

Related literature top

For related literature, see: Eddaoudi et al. (2001); Rizk et al. (2005).

Experimental top

A mixture of Tb₄O₇ (0.189 g, 0.25 mmol), isonicotinic acid (0.135 g, 1.5 mmol) and water (10 ml) in the presence of HClO₄ (0.385 mmol) was stirred vigorously for 20 min and then sealed into a Teflon-lined stainless-steel autoclave (20 ml capacity). The autoclave was heated to and maintained at 433 K for 3 days, and then cooled to room temperature at 5 K h^-1 to obtain colourless block-shaped crystals of the title compound suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atomic-numbering scheme. Displacement ellipsoids drawn at the 30% probability level. Only the major component of disorder is shown. [Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) -x, 1-y, 1-z].
	Fig. 2. The supramolecular network of the title compound viewed along the a axis. Only the major componentof disorder is shown.

catena-Poly[[[diaquaterbium(III)]-tri-µ₂-isonicotinato- κ⁶O:O'] tris(perchlorate) monohydrate] top

Crystal data top

[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O	Z = 2
M_r = 880.65	F(000) = 868
Triclinic, P1	D_x = 2.068 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5270 (4) Å	Cell parameters from 6377 reflections
b = 10.9508 (4) Å	θ = 1.7–28.0°
c = 15.1309 (6) Å	µ = 2.88 mm⁻¹
α = 104.402 (2)°	T = 296 K
β = 91.480 (2)°	Block, colourless
γ = 111.159 (2)°	0.20 × 0.18 × 0.15 mm
V = 1414.17 (10) Å³

Data collection top

Bruker APEXII area-detector diffractometer	6605 independent reflections
Radiation source: fine-focus sealed tube	6206 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scan	θ_max = 27.8°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	h = −12→12
T_min = 0.566, T_max = 0.646	k = −14→14
19700 measured reflections	l = −19→19

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.021P)² + 1.1255P] where P = (F_o² + 2F_c²)/3
6605 reflections	(Δ/σ)_max = 0.001
452 parameters	Δρ_max = 0.95 e Å⁻³
77 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O	γ = 111.159 (2)°
M_r = 880.65	V = 1414.17 (10) Å³
Triclinic, P1	Z = 2
a = 9.5270 (4) Å	Mo Kα radiation
b = 10.9508 (4) Å	µ = 2.88 mm⁻¹
c = 15.1309 (6) Å	T = 296 K
α = 104.402 (2)°	0.20 × 0.18 × 0.15 mm
β = 91.480 (2)°

