Bis[μ-4-(1H-imidazol-3-ium-1-yl)benzoato-κ2O:O′]bis­[(methanol)tris­(nitrato-κ2O,O′)terbium(III)]

Jung, Y.-M.; Lee, S.W.

doi:10.1107/S1600536811002443

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m253-m254

doi:10.1107/S1600536811002443

Open

access

Bis[μ-4-(1H-imidazol-3-ium-1-yl)benzoato-κ²O:O′]bis[(methanol)tris(nitrato-κ²O,O′)terbium(III)]

Yeong-Min Jung ^a and Soon W. Lee ^a ^*

^aDepartment of Chemistry (BK21), Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Republic of Korea
^*Correspondence e-mail: soonwlee@skku.edu

(Received 28 December 2010; accepted 18 January 2011; online 22 January 2011)

In the centrosymmetric dinuclear title complex, [Tb₂(NO₃)₆(C₁₀H₈N₂O₂)₂(CH₃OH)₂], the Tb atoms are bridged by the carboxylate groups of the two 4-(1H-imidazol-3-ium-1-yl)benzoate (iba) ligands. The iba ligand adopts a zwitterionic form with a protonated imidazole group. The Tb atom adopts a distorted tricapped trigonal–prismatic coordination geometry and is coordinated by six O atoms of three chelating nitrate ions, one O atom of the methanol molecule and two O atoms of two iba ligands. The intramolecular Tb⋯Tb separation is 5.1419 (3) Å. O—H⋯O and N—H⋯O hydrogen bonds connect complex molecules into a two-dimensional network.

Related literature

For the preparation of 4-(1H-imidazol-1-yl)benzoic acid (iba), see: Zhang et al. (2007a ). To the best of our knowledge, the title compound is the first f-block complex of the iba ligand. For d-block coordination compounds of the iba ligand, see: Aijaz et al. (2009 ); Bai et al. (2009 ); Gao et al. (2008 , 2009 ); Niu et al. (2009 ); Zhang et al. (2007a,b ).

Experimental

Crystal data

[Tb₂(NO₃)₆(C₁₀H₈N₂O₂)₂(CH₄O)₂]
M_r = 1130.35
Triclinic, $[P \overline 1]$
a = 8.2966 (3) Å
b = 9.6107 (3) Å
c = 11.6780 (4) Å
α = 95.328 (2)°
β = 101.271 (2)°
γ = 100.166 (2)°
V = 891.01 (5) Å³
Z = 1
Mo Kα radiation
μ = 4.05 mm⁻¹
T = 296 K
0.32 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.358, T_max = 0.498
14627 measured reflections
4356 independent reflections
3924 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.061
S = 1.04
4356 reflections
266 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected bond lengths (Å)

Tb1—O2ⁱ	2.245 (2)
Tb1—O1	2.275 (2)
Tb1—O12	2.385 (3)
Tb1—O3	2.441 (3)
Tb1—O6	2.461 (2)
Tb1—O4	2.464 (3)
Tb1—O10	2.509 (3)
Tb1—O7	2.529 (3)
Tb1—O9	2.553 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H1O⋯O10ⁱⁱ	0.81	2.15	2.960 (4)	173
N2—H2N⋯O6ⁱⁱⁱ	0.80 (5)	2.00 (5)	2.779 (4)	167 (5)
Symmetry codes: (ii) -x+1, -y+2, -z+2; (iii) -x, -y, -z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002443/gk2337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002443/gk2337Isup2.hkl

checkCIF report

Comment top

4-(1H-Imidazol-1-yl)benzoic acid (iba) is a potential bridging ligand possessing two coordinating groups: a carboxylate group and an imidazole group. This ligand was originally prepared by Chen's group (Zhang et al., 2007a). The iba ligand was recently employed to prepare a couple of discrete complexes of d-block metals such as Mn (Gao et al., 2008) and Ni (Zhang et al., 2007b). It was also utilized for the preparation of coordination polymers of d-block metals such as Co (Zhang et al., 2007a), Cu (Niu, et al., 2009), Zn (Bai et al., 2009), and Cd (Aijaz et al., 2009; Bai et al., 2009; Gao et al., 2009). By contrast, the corresponding f-block complexes, discrete or polymeric, are not known at present. In this context, we attempted to prepare f-block coordination polymers by using the iba ligand. Inconsistent with our expectation, however, a discrete molecular species (the title complex) was produced. We herein report the preparation and structure of a terbium complex, the first f-block complex of the iba ligand.

