catena-Poly[[[diaqua­[3-(pyridin-4-yl)benzoato-κ2O,O′]gadolinium(III)]-bis­[μ-3-(pyridin-4-yl)benzoato-κ2O:O′]] monohydrate]

Li, D.-Y.; Li, G.-T.

doi:10.1107/S1600536812026153

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m928-m929

https://doi.org/10.1107/S1600536812026153

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catena-Poly[[[diaqua[3-(pyridin-4-yl)benzoato-κ²O,O′]gadolinium(III)]-bis[μ-3-(pyridin-4-yl)benzoato-κ²O:O′]] monohydrate]

Dong-Ying Li ^a ^* and Guo-Ting Li ^a

^aDepartment of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: lidongying@ncwu.edu.cn

(Received 3 June 2012; accepted 9 June 2012; online 16 June 2012)

In the title coordination polymer, {[Gd(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O}_n, the Gd^III ion is ligated by one bidentate carboxylate group, four monodentate bridging carboxylate O atoms and two water molecules. The resulting GdO₈ polyhedron approximates to a square antiprism. The bridging ligands link the metal ions into a [100] chain, with each pair of adjacent metal ions being bridged by two ligands. Inter-chain O—H⋯O and O—H⋯N hydrogen bonds help to establish the packing.

Related literature

For metal-organic frameworks containing aromatic carboxylic ligands, see: Li et al. (2010). For lanthanide metal-organic frameworks based on aromatic carboxylic ligands, see: Zhang et al. (2010 ). For transition metal coordination complexes of 3-pyridin-4-ylbenzoate, see: Wu et al. (2011 ).

Experimental

Crystal data

[Gd(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O
M_r = 805.88
Triclinic, $[P \overline 1]$
a = 9.7252 (5) Å
b = 13.9535 (6) Å
c = 14.0829 (8) Å
α = 118.019 (5)°
β = 104.240 (5)°
γ = 90.089 (4)°
V = 1619.84 (14) Å³
Z = 2
Mo Kα radiation
μ = 2.11 mm⁻¹
T = 293 K
0.35 × 0.21 × 0.18 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 1.000
12338 measured reflections
5702 independent reflections
4844 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.061
S = 1.05
5702 reflections
460 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected bond lengths (Å)

Gd1—O5ⁱ	2.290 (2)
Gd1—O4ⁱⁱ	2.295 (2)
Gd1—O3	2.395 (2)
Gd1—O6	2.405 (2)
Gd1—O8	2.443 (2)
Gd1—O7	2.447 (2)
Gd1—O2	2.468 (2)
Gd1—O1	2.532 (2)
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O1ⁱ	0.71 (3)	2.12 (3)	2.826 (3)	173 (4)
O7—H7B⋯N1ⁱⁱⁱ	0.89 (4)	1.89 (4)	2.772 (4)	173 (3)
O8—H8B⋯O2ⁱⁱ	0.75 (3)	2.05 (3)	2.793 (3)	173 (4)
O8—H8A⋯N3^iv	0.84 (4)	1.95 (4)	2.789 (4)	175 (3)
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y, -z; (iii) x, y-1, z-1; (iv) x, y-1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: https://doi.org/10.1107/S1600536812026153/hb6834sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026153/hb6834Isup2.hkl

checkCIF report

Comment top

Aromatic carboxylic ligands have been widely used to construct metal-organic frameworks (MOFs) with novel structures and unique properties (Li et al., 2010). Especially, lanthanide MOFs of aromatic carboxylic ligands have largely drawn current attention (Zhang, et al., 2010) owing to their potential applications in medical imaging, sensors and electro-optical devices. 3-Pyridin-4-ylbenzoic acid (HL) which possess a pyridyl group and a benzoic acid group is a typical unsymmetrical spacer, and up to now only a serial of its transition metal coordination complexes was synthesized and characterized (Wu, et al., 2011). Herein we report the synthesis and structure of a gadolinium(III) complex of deprotonated 3-pyridin-4-ylbenzoic acid (HL), namely, [Gd(L)₃(H₂O)₂]_n (1).n(H₂O).