Data collection top

Bruker APEXII area-detector diffractometer	6605 independent reflections
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	6206 reflections with I > 2σ(I)
T_min = 0.566, T_max = 0.646	R_int = 0.024
19700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	77 restraints
wR(F²) = 0.048	H-atom parameters constrained
S = 1.04	Δρ_max = 0.95 e Å⁻³
6605 reflections	Δρ_min = −0.79 e Å⁻³
452 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	Occ. (<1)
C1	0.5075 (3)	0.5494 (2)	0.34089 (15)	0.0209 (4)
C2	0.5770 (3)	0.5734 (2)	0.25475 (15)	0.0226 (5)
C3	0.5067 (3)	0.6111 (3)	0.19077 (17)	0.0316 (5)
H3	0.4147	0.6209	0.1997	0.038*
C4	0.5740 (4)	0.6338 (3)	0.11420 (19)	0.0421 (7)
H4	0.5284	0.6602	0.0712	0.051*
C5	0.7756 (4)	0.5802 (3)	0.1610 (2)	0.0432 (7)
H5	0.8660	0.5686	0.1494	0.052*
C6	0.7134 (3)	0.5586 (3)	0.23913 (19)	0.0331 (6)
H6	0.7626	0.5341	0.2815	0.040*
C7	0.5896 (3)	0.7590 (2)	0.58623 (15)	0.0212 (4)
C8	0.6542 (3)	0.9101 (2)	0.63494 (16)	0.0231 (5)
C9	0.5830 (3)	0.9941 (3)	0.6193 (2)	0.0358 (6)
H9	0.4924	0.9581	0.5800	0.043*
C10	0.6474 (4)	1.1312 (3)	0.6624 (2)	0.0416 (7)
H10	0.6011	1.1889	0.6520	0.050*
C11	0.8452 (4)	1.1036 (3)	0.7370 (2)	0.0510 (8)
H11	0.9340	1.1423	0.7781	0.061*
C12	0.7861 (3)	0.9652 (3)	0.6950 (2)	0.0386 (7)
H12	0.8347	0.9101	0.7071	0.046*
C13	−0.0791 (2)	0.3637 (2)	0.35190 (15)	0.0189 (4)
C14	−0.1596 (3)	0.2516 (2)	0.26504 (15)	0.0214 (4)
C15	−0.3153 (3)	0.2093 (3)	0.24151 (18)	0.0316 (6)
H15	−0.3706	0.2529	0.2772	0.038*
C16	−0.3860 (4)	0.1024 (3)	0.1649 (2)	0.0432 (7)
H16	−0.4903	0.0716	0.1489	0.052*
C17	−0.1552 (4)	0.0837 (3)	0.13243 (19)	0.0426 (7)
H17	−0.1023	0.0413	0.0934	0.051*
C18	−0.0790 (3)	0.1880 (3)	0.20941 (17)	0.0314 (5)
H18	0.0252	0.2155	0.2239	0.038*
Cl1	0.19389 (9)	0.70180 (8)	0.03011 (5)	0.04494 (17)
Cl2	0.29246 (9)	0.22081 (7)	0.09772 (5)	0.04040 (16)
N1	0.7053 (3)	0.6179 (3)	0.10183 (17)	0.0461 (7)
H1	0.7463	0.6327	0.0536	0.055*
N2	0.7759 (3)	1.1812 (2)	0.71899 (18)	0.0424 (6)
H2	0.8156	1.2674	0.7449	0.051*
N3	−0.3051 (3)	0.0434 (2)	0.11387 (16)	0.0438 (6)
H3A	−0.3514	−0.0242	0.0665	0.053*
O1	0.3135 (4)	0.8310 (3)	0.0649 (2)	0.0980 (12)
O2	0.1590 (4)	0.6721 (3)	−0.06629 (17)	0.0719 (8)
O3	0.0636 (3)	0.7009 (3)	0.0738 (2)	0.0740 (8)
O4	0.2370 (4)	0.5967 (3)	0.0487 (2)	0.0825 (9)
O5	0.4033 (3)	0.2007 (3)	0.03987 (17)	0.0615 (7)
O6	0.2468 (4)	0.3225 (3)	0.0772 (2)	0.0801 (9)
O7	0.3532 (4)	0.2641 (3)	0.19129 (16)	0.0728 (8)
O8	0.1675 (3)	0.0947 (3)	0.0809 (2)	0.0852 (10)
O13	0.37551 (18)	0.54575 (17)	0.34757 (11)	0.0256 (3)