The local coordination environment of the Tb^III ion in the title complex is presented in Fig. 1, which shows two iba ligands linking two 9-coordinate Tb^III ions. The asymmetric unit consists of only half the formula unit, and the other half is generated by crystallographic inversion center. All atoms occupy general positions, and the inversion point is located at the center of the title complex. The imidazole nitrogen (N2) in the iba ligand remains uncoordinated and is protonated. As a result, the iba ligand has a net charge of zero and acts as a zwitterion in which a positive charge is on the imidazole N atom and a negative charge is on the carboxylate group. It would be meaningful to notice that the imidazole N atom is coordinated to the metals in all known d-block metal complexes and coordination polymers. Additional coordination of the iba carboxylate group to the metals led to the formation of 2-D or 3-D coordination polymers (Zhang et al., 2007a; Niu, et al., 2009; Bai et al., 2009; Aijaz et al., 2009; Bai et al., 2009; Gao et al., 2009). The fact that the N2 atom is not bonded to the Tb^III ion in the title complex can probably be explained on the basis of the hard–soft acid–base concept. The hard Tb^III ion is expected to have a preference to coordinating to the harder oxygen atom (in the carboxylate group) over the softer nitrogen atom (in the imidazole group).

Each Tb^III ion is coordinated to six O atoms from three NO₃^-, one O atom from CH₃OH, and two O atoms from two bis(monodentate) iba ligands. The [TbO₉] core forms a distorted tricapped trigonal prism. Two Tb^III ions and two carboxylate groups form a central eight-membered ring. All nitrate ligands act as bidentate ligands. The Tb···Tb separation is 5.1419 (3) Å, which is much longer than the sum (4.0 Å) of van der Waals radii of the two Tb^III ions and therefore rules out direct interaction between the two metal ions. The N–H of the imidazole group and O–H of the coordinated methanol molecule participate in the intermolecular hydrogen bonds, which connect the molecules of the title complexe into a two-dimensional network (Fig. 2).

Related literature top

For the preparation of 4-(1H-imidazol-1-yl)benzoic acid (iba), see: Zhang et al. (2007a). To the best of our knowledge, the title compound is the first f-block complex of the iba ligand. For d-block coordination compounds of the iba ligand, see: Aijaz et al. (2009); Bai et al. (2009); Gao et al. (2008, 2009); Niu et al. (2009); Zhang et al. (2007a,b).

Experimental top

A mixture of Tb(NO₃)₃.5H₂O (87 mg, 0.2 mmol), 4-(1H-imidazol-1-yl)benzoic acid (37 mg, 0.2 mmol), and CH₃OH (6 ml) was heated at 343 K for 24 h in a 23 ml Teflon-lined stainless-steel autoclave and then cooled slowly to room temperature for 24 h. The resulting colorless crystals were collected by filtration, washed by ethanol (5 ml × 3) and dichloromethane (5 ml × 3), and then air-dried to give the title complex (82 mg, 0.072 mmol, 37%). mp: 542–544 K. IR (KBr, cm^-1): 3889 (w), 3826 (w), 3751 (w), 2912 (m), 2628 (m), 2364 (m), 2069 (m), 1792 (m), 1591 (m), 943 (m).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title complex showing 50% probability displacement ellipsoids. Symmetry code for the atoms with A in their labels: -x + 1, -y + 1, -z + 2.
	Fig. 2. A two dimensional network formed by N—H···O and O—H···O hydrogen bonds.