In (1), the Gd atom is in an eight-coordinate environment of O₈ ligated by six carboxylato O atoms from five ligands L and two O atoms from water molecules (Fig. 1). The Gd—O bonds fall in the normal range from 2.290 (2) to 2.532 (2) Å. In (1), deprotonated ligands L act as bidentate ligands, and display two coordinating modes, namely, chelating and bridging coordination models of carboxyl groups without the nitrogen atoms of the pyridyl groups taking part in the coordination. Complex (1) is a two-stranded polymeric chain builted from two L simultaneously bridging adjacent two Gd side by side and two L chelating them up and down with the separations of the adjacent metal Gd ions bridged by the carboxylato O3 and O4 of one L, and by the carboxylato O5 and O6 of the other L being 4.833 and 4.895 Å, respectively (Fig. 2). Apart from intrachain O—H···O hydrogen bonds, the chains of complex (1) are connected by interchain O—H···N hydrogen bonds between the coordinated water molecules (as donors) and the uncoordinated pyridyl groups of L (as acceptors), leading to the formation of a three-dimensional network structure with uncoordinated water molecules residing in the accessible void.

Related literature top

For metal-organic frameworks containing aromatic carboxylic ligands, see: Li et al. (2010). For lanthanide metal-organic frameworks based on aromatic carboxylic ligands, see: Zhang et al. (2010). For transition metal coordination complexes of 3-pyridin-4-ylbenzoicate, see: Wu et al. (2011).

Experimental top

A mixture of Gd(NO₃)₃ (0.045 g, 0.1 mmol), HL (0.060 g, 0.3 mmol), NaOH (0.012 0.3 mmol) and deionized water (10 ml) was sealed into a 25 ml Teflon-lined stainless autoclave. The autoclave was heated at 180 °C for four days. As cooled to room temperature gradually, colourless block crystals of (I) were obtained in 37% yield (based on Gd). Selected IR (cm^-1, KBr pellet): 3440(s), 1611(m), 1545(m), 1436(s), 1396(s), 1384(s), 1282(w), 1173(s), 1131(s), 766(m), 719(m), 655(m).

Structure description top

For metal-organic frameworks containing aromatic carboxylic ligands, see: Li et al. (2010). For lanthanide metal-organic frameworks based on aromatic carboxylic ligands, see: Zhang et al. (2010). For transition metal coordination complexes of 3-pyridin-4-ylbenzoicate, see: Wu et al. (2011).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. Coordination environment of the Gd atom in (1). Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) -x, -y, -z; (ii) -x + 1, -y, -z.
	Fig. 2. View of infinite two-stranded chain bridged by L in (1). Symmetry code: (i) -x, -y, -z; (ii) -x + 1, -y, -z.

catena-Poly[[[diaqua[3-(pyridin-4-yl)benzoato- κ²O,O']gadolinium(III)]-bis[µ-3-(pyridin-4-yl)benzoato- κ²O:O']] monohydrate] top

Crystal data top

[Gd(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O	Z = 2
M_r = 805.88	F(000) = 806
Triclinic, P1	D_x = 1.652 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7252 (5) Å	Cell parameters from 8413 reflections
b = 13.9535 (6) Å	θ = 2.9–26.3°
c = 14.0829 (8) Å	µ = 2.11 mm⁻¹
α = 118.019 (5)°	T = 293 K
β = 104.240 (5)°	Block, colourless
γ = 90.089 (4)°	0.35 × 0.21 × 0.18 mm
V = 1619.84 (14) Å³

Data collection top

Siemens SMART CCD diffractometer	5702 independent reflections
Radiation source: fine-focus sealed tube	4844 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scan	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.970, T_max = 1.000	k = −16→16
12338 measured reflections	l = −16→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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0298P)² + 0.5641P] where P = (F_o² + 2F_c²)/3
5702 reflections	(Δ/σ)_max = 0.001
460 parameters	Δρ_max = 0.85 e Å⁻³
2 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Gd(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O	γ = 90.089 (4)°
M_r = 805.88	V = 1619.84 (14) Å³
Triclinic, P1	Z = 2
a = 9.7252 (5) Å	Mo Kα radiation
b = 13.9535 (6) Å	µ = 2.11 mm⁻¹
c = 14.0829 (8) Å	T = 293 K
α = 118.019 (5)°	0.35 × 0.21 × 0.18 mm
β = 104.240 (5)°

