Poly[[tetra­aqua-μ4-fumarato-di-μ3-fumarato-dineodymium(III)] trihydrate]

Chen, H.; Tang, T.; Wang, J.; Liu, P.; Zhuo, Z.

doi:10.1107/S1600536811046447

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1717-m1718

https://doi.org/10.1107/S1600536811046447

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Poly[[tetraaqua-μ₄-fumarato-di-μ₃-fumarato-dineodymium(III)] trihydrate]

Hong-ren Chen,^a Tian-sheng Tang,^a Jin Wang,^a Pei-lian Liu ^a and Zeng Zhuo ^a,^b ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: zhuosioc@yahoo.com.cn

(Received 28 September 2011; accepted 3 November 2011; online 9 November 2011)

The title coordination polymer, {[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O}, was synthesized by the reaction of neodymium(III) nitrate hexahydrate with fumaric acid in a water–methanol (7:3) solution. The asymmetric unit comprises two Nd³⁺ cations, three fumarate dianions (L²⁻), four aqua ligands and three uncoordinated water molecules. The carboxylate groups of the fumarate dianions exhibit different coordination modes. In one fumarate dianion, two carboxylate groups chelate two Nd³⁺ cations, while one of the O atoms is coordinated to another Nd³⁺ cation. Another fumarate dianion bridges three Nd³⁺ cations: one of the carboxylate groups chelates one Nd³⁺ cation, while the other carboxylate group bridges two Nd³⁺ cations in a monodentate mode. The third fumarate dianion bridges four Nd³⁺ cations, where one of the carboxylate groups chelates one Nd³⁺ cation and coordinates in a monodentate mode to a second Nd³⁺, while the second carboxylate groups bridges two Nd³⁺ cations in a monodentate mode and one O atom is coordinated to one Nd³⁺ cation. The Nd³⁺ cations are in a distorted tricapped–trigonal prismatic environment and coordinated by seven O atoms from the fumarate ligands and two O atoms from water molecules. The Nd³⁺ cations are linked by two carboxylate O atoms and two carboxylate groups, generating infinite Nd–O chains to form a three-dimensional framework. There are O—H⋯O and C—H⋯O hydrogen-bonding interactions between the coordinated and uncoordinated water molecules and carboxylate O atoms.

Related literature

For applications of metal complexes with carboxylato ligands, see: Eliseeva et al. (2010 ); Kim et al. (2001 ); Seki & Mori (2002 ).

Experimental

Crystal data

[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O
M_r = 756.76
Monoclinic, P 2₁ /n
a = 9.5810 (9) Å
b = 14.8675 (15) Å
c = 14.9056 (14) Å
β = 91.538 (5)°
V = 2122.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 298 K
0.16 × 0.15 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.459, T_max = 0.501
24284 measured reflections
5150 independent reflections
4060 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.075
S = 1.05
5150 reflections
306 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2WA⋯O1	0.85	2.57	3.103 (13)	122
O2W—H2WA⋯O3	0.85	2.52	3.319 (13)	158
O2W—H2WB⋯O1Wⁱ	0.85	2.53	2.98 (2)	114
O3W—H3WD⋯O24ⁱ	0.85	2.07	2.896 (6)	165
O3W—H3WC⋯O1W	0.85	2.12	2.60 (2)	115
O3W—H3WC⋯O2W	0.85	2.08	2.911 (13)	165
O1W—H1WD⋯O2W	0.85	2.06	2.634 (19)	124
O1W—H1WC⋯O6ⁱⁱ	0.85	2.11	2.959 (17)	178
O8—H8C⋯O3Wⁱⁱⁱ	0.85	2.05	2.829 (5)	152
O8—H8B⋯O1^iv	0.85	1.91	2.745 (5)	169
O13—H13A⋯O3Wⁱⁱⁱ	0.85	2.14	2.938 (6)	157
O13—H13B⋯O25^v	0.82	2.02	2.787 (5)	157
O14—H14A⋯O12^vi	0.86 (6)	1.88 (6)	2.740 (5)	172 (6)
O14—H14B⋯O4ⁱⁱⁱ	0.75 (5)	2.04 (6)	2.776 (5)	166 (6)
O16—H16A⋯O27^vii	0.72	2.02	2.714 (5)	160
O16—H16C⋯O2^viii	0.85	2.07	2.915 (5)	171
C3—H3⋯O24^v	0.93	2.53	3.345 (6)	147
C8—H8⋯O12^iv	0.93	2.58	3.417 (6)	150
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vi) -x+1, -y+2, -z+1; (vii) x+1, y, z; (viii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046447/ez2264sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046447/ez2264Isup2.hkl

checkCIF report

Comment top

Recently, many metal complexes of carboxylates and lanthanide complexes which display interesting properties have been reported: Mn dicarboxylate compounds present antiferromagnetic interactions (Kim et al., 2001), while Cu dicarboxylates have uniform micropores, high porosities and gas adsorption capacities (Seki et al., 2002). In addition, lanthanide complexes can be used as active materials in luminescent devices (Eliseeva et al., 2010). In this paper, we report the title complex, obtained by the reaction of neodymium(III) nitrate hexahydrate with fumaric acid in a water-methanol (7:3) solution.

