Poly[[tetra­aquadi-μ3-oxalato-μ2-oxalato-diprasedymium(III)] dihydrate]

Chen, J.-H.; Fang, H.-C.; Jia, H.-Y.; Li, S.-S.; Cai, Y.-P.

doi:10.1107/S1600536809053598

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m82

doi:10.1107/S1600536809053598

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Poly[[tetraaquadi-μ₃-oxalato-μ₂-oxalato-diprasedymium(III)] dihydrate]

Jian-Hong Chen,^a Hua-Cai Fang,^a Hong-Yang Jia,^a Shan-Shan Li ^a and Yue-Peng Cai ^a ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: ypcai8@yahoo.com

(Received 9 November 2009; accepted 12 December 2009; online 19 December 2009)

In the title compound, {[Pr₂(C₂O₄)₃(H₂O)₄]·2H₂O}_n, the three-dimensional network structure has the Pr^III ion coordinated by nine O atoms in a distorted tricapped trigonal-prismatic geometry. The coordinated and uncoordinated water molecules interact with the carboxylate O atoms to consolidate the network via O—H⋯O hydrogen bonds.

Related literature

For general background, see: Benson et al. (2000 ).

Experimental

Crystal data

[Pr₂(C₂O₄)₃(H₂O)₄]·2H₂O
M_r = 653.98
Monoclinic, P 2₁ /c
a = 9.8834 (5) Å
b = 8.2811 (4) Å
c = 10.1818 (5) Å
β = 99.053 (1)°
V = 822.95 (7) Å³
Z = 2
Mo Kα radiation
μ = 5.95 mm⁻¹
T = 298 K
0.26 × 0.22 × 0.16 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.307, T_max = 0.450
4111 measured reflections
1487 independent reflections
1397 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.035
S = 1.07
1487 reflections
139 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O9ⁱ	0.85 (1)	1.89 (1)	2.732 (3)	171 (3)
O7—H7B⋯O1ⁱⁱ	0.85 (1)	1.94 (2)	2.732 (3)	155 (4)
O8—H8A⋯O2ⁱⁱⁱ	0.84 (1)	2.06 (1)	2.900 (3)	175 (4)
O8—H8A⋯O3^iv	0.84 (1)	2.59 (4)	3.026 (3)	114 (3)
O8—H8B⋯O9^v	0.84 (1)	2.12 (2)	2.949 (4)	167 (6)
O9—H9B⋯O6^vi	0.83 (1)	1.99 (1)	2.820 (3)	178 (4)
O9—H9A⋯O8	0.84 (1)	2.05 (1)	2.881 (4)	173 (4)
Symmetry codes: (i) x, y-1, z; (ii) -x, -y, -z+1; (iii) -x, -y+1, -z+1; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z+1; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); 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 I, global. DOI: 10.1107/S1600536809053598/ng2682sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053598/ng2682Isup2.hkl

checkCIF report

Comment top

Though complexes including oxalato and praseodymium(III) have been extensively investigated, the crystal structure of praseodymium oxalate with one-dimensional, two-dimensional and three-dimensional topologies and different solvent molecules have constantly being reported recently. In this paper, we would like to report the synthesis and crystal structure of a three-dimensional network complex including oxalato and praseodymium(III) with one lattice water molecule per unsymmetrical unit. The hydrothermal reaction of Pr₆O₁₁ and oxalic acid in H₂O afforded the Pr^III title polymeric complex, [(Pr(C₂O₄)_1.5(H₂O)₂).H₂O]_n. The Pr^III ion is coordinated by nine O atoms from two water molecules and four carboxylate groups of oxalate ligands in an irregular coordination geometry (Figure 1). Two oxalate groups of the oxalate anions bridge two symmetry-related Pr^III atoms, giving rise to a layer-like structure extending along [100] (Figure 2). These parallel layers are further connected via chelating coordination of oxalate anions into a three-dimensional network (Figure 3) along [010] plane. Moreover, the coordinated/non-coordinated water molecules interact with the carboxylate oxygen atoms from the layers via O—H···O hydrogen bonds (Table 1), which contributes to the additional stability of the structure.

Related literature top

For general background, see Benson et al. (2000).

