Hydro-thermal synthesis and crystal structure of a new lanthanum(III) coordination polymer with fumaric acid.

The title compound, poly[di-aqua-tris-(μ4-but-2-enedioato)(μ2-but-2-enedioic acid)dilanthanum(III)], [La2(C4H2O4)3(C4H4O4)(H2O)2] n , was synthesized by the reaction of lanthanum chloride penta-hydrate with fumaric acid under hydro-thermal conditions. The asymmetric unit comprises an La(III) cation, one and a half fumarate dianions (L (2-)), one a half-mol-ecule of fumaric acid (H2 L) and one coordinated water mol-ecule. Each La(III) cation has the same nine-coordinate environment and is surrounded by eight O atoms from seven distinct fumarate moieties, including one proton-ated fumarate unit and one water mol-ecule in a distorted tricapped trigonal-prismatic environment. The LaO8(H2O) polyhedra centres are edge-shared through three carboxyl-ate bridges of the fumarate ligand, forming chains in three dimensions to construct the MOF. 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, and also between oxygen atoms of fumaric acid.

Related literature

For general background to metal coordination polymers, see: Fujita et al. (1994 ▸); Bénard et al. (2000 ▸); Zhang et al. (2000 ▸). For structures involving fumarate ligands and transition metals, see: Dalai et al. (2002 ▸); Xie et al. (2003 ▸); Devereux et al. (2000 ▸). For rare earth fumarates, see: Zhang et al. (2006 ▸); Li & Zou (2006 ▸); Liu et al. (2011 ▸). For reported La—O distances, see: Dan et al. (2005 ▸).

Experimental

Crystal data

[La2(C4H2O4)3(C4H4O4)(H2O)2]

M = 386.05

Monoclinic,

a = 8.4299 (5) Å

b = 14.6789 (8) Å

c = 8.8096 (5) Å

β = 103.318 (3)°

V = 1060.80 (11) Å3

Z = 4

Mo Kα radiation

μ = 4.07 mm−1

T = 295 K

0.12 × 0.11 × 0.08 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▸) T min = 0.677, T max = 0.796

17677 measured reflections

4523 independent reflections

3901 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.043

S = 1.02

4523 reflections

171 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.06 e Å−3

Δρmin = −0.67 e Å−3

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg & Berndt, 2001 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and CRYSCAL (T. Roisnel, local program).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015007008/lh5759sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007008/lh5759Isup2.hkl

Click here for additional data file.

ORTEP-3 . DOI: 10.1107/S2056989015007008/lh5759fig1.tif

An ORTEP-3 (Farrugia, 2012) drawing of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015007008/lh5759fig2.tif

A packing diagram of (I), showing the two-dimensional layered framework structure.

Click here for additional data file.

. DOI: 10.1107/S2056989015007008/lh5759fig3.tif

A packing diagram of (I), showing the three-dimensional open-framework structure.

CCDC reference: 1058359

Additional supporting information: crystallographic information; 3D view; checkCIF report

[La2(C4H2O4)3(C4H4O4)(H2O)2]	F(000) = 736
Mr = 386.05	Dx = 2.417 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7844 reflections
a = 8.4299 (5) Å	θ = 2.8–34.5°
b = 14.6789 (8) Å	µ = 4.07 mm−1
c = 8.8096 (5) Å	T = 295 K
β = 103.318 (3)°	Prism, brown
V = 1060.80 (11) Å3	0.12 × 0.11 × 0.08 mm
Z = 4

Bruker APEXII diffractometer	3901 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
CCD rotation images, thin slices scans	θmax = 34.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −13→13
Tmin = 0.677, Tmax = 0.796	k = −23→22
17677 measured reflections	l = −14→14
4523 independent reflections