The structure of the asymmetric unit of the title complex is shown in Fig. 1. It comprises two Nd³⁺ cations, three fumarate dianions (L^2-), four aqua ligands and three uncoordinated water molecules. The carboxylate groups of the fumarate dianion exhibit different coordination modes. In one fumarate dianion two carboxylate groups chelate with two Nd³⁺ cations, while one of the O atoms (O11) is coordinated with another Nd³⁺ cation. The second fumarate dianion bridges three Nd³⁺ cations, one of carboxylate groups chelating with one Nd³⁺ cation and the other carboxylate groups bridging two Nd³⁺ cations in monodentate mode. The third fumarate ligand bridges four Nd³⁺ cations, one of carboxylate groups chelating with one Nd³⁺ cation and one of carboxylate groups bridging two Nd³⁺ cations in monodentate mode, while one O atom (O3) is coordinated with a third Nd³⁺ cation. The Nd³⁺ cations are situated within a distorted tricapped trigonal prism and coordinated by seven O atoms from the fumarate dianion ligands and two O atom from water molecules. The Nd—O bond distances range from 2.387 (3) to 2.655 (3) Å. The O—Nd—O bond angles range from 73.4 (1) to 155.0 (1)°. The Nd³⁺ cations are linked by two carboxylate O atoms (O3 and O11) and two carboxylate groups (O5—C5—O6 and O26—C18—O27) to generate infinite neodymium-oxygen chains (Fig. 2). The chains are further connected by the ligands to form a three-dimensional framework. The crystal is stabilized by hydrogen bond interactions between the coordinated and uncoordinated water molecules and the carboxylate O atoms (Table 1).

Related literature top

For applications of metal complexes of carboxylates, see: Eliseeva et al. (2010); Kim et al. (2001); Seki & Mori (2002).

Experimental top

Fumaric acid (0.3 mmol, 0.035 g) and neodymium(III) nitrate hexahydrate(0.5 mmol, 0.22 g) were dissolved in a water-methanol(7:3) solution (10 ml). The mixture was transferred to a 20 ml Teflon-lined stainless steel autoclave, which was heated at 443 K for 96 h. The reactor was cooled to room temperature over a period of 24 h. Green crystals were obtained after filtration, washing with water and vacum drying.

Structure description top

For applications of metal complexes of carboxylates, see: Eliseeva et al. (2010); Kim et al. (2001); Seki & Mori (2002).

Computing details top

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

Figures top

	Fig. 1. View of the local coordination sphere around the neodymium(III) centers with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (A)1 + x,y,z; (B)2 - x,1 - y,1 - z; (C)1/2 + x,3/2 - y,1/2 + z.]
	Fig. 2. Perspective view of the crystal packing.

Poly[[tetraaqua-µ₄-fumarato-di-µ₃-fumarato-dineodymium(III)] trihydrate] top

Crystal data top

[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O	F(000) = 1456.0
M_r = 756.76	D_x = 2.368 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6284 reflections
a = 9.5810 (9) Å	θ = 2.5–28.0°
b = 14.8675 (15) Å	µ = 4.93 mm⁻¹
c = 14.9056 (14) Å	T = 298 K
β = 91.538 (5)°	Block, green
V = 2122.5 (4) Å³	0.16 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5150 independent reflections
Radiation source: fine-focus sealed tube	4060 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
phi and ω scans	θ_max = 28.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.459, T_max = 0.501	k = −19→19
24284 measured reflections	l = −15→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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0302P)² + 2.6259P] where P = (F_o² + 2F_c²)/3
5150 reflections	(Δ/σ)_max = 0.002
306 parameters	Δρ_max = 1.36 e Å⁻³
0 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O	V = 2122.5 (4) Å³
M_r = 756.76	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5810 (9) Å	µ = 4.93 mm⁻¹
b = 14.8675 (15) Å	T = 298 K
c = 14.9056 (14) Å	0.16 × 0.15 × 0.14 mm
β = 91.538 (5)°