Experimental top

A suspension of praseodymium oxide (205 mg, 0.20 mmol) in in water (20 ml) was slowly added to a solution of oxalic acid (0.10 mmol) in water (10 ml). The resultant mixture was sealed in a 50 cm³ stainless steel reactor with Teflon liner and kept under autogenous pressure at 100 ° for 78 h, and then cooled to room temperature at a rate of 0.5 °. min^-1. Colorless block crystals of the compound suited for single-crystal X-ray diffraction analyses formed with a yield of approximate 65%. The assigned structure was substantiated by elemental analysis; calculated for C₃H₆O₉Pr: C 11.01, H 1.83%; found: C 10.96, H 1.95%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound (I) with 30% probability ellipsoids. Symmetry code a: 1 - x,-y,1 - z; b: -x,-1/2 + y,0.5 - z; c: -x,-y,1 - z; d: x,0.5 - y,1/2 + z.
	Fig. 2. A view of one-dimensional chain constructed by hydrogen bonding interactions. Symmetry code a: x - 1,y,z.

Poly[[tetraaquadi-µ₃-oxalato-µ₂-oxalato-diprasedymium(III)] dihydrate] top

Crystal data top

[Pr₂(C₂O₄)₃(H₂O)₄]·2H₂O	F(000) = 620
M_r = 653.98	D_x = 2.639 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.8834 (5) Å	Cell parameters from 3328 reflections
b = 8.2811 (4) Å	θ = 3.2–28.6°
c = 10.1818 (5) Å	µ = 5.95 mm⁻¹
β = 99.053 (1)°	T = 298 K
V = 822.95 (7) Å³	Block, yellow
Z = 2	0.26 × 0.22 × 0.16 mm

Data collection top

Bruker SMART diffractometer	1487 independent reflections
Radiation source: fine-focus sealed tube	1397 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.307, T_max = 0.450	k = −9→9
4111 measured reflections	l = −12→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.035	w = 1/[σ²(F_o²) + (0.0087P)² + 0.7364P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.007
1487 reflections	Δρ_max = 0.44 e Å⁻³
139 parameters	Δρ_min = −0.54 e Å⁻³
9 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0127 (4)

Crystal data top

[Pr₂(C₂O₄)₃(H₂O)₄]·2H₂O	V = 822.95 (7) Å³
M_r = 653.98	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8834 (5) Å	µ = 5.95 mm⁻¹
b = 8.2811 (4) Å	T = 298 K
c = 10.1818 (5) Å	0.26 × 0.22 × 0.16 mm
β = 99.053 (1)°

Data collection top

Bruker SMART diffractometer	1487 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1397 reflections with I > 2σ(I)
T_min = 0.307, T_max = 0.450	R_int = 0.023
4111 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	9 restraints
wR(F²) = 0.035	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.44 e Å⁻³
1487 reflections	Δρ_min = −0.54 e Å⁻³
139 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
Pr1	0.185002 (15)	0.098389 (18)	0.437068 (15)	0.01483 (9)
O1	0.0042 (2)	0.3167 (2)	0.4302 (2)	0.0210 (5)
O2	−0.1229 (2)	0.4945 (3)	0.2991 (2)	0.0249 (5)
O3	0.1838 (2)	0.3092 (3)	0.2610 (2)	0.0229 (5)
O4	0.0564 (2)	0.4802 (3)	0.12614 (19)	0.0196 (5)
O5	0.4011 (2)	0.0665 (3)	0.3529 (2)	0.0275 (5)
O6	0.6199 (2)	−0.0090 (3)	0.3924 (2)	0.0287 (5)
O7	0.1928 (2)	−0.2047 (3)	0.4324 (3)	0.0357 (6)
H7A	0.255 (3)	−0.260 (3)	0.406 (4)	0.054*
H7B	0.153 (3)	−0.250 (4)	0.490 (3)	0.054*
O8	0.3072 (3)	0.3550 (3)	0.5421 (2)	0.0296 (5)
H8A	0.252 (3)	0.393 (4)	0.589 (3)	0.044*
O9	0.3963 (3)	0.5983 (3)	0.3724 (3)	0.0353 (6)
H9B	0.393 (4)	0.566 (5)	0.2945 (16)	0.053*
C1	−0.0222 (3)	0.4050 (3)	0.3291 (3)	0.0172 (6)
C2	0.0829 (3)	0.3968 (3)	0.2319 (3)	0.0162 (6)
C3	0.5054 (3)	0.0165 (4)	0.4261 (3)	0.0200 (7)
H8B	0.3907 (13)	0.358 (8)	0.576 (4)	0.13 (3)*
H9A	0.370 (7)	0.534 (5)	0.427 (3)	0.13 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pr1	0.01116 (11)	0.01772 (12)	0.01591 (11)	0.00145 (6)	0.00305 (7)	0.00222 (6)
O1	0.0236 (11)	0.0229 (11)	0.0185 (11)	0.0044 (9)	0.0094 (9)	0.0063 (9)
O2	0.0248 (12)	0.0312 (12)	0.0191 (11)	0.0126 (10)	0.0051 (10)	0.0018 (9)
O3	0.0186 (11)	0.0244 (11)	0.0274 (12)	0.0049 (9)	0.0090 (10)	0.0067 (10)
O4	0.0179 (11)	0.0261 (11)	0.0149 (11)	0.0013 (9)	0.0033 (9)	0.0049 (9)
O5	0.0183 (12)	0.0451 (14)	0.0198 (12)	0.0077 (10)	0.0052 (10)	0.0090 (10)
O6	0.0195 (12)	0.0478 (14)	0.0204 (12)	0.0121 (10)	0.0078 (10)	0.0095 (11)
O7	0.0351 (14)	0.0252 (13)	0.0533 (17)	0.0080 (11)	0.0273 (13)	0.0110 (11)
O8	0.0303 (14)	0.0317 (13)	0.0272 (13)	−0.0058 (11)	0.0057 (11)	−0.0034 (10)
O9	0.0397 (15)	0.0410 (15)	0.0274 (14)	0.0031 (12)	0.0118 (13)	−0.0034 (12)
C1	0.0182 (16)	0.0162 (14)	0.0170 (15)	−0.0001 (12)	0.0023 (13)	−0.0043 (12)
C2	0.0188 (16)	0.0156 (14)	0.0141 (15)	−0.0066 (12)	0.0022 (12)	−0.0034 (12)
C3	0.0170 (16)	0.0257 (16)	0.0183 (16)	0.0030 (13)	0.0064 (13)	0.0042 (13)