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.043	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0198P)2 + 0.4033P] where P = (Fo2 + 2Fc2)/3
4523 reflections	(Δ/σ)max = 0.003
171 parameters	Δρmax = 2.06 e Å−3
0 restraints	Δρmin = −0.67 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	0.91794 (19)	0.17630 (11)	0.3525 (2)	0.0094 (3)
C2	1.09547 (19)	0.16975 (12)	0.3538 (2)	0.0116 (3)
H2	1.1677	0.1528	0.4461	0.014*
C3	1.1551 (2)	0.18705 (11)	0.22925 (19)	0.0104 (3)
H3	1.0842	0.2006	0.1344	0.012*
C4	1.33672 (18)	0.18480 (11)	0.24064 (19)	0.0091 (3)
C5	0.9759 (2)	0.43916 (12)	0.3056 (2)	0.0136 (3)
C6	1.0339 (2)	0.50146 (12)	0.4385 (2)	0.0137 (3)
H6	1.1173	0.5426	0.4366	0.016*
C7	0.53342 (19)	0.10280 (11)	−0.12552 (19)	0.0100 (3)
C8	0.5242 (2)	0.04320 (11)	0.0094 (2)	0.0115 (3)
H8	0.5533	0.0672	0.1098	0.014*
O1	0.81442 (14)	0.18896 (8)	0.22694 (15)	0.0121 (2)
O2	0.88376 (15)	0.16822 (9)	0.48504 (15)	0.0135 (2)
O1W	0.68340 (16)	0.47790 (9)	0.02557 (17)	0.0140 (2)
O3	1.38637 (14)	0.22346 (9)	0.13278 (15)	0.0128 (2)
O4	1.42800 (14)	0.14400 (8)	0.35629 (14)	0.0113 (2)
O5	1.05314 (17)	0.44700 (11)	0.19286 (17)	0.0232 (3)
H5	1.0152	0.4107	0.1232	0.035*
O6	0.86412 (16)	0.38537 (9)	0.30246 (15)	0.0165 (3)
O7	0.59366 (15)	0.18252 (8)	−0.09912 (15)	0.0106 (2)
O8	0.48750 (15)	0.07304 (9)	−0.26313 (14)	0.0145 (2)
La1	0.631512 (10)	0.309568 (6)	0.097101 (10)	0.00675 (3)
H1W	0.656 (3)	0.4969 (19)	−0.062 (4)	0.030 (7)*
H2W	0.651 (3)	0.513 (2)	0.071 (4)	0.036 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0093 (6)	0.0092 (7)	0.0107 (7)	0.0008 (5)	0.0044 (5)	0.0017 (5)
C2	0.0082 (6)	0.0166 (8)	0.0099 (7)	0.0000 (5)	0.0019 (5)	0.0009 (6)
C3	0.0115 (6)	0.0117 (7)	0.0090 (6)	−0.0008 (5)	0.0045 (5)	0.0017 (6)
C4	0.0075 (6)	0.0111 (7)	0.0088 (6)	−0.0007 (5)	0.0021 (5)	−0.0002 (5)
C5	0.0131 (7)	0.0166 (8)	0.0108 (7)	−0.0010 (6)	0.0021 (6)	−0.0006 (6)
C6	0.0142 (7)	0.0153 (8)	0.0113 (7)	−0.0037 (6)	0.0021 (6)	−0.0020 (6)
C7	0.0113 (6)	0.0107 (7)	0.0088 (7)	−0.0007 (5)	0.0036 (5)	−0.0001 (5)
C8	0.0170 (7)	0.0099 (7)	0.0085 (7)	−0.0018 (6)	0.0046 (6)	0.0000 (5)
O1	0.0097 (5)	0.0139 (6)	0.0117 (5)	0.0015 (4)	0.0005 (4)	0.0016 (5)
O2	0.0118 (5)	0.0187 (6)	0.0117 (6)	0.0027 (4)	0.0063 (4)	0.0031 (5)
O1W	0.0171 (6)	0.0110 (6)	0.0141 (6)	0.0019 (4)	0.0040 (5)	0.0016 (5)
O3	0.0105 (5)	0.0175 (6)	0.0113 (6)	−0.0030 (4)	0.0043 (4)	0.0025 (5)
O4	0.0095 (5)	0.0133 (6)	0.0102 (5)	0.0009 (4)	0.0006 (4)	0.0002 (4)
O5	0.0213 (7)	0.0347 (8)	0.0161 (6)	−0.0129 (6)	0.0094 (5)	−0.0119 (6)
O6	0.0180 (6)	0.0191 (7)	0.0118 (6)	−0.0075 (5)	0.0024 (5)	−0.0026 (5)
O7	0.0138 (5)	0.0082 (5)	0.0108 (5)	−0.0019 (4)	0.0051 (4)	−0.0010 (4)
O8	0.0218 (6)	0.0138 (6)	0.0086 (5)	−0.0061 (5)	0.0051 (5)	−0.0017 (5)
La1	0.00657 (4)	0.00743 (4)	0.00650 (4)	−0.00024 (3)	0.00204 (3)	−0.00044 (3)