Bis[µ-4-(1H-imidazol-3-ium-1-yl)benzoato- κ²O:O']bis[(methanol)tris(nitrato- κ²O,O')terbium(III)] top

Crystal data top

[Tb₂(NO₃)₆(C₁₀H₈N₂O₂)₂(CH₄O)₂]	Z = 1
M_r = 1130.35	F(000) = 548
Triclinic, P1	D_x = 2.107 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2966 (3) Å	Cell parameters from 9939 reflections
b = 9.6107 (3) Å	θ = 2.7–28.5°
c = 11.6780 (4) Å	µ = 4.05 mm⁻¹
α = 95.328 (2)°	T = 296 K
β = 101.271 (2)°	Block, colourless
γ = 100.166 (2)°	0.32 × 0.24 × 0.20 mm
V = 891.01 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4356 independent reflections
Radiation source: sealed tube	3924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.358, T_max = 0.498	k = −12→12
14627 measured reflections	l = −15→15

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0361P)²] where P = (F_o² + 2F_c²)/3
4356 reflections	(Δ/σ)_max = 0.002
266 parameters	Δρ_max = 1.01 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Tb₂(NO₃)₆(C₁₀H₈N₂O₂)₂(CH₄O)₂]	γ = 100.166 (2)°
M_r = 1130.35	V = 891.01 (5) Å³
Triclinic, P1	Z = 1
a = 8.2966 (3) Å	Mo Kα radiation
b = 9.6107 (3) Å	µ = 4.05 mm⁻¹
c = 11.6780 (4) Å	T = 296 K
α = 95.328 (2)°	0.32 × 0.24 × 0.20 mm
β = 101.271 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4356 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3924 reflections with I > 2σ(I)
T_min = 0.358, T_max = 0.498	R_int = 0.037
14627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.01 e Å⁻³
4356 reflections	Δρ_min = −0.49 e Å⁻³
266 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	0.457118 (19)	0.675119 (14)	0.848450 (11)	0.03284 (6)
O1	0.2845 (3)	0.4704 (2)	0.8671 (2)	0.0460 (6)
O2	0.3792 (4)	0.3116 (3)	0.9719 (2)	0.0512 (6)
O3	0.7282 (4)	0.6892 (3)	0.7935 (3)	0.0581 (7)
O4	0.5994 (4)	0.4789 (3)	0.8034 (3)	0.0553 (7)
O5	0.8288 (6)	0.5102 (5)	0.7405 (4)	0.1010 (14)
O6	0.3662 (4)	0.5789 (3)	0.6383 (2)	0.0515 (6)
O7	0.1885 (4)	0.6835 (3)	0.7055 (3)	0.0592 (7)
O8	0.1450 (6)	0.6100 (4)	0.5188 (3)	0.1017 (15)
O9	0.4888 (5)	0.8709 (3)	0.7163 (2)	0.0649 (8)
O10	0.5819 (4)	0.9363 (3)	0.9002 (2)	0.0550 (7)
O11	0.6051 (5)	1.0899 (3)	0.7783 (3)	0.0784 (10)
O12	0.2864 (4)	0.7787 (3)	0.9605 (2)	0.0573 (7)
H1O	0.3305	0.8559	0.9989	0.086*
N1	−0.1852 (3)	−0.0986 (3)	0.5742 (2)	0.0356 (5)
N2	−0.3091 (5)	−0.3070 (3)	0.4848 (3)	0.0497 (8)
N3	0.7211 (5)	0.5573 (4)	0.7785 (3)	0.0555 (8)
N4	0.2299 (5)	0.6250 (3)	0.6183 (3)	0.0523 (8)
N5	0.5595 (4)	0.9700 (3)	0.7973 (3)	0.0472 (7)
C1	0.2827 (4)	0.3458 (3)	0.8879 (3)	0.0344 (6)
C2	0.1576 (4)	0.2281 (3)	0.8068 (3)	0.0326 (6)
C3	0.1500 (5)	0.0880 (4)	0.8264 (3)	0.0488 (9)
H3	0.2213	0.0662	0.8912	0.059*
C4	0.0369 (6)	−0.0201 (4)	0.7502 (3)	0.0538 (10)
H4	0.0328	−0.1145	0.7632	0.065*
C5	−0.0694 (4)	0.0123 (3)	0.6554 (3)	0.0332 (6)
C6	−0.0660 (5)	0.1519 (4)	0.6361 (3)	0.0446 (8)
