Poly[diaquabis-(μ(4)-fumarato-κO:O:O:O)(μ(4)-fumarato-κO:O,O:O:O,O)(μ(2)-fumaric acid-κO:O)dipraseodymium(III)].

The title complex, [Pr(2)(C(4)H(2)O(4))(3)(C(4)H(4)O(4))(H(2)O)(2)](n), was synthesized by reaction of praseodymium(III) nitrate hexa-hydrate with fumaric acid in a water-ethanol (4:1) solution. The asymmetric unit comprises a Pr(3+) cation, one and a half fumarate dianions (L(2-)), one half-mol-ecule of fumaric acid (H(2)L) and one coordinated water mol-ecule. The carboxyl-ate groups of the fumarate dianion and fumaric acid exhibit different coordination modes. In one fumarate dianion, two carboxyl-ate groups are chelating with two Pr(3+) cations, and the other two O atoms each coordinate a Pr(3+) cation. Each O atom of the second fumarate dianion binds to a different Pr(3+) cation. The fumaric acid employs one O atom at each end to bridge two Pr(3+) cations. The Pr(3+) cation is coordinated in a distorted tricapped trigonal-prismatic environment by eight O atoms of fumarate dianion or fumaric acid ligands and one water O atom. The PrO(9) coordination polyhedra are edge-shared through one carboxyl-ate O atom and two carboxyl-ate groups, generating infinite praseodymium-oxygen chains, which are further connected by the ligands into a three-dimensional framework. The crystal structure is stabilized by O-H⋯O hydrogen-bond inter-actions between the coordin-ated water mol-ecule and the carboxyl-ate O atoms.

Related literature

For the structural diversity and potential use as superconductors and magnetic materials of metal complexes of carboxyl­ates, see: Kim et al. (2004 ▶); Ye et al. (2005 ▶). For applications of rare earth carboxyl­ates, see: Baggio & Perec (2004 ▶); Seo et al. (2000 ▶).

Experimental

Crystal data

[Pr2(C4H2O4)3(C4H4O4)(H2O)2]]

M = 776.10

Monoclinic,

a = 8.3714 (3) Å

b = 14.6034 (6) Å

c = 8.7518 (4) Å

β = 103.118 (2)°

V = 1042.00 (7) Å3

Z = 2

Mo Kα radiation

μ = 4.72 mm−1

T = 298 K

0.26 × 0.19 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.355, T max = 0.493

10102 measured reflections

2394 independent reflections

2175 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.041

S = 1.05

2394 reflections

170 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.75 e Å−3

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: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038347/hg5089sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038347/hg5089Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pr2(C4H2O4)3(C4H4O4)(H2O)2]	F(000) = 744
Mr = 776.10	Dx = 2.474 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7002 reflections
a = 8.3714 (3) Å	θ = 2.5–27.5°
b = 14.6034 (6) Å	µ = 4.72 mm−1
c = 8.7518 (4) Å	T = 298 K
β = 103.118 (2)°	Block, blue
V = 1042.00 (7) Å3	0.26 × 0.19 × 0.15 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	2394 independent reflections
Radiation source: fine-focus sealed tube	2175 reflections with I > 2σ(I)
graphite	Rint = 0.027
phi and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.355, Tmax = 0.493	k = −16→18
10102 measured reflections	l = −11→6