O14	0.58826 (19)	0.53420 (17)	0.40081 (11)	0.0272 (4)
O15	0.45551 (18)	0.70996 (16)	0.54760 (12)	0.0265 (4)
O16	0.67592 (18)	0.69729 (16)	0.58981 (12)	0.0259 (4)
O17	−0.14890 (19)	0.43444 (17)	0.39150 (11)	0.0275 (4)
O18	0.05161 (18)	0.37668 (17)	0.37767 (12)	0.0281 (4)
Tb1	0.270670 (11)	0.491645 (10)	0.483309 (7)	0.01654 (4)
O1W	0.1147 (2)	0.53818 (19)	0.22458 (14)	0.0412 (5)
H1W	0.1025	0.4998	0.1681	0.062*
H2W	0.1711	0.5100	0.2502	0.062*
O2W	0.18165 (19)	0.66276 (17)	0.44776 (12)	0.0298 (4)
H4W	0.0905	0.6479	0.4333	0.045*
H3W	0.2191	0.7391	0.4861	0.045*
O3W	0.0974 (2)	0.28637 (18)	0.52869 (13)	0.0323 (4)
H5W	0.1357	0.2549	0.5636	0.048*
H6W	0.0490	0.2213	0.4832	0.048*
Cl3	0.21484 (9)	0.04724 (7)	0.62478 (5)	0.04379 (17)	0.561 (17)
O9	0.3356 (12)	0.1332 (11)	0.5842 (9)	0.062 (3)	0.561 (17)
O10	0.3010 (12)	0.0741 (6)	0.7152 (4)	0.065 (2)	0.561 (17)
O11	0.1764 (12)	−0.0885 (8)	0.5784 (8)	0.066 (2)	0.561 (17)
O12	0.0975 (11)	0.0931 (12)	0.6326 (9)	0.109 (4)	0.561 (17)
Cl3'	0.21484 (9)	0.04724 (7)	0.62478 (5)	0.04379 (17)	0.439 (17)
O9'	0.2951 (16)	0.1488 (12)	0.5860 (10)	0.056 (3)	0.439 (17)
O10'	0.2119 (17)	0.0782 (8)	0.7181 (5)	0.070 (3)	0.439 (17)
O11'	0.2277 (15)	−0.0826 (11)	0.5862 (10)	0.065 (3)	0.439 (17)
O12'	0.0520 (9)	0.0154 (16)	0.5847 (10)	0.108 (4)	0.439 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0267 (11)	0.0172 (10)	0.0180 (10)	0.0069 (9)	0.0022 (8)	0.0055 (8)
C2	0.0243 (11)	0.0208 (11)	0.0200 (11)	0.0060 (9)	0.0040 (9)	0.0047 (9)
C3	0.0322 (13)	0.0395 (14)	0.0264 (13)	0.0141 (11)	0.0057 (10)	0.0141 (11)
C4	0.0515 (18)	0.0481 (17)	0.0271 (14)	0.0144 (14)	0.0052 (12)	0.0180 (13)
C5	0.0402 (16)	0.0495 (18)	0.0404 (16)	0.0183 (14)	0.0189 (13)	0.0098 (14)
C6	0.0320 (13)	0.0383 (14)	0.0327 (14)	0.0170 (11)	0.0088 (11)	0.0104 (11)
C7	0.0236 (11)	0.0185 (10)	0.0199 (11)	0.0064 (9)	0.0062 (8)	0.0046 (8)
C8	0.0238 (11)	0.0186 (11)	0.0241 (11)	0.0067 (9)	0.0045 (9)	0.0028 (9)
C9	0.0327 (14)	0.0224 (12)	0.0481 (17)	0.0093 (11)	−0.0036 (12)	0.0052 (11)
C10	0.0456 (17)	0.0229 (13)	0.0564 (19)	0.0149 (12)	0.0067 (14)	0.0085 (12)
C11	0.0418 (17)	0.0331 (16)	0.058 (2)	0.0070 (13)	−0.0149 (15)	−0.0099 (14)
C12	0.0378 (15)	0.0268 (13)	0.0439 (16)	0.0129 (11)	−0.0090 (12)	−0.0022 (12)
C13	0.0198 (10)	0.0184 (10)	0.0178 (10)	0.0056 (8)	0.0013 (8)	0.0065 (8)
C14	0.0254 (11)	0.0209 (11)	0.0174 (10)	0.0083 (9)	0.0008 (8)	0.0054 (9)
C15	0.0279 (13)	0.0347 (14)	0.0271 (13)	0.0088 (11)	−0.0016 (10)	0.0050 (11)