Geometric parameters (Å, º) top

Pr1—O5	2.438 (2)	O4—Pr1^v	2.552 (2)
Pr1—O6ⁱ	2.495 (2)	O4—Pr1^iv	2.566 (2)
Pr1—O3	2.501 (2)	O5—C3	1.244 (4)
Pr1—O7	2.512 (2)	O6—C3	1.251 (4)
Pr1—O1	2.535 (2)	O6—Pr1ⁱ	2.495 (2)
Pr1—O2ⁱⁱ	2.537 (2)	O7—H7A	0.847 (10)
Pr1—O4ⁱⁱⁱ	2.552 (2)	O7—H7B	0.845 (10)
Pr1—O4ⁱⁱ	2.566 (2)	O8—H8A	0.842 (10)
Pr1—O8	2.590 (2)	O8—H8B	0.844 (10)
O1—C1	1.257 (4)	O9—H9B	0.832 (10)
O2—C1	1.240 (4)	O9—H9A	0.839 (10)
O2—Pr1^iv	2.537 (2)	C1—C2	1.545 (4)
O3—C2	1.231 (4)	C3—C3ⁱ	1.549 (6)
O4—C2	1.271 (4)

O5—Pr1—O6ⁱ	65.72 (7)	O3—Pr1—O8	70.89 (8)
O5—Pr1—O3	74.28 (7)	O7—Pr1—O8	144.46 (8)
O6ⁱ—Pr1—O3	128.45 (7)	O1—Pr1—O8	72.97 (8)
O5—Pr1—O7	81.61 (7)	O2ⁱⁱ—Pr1—O8	134.18 (7)
O6ⁱ—Pr1—O7	72.19 (8)	O4ⁱⁱⁱ—Pr1—O8	98.79 (7)
O3—Pr1—O7	132.90 (8)	O4ⁱⁱ—Pr1—O8	140.47 (7)
O5—Pr1—O1	136.09 (7)	C1—O1—Pr1	119.53 (18)
O6ⁱ—Pr1—O1	134.01 (7)	C1—O2—Pr1^iv	120.07 (19)
O3—Pr1—O1	63.82 (6)	C2—O3—Pr1	119.75 (18)
O7—Pr1—O1	137.35 (7)	C2—O4—Pr1^v	116.09 (18)
O5—Pr1—O2ⁱⁱ	74.00 (7)	C2—O4—Pr1^iv	118.63 (18)
O6ⁱ—Pr1—O2ⁱⁱ	127.17 (7)	Pr1^v—O4—Pr1^iv	117.51 (8)
O3—Pr1—O2ⁱⁱ	65.42 (7)	C3—O5—Pr1	120.94 (18)
O7—Pr1—O2ⁱⁱ	69.33 (8)	C3—O6—Pr1ⁱ	119.5 (2)
O1—Pr1—O2ⁱⁱ	98.71 (7)	Pr1—O7—H7A	125 (2)
O5—Pr1—O4ⁱⁱⁱ	143.64 (7)	Pr1—O7—H7B	114 (2)
O6ⁱ—Pr1—O4ⁱⁱⁱ	79.71 (7)	H7A—O7—H7B	115.0 (15)
O3—Pr1—O4ⁱⁱⁱ	140.53 (7)	Pr1—O8—H8A	104 (2)
O7—Pr1—O4ⁱⁱⁱ	77.27 (7)	Pr1—O8—H8B	124 (4)
O1—Pr1—O4ⁱⁱⁱ	76.71 (6)	H8A—O8—H8B	115.7 (15)
O2ⁱⁱ—Pr1—O4ⁱⁱⁱ	123.63 (6)	H9B—O9—H9A	117.4 (16)
O5—Pr1—O4ⁱⁱ	134.60 (7)	O2—C1—O1	127.3 (3)
O6ⁱ—Pr1—O4ⁱⁱ	130.37 (7)	O2—C1—C2	117.6 (3)
O3—Pr1—O4ⁱⁱ	100.79 (7)	O1—C1—C2	115.1 (3)
O7—Pr1—O4ⁱⁱ	69.15 (7)	O3—C2—O4	125.1 (3)
O1—Pr1—O4ⁱⁱ	68.99 (7)	O3—C2—C1	118.2 (3)
O2ⁱⁱ—Pr1—O4ⁱⁱ	63.66 (6)	O4—C2—C1	116.7 (3)
O4ⁱⁱⁱ—Pr1—O4ⁱⁱ	62.49 (8)	O5—C3—O6	126.3 (3)
O5—Pr1—O8	81.77 (8)	O5—C3—C3ⁱ	117.6 (3)
O6ⁱ—Pr1—O8	72.37 (8)	O6—C3—C3ⁱ	116.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O9^vi	0.85 (1)	1.89 (1)	2.732 (3)	171 (3)
O7—H7B···O1^vii	0.85 (1)	1.94 (2)	2.732 (3)	155 (4)