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.041	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0212P)2 + 0.5013P] where P = (Fo2 + 2Fc2)/3
2394 reflections	(Δ/σ)max = 0.001
170 parameters	Δρmax = 0.44 e Å−3
3 restraints	Δρmin = −0.75 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.3406 (3)	0.31371 (13)	0.2443 (3)	0.0132 (5)
C2	0.1598 (3)	0.31134 (14)	0.2330 (3)	0.0170 (5)
H2	0.0902	0.2974	0.1369	0.020*
C3	0.0955 (3)	0.32820 (15)	0.3540 (3)	0.0155 (4)
H3	0.1665	0.3451	0.4476	0.019*
C4	−0.0831 (3)	0.32223 (14)	0.3522 (3)	0.0128 (4)
C5	0.5360 (3)	0.10365 (14)	0.3762 (2)	0.0133 (4)
C6	0.5244 (3)	0.04325 (14)	0.5105 (3)	0.0160 (4)
H6	0.5522	0.0668	0.6118	0.019*
C8	0.9749 (3)	0.06063 (16)	0.3044 (3)	0.0191 (5)
O1	0.8615 (2)	0.11349 (12)	0.30016 (19)	0.0244 (4)
O2	1.0535 (2)	0.05332 (15)	0.1918 (2)	0.0356 (5)
H2A	1.0106	0.0868	0.1187	0.053*
C7	1.0333 (3)	−0.00121 (16)	0.4388 (3)	0.0199 (5)
H7	1.1178	−0.0422	0.4369	0.024*
O4	0.5972 (2)	0.18329 (9)	0.40478 (19)	0.0143 (3)
O5	0.4920 (2)	0.07499 (11)	0.23774 (17)	0.0208 (4)
O6	0.39185 (18)	0.27539 (11)	0.13689 (17)	0.0174 (3)
O7	0.43025 (18)	0.35433 (10)	0.36074 (17)	0.0149 (3)
O8	−0.1853 (2)	0.30866 (10)	0.2257 (2)	0.0174 (4)
O9	−0.1193 (2)	0.33071 (11)	0.48376 (19)	0.0182 (3)
O1W	0.6829 (2)	0.02369 (11)	0.02361 (19)	0.0198 (4)
H2W	0.645 (3)	−0.0181 (14)	0.068 (2)	0.030*
H1W	0.656 (3)	0.0080 (17)	−0.0692 (12)	0.030*
Pr1	0.632685 (13)	0.190489 (7)	0.097718 (13)	0.00921 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0123 (11)	0.0141 (11)	0.0138 (12)	0.0023 (7)	0.0040 (9)	0.0036 (8)
C2	0.0118 (11)	0.0233 (13)	0.0153 (13)	−0.0014 (8)	0.0018 (10)	−0.0034 (8)
C3	0.0116 (10)	0.0221 (11)	0.0132 (11)	−0.0022 (8)	0.0035 (9)	−0.0013 (9)
C4	0.0139 (11)	0.0108 (10)	0.0139 (11)	−0.0008 (8)	0.0039 (9)	−0.0009 (8)
C5	0.0156 (10)	0.0123 (10)	0.0139 (11)	−0.0005 (8)	0.0071 (9)	−0.0005 (8)
C6	0.0226 (12)	0.0147 (11)	0.0117 (11)	−0.0013 (9)	0.0063 (9)	0.0005 (8)
C8	0.0173 (11)	0.0225 (12)	0.0171 (12)	0.0025 (9)	0.0031 (10)	0.0016 (9)
O1	0.0270 (9)	0.0292 (10)	0.0171 (9)	0.0133 (7)	0.0055 (8)	0.0058 (7)
O2	0.0323 (11)	0.0532 (13)	0.0258 (10)	0.0204 (9)	0.0160 (9)	0.0184 (9)
C7	0.0188 (11)	0.0219 (12)	0.0174 (12)	0.0080 (9)	0.0008 (9)	0.0023 (9)
O4	0.0200 (8)	0.0108 (7)	0.0129 (8)	−0.0021 (6)	0.0054 (7)	−0.0012 (6)
O5	0.0348 (10)	0.0173 (8)	0.0117 (8)	−0.0093 (7)	0.0082 (7)	−0.0021 (6)
O6	0.0152 (8)	0.0242 (8)	0.0144 (8)	0.0039 (6)	0.0068 (7)	−0.0032 (6)
O7	0.0135 (7)	0.0168 (8)	0.0136 (8)	0.0011 (6)	0.0013 (6)	−0.0012 (6)
O8	0.0142 (8)	0.0217 (9)	0.0152 (9)	−0.0037 (6)	0.0013 (7)	−0.0020 (6)
O9	0.0172 (8)	0.0240 (8)	0.0159 (9)	−0.0035 (7)	0.0089 (7)	−0.0041 (7)
O1W	0.0248 (9)	0.0150 (8)	0.0201 (9)	−0.0034 (6)	0.0057 (8)	−0.0025 (7)
Pr1	0.00954 (7)	0.01013 (7)	0.00840 (8)	0.00028 (4)	0.00300 (5)	0.00065 (4)