C16	0.0391 (16)	0.0383 (16)	0.0384 (16)	0.0031 (13)	−0.0131 (12)	0.0062 (13)
C17	0.065 (2)	0.0353 (15)	0.0265 (14)	0.0237 (14)	0.0060 (13)	−0.0009 (12)
C18	0.0370 (14)	0.0313 (13)	0.0256 (12)	0.0154 (11)	0.0048 (10)	0.0041 (10)
Cl1	0.0505 (4)	0.0462 (4)	0.0342 (4)	0.0140 (3)	0.0078 (3)	0.0105 (3)
Cl2	0.0534 (4)	0.0382 (4)	0.0268 (3)	0.0162 (3)	0.0091 (3)	0.0056 (3)
N1	0.0547 (16)	0.0498 (15)	0.0274 (12)	0.0105 (13)	0.0208 (11)	0.0122 (11)
N2	0.0426 (14)	0.0191 (11)	0.0502 (15)	0.0027 (10)	0.0063 (11)	−0.0033 (10)
N3	0.0626 (17)	0.0297 (12)	0.0244 (12)	0.0088 (12)	−0.0121 (11)	−0.0029 (9)
O1	0.076 (2)	0.072 (2)	0.092 (2)	−0.0128 (16)	0.0228 (18)	−0.0111 (17)
O2	0.122 (2)	0.0698 (18)	0.0360 (13)	0.0448 (17)	0.0139 (14)	0.0228 (12)
O3	0.0541 (15)	0.089 (2)	0.0655 (17)	0.0209 (14)	0.0186 (13)	0.0063 (15)
O4	0.112 (3)	0.099 (2)	0.0642 (18)	0.065 (2)	0.0037 (17)	0.0356 (17)
O5	0.0657 (16)	0.0725 (17)	0.0480 (14)	0.0280 (13)	0.0226 (12)	0.0155 (12)
O6	0.116 (3)	0.091 (2)	0.0670 (18)	0.068 (2)	0.0267 (17)	0.0357 (17)
O7	0.112 (2)	0.0620 (16)	0.0280 (12)	0.0186 (16)	0.0000 (13)	0.0070 (11)
O8	0.0703 (19)	0.0567 (17)	0.089 (2)	−0.0050 (14)	0.0157 (16)	−0.0055 (15)
O13	0.0243 (8)	0.0332 (9)	0.0235 (8)	0.0135 (7)	0.0070 (6)	0.0111 (7)
O14	0.0298 (9)	0.0293 (9)	0.0227 (8)	0.0099 (7)	−0.0030 (7)	0.0102 (7)
O15	0.0225 (8)	0.0180 (8)	0.0336 (9)	0.0046 (6)	−0.0021 (7)	0.0027 (7)
O16	0.0263 (9)	0.0224 (8)	0.0297 (9)	0.0125 (7)	0.0043 (7)	0.0034 (7)
O17	0.0313 (9)	0.0303 (9)	0.0231 (8)	0.0173 (7)	0.0062 (7)	0.0026 (7)
O18	0.0218 (8)	0.0278 (9)	0.0296 (9)	0.0086 (7)	−0.0055 (7)	0.0014 (7)
Tb1	0.01613 (6)	0.01654 (6)	0.01645 (6)	0.00657 (4)	0.00083 (4)	0.00326 (4)
O1W	0.0515 (12)	0.0314 (10)	0.0364 (11)	0.0131 (9)	−0.0026 (9)	0.0068 (8)
O2W	0.0266 (9)	0.0266 (9)	0.0377 (10)	0.0130 (7)	0.0011 (7)	0.0073 (8)
O3W	0.0319 (9)	0.0255 (9)	0.0367 (10)	0.0071 (7)	0.0033 (8)	0.0094 (8)
Cl3	0.0564 (4)	0.0332 (3)	0.0465 (4)	0.0181 (3)	0.0120 (3)	0.0168 (3)
O9	0.067 (5)	0.052 (4)	0.069 (4)	0.017 (3)	0.020 (3)	0.026 (3)
O10	0.092 (5)	0.047 (3)	0.042 (3)	0.007 (3)	−0.009 (3)	0.018 (2)
O11	0.069 (5)	0.027 (3)	0.081 (4)	0.006 (3)	−0.027 (4)	−0.001 (2)
O12	0.083 (5)	0.120 (7)	0.144 (7)	0.066 (5)	0.042 (5)	0.029 (5)
Cl3'	0.0564 (4)	0.0332 (3)	0.0465 (4)	0.0181 (3)	0.0120 (3)	0.0168 (3)
O9'	0.075 (6)	0.035 (4)	0.056 (4)	0.012 (4)	0.018 (4)	0.024 (3)
O10'	0.101 (7)	0.052 (4)	0.049 (4)	0.020 (4)	0.018 (4)	0.016 (3)
O11'	0.067 (6)	0.041 (4)	0.078 (6)	0.022 (4)	−0.002 (5)	0.000 (3)
O12'	0.063 (5)	0.128 (8)	0.129 (8)	0.051 (5)	0.002 (5)	0.008 (6)