Data collection top

Bruker APEXII CCD diffractometer	5150 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4060 reflections with I > 2σ(I)
T_min = 0.459, T_max = 0.501	R_int = 0.052
24284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.36 e Å⁻³
5150 reflections	Δρ_min = −0.89 e Å⁻³
306 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
Nd1	1.02953 (3)	0.663992 (15)	0.246217 (16)	0.01439 (7)
Nd2	0.80991 (2)	0.846421 (15)	0.405801 (16)	0.01358 (7)
O1	0.5842 (3)	0.7709 (2)	0.4569 (2)	0.0234 (8)
C3	0.2687 (5)	0.8568 (3)	0.3655 (3)	0.0227 (11)
H3	0.3058	0.8783	0.3127	0.027*
O2	0.5619 (3)	0.8871 (2)	0.3665 (2)	0.0264 (8)
C1	0.5090 (5)	0.8282 (3)	0.4166 (3)	0.0189 (10)
C2	0.3555 (5)	0.8281 (4)	0.4280 (4)	0.0291 (12)
H2	0.3202	0.8068	0.4815	0.035*
O3	0.7836 (3)	0.7226 (2)	0.2985 (2)	0.0248 (8)
O4	0.7899 (3)	0.6470 (2)	0.1732 (2)	0.0241 (8)
C4	0.7199 (5)	0.6861 (3)	0.2319 (3)	0.0186 (10)
O6	1.0906 (4)	0.6561 (2)	0.4082 (2)	0.0288 (8)
C5	1.0122 (6)	0.6644 (3)	0.4739 (3)	0.0215 (11)
O5	0.9116 (4)	0.7183 (2)	0.4785 (2)	0.0312 (9)
O8	1.0189 (4)	0.7802 (2)	0.1277 (2)	0.0342 (9)
H8B	1.0470	0.7594	0.0782	0.041*
H8C	1.0621	0.8282	0.1422	0.041*
C8	0.4972 (5)	0.6643 (3)	0.1528 (3)	0.0229 (11)
H8	0.5490	0.6512	0.1025	0.028*
C6	0.1155 (5)	0.8573 (3)	0.3732 (3)	0.0167 (10)
C7	0.5665 (5)	0.6870 (3)	0.2248 (3)	0.0249 (11)
H7	0.5169	0.7049	0.2745	0.030*
C10	1.0375 (5)	0.6029 (3)	0.5517 (3)	0.0238 (11)
H10	1.1223	0.5725	0.5560	0.029*
C9	0.9469 (6)	0.5895 (3)	0.6139 (3)	0.0284 (12)
H9	0.8705	0.6280	0.6170	0.034*
O11	0.0390 (3)	0.8180 (2)	0.3136 (2)	0.0191 (7)
O12	0.0605 (3)	0.8974 (2)	0.4368 (2)	0.0283 (8)
O14	0.7818 (4)	1.0060 (2)	0.4411 (3)	0.0310 (9)
O13	0.8092 (4)	0.9288 (3)	0.2613 (2)	0.0359 (9)
H13A	0.8857	0.9226	0.2344	0.043*
H13B	0.7472	0.9489	0.2284	0.043*
O16	1.0338 (3)	0.5710 (2)	0.1065 (2)	0.0244 (8)
H16C	1.0155	0.5158	0.1155	0.029*
H16A	1.1004	0.5787	0.0861	0.029*
C17	0.9609 (6)	0.5154 (3)	0.6799 (3)	0.0229 (11)
O25	1.0774 (4)	0.4770 (2)	0.6945 (2)	0.0268 (8)
O24	0.8508 (4)	0.4865 (2)	0.7148 (2)	0.0280 (8)
C18	0.3435 (5)	0.6570 (3)	0.1423 (3)	0.0172 (10)
O26	0.2692 (3)	0.6793 (2)	0.2068 (2)	0.0264 (8)
O27	0.2955 (3)	0.6265 (2)	0.0686 (2)	0.0234 (8)
O2W	0.6477 (13)	0.5680 (8)	0.4310 (8)	0.236 (5)
H2WA	0.6803	0.6169	0.4106	0.354*
H2WB	0.7017	0.5507	0.4737	0.354*
O3W	0.4332 (5)	0.4644 (3)	0.3352 (3)	0.0568 (13)
H3WC	0.4845	0.5021	0.3634	0.085*
H3WD	0.3534	0.4878	0.3252	0.085*
H14A	0.833 (6)	1.032 (4)	0.482 (4)	0.043 (19)*
H14B	0.776 (6)	1.044 (4)	0.408 (4)	0.023 (16)*