H6	−0.1396	0.1735	0.5724	0.054*
C7	0.0478 (4)	0.2594 (3)	0.7121 (3)	0.0409 (7)
H7	0.0506	0.3538	0.6995	0.049*
C8	−0.3167 (5)	−0.0831 (4)	0.4857 (3)	0.0526 (9)
H8	−0.3467	0.0022	0.4670	0.063*
C9	−0.3922 (5)	−0.2143 (5)	0.4321 (3)	0.0554 (10)
H9	−0.4852	−0.2370	0.3698	0.066*
C10	−0.1834 (5)	−0.2376 (4)	0.5700 (3)	0.0434 (7)
H10	−0.1070	−0.2784	0.6186	0.052*
C11	0.1366 (7)	0.7167 (6)	0.9925 (5)	0.0750 (14)
H11A	0.0994	0.7879	1.0384	0.113*
H11B	0.1569	0.6410	1.0381	0.113*
H11C	0.0518	0.6792	0.9227	0.113*
H2N	−0.325 (6)	−0.389 (6)	0.460 (4)	0.064 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.03738 (9)	0.02521 (8)	0.03241 (8)	0.00405 (6)	0.00267 (5)	0.00046 (5)
O1	0.0431 (14)	0.0275 (11)	0.0608 (14)	−0.0002 (10)	0.0031 (11)	0.0038 (10)
O2	0.0586 (17)	0.0418 (13)	0.0407 (12)	−0.0013 (12)	−0.0077 (11)	0.0037 (10)
O3	0.0486 (16)	0.0517 (16)	0.0746 (18)	0.0049 (13)	0.0199 (13)	0.0076 (13)
O4	0.0537 (17)	0.0403 (14)	0.0748 (17)	0.0140 (13)	0.0172 (13)	0.0072 (12)
O5	0.093 (3)	0.098 (3)	0.148 (4)	0.056 (3)	0.072 (3)	0.029 (3)
O6	0.0658 (18)	0.0396 (13)	0.0424 (12)	0.0117 (12)	0.0008 (11)	−0.0071 (10)
O7	0.0545 (17)	0.0576 (17)	0.0631 (17)	0.0208 (14)	−0.0009 (13)	0.0064 (13)
O8	0.128 (4)	0.090 (3)	0.0587 (19)	0.019 (3)	−0.045 (2)	0.0059 (18)
O9	0.096 (2)	0.0408 (14)	0.0464 (14)	0.0011 (15)	−0.0020 (14)	0.0055 (11)
O10	0.082 (2)	0.0377 (13)	0.0405 (12)	0.0010 (13)	0.0129 (12)	0.0018 (10)
O11	0.105 (3)	0.0331 (14)	0.088 (2)	−0.0013 (16)	0.007 (2)	0.0200 (14)
O12	0.0515 (16)	0.0553 (16)	0.0598 (15)	0.0053 (13)	0.0147 (12)	−0.0152 (12)
N1	0.0358 (14)	0.0319 (13)	0.0357 (12)	0.0046 (11)	0.0036 (10)	0.0007 (10)
N2	0.058 (2)	0.0338 (15)	0.0493 (16)	−0.0016 (14)	0.0080 (14)	−0.0071 (12)
N3	0.049 (2)	0.062 (2)	0.0601 (19)	0.0181 (17)	0.0164 (15)	0.0073 (16)
N4	0.063 (2)	0.0357 (15)	0.0472 (16)	0.0061 (15)	−0.0106 (15)	0.0071 (12)
N5	0.0543 (19)	0.0322 (14)	0.0536 (17)	0.0057 (13)	0.0103 (14)	0.0056 (12)
C1	0.0349 (16)	0.0320 (15)	0.0330 (14)	0.0000 (12)	0.0068 (12)	0.0010 (11)
C2	0.0350 (16)	0.0283 (14)	0.0334 (13)	0.0037 (12)	0.0073 (11)	0.0033 (10)
C3	0.059 (2)	0.0328 (16)	0.0434 (17)	0.0047 (16)	−0.0126 (15)	0.0060 (13)
C4	0.068 (3)	0.0260 (15)	0.056 (2)	0.0059 (16)	−0.0117 (18)	0.0060 (14)
C5	0.0344 (16)	0.0284 (14)	0.0346 (14)	0.0049 (12)	0.0053 (11)	0.0003 (11)
C6	0.046 (2)	0.0334 (16)	0.0474 (17)	0.0078 (15)	−0.0082 (14)	0.0083 (13)
C7	0.0440 (19)	0.0258 (14)	0.0479 (17)	0.0042 (13)	−0.0005 (14)	0.0078 (12)
C8	0.054 (2)	0.0432 (19)	0.0512 (19)	0.0102 (17)	−0.0090 (16)	0.0002 (15)
C9	0.051 (2)	0.055 (2)	0.0496 (19)	0.0078 (19)	−0.0028 (16)	−0.0081 (16)
C10	0.048 (2)	0.0325 (16)	0.0457 (17)	0.0038 (14)	0.0073 (14)	0.0013 (13)
C11	0.064 (3)	0.089 (4)	0.078 (3)	0.014 (3)	0.034 (2)	0.004 (3)