C1—O1	1.255 (2)	C8—H8	0.93
C1—O2	1.271 (2)	O1W—H1W	0.80 (3)
C1—C2	1.497 (2)	O1W—H2W	0.75 (3)
C2—C3	1.332 (2)	O3—La1iv	2.5032 (11)
C2—H2	0.93	O4—La1v	2.4963 (12)
C3—C4	1.512 (2)	O5—H5	0.82
C3—H3	0.93	La1—C7vi	3.0398 (15)
C4—O3	1.2583 (19)	O6—La1	2.5926 (13)
C4—O4	1.276 (2)	O7—La1	2.5127 (12)
C5—O6	1.225 (2)	O1—La1	2.4510 (12)
C5—O5	1.312 (2)	O1W—La1	2.6117 (13)
C5—C6	1.477 (2)	O2—La1vi	2.5631 (11)
C6—C6i	1.338 (3)	O7—La1ii	2.7696 (12)
C6—H6	0.93	O8—La1ii	2.5784 (12)
C7—O8	1.263 (2)	La1—O4vii	2.4963 (12)
C7—O7	1.2755 (19)	La1—O3viii	2.5032 (11)
C7—C8	1.492 (2)	La1—O2ii	2.5631 (11)
C7—La1ii	3.0398 (15)	La1—O8vi	2.5784 (12)
C8—C8iii	1.331 (3)	La1—O7vi	2.7696 (12)
O1—C1—O2	124.39 (15)	O1—La1—O7	75.61 (4)
O1—C1—C2	120.47 (14)	O4vii—La1—O7	70.40 (4)
O2—C1—C2	115.14 (15)	O3viii—La1—O7	74.57 (4)
C3—C2—C1	123.19 (16)	O1—La1—O2ii	77.47 (4)
C3—C2—H2	118.4	O4vii—La1—O2ii	96.12 (4)
C1—C2—H2	118.4	O3viii—La1—O2ii	153.47 (4)
C2—C3—C4	120.64 (15)	O7—La1—O2ii	79.32 (4)
C2—C3—H3	119.7	O1—La1—O8vi	125.08 (4)
C4—C3—H3	119.7	O4vii—La1—O8vi	85.20 (4)
O3—C4—O4	124.78 (14)	O3viii—La1—O8vi	77.55 (4)
O3—C4—C3	116.62 (14)	O7—La1—O8vi	145.63 (4)
O4—C4—C3	118.60 (13)	O2ii—La1—O8vi	128.50 (4)
O6—C5—O5	123.56 (17)	O1—La1—O6	72.00 (4)
O6—C5—C6	121.97 (15)	O4vii—La1—O6	137.48 (4)
O5—C5—C6	114.46 (15)	O3viii—La1—O6	129.99 (4)
C6i—C6—C5	119.8 (2)	O7—La1—O6	138.97 (4)
C6i—C6—H6	120.1	O2ii—La1—O6	69.69 (4)
C5—C6—H6	120.1	O8vi—La1—O6	75.14 (4)
O8—C7—O7	120.91 (15)	O1—La1—O1W	132.35 (4)
O8—C7—C8	120.09 (15)	O4vii—La1—O1W	69.95 (4)
O7—C7—C8	118.95 (15)	O3viii—La1—O1W	134.19 (4)
O8—C7—La1ii	56.95 (8)	O7—La1—O1W	122.55 (4)
O7—C7—La1ii	65.65 (8)	O2ii—La1—O1W	65.59 (4)
C8—C7—La1ii	164.17 (11)	O8vi—La1—O1W	66.82 (4)
C8iii—C8—C7	122.0 (2)	O6—La1—O1W	67.70 (4)
C8iii—C8—H8	119	O1—La1—O7vi	77.26 (4)
C7—C8—H8	119	O4vii—La1—O7vi	126.88 (4)
C1—O1—La1	138.87 (11)	O3viii—La1—O7vi	67.52 (4)
C1—O2—La1vi	136.53 (11)	O7—La1—O7vi	132.16 (3)
La1—O1W—H1W	122 (2)	O2ii—La1—O7vi	131.09 (4)
La1—O1W—H2W	116 (2)	O8vi—La1—O7vi	48.61 (4)
H1W—O1W—H2W	102 (3)	O6—La1—O7vi	62.92 (4)
C4—O3—La1iv	138.62 (11)	O1W—La1—O7vi	104.86 (4)
C4—O4—La1v	136.10 (11)	O1—La1—C7vi	100.89 (4)
C5—O5—H5	109.5	O4vii—La1—C7vi	107.86 (4)
C5—O6—La1	138.30 (12)	O3viii—La1—C7vi	74.18 (4)
C7—O7—La1	142.04 (10)	O7—La1—C7vi	148.44 (4)