O1W	0.3772 (16)	0.5909 (13)	0.4489 (10)	0.342 (10)
H1WD	0.4418	0.6067	0.4142	0.514*
H1WC	0.2950	0.6105	0.4385	0.514*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.01165 (14)	0.01670 (12)	0.01485 (13)	−0.00010 (9)	0.00092 (10)	−0.00118 (9)
Nd2	0.00971 (14)	0.01650 (12)	0.01448 (13)	0.00087 (9)	−0.00055 (9)	−0.00120 (9)
O1	0.0173 (19)	0.0271 (18)	0.0256 (19)	0.0033 (15)	−0.0008 (14)	0.0066 (15)
C3	0.016 (3)	0.030 (3)	0.022 (3)	−0.005 (2)	0.006 (2)	0.002 (2)
O2	0.0102 (18)	0.0298 (19)	0.039 (2)	0.0005 (14)	−0.0017 (15)	0.0124 (16)
C1	0.019 (3)	0.025 (2)	0.013 (2)	−0.003 (2)	0.0025 (19)	−0.0046 (18)
C2	0.016 (3)	0.045 (3)	0.026 (3)	0.001 (2)	0.006 (2)	0.009 (2)
O3	0.0194 (19)	0.0286 (18)	0.0262 (19)	−0.0038 (15)	−0.0014 (15)	−0.0119 (15)
O4	0.0141 (18)	0.0347 (19)	0.0235 (19)	−0.0003 (15)	−0.0001 (14)	−0.0118 (15)
C4	0.016 (3)	0.017 (2)	0.022 (3)	0.0004 (19)	0.002 (2)	0.0004 (19)
O6	0.040 (2)	0.0298 (19)	0.0168 (18)	0.0040 (16)	0.0007 (16)	0.0004 (14)
C5	0.031 (3)	0.017 (2)	0.016 (2)	0.000 (2)	−0.002 (2)	0.0009 (18)
O5	0.034 (2)	0.0296 (19)	0.030 (2)	0.0101 (17)	0.0015 (17)	0.0109 (16)
O8	0.052 (3)	0.0264 (19)	0.024 (2)	−0.0025 (18)	0.0027 (18)	−0.0020 (16)
C8	0.016 (3)	0.034 (3)	0.019 (3)	0.004 (2)	0.005 (2)	−0.002 (2)
C6	0.013 (2)	0.020 (2)	0.017 (2)	0.0006 (19)	0.0011 (19)	0.0031 (18)
C7	0.015 (3)	0.034 (3)	0.025 (3)	0.001 (2)	0.002 (2)	−0.011 (2)
C10	0.029 (3)	0.021 (2)	0.021 (3)	0.005 (2)	−0.005 (2)	0.004 (2)
C9	0.035 (3)	0.021 (2)	0.030 (3)	0.009 (2)	0.001 (2)	0.006 (2)
O11	0.0153 (18)	0.0236 (16)	0.0183 (17)	−0.0007 (14)	−0.0018 (14)	−0.0039 (13)
O12	0.0138 (18)	0.041 (2)	0.031 (2)	−0.0051 (16)	0.0035 (15)	−0.0138 (17)
O14	0.043 (3)	0.0159 (18)	0.033 (2)	0.0024 (17)	−0.0169 (19)	−0.0004 (17)
O13	0.029 (2)	0.049 (2)	0.030 (2)	0.0144 (19)	0.0089 (17)	0.0166 (18)
O16	0.0199 (19)	0.0240 (17)	0.030 (2)	−0.0037 (15)	0.0067 (15)	−0.0051 (15)
C17	0.033 (3)	0.018 (2)	0.018 (2)	0.000 (2)	0.000 (2)	0.0011 (19)
O25	0.025 (2)	0.0219 (17)	0.033 (2)	−0.0031 (15)	−0.0052 (16)	0.0079 (15)
O24	0.030 (2)	0.0263 (18)	0.028 (2)	0.0038 (16)	0.0063 (16)	0.0026 (15)
C18	0.011 (2)	0.020 (2)	0.020 (2)	0.0007 (18)	0.0020 (19)	0.0015 (18)
O26	0.0138 (19)	0.042 (2)	0.0239 (19)	−0.0025 (15)	0.0050 (15)	−0.0083 (16)
O27	0.0188 (19)	0.0361 (19)	0.0151 (17)	−0.0072 (15)	−0.0027 (14)	0.0018 (14)
O2W	0.251 (14)	0.170 (10)	0.285 (15)	−0.001 (10)	−0.021 (11)	0.011 (10)
O3W	0.054 (3)	0.040 (3)	0.076 (4)	0.005 (2)	−0.001 (3)	−0.011 (2)
O1W	0.264 (16)	0.44 (3)	0.32 (2)	−0.100 (17)	−0.051 (14)	0.098 (19)