Geometric parameters (Å, º) top

Tb1—O2ⁱ	2.245 (2)	N1—C10	1.335 (4)
Tb1—O1	2.275 (2)	N1—C8	1.388 (5)
Tb1—O12	2.385 (3)	N1—C5	1.433 (4)
Tb1—O3	2.441 (3)	N2—C10	1.323 (5)
Tb1—O6	2.461 (2)	N2—C9	1.342 (6)
Tb1—O4	2.464 (3)	N2—H2N	0.80 (5)
Tb1—O10	2.509 (3)	C1—C2	1.502 (4)
Tb1—O7	2.529 (3)	C2—C3	1.379 (5)
Tb1—O9	2.553 (3)	C2—C7	1.380 (4)
Tb1—N3	2.855 (3)	C3—C4	1.382 (5)
Tb1—N4	2.910 (3)	C3—H3	0.9300
O1—C1	1.242 (4)	C4—C5	1.371 (5)
O2—C1	1.248 (4)	C4—H4	0.9300
O2—Tb1ⁱ	2.245 (2)	C5—C6	1.378 (5)
O3—N3	1.253 (5)	C6—C7	1.380 (4)
O4—N3	1.248 (4)	C6—H6	0.9300
O5—N3	1.209 (5)	C7—H7	0.9300
O6—N4	1.274 (5)	C8—C9	1.340 (5)
O7—N4	1.252 (5)	C8—H8	0.9300
O8—N4	1.216 (4)	C9—H9	0.9300
O9—N5	1.251 (4)	C10—H10	0.9300
O10—N5	1.261 (4)	C11—H11A	0.9600
O11—N5	1.203 (4)	C11—H11B	0.9600
O12—C11	1.415 (6)	C11—H11C	0.9600
O12—H1O	0.8147