Data collection top

Siemens SMART CCD diffractometer	5702 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4844 reflections with I > 2σ(I)
T_min = 0.970, T_max = 1.000	R_int = 0.023
12338 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	2 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.85 e Å⁻³
5702 reflections	Δρ_min = −0.66 e Å⁻³
460 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
Gd1	0.252518 (15)	−0.002199 (12)	0.002647 (12)	0.01875 (6)
O1	0.2075 (2)	0.17870 (18)	0.15035 (19)	0.0298 (5)
O2	0.3835 (2)	0.18197 (17)	0.07980 (19)	0.0290 (5)
O3	0.4213 (2)	0.03112 (19)	0.17419 (19)	0.0307 (5)
O4	0.6183 (2)	0.02697 (19)	0.12145 (18)	0.0284 (5)
O5	−0.0958 (2)	0.04584 (19)	−0.0786 (2)	0.0310 (5)
O6	0.1155 (2)	0.08726 (18)	−0.0915 (2)	0.0295 (5)
O7	0.0774 (2)	−0.1512 (2)	−0.1568 (2)	0.0312 (6)
O8	0.3516 (3)	−0.17299 (19)	−0.0343 (2)	0.0333 (6)
O9	0.3749 (6)	0.2281 (5)	−0.1164 (5)	0.1291 (19)
N1	0.1269 (4)	0.6874 (3)	0.6483 (3)	0.0487 (9)
N2	1.3290 (4)	0.2014 (3)	0.5396 (4)	0.0674 (11)
N3	0.2287 (4)	0.6204 (3)	−0.0892 (3)	0.0560 (10)
C1	0.3436 (3)	0.3525 (3)	0.2204 (3)	0.0268 (7)
C2	0.2774 (3)	0.4068 (3)	0.3048 (3)	0.0285 (7)
H2	0.2038	0.3674	0.3114	0.034*
C3	0.3178 (4)	0.5181 (3)	0.3797 (3)	0.0320 (8)
C4	0.4266 (4)	0.5753 (3)	0.3694 (3)	0.0384 (9)
H4	0.4578	0.6507	0.4217	0.046*
C5	0.4884 (4)	0.5218 (3)	0.2832 (3)	0.0441 (10)
H5	0.5597	0.5613	0.2746	0.053*
C6	0.4478 (4)	0.4114 (3)	0.2092 (3)	0.0349 (8)
H6	0.4914	0.3755	0.1503	0.042*
C7	0.2509 (4)	0.5773 (3)	0.4722 (3)	0.0343 (8)
C8	0.3328 (5)	0.6354 (3)	0.5820 (3)	0.0514 (11)
H8	0.4341	0.6393	0.5998	0.062*
C9	0.2673 (5)	0.6879 (4)	0.6658 (4)	0.0609 (13)
H9	0.3263	0.7268	0.7408	0.073*
C10	0.0485 (5)	0.6331 (3)	0.5419 (4)	0.0509 (11)
H10	−0.0522	0.6332	0.5267	0.061*
C11	0.1031 (4)	0.5768 (3)	0.4523 (3)	0.0444 (10)
H11	0.0413	0.5384	0.3782	0.053*
C12	0.3088 (3)	0.2315 (3)	0.1464 (3)	0.0246 (7)
C13	0.6422 (3)	0.0531 (3)	0.3047 (3)	0.0264 (7)
C14	0.7906 (3)	0.0751 (3)	0.3354 (3)	0.0276 (7)
H14	0.8363	0.0731	0.2823	0.033*
C15	0.8737 (3)	0.0999 (3)	0.4416 (3)	0.0299 (8)
C16	0.8041 (4)	0.0999 (4)	0.5168 (3)	0.0477 (11)
H16	0.8584	0.1169	0.5901	0.057*
C17	0.6570 (4)	0.0754 (4)	0.4861 (3)	0.0563 (12)
H17	0.6113	0.0735	0.5377	0.068*
C18	0.5758 (4)	0.0535 (3)	0.3811 (3)	0.0404 (9)
H18	0.4744	0.0387	0.3614	0.048*
C19	1.0316 (4)	0.1321 (3)	0.4756 (3)	0.0341 (8)
C20	1.1051 (4)	0.1240 (3)	0.3992 (4)	0.0446 (10)
H20	1.0552	0.0931	0.3220	0.053*