Geometric parameters (Å, º) top

Nd1—O26ⁱ	2.397 (3)	O8—H8C	0.8501
Nd1—O8	2.471 (3)	C8—C7	1.291 (7)
Nd1—O6	2.473 (3)	C8—C18	1.480 (7)
Nd1—O11ⁱ	2.501 (3)	C8—H8	0.9300
Nd1—O16	2.502 (3)	C6—O12	1.249 (5)
Nd1—O25ⁱⁱ	2.504 (3)	C6—O11	1.276 (5)
Nd1—O4	2.527 (3)	C6—Nd2^iv	2.985 (5)
Nd1—O4	2.527 (3)	C7—H7	0.9300
Nd1—O24ⁱⁱ	2.573 (3)	C10—C9	1.302 (7)
Nd1—O3	2.649 (3)	C10—H10	0.9300
Nd1—O3	2.649 (3)	C9—C17	1.482 (6)
Nd1—C17ⁱⁱ	2.886 (5)	C9—H9	0.9300
Nd2—O5	2.387 (3)	O11—Nd1^iv	2.501 (3)
Nd2—O14	2.446 (4)	O11—Nd2^iv	2.655 (3)
Nd2—O3	2.447 (3)	O12—Nd2^iv	2.548 (3)
Nd2—O3	2.447 (3)	O14—H14A	0.86 (6)
Nd2—O27ⁱⁱⁱ	2.467 (3)	O14—H14B	0.75 (5)
Nd2—O13	2.477 (3)	O13—H13A	0.8499
Nd2—O2	2.507 (3)	O13—H13B	0.8175
Nd2—O12ⁱ	2.548 (3)	O16—H16C	0.8499
Nd2—O1	2.570 (3)	O16—H16A	0.7231
Nd2—O11ⁱ	2.655 (3)	C17—O24	1.265 (6)
Nd2—C6ⁱ	2.985 (5)	C17—O25	1.267 (6)
O1—C1	1.258 (5)	C17—Nd1ⁱⁱ	2.886 (5)
C3—C2	1.304 (7)	O25—Nd1ⁱⁱ	2.504 (3)
C3—C6	1.475 (7)	O24—Nd1ⁱⁱ	2.573 (3)
C3—H3	0.9300	C18—O26	1.257 (5)
O2—C1	1.266 (5)	C18—O27	1.264 (6)
C1—C2	1.484 (7)	O26—Nd1^iv	2.397 (3)
C2—H2	0.9300	O27—Nd2^v	2.467 (3)
O3—O3	0.000 (7)	O2W—O2W	0.00 (2)
O3—C4	1.274 (5)	O2W—O2W	0.00 (2)
O4—O4	0.000 (7)	O2W—H2WA	0.8500
O4—C4	1.259 (5)	O2W—H2WB	0.8499
C4—O4	1.259 (5)	O3W—O3W	0.000 (16)
C4—O3	1.274 (5)	O3W—H3WC	0.8500
C4—C7	1.471 (7)	O3W—H3WD	0.8500
O6—C5	1.256 (6)	O1W—O1W	0.00 (4)
C5—O5	1.256 (6)	O1W—H1WD	0.8500
C5—C10	1.492 (6)	O1W—H1WC	0.8502
O8—H8B	0.8500