O2ⁱ—Tb1—O1	93.66 (9)	N5—O10—Tb1	98.07 (18)
O2ⁱ—Tb1—O12	81.77 (11)	C11—O12—Tb1	130.4 (3)
O1—Tb1—O12	81.94 (10)	C11—O12—H1O	112.9
O2ⁱ—Tb1—O3	80.85 (11)	Tb1—O12—H1O	115.1
O1—Tb1—O3	125.28 (10)	C10—N1—C8	107.5 (3)
O12—Tb1—O3	148.43 (10)	C10—N1—C5	125.2 (3)
O2ⁱ—Tb1—O6	152.13 (11)	C8—N1—C5	127.3 (3)
O1—Tb1—O6	81.95 (9)	C10—N2—C9	109.9 (3)
O12—Tb1—O6	124.33 (10)	C10—N2—H2N	126 (4)
O3—Tb1—O6	79.46 (10)	C9—N2—H2N	123 (3)
O2ⁱ—Tb1—O4	82.58 (10)	O5—N3—O4	122.5 (4)
O1—Tb1—O4	73.61 (10)	O5—N3—O3	120.1 (4)
O12—Tb1—O4	149.92 (11)	O4—N3—O3	117.4 (3)
O3—Tb1—O4	51.67 (10)	O5—N3—Tb1	175.0 (3)
O6—Tb1—O4	69.74 (9)	O4—N3—Tb1	59.30 (18)
O2ⁱ—Tb1—O10	76.79 (9)	O3—N3—Tb1	58.31 (19)
O1—Tb1—O10	153.55 (10)	O8—N4—O7	122.8 (4)
O12—Tb1—O10	72.39 (10)	O8—N4—O6	120.4 (4)
O3—Tb1—O10	78.08 (10)	O7—N4—O6	116.8 (3)
O6—Tb1—O10	117.71 (8)	O8—N4—Tb1	174.9 (4)
O4—Tb1—O10	128.09 (10)	O7—N4—Tb1	60.03 (17)
O2ⁱ—Tb1—O7	154.61 (11)	O6—N4—Tb1	57.02 (15)
O1—Tb1—O7	77.57 (10)	O11—N5—O9	122.2 (3)
O12—Tb1—O7	73.48 (10)	O11—N5—O10	121.9 (3)
O3—Tb1—O7	123.72 (10)	O9—N5—O10	115.9 (3)
O6—Tb1—O7	51.06 (10)	O1—C1—O2	124.1 (3)
O4—Tb1—O7	116.66 (10)	O1—C1—C2	118.3 (3)
O10—Tb1—O7	100.48 (10)	O2—C1—C2	117.6 (3)
O2ⁱ—Tb1—O9	123.29 (9)	C3—C2—C7	119.3 (3)
O1—Tb1—O9	142.55 (9)	C3—C2—C1	120.5 (3)
O12—Tb1—O9	96.38 (12)	C7—C2—C1	120.2 (3)
O3—Tb1—O9	71.99 (11)	C2—C3—C4	120.3 (3)
O6—Tb1—O9	68.14 (9)	C2—C3—H3	119.9
O4—Tb1—O9	113.68 (11)	C4—C3—H3	119.9
O10—Tb1—O9	49.74 (8)	C5—C4—C3	119.8 (3)
O7—Tb1—O9	66.28 (11)	C5—C4—H4	120.1
O2ⁱ—Tb1—N3	82.04 (11)	C3—C4—H4	120.1
O1—Tb1—N3	99.40 (10)	C4—C5—C6	120.6 (3)
O12—Tb1—N3	163.80 (11)	C4—C5—N1	120.6 (3)
O3—Tb1—N3	25.90 (10)	C6—C5—N1	118.8 (3)
O6—Tb1—N3	71.67 (10)	C5—C6—C7	119.3 (3)
O4—Tb1—N3	25.83 (10)	C5—C6—H6	120.4
O10—Tb1—N3	103.51 (11)	C7—C6—H6	120.4
O7—Tb1—N3	122.65 (10)	C6—C7—C2	120.7 (3)
O9—Tb1—N3	92.25 (12)	C6—C7—H7	119.7
O2ⁱ—Tb1—N4	173.59 (9)	C2—C7—H7	119.7
O1—Tb1—N4	80.14 (9)	C9—C8—N1	107.0 (3)
O12—Tb1—N4	98.87 (11)	C9—C8—H8	126.5
O3—Tb1—N4	101.31 (11)	N1—C8—H8	126.5
O6—Tb1—N4	25.75 (10)	C8—C9—N2	107.6 (3)
O4—Tb1—N4	94.00 (10)	C8—C9—H9	126.2
O10—Tb1—N4	109.53 (8)	N2—C9—H9	126.2
O7—Tb1—N4	25.40 (10)	N2—C10—N1	108.0 (3)
O9—Tb1—N4	63.06 (9)	N2—C10—H10	126.0
N3—Tb1—N4	97.26 (11)	N1—C10—H10	126.0
C1—O1—Tb1	143.1 (2)	O12—C11—H11A	109.5
C1—O2—Tb1ⁱ	159.8 (2)	O12—C11—H11B	109.5
N3—O3—Tb1	95.8 (2)	H11A—C11—H11B	109.5
N3—O4—Tb1	94.9 (2)	O12—C11—H11C	109.5
N4—O6—Tb1	97.2 (2)	H11A—C11—H11C	109.5
N4—O7—Tb1	94.6 (2)	H11B—C11—H11C	109.5
N5—O9—Tb1	96.2 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H1O···O10ⁱⁱ	0.81	2.15	2.960 (4)	173
N2—H2N···O6ⁱⁱⁱ	0.80 (5)	2.00 (5)	2.779 (4)	167 (5)