C21	1.2497 (4)	0.1605 (4)	0.4350 (4)	0.0548 (11)
H21	1.2952	0.1559	0.3808	0.066*
C22	1.2615 (5)	0.2065 (4)	0.6113 (4)	0.0720 (15)
H22	1.3162	0.2343	0.6871	0.086*
C23	1.1152 (4)	0.1742 (4)	0.5848 (4)	0.0566 (12)
H23	1.0733	0.1812	0.6416	0.068*
C24	0.5544 (3)	0.0352 (3)	0.1922 (3)	0.0236 (7)
C25	−0.0766 (3)	0.1751 (3)	−0.1399 (3)	0.0234 (7)
C26	0.0122 (3)	0.2600 (3)	−0.1274 (3)	0.0268 (7)
H26	0.1128	0.2649	−0.0993	0.032*
C27	−0.0424 (4)	0.3386 (3)	−0.1553 (3)	0.0314 (8)
C28	−0.1895 (4)	0.3258 (3)	−0.2000 (4)	0.0465 (10)
H28	−0.2296	0.3774	−0.2209	0.056*
C29	−0.2787 (4)	0.2405 (3)	−0.2148 (4)	0.0463 (10)
H29	−0.3789	0.2332	−0.2466	0.056*
C30	−0.2230 (4)	0.1656 (3)	−0.1837 (3)	0.0316 (8)
H30	−0.2848	0.1077	−0.1922	0.038*
C31	0.0522 (4)	0.4346 (3)	−0.1337 (3)	0.0349 (8)
C32	−0.0024 (5)	0.5242 (3)	−0.1383 (3)	0.0491 (11)
H32	−0.1030	0.5246	−0.1565	0.059*
C33	0.0871 (6)	0.6126 (3)	−0.1170 (4)	0.0559 (12)
H33	0.0448	0.6718	−0.1224	0.067*
C34	0.2818 (5)	0.5352 (4)	−0.0836 (5)	0.0685 (14)
H34	0.3830	0.5385	−0.0628	0.082*
C35	0.2005 (5)	0.4419 (3)	−0.1060 (4)	0.0586 (13)
H35	0.2459	0.3830	−0.1024	0.070*
C36	−0.0144 (3)	0.0968 (2)	−0.1011 (2)	0.0203 (7)
H7A	0.004 (4)	−0.156 (3)	−0.158 (3)	0.030*
H8A	0.318 (4)	−0.235 (3)	−0.047 (3)	0.030*
H7B	0.088 (3)	−0.207 (3)	−0.219 (3)	0.030*
H8B	0.422 (4)	−0.181 (3)	−0.048 (3)	0.030*
H9B	0.450 (3)	0.198 (3)	−0.132 (3)	0.030*
H9A	0.359 (4)	0.189 (3)	−0.087 (3)	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Gd1	0.01859 (9)	0.01705 (9)	0.02183 (9)	0.00224 (6)	0.00914 (6)	0.00871 (7)
O1	0.0271 (12)	0.0209 (12)	0.0364 (14)	0.0000 (10)	0.0167 (11)	0.0063 (11)
O2	0.0239 (12)	0.0224 (12)	0.0353 (14)	0.0021 (10)	0.0154 (11)	0.0065 (11)
O3	0.0215 (12)	0.0426 (15)	0.0293 (13)	0.0027 (10)	0.0080 (10)	0.0181 (12)
O4	0.0270 (12)	0.0393 (14)	0.0239 (12)	0.0062 (10)	0.0126 (10)	0.0164 (11)
O5	0.0294 (13)	0.0361 (14)	0.0416 (15)	0.0049 (11)	0.0149 (11)	0.0274 (13)
O6	0.0198 (12)	0.0311 (14)	0.0434 (15)	0.0055 (10)	0.0073 (11)	0.0234 (12)
O7	0.0210 (13)	0.0284 (14)	0.0306 (14)	0.0001 (11)	0.0099 (12)	0.0023 (11)
O8	0.0273 (14)	0.0206 (13)	0.0557 (17)	0.0068 (11)	0.0211 (13)	0.0170 (13)
O9	0.155 (5)	0.143 (5)	0.166 (5)	0.077 (4)	0.082 (4)	0.117 (4)
N1	0.067 (3)	0.035 (2)	0.044 (2)	0.0145 (18)	0.029 (2)	0.0121 (17)
N2	0.037 (2)	0.074 (3)	0.074 (3)	−0.008 (2)	0.010 (2)	0.025 (2)
N3	0.078 (3)	0.032 (2)	0.068 (3)	−0.0022 (19)	0.033 (2)	0.0253 (19)
C1	0.0235 (17)	0.0210 (18)	0.0311 (19)	0.0030 (14)	0.0040 (15)	0.0107 (15)