O26ⁱ—Nd1—O8	77.26 (12)	O2—Nd2—O11ⁱ	135.19 (11)
O26ⁱ—Nd1—O6	92.32 (12)	O12ⁱ—Nd2—O11ⁱ	49.67 (10)
O8—Nd1—O6	137.38 (11)	O1—Nd2—O11ⁱ	142.94 (10)
O26ⁱ—Nd1—O11ⁱ	89.22 (11)	O5—Nd2—C6ⁱ	74.15 (12)
O8—Nd1—O11ⁱ	69.37 (11)	O14—Nd2—C6ⁱ	95.55 (13)
O6—Nd1—O11ⁱ	69.27 (11)	O3—Nd2—C6ⁱ	91.06 (12)
O26ⁱ—Nd1—O16	79.13 (11)	O3—Nd2—C6ⁱ	91.06 (12)
O8—Nd1—O16	78.01 (11)	O27ⁱⁱⁱ—Nd2—C6ⁱ	103.44 (12)
O6—Nd1—O16	141.11 (11)	O13—Nd2—C6ⁱ	79.12 (12)
O11ⁱ—Nd1—O16	147.08 (11)	O2—Nd2—C6ⁱ	151.25 (12)
O26ⁱ—Nd1—O25ⁱⁱ	124.75 (12)	O12ⁱ—Nd2—C6ⁱ	24.49 (11)
O8—Nd1—O25ⁱⁱ	145.90 (12)	O1—Nd2—C6ⁱ	155.32 (11)
O6—Nd1—O25ⁱⁱ	72.77 (11)	O11ⁱ—Nd2—C6ⁱ	25.30 (11)
O11ⁱ—Nd1—O25ⁱⁱ	129.43 (11)	C1—O1—Nd2	92.2 (3)
O16—Nd1—O25ⁱⁱ	81.22 (11)	C2—C3—C6	124.3 (5)
O26ⁱ—Nd1—O4	140.31 (11)	C2—C3—H3	117.8
O8—Nd1—O4	75.09 (12)	C6—C3—H3	117.8
O6—Nd1—O4	127.20 (12)	C1—O2—Nd2	95.0 (3)
O11ⁱ—Nd1—O4	106.71 (10)	O1—C1—O2	121.1 (4)
O16—Nd1—O4	67.72 (10)	O1—C1—C2	120.1 (4)
O25ⁱⁱ—Nd1—O4	72.11 (11)	O2—C1—C2	118.8 (4)
O26ⁱ—Nd1—O4	140.31 (11)	C3—C2—C1	122.2 (5)
O8—Nd1—O4	75.09 (12)	C3—C2—H2	118.9
O6—Nd1—O4	127.20 (12)	C1—C2—H2	118.9
O11ⁱ—Nd1—O4	106.71 (10)	O3—O3—C4	0 (10)
O16—Nd1—O4	67.72 (10)	O3—O3—Nd2	0 (10)
O25ⁱⁱ—Nd1—O4	72.11 (11)	C4—O3—Nd2	150.4 (3)
O4—Nd1—O4	0.00 (16)	O3—O3—Nd1	0 (6)
O26ⁱ—Nd1—O24ⁱⁱ	73.38 (12)	C4—O3—Nd1	92.4 (3)
O8—Nd1—O24ⁱⁱ	141.13 (11)	Nd2—O3—Nd1	111.28 (12)
O6—Nd1—O24ⁱⁱ	69.25 (11)	O4—O4—C4	0 (10)
O11ⁱ—Nd1—O24ⁱⁱ	133.95 (11)	O4—O4—Nd1	0 (3)
O16—Nd1—O24ⁱⁱ	71.95 (11)	C4—O4—Nd1	98.6 (3)
O25ⁱⁱ—Nd1—O24ⁱⁱ	51.45 (11)	O4—C4—O4	0.0 (3)
O4—Nd1—O24ⁱⁱ	113.85 (11)	O4—C4—O3	119.0 (4)
O4—Nd1—O24ⁱⁱ	113.85 (11)	O4—C4—O3	119.0 (4)
O26ⁱ—Nd1—O3	155.04 (11)	O4—C4—O3	119.0 (4)
O8—Nd1—O3	87.75 (11)	O4—C4—O3	119.0 (4)
O6—Nd1—O3	85.27 (11)	O3—C4—O3	0.0 (3)
O11ⁱ—Nd1—O3	66.66 (10)	O4—C4—C7	120.3 (4)
O16—Nd1—O3	117.47 (10)	O4—C4—C7	120.3 (4)
O25ⁱⁱ—Nd1—O3	78.22 (11)	O3—C4—C7	120.6 (4)
O4—Nd1—O3	49.80 (10)	O3—C4—C7	120.6 (4)
O4—Nd1—O3	49.80 (10)	C5—O6—Nd1	128.7 (3)
O24ⁱⁱ—Nd1—O3	127.89 (11)	O6—C5—O5	125.6 (4)
O26ⁱ—Nd1—O3	155.04 (11)	O6—C5—C10	117.2 (4)
O8—Nd1—O3	87.75 (11)	O5—C5—C10	117.2 (4)
O6—Nd1—O3	85.27 (11)	C5—O5—Nd2	142.0 (3)
O11ⁱ—Nd1—O3	66.66 (10)	Nd1—O8—H8B	111.0
O16—Nd1—O3	117.47 (10)	Nd1—O8—H8C	113.2
O25ⁱⁱ—Nd1—O3	78.22 (11)	H8B—O8—H8C	111.4
O4—Nd1—O3	49.80 (10)	C7—C8—C18	126.5 (5)
O4—Nd1—O3	49.80 (10)	C7—C8—H8	116.8
O24ⁱⁱ—Nd1—O3	127.89 (11)	C18—C8—H8	116.8
O3—Nd1—O3	0.00 (6)	O12—C6—O11	120.1 (4)
O26ⁱ—Nd1—C17ⁱⁱ	99.25 (14)	O12—C6—C3	120.1 (4)
O8—Nd1—C17ⁱⁱ	156.81 (12)	O11—C6—C3	119.8 (4)
O6—Nd1—C17ⁱⁱ	65.09 (12)	O12—C6—Nd2^iv	57.8 (2)
O11ⁱ—Nd1—C17ⁱⁱ	133.80 (12)	O11—C6—Nd2^iv	62.7 (2)
O16—Nd1—C17ⁱⁱ	78.82 (12)	C3—C6—Nd2^iv	174.0 (3)
O25ⁱⁱ—Nd1—C17ⁱⁱ	25.97 (12)	C8—C7—C4	123.2 (5)
O4—Nd1—C17ⁱⁱ	95.22 (13)	C8—C7—H7	118.4
O4—Nd1—C17ⁱⁱ	95.22 (13)	C4—C7—H7	118.4