C1—O6	1.251 (3)	O1—Pr1	2.5560 (16)
C1—O7	1.268 (3)	O2—H2A	0.8200
C1—O7	1.268 (3)	C7—C7ii	1.316 (5)
C1—C2	1.495 (3)	C7—H7	0.9300
C2—C3	1.315 (3)	O4—Pr1iii	2.4717 (14)
C2—H2	0.9300	O4—Pr1	2.7719 (16)
C3—C4	1.495 (3)	O5—Pr1	2.5278 (15)
C3—H3	0.9300	O6—Pr1	2.4563 (14)
C4—O8	1.252 (3)	O7—Pr1iii	2.4508 (15)
C4—O9	1.261 (3)	O8—Pr1iv	2.4040 (15)
C5—O5	1.256 (2)	O9—Pr1v	2.5184 (15)
C5—O4	1.273 (2)	O1W—Pr1	2.5795 (16)
C5—C6	1.490 (3)	O1W—H2W	0.825 (10)
C6—C6i	1.328 (4)	O1W—H1W	0.824 (9)
C6—H6	0.9300	Pr1—O8vi	2.4040 (15)
C8—O1	1.218 (3)	Pr1—O7vii	2.4508 (15)
C8—O2	1.308 (3)	Pr1—O4vii	2.4717 (14)
C8—C7	1.475 (3)	Pr1—O9viii	2.5184 (15)
O6—C1—O7	124.9 (2)	H2W—O1W—H1W	102.5 (14)
O6—C1—O7	124.9 (2)	O8vi—Pr1—O7vii	146.04 (5)
O6—C1—C2	117.1 (2)	O8vi—Pr1—O6	91.49 (5)
O7—C1—C2	118.04 (19)	O7vii—Pr1—O6	79.69 (5)
O7—C1—C2	118.04 (19)	O8vi—Pr1—O4vii	75.42 (5)
C3—C2—C1	122.4 (2)	O7vii—Pr1—O4vii	70.62 (5)
C3—C2—H2	118.8	O6—Pr1—O4vii	75.15 (5)
C1—C2—H2	118.8	O8vi—Pr1—O9viii	77.32 (5)
C2—C3—C4	124.9 (2)	O7vii—Pr1—O9viii	96.08 (5)
C2—C3—H3	117.6	O6—Pr1—O9viii	153.38 (5)
C4—C3—H3	117.6	O4vii—Pr1—O9viii	78.65 (5)
O8—C4—O9	124.4 (2)	O8vi—Pr1—O5	124.67 (5)
O8—C4—C3	120.0 (2)	O7vii—Pr1—O5	85.60 (5)
O9—C4—C3	115.6 (2)	O6—Pr1—O5	77.38 (6)
O5—C5—O4	120.73 (19)	O4vii—Pr1—O5	146.29 (5)
O5—C5—C6	120.43 (19)	O9viii—Pr1—O5	128.82 (5)
O4—C5—C6	118.78 (19)	O8vi—Pr1—O1	72.35 (5)
C6i—C6—C5	121.8 (3)	O7vii—Pr1—O1	137.28 (5)
C6i—C6—H6	119.1	O6—Pr1—O1	129.43 (5)
C5—C6—H6	119.1	O4vii—Pr1—O1	139.16 (5)
O1—C8—O2	123.4 (2)	O9viii—Pr1—O1	70.41 (5)
O1—C8—C7	121.8 (2)	O5—Pr1—O1	74.27 (5)
O2—C8—C7	114.8 (2)	O8vi—Pr1—O1W	132.29 (5)
C8—O1—Pr1	139.18 (16)	O7vii—Pr1—O1W	69.87 (5)
C8—O2—H2A	109.5	O6—Pr1—O1W	134.22 (5)
C7ii—C7—C8	120.5 (3)	O4vii—Pr1—O1W	122.25 (5)
C7ii—C7—H7	119.7	O9viii—Pr1—O1W	65.70 (5)
C8—C7—H7	119.7	O5—Pr1—O1W	67.18 (5)
C5—O4—Pr1iii	142.77 (14)	O1—Pr1—O1W	67.64 (5)
C5—O4—Pr1	88.35 (12)	O8vi—Pr1—O4	76.79 (5)
Pr1iii—O4—Pr1	127.68 (5)	O7vii—Pr1—O4	127.21 (5)
C5—O5—Pr1	100.28 (12)	O6—Pr1—O4	67.16 (5)
C1—O6—Pr1	139.76 (15)	O4vii—Pr1—O4	131.91 (3)
C1—O7—Pr1iii	136.47 (13)	O9viii—Pr1—O4	131.20 (5)
C4—O8—Pr1iv	139.42 (14)	O5—Pr1—O4	48.73 (4)
C4—O9—Pr1v	137.70 (14)	O1—Pr1—O4	62.59 (5)
Pr1—O1W—H2W	118.5 (18)	O1W—Pr1—O4	105.50 (5)
Pr1—O1W—H1W	119.2 (19)