Geometric parameters (Å, º) top

C1—O13	1.251 (3)	Cl1—O2	1.416 (3)
C1—O14	1.255 (3)	Cl1—O1	1.419 (3)
C1—C2	1.515 (3)	Cl1—O3	1.419 (3)
C2—C6	1.385 (3)	Cl1—O4	1.438 (3)
C2—C3	1.386 (3)	Cl2—O7	1.411 (2)
C3—C4	1.372 (4)	Cl2—O8	1.419 (3)
C3—H3	0.9300	Cl2—O6	1.428 (3)
C4—N1	1.336 (4)	Cl2—O5	1.432 (2)
C4—H4	0.9300	N1—H1	0.8600
C5—N1	1.332 (4)	N2—H2	0.8600
C5—C6	1.370 (4)	N3—H3A	0.8600
C5—H5	0.9300	O13—Tb1	2.4189 (16)
C6—H6	0.9300	O14—Tb1ⁱ	2.3152 (16)
C7—O16	1.246 (3)	O15—Tb1	2.3406 (15)
C7—O15	1.254 (3)	O16—Tb1ⁱ	2.3268 (16)
C7—C8	1.515 (3)	O17—Tb1ⁱⁱ	2.3702 (16)
C8—C12	1.375 (4)	O18—Tb1	2.3293 (15)
C8—C9	1.383 (4)	Tb1—O14ⁱ	2.3152 (16)
C9—C10	1.372 (4)	Tb1—O16ⁱ	2.3268 (16)
C9—H9	0.9300	Tb1—O17ⁱⁱ	2.3701 (16)
C10—N2	1.327 (4)	Tb1—O2W	2.4789 (17)
C10—H10	0.9300	Tb1—O3W	2.5292 (17)
C11—N2	1.321 (4)	O1W—H1W	0.8376
C11—C12	1.380 (4)	O1W—H2W	0.8389
C11—H11	0.9300	O2W—H4W	0.8361
C12—H12	0.9300	O2W—H3W	0.8339
C13—O18	1.242 (3)	O3W—H5W	0.8383
C13—O17	1.250 (3)	O3W—H6W	0.8343
C13—C14	1.512 (3)	Cl3—O10'	1.371 (7)
C14—C18	1.382 (3)	Cl3—O12	1.378 (6)
C14—C15	1.391 (3)	Cl3—O9'	1.378 (9)
C15—C16	1.372 (4)	Cl3—O11	1.382 (8)
C15—H15	0.9300	Cl3—O11'	1.447 (9)
C16—N3	1.323 (4)	Cl3—O9	1.459 (8)
C16—H16	0.9300	Cl3—O10	1.484 (6)
C17—N3	1.333 (4)	Cl3—O12'	1.534 (8)
C17—C18	1.373 (4)	O10—O10'	0.867 (9)
C17—H17	0.9300	O12—O12'	0.921 (10)
C18—H18	0.9300	O12—O10'	1.745 (12)