C2	0.0273 (18)	0.0241 (18)	0.0302 (19)	0.0036 (14)	0.0093 (15)	0.0096 (16)
C3	0.0324 (19)	0.0254 (19)	0.032 (2)	0.0078 (15)	0.0069 (16)	0.0101 (16)
C4	0.046 (2)	0.0195 (19)	0.037 (2)	−0.0030 (16)	0.0090 (18)	0.0049 (17)
C5	0.047 (2)	0.028 (2)	0.055 (3)	−0.0019 (17)	0.022 (2)	0.014 (2)
C6	0.037 (2)	0.0244 (19)	0.042 (2)	0.0016 (16)	0.0195 (18)	0.0117 (17)
C7	0.043 (2)	0.0203 (18)	0.033 (2)	0.0084 (16)	0.0128 (17)	0.0071 (16)
C8	0.052 (3)	0.050 (3)	0.036 (2)	0.022 (2)	0.012 (2)	0.008 (2)
C9	0.081 (4)	0.050 (3)	0.035 (2)	0.022 (3)	0.013 (2)	0.009 (2)
C10	0.053 (3)	0.036 (2)	0.058 (3)	0.009 (2)	0.029 (2)	0.012 (2)
C11	0.045 (2)	0.034 (2)	0.039 (2)	−0.0008 (18)	0.0153 (19)	0.0045 (18)
C12	0.0183 (16)	0.0211 (17)	0.0310 (19)	0.0031 (13)	0.0070 (14)	0.0098 (15)
C13	0.0256 (18)	0.0285 (19)	0.0255 (18)	0.0029 (14)	0.0093 (15)	0.0124 (15)
C14	0.0267 (18)	0.0315 (19)	0.0283 (19)	0.0052 (15)	0.0116 (15)	0.0156 (16)
C15	0.0251 (18)	0.033 (2)	0.0283 (19)	0.0023 (15)	0.0048 (15)	0.0136 (16)
C16	0.040 (2)	0.077 (3)	0.032 (2)	−0.002 (2)	0.0036 (18)	0.033 (2)
C17	0.039 (2)	0.103 (4)	0.037 (2)	−0.003 (2)	0.0124 (19)	0.041 (3)
C18	0.0252 (19)	0.067 (3)	0.032 (2)	−0.0013 (18)	0.0079 (16)	0.026 (2)
C19	0.0296 (19)	0.033 (2)	0.036 (2)	0.0032 (16)	0.0070 (17)	0.0143 (17)
C20	0.027 (2)	0.055 (3)	0.050 (3)	0.0052 (18)	0.0067 (18)	0.026 (2)
C21	0.034 (2)	0.067 (3)	0.066 (3)	0.006 (2)	0.016 (2)	0.034 (3)
C22	0.040 (3)	0.086 (4)	0.051 (3)	−0.009 (3)	−0.011 (2)	0.014 (3)
C23	0.037 (2)	0.079 (3)	0.037 (2)	−0.004 (2)	0.0046 (19)	0.017 (2)
C24	0.0217 (17)	0.0223 (17)	0.0269 (18)	0.0034 (13)	0.0084 (14)	0.0112 (15)
C25	0.0238 (17)	0.0247 (18)	0.0242 (17)	0.0043 (14)	0.0076 (14)	0.0134 (15)
C26	0.0243 (17)	0.0266 (18)	0.0304 (19)	0.0049 (14)	0.0065 (15)	0.0151 (16)
C27	0.038 (2)	0.0240 (19)	0.036 (2)	0.0067 (15)	0.0121 (17)	0.0170 (17)
C28	0.043 (2)	0.045 (3)	0.064 (3)	0.0128 (19)	0.008 (2)	0.039 (2)
C29	0.025 (2)	0.053 (3)	0.069 (3)	0.0071 (18)	0.0040 (19)	0.041 (2)
C30	0.0281 (19)	0.032 (2)	0.037 (2)	0.0001 (15)	0.0078 (16)	0.0185 (17)
C31	0.050 (2)	0.028 (2)	0.035 (2)	0.0037 (17)	0.0189 (18)	0.0182 (17)
C32	0.060 (3)	0.037 (2)	0.057 (3)	0.003 (2)	0.010 (2)	0.031 (2)
C33	0.095 (4)	0.031 (2)	0.051 (3)	0.007 (2)	0.021 (3)	0.027 (2)
C34	0.059 (3)	0.048 (3)	0.112 (4)	0.001 (2)	0.036 (3)	0.044 (3)
C35	0.055 (3)	0.041 (3)	0.101 (4)	0.010 (2)	0.033 (3)	0.046 (3)
C36	0.0264 (18)	0.0155 (16)	0.0164 (16)	−0.0001 (13)	0.0068 (13)	0.0054 (13)