O6—C1—C2—C3	162.7 (2)	C1—O6—Pr1—O1	16.7 (3)
O7—C1—C2—C3	−17.5 (3)	C1—O6—Pr1—O1W	113.2 (2)
O7—C1—C2—C3	−17.5 (3)	C1—O6—Pr1—O4	23.5 (2)
C1—C2—C3—C4	−176.7 (2)	C5—O5—Pr1—O8vi	4.60 (16)
C2—C3—C4—O8	−7.0 (3)	C5—O5—Pr1—O7vii	−158.77 (14)
C2—C3—C4—O9	172.2 (2)	C5—O5—Pr1—O6	−78.37 (13)
O5—C5—C6—C6i	3.3 (4)	C5—O5—Pr1—O4vii	−114.41 (14)
O4—C5—C6—C6i	−173.9 (3)	C5—O5—Pr1—O9viii	106.95 (14)
O2—C8—O1—Pr1	29.0 (4)	C5—O5—Pr1—O1	59.30 (13)
C7—C8—O1—Pr1	−150.46 (18)	C5—O5—Pr1—O1W	131.23 (14)
O1—C8—C7—C7ii	−2.2 (5)	C5—O5—Pr1—O4	−7.80 (12)
O2—C8—C7—C7ii	178.3 (3)	C8—O1—Pr1—O8vi	−115.0 (3)
O5—C5—O4—Pr1iii	153.25 (17)	C8—O1—Pr1—O7vii	44.8 (3)
C6—C5—O4—Pr1iii	−29.5 (3)	C8—O1—Pr1—O6	168.1 (2)
O5—C5—O4—Pr1	−13.4 (2)	C8—O1—Pr1—O4vii	−75.5 (3)
C6—C5—O4—Pr1	163.80 (18)	C8—O1—Pr1—O9viii	−32.5 (2)
O4—C5—O5—Pr1	15.0 (2)	C8—O1—Pr1—O5	109.8 (3)
C6—C5—O5—Pr1	−162.19 (17)	C8—O1—Pr1—O1W	38.5 (2)
O7—C1—O6—Pr1	33.2 (3)	C8—O1—Pr1—O4	161.1 (3)
O7—C1—O6—Pr1	33.2 (3)	C5—O4—Pr1—O8vi	−161.98 (13)
C2—C1—O6—Pr1	−147.04 (17)	Pr1iii—O4—Pr1—O8vi	28.18 (8)
O6—C1—O7—O7	0.00 (13)	C5—O4—Pr1—O7vii	44.97 (14)
C2—C1—O7—O7	0.00 (7)	Pr1iii—O4—Pr1—O7vii	−124.87 (8)
O6—C1—O7—Pr1iii	−70.6 (3)	C5—O4—Pr1—O6	100.68 (13)
O7—C1—O7—Pr1iii	0(100)	Pr1iii—O4—Pr1—O6	−69.17 (8)
C2—C1—O7—Pr1iii	109.6 (2)	C5—O4—Pr1—O4vii	141.96 (10)
O9—C4—O8—Pr1iv	−69.1 (3)	Pr1iii—O4—Pr1—O4vii	−27.89 (15)
C3—C4—O8—Pr1iv	110.1 (2)	C5—O4—Pr1—O9viii	−102.32 (13)
O8—C4—O9—Pr1v	9.8 (3)	Pr1iii—O4—Pr1—O9viii	87.84 (9)
C3—C4—O9—Pr1v	−169.47 (15)	C5—O4—Pr1—O5	7.57 (12)
C1—O6—Pr1—O8vi	−51.5 (2)	Pr1iii—O4—Pr1—O5	−162.27 (11)
C1—O6—Pr1—O7vii	161.5 (2)	C5—O4—Pr1—O1	−85.22 (13)
C1—O6—Pr1—O4vii	−126.0 (2)	Pr1iii—O4—Pr1—O1	104.93 (9)
C1—O6—Pr1—O9viii	−115.5 (2)	C5—O4—Pr1—O1W	−31.27 (13)
C1—O6—Pr1—O5	73.8 (2)	Pr1iii—O4—Pr1—O1W	158.88 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O7	0.93	2.50	2.815 (3)	100.
O1W—H2W···O7ix	0.83 (1)	2.11 (1)	2.911 (2)	165 (2)
O2—H2A···O9viii	0.82	1.86	2.661 (2)	167.
O1W—H1W···O5x	0.82 (1)	2.09 (2)	2.816 (2)	147 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O7	0.93	2.50	2.815 (3)	100
O1W—H2W⋯O7i	0.83 (1)	2.11 (1)	2.911 (2)	165 (2)
O2—H2A⋯O9ii	0.82	1.86	2.661 (2)	167
O1W—H1W⋯O5iii	0.82 (1)	2.09 (2)	2.816 (2)	147 (2)

Symmetry codes: (i) ; (ii) ; (iii) .