O13—C1—O14	124.7 (2)	C17—N3—H3A	118.5
O13—C1—C2	118.7 (2)	C1—O13—Tb1	115.63 (14)
O14—C1—C2	116.6 (2)	C1—O14—Tb1ⁱ	177.12 (16)
C6—C2—C3	118.9 (2)	C7—O15—Tb1	136.30 (15)
C6—C2—C1	120.1 (2)	C7—O16—Tb1ⁱ	144.47 (15)
C3—C2—C1	121.0 (2)	C13—O17—Tb1ⁱⁱ	152.03 (16)
C4—C3—C2	119.5 (3)	C13—O18—Tb1	148.90 (15)
C4—C3—H3	120.3	O14ⁱ—Tb1—O16ⁱ	76.86 (6)
C2—C3—H3	120.3	O14ⁱ—Tb1—O18	142.30 (6)
N1—C4—C3	119.6 (3)	O16ⁱ—Tb1—O18	81.76 (6)
N1—C4—H4	120.2	O14ⁱ—Tb1—O15	75.81 (6)
C3—C4—H4	120.2	O16ⁱ—Tb1—O15	124.12 (6)
N1—C5—C6	119.4 (3)	O18—Tb1—O15	141.36 (6)
N1—C5—H5	120.3	O14ⁱ—Tb1—O17ⁱⁱ	81.73 (6)
C6—C5—H5	120.3	O16ⁱ—Tb1—O17ⁱⁱ	140.19 (6)
C5—C6—C2	119.8 (3)	O18—Tb1—O17ⁱⁱ	95.97 (6)
C5—C6—H6	120.1	O15—Tb1—O17ⁱⁱ	81.27 (6)
C2—C6—H6	120.1	O14ⁱ—Tb1—O13	122.25 (6)
O16—C7—O15	127.4 (2)	O16ⁱ—Tb1—O13	76.08 (6)
O16—C7—C8	116.1 (2)	O18—Tb1—O13	81.06 (6)
O15—C7—C8	116.6 (2)	O15—Tb1—O13	78.95 (6)
C12—C8—C9	119.3 (2)	O17ⁱⁱ—Tb1—O13	143.18 (6)
C12—C8—C7	119.7 (2)	O14ⁱ—Tb1—O2W	140.16 (6)
C9—C8—C7	121.0 (2)	O16ⁱ—Tb1—O2W	140.79 (6)
C10—C9—C8	119.3 (3)	O18—Tb1—O2W	71.74 (6)
C10—C9—H9	120.3	O15—Tb1—O2W	70.71 (6)
C8—C9—H9	120.3	O17ⁱⁱ—Tb1—O2W	72.52 (6)
N2—C10—C9	119.7 (3)	O13—Tb1—O2W	71.74 (6)
N2—C10—H10	120.1	O14ⁱ—Tb1—O3W	73.90 (6)
C9—C10—H10	120.1	O16ⁱ—Tb1—O3W	71.06 (6)
N2—C11—C12	120.1 (3)	O18—Tb1—O3W	69.91 (6)
N2—C11—H11	120.0	O15—Tb1—O3W	141.20 (6)
C12—C11—H11	120.0	O17ⁱⁱ—Tb1—O3W	70.93 (6)
C8—C12—C11	119.0 (3)	O13—Tb1—O3W	138.50 (6)
C8—C12—H12	120.5	O2W—Tb1—O3W	122.65 (6)
C11—C12—H12	120.5	H1W—O1W—H2W	107.2
O18—C13—O17	125.8 (2)	Tb1—O2W—H4W	123.7
O18—C13—C14	116.4 (2)	Tb1—O2W—H3W	113.6
O17—C13—C14	117.84 (19)	H4W—O2W—H3W	107.2
C18—C14—C15	119.4 (2)	Tb1—O3W—H5W	118.0
C18—C14—C13	120.0 (2)	Tb1—O3W—H6W	112.5
C15—C14—C13	120.6 (2)	H5W—O3W—H6W	106.9
C16—C15—C14	119.1 (3)	O10'—Cl3—O12	78.8 (5)
C16—C15—H15	120.5	O10'—Cl3—O9'	119.3 (7)
C14—C15—H15	120.5	O12—Cl3—O9'	91.0 (7)
N3—C16—C15	119.7 (3)	O10'—Cl3—O11	117.0 (7)
N3—C16—H16	120.2	O12—Cl3—O11	116.2 (5)
C15—C16—H16	120.2	O9'—Cl3—O11	121.0 (9)
N3—C17—C18	119.7 (3)	O10'—Cl3—O11'	113.6 (7)
N3—C17—H17	120.1	O12—Cl3—O11'	135.4 (6)
C18—C17—H17	120.1	O9'—Cl3—O11'	114.8 (8)
C17—C18—C14	119.0 (3)	O10'—Cl3—O9	121.1 (7)
C17—C18—H18	120.5	O12—Cl3—O9	110.0 (5)
C14—C18—H18	120.5	O11—Cl3—O9	110.2 (6)
O2—Cl1—O1	110.4 (2)	O11'—Cl3—O9	99.6 (8)
O2—Cl1—O3	109.95 (19)	O12—Cl3—O10	112.4 (4)
O1—Cl1—O3	109.64 (19)	O9'—Cl3—O10	107.3 (8)
O2—Cl1—O4	108.26 (17)	O11—Cl3—O10	108.0 (5)
O1—Cl1—O4	110.4 (2)	O11'—Cl3—O10	94.6 (6)
O3—Cl1—O4	108.2 (2)	O9—Cl3—O10	98.6 (6)
O7—Cl2—O8	108.89 (19)	O10'—Cl3—O12'	104.2 (6)
O7—Cl2—O6	109.02 (18)	O9'—Cl3—O12'	100.7 (7)
O8—Cl2—O6	111.1 (2)	O11—Cl3—O12'	81.5 (6)
O7—Cl2—O5	110.65 (18)	O11'—Cl3—O12'	100.6 (5)
O8—Cl2—O5	108.17 (17)	O9—Cl3—O12'	116.1 (6)
O6—Cl2—O5	109.06 (17)	O10—Cl3—O12'	138.6 (5)
C5—N1—C4	122.8 (2)	O10'—O10—Cl3	65.4 (6)
C5—N1—H1	118.6	O12'—O12—Cl3	81.1 (7)
C4—N1—H1	118.6	O12'—O12—O10'	115.2 (10)
C11—N2—C10	122.6 (2)	Cl3—O12—O10'	50.4 (3)
C11—N2—H2	118.7	O10—O10'—Cl3	79.5 (7)
C10—N2—H2	118.7	O10—O10'—O12	127.9 (9)
C16—N3—C17	123.1 (2)	Cl3—O10'—O12	50.8 (4)
C16—N3—H3A	118.5	O12—O12'—Cl3	62.5 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱⁱⁱ	0.86	2.15	2.949 (4)	154
N2—H2···O1W^iv	0.86	1.91	2.756 (3)	166
N3—H3A···O5^v	0.86	2.07	2.902 (3)	162
O1W—H1W···O4	0.84	2.48	3.054 (4)	127
O1W—H2W···O13	0.84	2.26	3.030 (3)	152
O2W—H4W···O3Wⁱⁱ	0.84	2.20	2.920 (3)	145
O2W—H4W···O17	0.84	2.53	3.164 (2)	133
O2W—H3W···O11^vi	0.83	2.23	2.959 (9)	147
O3W—H5W···O12	0.84	2.20	2.934 (9)	146
O3W—H6W···O11^vii	0.83	2.14	2.843 (9)	142