O24ⁱⁱ—Nd1—C17ⁱⁱ	25.99 (12)	C9—C10—C5	123.3 (5)
O3—Nd1—C17ⁱⁱ	102.18 (13)	C9—C10—H10	118.3
O3—Nd1—C17ⁱⁱ	102.18 (13)	C5—C10—H10	118.3
O5—Nd2—O14	136.23 (13)	C10—C9—C17	122.4 (5)
O5—Nd2—O3	74.35 (12)	C10—C9—H9	118.8
O14—Nd2—O3	149.32 (13)	C17—C9—H9	118.8
O5—Nd2—O3	74.35 (12)	C6—O11—Nd1^iv	135.4 (3)
O14—Nd2—O3	149.32 (13)	C6—O11—Nd2^iv	92.0 (3)
O3—Nd2—O3	0.00 (10)	Nd1^iv—O11—Nd2^iv	109.38 (11)
O5—Nd2—O27ⁱⁱⁱ	73.51 (12)	C6—O12—Nd2^iv	97.7 (3)
O14—Nd2—O27ⁱⁱⁱ	67.73 (13)	Nd2—O14—H14A	121 (4)
O3—Nd2—O27ⁱⁱⁱ	139.28 (12)	Nd2—O14—H14B	127 (4)
O3—Nd2—O27ⁱⁱⁱ	139.28 (12)	H14A—O14—H14B	100 (5)
O5—Nd2—O13	141.36 (12)	Nd2—O13—H13A	112.0
O14—Nd2—O13	73.12 (14)	Nd2—O13—H13B	133.5
O3—Nd2—O13	78.82 (12)	H13A—O13—H13B	112.2
O3—Nd2—O13	78.82 (12)	Nd1—O16—H16C	113.1
O27ⁱⁱⁱ—Nd2—O13	140.84 (12)	Nd1—O16—H16A	107.2
O5—Nd2—O2	132.21 (12)	H16C—O16—H16A	114.1
O14—Nd2—O2	72.98 (13)	O24—C17—O25	121.1 (4)
O3—Nd2—O2	87.02 (12)	O24—C17—C9	117.7 (5)
O3—Nd2—O2	87.02 (12)	O25—C17—C9	120.9 (5)
O27ⁱⁱⁱ—Nd2—O2	96.50 (11)	O24—C17—Nd1ⁱⁱ	63.1 (2)
O13—Nd2—O2	72.36 (11)	O25—C17—Nd1ⁱⁱ	60.0 (2)
O5—Nd2—O12ⁱ	77.49 (12)	C9—C17—Nd1ⁱⁱ	160.5 (3)
O14—Nd2—O12ⁱ	77.37 (13)	C17—O25—Nd1ⁱⁱ	94.1 (3)
O3—Nd2—O12ⁱ	114.97 (11)	C17—O24—Nd1ⁱⁱ	91.0 (3)
O3—Nd2—O12ⁱ	114.97 (11)	O26—C18—O27	124.1 (4)
O27ⁱⁱⁱ—Nd2—O12ⁱ	81.39 (11)	O26—C18—C8	118.8 (4)
O13—Nd2—O12ⁱ	89.50 (12)	O27—C18—C8	117.1 (4)
O2—Nd2—O12ⁱ	148.62 (12)	C18—O26—Nd1^iv	136.8 (3)
O5—Nd2—O1	81.57 (11)	C18—O27—Nd2^v	140.2 (3)
O14—Nd2—O1	105.16 (13)	O2W—O2W—O2W	0 (10)
O3—Nd2—O1	78.02 (11)	O2W—O2W—H2WA	0.0
O3—Nd2—O1	78.02 (11)	O2W—O2W—H2WA	0.0
O27ⁱⁱⁱ—Nd2—O1	73.15 (11)	O2W—O2W—H2WB	0.0
O13—Nd2—O1	119.40 (12)	O2W—O2W—H2WB	0.0
O2—Nd2—O1	51.29 (10)	H2WA—O2W—H2WB	107.7
O12ⁱ—Nd2—O1	150.73 (11)	O3W—O3W—H3WC	0.0
O5—Nd2—O11ⁱ	76.98 (11)	O3W—O3W—H3WD	0.0
O14—Nd2—O11ⁱ	111.28 (12)	H3WC—O3W—H3WD	108.7
O3—Nd2—O11ⁱ	67.31 (10)	O1W—O1W—H1WD	0.0
O3—Nd2—O11ⁱ	67.31 (10)	O1W—O1W—H1WC	0.0
O27ⁱⁱⁱ—Nd2—O11ⁱ	127.13 (10)	H1WD—O1W—H1WC	118.8
O13—Nd2—O11ⁱ	67.16 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O1	0.85	2.57	3.103 (13)	122
O2W—H2WA···O3	0.85	2.52	3.319 (13)	158
O2W—H2WB···O1W^vi	0.85	2.53	2.98 (2)	114
O3W—H3WD···O24^vi	0.85	2.07	2.896 (6)	165
O3W—H3WC···O1W	0.85	2.12	2.60 (2)	115
O3W—H3WC···O2W	0.85	2.08	2.911 (13)	165
O1W—H1WD···O2W	0.85	2.06	2.634 (19)	124
O1W—H1WC···O6^iv	0.85	2.11	2.959 (17)	178
O8—H8C···O3W^vii	0.85	2.05	2.829 (5)	152
O8—H8B···O1^viii	0.85	1.91	2.745 (5)	169
O13—H13A···O3W^vii	0.85	2.14	2.938 (6)	157
O13—H13B···O25^v	0.82	2.02	2.787 (5)	157
O14—H14A···O12^ix	0.86 (6)	1.88 (6)	2.740 (5)	172 (6)
O14—H14B···O4^vii	0.75 (5)	2.04 (6)	2.776 (5)	166 (6)
O16—H16A···O27ⁱ	0.72	2.02	2.714 (5)	160
O16—H16C···O2^x	0.85	2.07	2.915 (5)	171
C3—H3···O24^v	0.93	2.53	3.345 (6)	147
C8—H8···O12^viii	0.93	2.58	3.417 (6)	150