O8—H8A···O2^viii	0.84 (1)	2.06 (1)	2.900 (3)	175 (4)
O8—H8A···O3ⁱⁱⁱ	0.84 (1)	2.59 (4)	3.026 (3)	114 (3)
O8—H8B···O9^ix	0.84 (1)	2.12 (2)	2.949 (4)	167 (6)
O9—H9B···O6^x	0.83 (1)	1.99 (1)	2.820 (3)	178 (4)
O9—H9A···O8	0.84 (1)	2.05 (1)	2.881 (4)	173 (4)

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

Experimental details

Crystal data
Chemical formula	[Pr₂(C₂O₄)₃(H₂O)₄]·2H₂O
M_r	653.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.8834 (5), 8.2811 (4), 10.1818 (5)
β (°)	99.053 (1)
V (Å³)	822.95 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.95
Crystal size (mm)	0.26 × 0.22 × 0.16

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.307, 0.450
No. of measured, independent and observed [I > 2σ(I)] reflections	4111, 1487, 1397
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.035, 1.07
No. of reflections	1487
No. of parameters	139
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.54

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), 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
O7—H7A···O9ⁱ	0.847 (10)	1.892 (13)	2.732 (3)	171 (3)
O7—H7B···O1ⁱⁱ	0.845 (10)	1.942 (17)	2.732 (3)	155 (4)
O8—H8A···O2ⁱⁱⁱ	0.842 (10)	2.060 (11)	2.900 (3)	175 (4)
O8—H8A···O3^iv	0.842 (10)	2.59 (4)	3.026 (3)	114 (3)
O8—H8B···O9^v	0.844 (10)	2.120 (17)	2.949 (4)	167 (6)
O9—H9B···O6^vi	0.832 (10)	1.988 (11)	2.820 (3)	178 (4)
O9—H9A···O8	0.839 (10)	2.047 (14)	2.881 (4)	173 (4)

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

Acknowledgements

The work was supported by the National Natural Science Foundation of China (No. 20772037) and the NSF of Guangdong Province, China (grant Nos. 9251063101000006 and 06025033).

References

Benson, D. A., Karsch-Mizrachi, I., Lipman, D. J., Ostell, J., Rapp, B. A. & Wheeler, D. L. (2000). Genbank. Nucl. Acids Res. 28, 15–18. Web of Science CrossRef CAS Google Scholar
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