Geometric parameters (Å, º) top

Gd1—O5ⁱ	2.290 (2)	C9—H9	0.9500
Gd1—O4ⁱⁱ	2.295 (2)	C10—C11	1.375 (5)
Gd1—O3	2.395 (2)	C10—H10	0.9500
Gd1—O6	2.405 (2)	C11—H11	0.9500
Gd1—O8	2.443 (2)	C13—C18	1.382 (4)
Gd1—O7	2.447 (2)	C13—C14	1.389 (4)
Gd1—O2	2.468 (2)	C13—C24	1.505 (4)
Gd1—O1	2.532 (2)	C14—C15	1.388 (4)
O1—C12	1.257 (4)	C14—H14	0.9500
O2—C12	1.270 (4)	C15—C16	1.390 (5)
O3—C24	1.252 (3)	C15—C19	1.491 (5)
O4—C24	1.261 (3)	C16—C17	1.381 (5)
O4—Gd1ⁱⁱ	2.295 (2)	C16—H16	0.9500
O5—C36	1.252 (3)	C17—C18	1.379 (5)
O5—Gd1ⁱ	2.290 (2)	C17—H17	0.9500
O6—C36	1.251 (3)	C18—H18	0.9500
O7—H7A	0.71 (3)	C19—C23	1.380 (5)
O7—H7B	0.89 (4)	C19—C20	1.395 (5)
O8—H8A	0.84 (4)	C20—C21	1.378 (5)
O8—H8B	0.75 (3)	C20—H20	0.9500
O9—H9B	0.872 (10)	C21—H21	0.9500
O9—H9A	0.868 (10)	C22—C23	1.394 (6)
N1—C9	1.325 (5)	C22—H22	0.9500
N1—C10	1.331 (5)	C23—H23	0.9500
N2—C22	1.310 (6)	C25—C26	1.381 (4)
N2—C21	1.320 (6)	C25—C30	1.384 (4)
N3—C33	1.325 (6)	C25—C36	1.502 (4)
N3—C34	1.325 (5)	C26—C27	1.394 (4)
C1—C6	1.387 (4)	C26—H26	0.9500
C1—C2	1.390 (4)	C27—C28	1.387 (5)
C1—C12	1.490 (4)	C27—C31	1.486 (5)
C2—C3	1.391 (5)	C28—C29	1.373 (5)
C2—H2	0.9500	C28—H28	0.9500
C3—C4	1.398 (5)	C29—C30	1.376 (5)
C3—C7	1.488 (5)	C29—H29	0.9500
C4—C5	1.380 (5)	C30—H30	0.9500
C4—H4	0.9500	C31—C32	1.382 (5)
C5—C6	1.379 (5)	C31—C35	1.389 (5)
C5—H5	0.9500	C32—C33	1.374 (6)
C6—H6	0.9500	C32—H32	0.9500
C7—C8	1.377 (5)	C33—H33	0.9500
C7—C11	1.394 (5)	C34—C35	1.381 (5)
C8—C9	1.376 (5)	C34—H34	0.9500
C8—H8	0.9500	C35—H35	0.9500