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

Experimental details

Crystal data
Chemical formula	[Tb₂(NO₃)₆(C₁₀H₈N₂O₂)₂(CH₄O)₂]
M_r	1130.35
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.2966 (3), 9.6107 (3), 11.6780 (4)
α, β, γ (°)	95.328 (2), 101.271 (2), 100.166 (2)
V (Å³)	891.01 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.05
Crystal size (mm)	0.32 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.358, 0.498
No. of measured, independent and observed [I > 2σ(I)] reflections	14627, 4356, 3924
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.061, 1.04
No. of reflections	4356
No. of parameters	266
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.49

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Tb1—O2ⁱ	2.245 (2)	Tb1—O4	2.464 (3)
Tb1—O1	2.275 (2)	Tb1—O10	2.509 (3)
Tb1—O12	2.385 (3)	Tb1—O7	2.529 (3)
Tb1—O3	2.441 (3)	Tb1—O9	2.553 (3)
Tb1—O6	2.461 (2)

C10—N2—C9	109.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H1O···O10ⁱⁱ	0.81	2.15	2.960 (4)	173
N2—H2N···O6ⁱⁱⁱ	0.80 (5)	2.00 (5)	2.779 (4)	167 (5)

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

Acknowledgements

This work was supported by the Mid-career Researcher Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science, and Technology (No. 2009–0079916).

References

Aijaz, A., Barea, E. & Bharadwaj, P. K. (2009). Cryst. Growth Des. 9, 4480–4486. Web of Science CSD CrossRef CAS Google Scholar
Bai, Z. S., Chen, S. S., Zhang, Z. H., Chen, M. S., Liu, G. X. & Sun, W. Y. (2009). Sci. China Ser. B Chem. 52, 459–464. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gao, J., Wei, K. J., Ni, J. & Zhang, J. Z. (2008). Synth. React. Inorg. Met. Org. Nano-Met. Chem. 38, 562–566. CAS Google Scholar
Gao, J., Wei, K. J., Ni, J. & Zhang, J. Z. (2009). J. Coord. Chem. 62, 257–265. Web of Science CSD CrossRef CAS Google Scholar
Niu, H. L., Chen, J. T., Zhang, J. Z., Cao, W. R. & Chen, Q. W. (2009). Open Crystallogr. J. 2, 15–18. 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
Zhang, J. Z., Cao, W. R., Pan, J. X. & Chen, Q. W. (2007a). Inorg. Chem. Commun. 10, 1360–1364. Web of Science CSD CrossRef CAS Google Scholar
Zhang, J.-Z., Pan, J.-X., Cao, W.-R. & Chen, Q.-W. (2007b). Acta Cryst. E63, m1042–m1043. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.