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

Experimental details

Crystal data
Chemical formula	[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O
M_r	756.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.5810 (9), 14.8675 (15), 14.9056 (14)
β (°)	91.538 (5)
V (Å³)	2122.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.93
Crystal size (mm)	0.16 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.459, 0.501
No. of measured, independent and observed [I > 2σ(I)] reflections	24284, 5150, 4060
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.05
No. of reflections	5150
No. of parameters	306
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.36, −0.89

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O1	0.85	2.57	3.103 (13)	121.9
O2W—H2WA···O3	0.85	2.52	3.319 (13)	157.8
O2W—H2WB···O1Wⁱ	0.85	2.53	2.98 (2)	114.2
O3W—H3WD···O24ⁱ	0.85	2.07	2.896 (6)	165.3
O3W—H3WC···O1W	0.85	2.12	2.60 (2)	115.1
O3W—H3WC···O2W	0.85	2.08	2.911 (13)	165.2
O1W—H1WD···O2W	0.85	2.06	2.634 (19)	124.0
O1W—H1WC···O6ⁱⁱ	0.85	2.11	2.959 (17)	177.8
O8—H8C···O3Wⁱⁱⁱ	0.85	2.05	2.829 (5)	151.5
O8—H8B···O1^iv	0.85	1.91	2.745 (5)	168.7
O13—H13A···O3Wⁱⁱⁱ	0.85	2.14	2.938 (6)	156.8
O13—H13B···O25^v	0.82	2.02	2.787 (5)	156.6
O14—H14A···O12^vi	0.86 (6)	1.88 (6)	2.740 (5)	172 (6)
O14—H14B···O4ⁱⁱⁱ	0.75 (5)	2.04 (6)	2.776 (5)	166 (6)
O16—H16A···O27^vii	0.72	2.02	2.714 (5)	159.9
O16—H16C···O2^viii	0.85	2.07	2.915 (5)	170.9
C3—H3···O24^v	0.93	2.53	3.345 (6)	146.9
C8—H8···O12^iv	0.93	2.58	3.417 (6)	150.1

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

Acknowledgements

The authors gratefully acknowledge the support of the Department of Science and Technology, Guangdong Province (grant No. 2010 A020507001–76, 5300410, FIPL-05–003)

References

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