C7—O7—La1ii	89.54 (9)	O2ii—La1—C7vi	131.24 (4)
La1—O7—La1ii	127.52 (4)	O8vi—La1—C7vi	24.23 (4)
C7—O8—La1ii	98.82 (10)	O6—La1—C7vi	63.86 (4)
O1—La1—O4vii	146.01 (4)	O1W—La1—C7vi	83.41 (4)
O1—La1—O3viii	91.46 (4)	O7vi—La1—C7vi	24.81 (4)
O4vii—La1—O3viii	79.57 (4)
O1—C1—C2—C3	8.0 (3)	C1—O1—La1—O6	22.16 (15)
O2—C1—C2—C3	−171.99 (16)	C1—O1—La1—O1W	55.44 (17)
C1—C2—C3—C4	176.25 (15)	C1—O1—La1—O7vi	−43.17 (16)
C2—C3—C4—O3	−162.53 (16)	C1—O1—La1—C7vi	−35.55 (16)
C2—C3—C4—O4	18.0 (2)	C7—O7—La1—O1	70.34 (18)
O6—C5—C6—C6i	1.5 (3)	La1ii—O7—La1—O1	−124.25 (6)
O5—C5—C6—C6i	−178.9 (2)	C7—O7—La1—O4vii	−109.49 (18)
O8—C7—C8—C8iii	3.3 (3)	La1ii—O7—La1—O4vii	55.92 (6)
O7—C7—C8—C8iii	−174.2 (2)	C7—O7—La1—O3viii	−25.29 (17)
La1ii—C7—C8—C8iii	−71.3 (5)	La1ii—O7—La1—O3viii	140.12 (7)
O2—C1—O1—La1	70.6 (2)	C7—O7—La1—O2ii	150.00 (18)
C2—C1—O1—La1	−109.40 (17)	La1ii—O7—La1—O2ii	−44.59 (6)
O1—C1—O2—La1vi	−9.9 (3)	C7—O7—La1—O8vi	−62.2 (2)
C2—C1—O2—La1vi	170.08 (11)	La1ii—O7—La1—O8vi	103.23 (7)
O4—C4—O3—La1iv	−33.2 (3)	C7—O7—La1—O6	109.01 (17)
C3—C4—O3—La1iv	147.30 (13)	La1ii—O7—La1—O6	−85.58 (8)
O3—C4—O4—La1v	72.1 (2)	C7—O7—La1—O1W	−158.26 (17)
C3—C4—O4—La1v	−108.47 (15)	La1ii—O7—La1—O1W	7.15 (8)
O5—C5—O6—La1	−30.8 (3)	C7—O7—La1—O7vi	13.0 (2)
C6—C5—O6—La1	148.76 (14)	La1ii—O7—La1—O7vi	178.394 (15)
O8—C7—O7—La1	154.08 (13)	C7—O7—La1—C7vi	−17.1 (2)
C8—C7—O7—La1	−28.5 (3)	La1ii—O7—La1—C7vi	148.33 (6)
La1ii—C7—O7—La1	168.47 (17)	C5—O6—La1—O1	117.06 (19)
O8—C7—O7—La1ii	−14.40 (15)	C5—O6—La1—O4vii	−42.3 (2)
C8—C7—O7—La1ii	163.03 (13)	C5—O6—La1—O3viii	−166.68 (17)
O7—C7—O8—La1ii	15.68 (17)	C5—O6—La1—O7	77.5 (2)
C8—C7—O8—La1ii	−161.72 (12)	C5—O6—La1—O2ii	34.12 (18)
C1—O1—La1—O4vii	176.91 (14)	C5—O6—La1—O8vi	−107.59 (19)
C1—O1—La1—O3viii	−109.72 (16)	C5—O6—La1—O1W	−36.94 (18)
C1—O1—La1—O7	176.62 (16)	C5—O6—La1—O7vi	−158.3 (2)
C1—O1—La1—O2ii	94.61 (16)	C5—O6—La1—C7vi	−130.57 (19)
C1—O1—La1—O8vi	−33.94 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O8ix	0.80 (3)	2.06 (3)	2.7995 (19)	154 (3)
O1W—H2W···O4x	0.75 (3)	2.17 (3)	2.8913 (18)	163 (3)
O5—H5···O2ii	0.82	1.85	2.655 (2)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1WH1WO8i	0.80(3)	2.06(3)	2.7995(19)	154(3)
O1WH2WO4ii	0.75(3)	2.17(3)	2.8913(18)	163(3)
O5H5O2iii	0.82	1.85	2.655(2)	167

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