O5ⁱ—Gd1—O4ⁱⁱ	158.30 (9)	O1—C12—C1	120.5 (3)
O5ⁱ—Gd1—O3	82.32 (8)	O2—C12—C1	119.3 (3)
O4ⁱⁱ—Gd1—O3	106.79 (7)	O1—C12—Gd1	61.50 (16)
O5ⁱ—Gd1—O6	103.62 (7)	O2—C12—Gd1	58.66 (16)
O4ⁱⁱ—Gd1—O6	81.10 (7)	C1—C12—Gd1	177.8 (2)
O3—Gd1—O6	143.19 (8)	C18—C13—C14	119.1 (3)
O5ⁱ—Gd1—O8	89.77 (8)	C18—C13—C24	120.3 (3)
O4ⁱⁱ—Gd1—O8	74.67 (8)	C14—C13—C24	120.5 (3)
O3—Gd1—O8	73.33 (9)	C15—C14—C13	121.8 (3)
O6—Gd1—O8	141.74 (9)	C15—C14—H14	119.1
O5ⁱ—Gd1—O7	74.87 (9)	C13—C14—H14	119.1
O4ⁱⁱ—Gd1—O7	85.95 (8)	C14—C15—C16	117.9 (3)
O3—Gd1—O7	138.81 (8)	C14—C15—C19	120.8 (3)
O6—Gd1—O7	76.44 (8)	C16—C15—C19	121.2 (3)
O8—Gd1—O7	72.76 (9)	C17—C16—C15	120.7 (3)
O5ⁱ—Gd1—O2	125.02 (8)	C17—C16—H16	119.6
O4ⁱⁱ—Gd1—O2	76.66 (8)	C15—C16—H16	119.6
O3—Gd1—O2	74.77 (8)	C18—C17—C16	120.5 (4)
O6—Gd1—O2	72.28 (8)	C18—C17—H17	119.7
O8—Gd1—O2	127.98 (8)	C16—C17—H17	119.7
O7—Gd1—O2	146.07 (9)	C17—C18—C13	119.9 (3)
O5ⁱ—Gd1—O1	74.17 (8)	C17—C18—H18	120.1
O4ⁱⁱ—Gd1—O1	126.86 (7)	C13—C18—H18	120.1
O3—Gd1—O1	74.94 (8)	C23—C19—C20	115.1 (3)
O6—Gd1—O1	72.06 (8)	C23—C19—C15	122.8 (3)
O8—Gd1—O1	146.02 (9)	C20—C19—C15	122.1 (3)
O7—Gd1—O1	128.36 (7)	C21—C20—C19	120.4 (4)
O2—Gd1—O1	51.95 (7)	C21—C20—H20	119.8
C12—O1—Gd1	92.62 (18)	C19—C20—H20	119.8
C12—O2—Gd1	95.27 (18)	N2—C21—C20	124.2 (4)
C24—O3—Gd1	126.2 (2)	N2—C21—H21	117.9
C24—O4—Gd1ⁱⁱ	174.8 (2)	C20—C21—H21	117.9
C36—O5—Gd1ⁱ	163.6 (2)	N2—C22—C23	124.8 (4)
C36—O6—Gd1	125.31 (18)	N2—C22—H22	117.6
Gd1—O7—H7A	121 (3)	C23—C22—H22	117.6
Gd1—O7—H7B	131 (2)	C19—C23—C22	119.7 (4)
H7A—O7—H7B	108 (4)	C19—C23—H23	120.2
Gd1—O8—H8A	134 (2)	C22—C23—H23	120.2
Gd1—O8—H8B	120 (3)	O3—C24—O4	123.2 (3)
H8A—O8—H8B	105 (3)	O3—C24—C13	118.2 (3)
H9B—O9—H9A	93 (3)	O4—C24—C13	118.5 (3)
C9—N1—C10	115.9 (4)	C26—C25—C30	119.6 (3)
C22—N2—C21	115.7 (4)	C26—C25—C36	119.8 (3)
C33—N3—C34	115.4 (4)	C30—C25—C36	120.5 (3)
C6—C1—C2	119.2 (3)	C25—C26—C27	121.5 (3)
C6—C1—C12	120.2 (3)	C25—C26—H26	119.3
C2—C1—C12	120.6 (3)	C27—C26—H26	119.3
C1—C2—C3	120.7 (3)	C28—C27—C26	117.2 (3)
C1—C2—H2	119.6	C28—C27—C31	121.4 (3)
C3—C2—H2	119.6	C26—C27—C31	121.4 (3)
C2—C3—C4	119.2 (3)	C29—C28—C27	121.9 (3)
C2—C3—C7	121.6 (3)	C29—C28—H28	119.1
C4—C3—C7	119.2 (3)	C27—C28—H28	119.1
C5—C4—C3	119.8 (3)	C28—C29—C30	120.0 (3)
C5—C4—H4	120.1	C28—C29—H29	120.0
C3—C4—H4	120.1	C30—C29—H29	120.0
C6—C5—C4	120.7 (3)	C29—C30—C25	119.8 (3)
C6—C5—H5	119.7	C29—C30—H30	120.1
C4—C5—H5	119.7	C25—C30—H30	120.1
C5—C6—C1	120.4 (3)	C32—C31—C35	115.2 (3)
C5—C6—H6	119.8	C32—C31—C27	121.8 (3)
C1—C6—H6	119.8	C35—C31—C27	123.0 (3)
C8—C7—C11	116.9 (3)	C33—C32—C31	120.9 (4)
C8—C7—C3	121.2 (3)	C33—C32—H32	119.5
C11—C7—C3	121.8 (3)	C31—C32—H32	119.5
C9—C8—C7	119.7 (4)	N3—C33—C32	124.0 (4)
C9—C8—H8	120.1	N3—C33—H33	118.0
C7—C8—H8	120.1	C32—C33—H33	118.0
N1—C9—C8	124.1 (4)	N3—C34—C35	124.7 (4)
N1—C9—H9	118.0	N3—C34—H34	117.7
C8—C9—H9	118.0	C35—C34—H34	117.7
N1—C10—C11	124.5 (4)	C34—C35—C31	119.7 (4)
N1—C10—H10	117.7	C34—C35—H35	120.1
C11—C10—H10	117.7	C31—C35—H35	120.1
C10—C11—C7	118.8 (4)	O6—C36—O5	123.6 (3)
C10—C11—H11	120.6	O6—C36—C25	118.6 (3)
C7—C11—H11	120.6	O5—C36—C25	117.8 (3)
O1—C12—O2	120.2 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O1ⁱ	0.71 (3)	2.12 (3)	2.826 (3)	173 (4)
O7—H7B···N1ⁱⁱⁱ	0.89 (4)	1.89 (4)	2.772 (4)	173 (3)
O8—H8B···O2ⁱⁱ	0.75 (3)	2.05 (3)	2.793 (3)	173 (4)
O8—H8A···N3^iv	0.84 (4)	1.95 (4)	2.789 (4)	175 (3)