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

Experimental details

Crystal data
Chemical formula	[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O
M_r	880.65
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.5270 (4), 10.9508 (4), 15.1309 (6)
α, β, γ (°)	104.402 (2), 91.480 (2), 111.159 (2)
V (Å³)	1414.17 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.88
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS, Sheldrick, 1996)
T_min, T_max	0.566, 0.646
No. of measured, independent and observed [I > 2σ(I)] reflections	19700, 6605, 6206
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.048, 1.04
No. of reflections	6605
No. of parameters	452
No. of restraints	77
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.79

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.86	2.15	2.949 (4)	154.3
N2—H2···O1Wⁱⁱ	0.86	1.91	2.756 (3)	166.4
N3—H3A···O5ⁱⁱⁱ	0.86	2.07	2.902 (3)	161.9
O1W—H1W···O4	0.84	2.48	3.054 (4)	127.0
O1W—H2W···O13	0.84	2.26	3.030 (3)	151.8
O2W—H4W···O3W^iv	0.84	2.20	2.920 (3)	144.5
O2W—H4W···O17	0.84	2.53	3.164 (2)	133.4
O2W—H3W···O11^v	0.83	2.23	2.959 (9)	146.8
O3W—H5W···O12	0.84	2.20	2.934 (9)	146.4
O3W—H6W···O11^vi	0.83	2.14	2.843 (9)	142.4

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

Acknowledgements

The authors acknowledge South China Normal University for supporting this work.

References

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Eddaoudi, M., Moler, D. B., Li, H. L., Chen, B. L., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330. Web of Science CrossRef PubMed CAS Google Scholar
Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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