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

Experimental details

Crystal data
Chemical formula	[Gd(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O
M_r	805.88
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.7252 (5), 13.9535 (6), 14.0829 (8)
α, β, γ (°)	118.019 (5), 104.240 (5), 90.089 (4)
V (Å³)	1619.84 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.11
Crystal size (mm)	0.35 × 0.21 × 0.18

Data collection
Diffractometer	Siemens SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12338, 5702, 4844
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.061, 1.05
No. of reflections	5702
No. of parameters	460
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.66

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Gd1—O5ⁱ	2.290 (2)	Gd1—O8	2.443 (2)
Gd1—O4ⁱⁱ	2.295 (2)	Gd1—O7	2.447 (2)
Gd1—O3	2.395 (2)	Gd1—O2	2.468 (2)
Gd1—O6	2.405 (2)	Gd1—O1	2.532 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O1ⁱ	0.71 (3)	2.12 (3)	2.826 (3)	173 (4)
O7—H7B···N1ⁱⁱⁱ	0.89 (4)	1.89 (4)	2.772 (4)	173 (3)
O8—H8B···O2ⁱⁱ	0.75 (3)	2.05 (3)	2.793 (3)	173 (4)
O8—H8A···N3^iv	0.84 (4)	1.95 (4)	2.789 (4)	175 (3)

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

Acknowledgements

This work was supported by the Natural Science Foundation of China.

References

Li, X., Wu, B., Wang, R., Zhang, H., Niu, C., Niu, Y. & Hou, H. (2010). Inorg. Chem. 49, 2600–2613. Web of Science CSD CrossRef CAS PubMed Google Scholar
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