Poly[[tetra-μ(3)-acetato-hexa-μ(2)-acetato-diaqua-μ(2)-oxalato-tetra-lanthanum(III)] dihydrate].

The title compound, {[La(4)(CH(3)CO(2))(10)(C(2)O(4))(H(2)O)(2)]·2H(2)O}(n), exhibits a two-dimensional layered structure with the oxalate and acetate ligands acting as bridges. The asymmetric unit contains two crystallographically independent lanthanum(III) ions, half of an oxalate ligand, five acetate ligands, one coordinated water mol-ecule and one uncoordinated water mol-ecule. The coordination numbers of the two La ions are 9 and 10. Adjacent layers of the structure, which extend parallel to (100), are linked by O-H⋯O hydrogen bonds and are also held together by van der Waals inter-actions between the CH(3) groups of the acetate anions.

Related literature

For properties of lanthanide compounds with metal-organic framework structures, see: Zhu et al. (2006 ▶); Deng et al. (2009 ▶); Bünzli & Piguet (2005 ▶); Zhang et al. (2008 ▶). For metal oxalates, see: Kustaryono et al. (2010 ▶); Roméro & Trombe (1999 ▶); Yu et al. (2006 ▶); Ohba et al. (1993 ▶). For lanthanide oxalates obtained from oxalate-containing starting materials, see: Zhang et al. (2009 ▶); Trombe et al. (2005 ▶). For lanthanide oxalates with oxalate formed in the course of the synthesis by decomposition of organic compounds or other unconventional reactions, see: Koner & Goldberg (2009 ▶); Li et al. (2003 ▶); Min & Lee (2002 ▶); Mohapatra et al. (2009 ▶). For oxidation of acetate to oxalate, see: Zieliński (1983 ▶). For La—O bond lengths, see: Trombe & Roméro (2000 ▶); Deng et al. (2009 ▶). For coordination modes of acetate groups, see: Zhang et al. (2009 ▶); Dan et al. (2006 ▶); Koner & Goldberg (2009 ▶); Mazurek et al. (1985 ▶).

Experimental

Crystal data

[La4(C2H3O2)10(C2O4)(H2O)2]·2H2O

M = 653.08

Monoclinic,

a = 9.4139 (19) Å

b = 13.310 (3) Å

c = 16.087 (3) Å

β = 103.10 (3)°

V = 1963.2 (7) Å3

Z = 4

Mo Kα radiation

μ = 4.36 mm−1

T = 295 K

0.19 × 0.18 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.454, T max = 0.456

14917 measured reflections

3432 independent reflections

3185 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.042

S = 1.12

3432 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.40 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg & Putz, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038037/qk2021sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038037/qk2021Isup2.hkl

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

[La4(C2H3O2)10(C2O4)(H2O)2]·2H2O	F(000) = 1244
Mr = 653.08	Dx = 2.210 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3432 reflections
a = 9.4139 (19) Å	θ = 3.0–25.0°
b = 13.310 (3) Å	µ = 4.36 mm−1
c = 16.087 (3) Å	T = 295 K
β = 103.10 (3)°	Block, colourless
V = 1963.2 (7) Å3	0.19 × 0.18 × 0.18 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	3432 independent reflections
Radiation source: fine-focus sealed tube	3185 reflections with I > 2σ(I)
graphite	Rint = 0.023
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi,1995)	h = −11→11
Tmin = 0.454, Tmax = 0.456	k = −15→15
14917 measured reflections	l = −19→18

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)] = 0.019	H-atom parameters constrained
wR(F2) = 0.042	w = 1/[σ2(Fo2) + (0.014P)2 + 3.2282P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.002
3432 reflections	Δρmax = 0.56 e Å−3
245 parameters	Δρmin = −0.40 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00041 (8)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
La1	0.49400 (2)	0.626091 (13)	0.826328 (11)	0.01839 (7)
La2	0.43860 (2)	0.927787 (13)	0.868342 (11)	0.01851 (7)
O1	0.3617 (3)	0.57173 (19)	0.93738 (15)	0.0334 (6)
O2	0.3667 (3)	0.4876 (2)	1.05838 (16)	0.0388 (6)
O3	0.7514 (3)	0.6156 (2)	0.81474 (18)	0.0488 (8)
O4	0.7413 (4)	0.4615 (3)	0.76263 (18)	0.0636 (10)
O5	0.2212 (3)	0.64689 (19)	0.75919 (16)	0.0370 (6)
O6	0.2988 (3)	0.76927 (17)	0.84850 (14)	0.0282 (5)
O7	0.4657 (3)	0.89359 (17)	1.16394 (13)	0.0291 (6)
O8	0.4577 (3)	0.91183 (17)	1.02914 (13)	0.0267 (5)
O9	0.7158 (3)	0.90241 (17)	0.93121 (15)	0.0299 (6)
O10	0.6023 (3)	0.75914 (17)	0.93639 (13)	0.0272 (5)
O11	0.5756 (3)	0.95427 (17)	0.73455 (15)	0.0335 (6)
O12	0.5291 (3)	0.80015 (16)	0.76449 (14)	0.0275 (5)
O13	0.2161 (3)	1.0002 (2)	0.90822 (16)	0.0474 (8)
H13B	0.2400	1.0278	0.9549	0.071*
H13A	0.1270	0.9998	0.8919	0.071*
O14	−0.0721 (3)	1.0087 (3)	0.8562 (2)	0.0745 (12)
H14B	−0.1085	0.9687	0.8892	0.050*
H14A	−0.1241	1.0501	0.8208	0.050*
C1	0.4214 (4)	0.5171 (2)	0.9990 (2)	0.0258 (7)
C2	0.8037 (4)	0.5293 (3)	0.8105 (2)	0.0347 (9)
C3	0.9496 (5)	0.5054 (4)	0.8655 (3)	0.0589 (13)
H3A	0.9749	0.4372	0.8556	0.088*
H3B	0.9467	0.5134	0.9244	0.088*
H3C	1.0212	0.5500	0.8520	0.088*
C4	0.1955 (4)	0.7242 (3)	0.7973 (2)	0.0268 (8)
C5	0.0446 (5)	0.7640 (3)	0.7823 (3)	0.0584 (13)
H5A	0.0469	0.8360	0.7797	0.088*
H5B	0.0011	0.7436	0.8281	0.088*
H5C	−0.0119	0.7381	0.7293	0.088*
C6	0.4177 (4)	0.8653 (2)	1.08777 (19)	0.0206 (7)
C7	0.3107 (5)	0.7813 (3)	1.0678 (2)	0.0392 (9)
H7A	0.2863	0.7697	1.0074	0.059*
H7B	0.2241	0.7985	1.0867	0.059*
H7C	0.3528	0.7215	1.0966	0.059*
C8	0.7178 (4)	0.8098 (3)	0.95129 (19)	0.0257 (8)
C9	0.8593 (5)	0.7623 (3)	0.9952 (3)	0.0455 (10)
H9A	0.8595	0.6930	0.9788	0.068*
H9B	0.8705	0.7669	1.0558	0.068*
H9C	0.9385	0.7967	0.9789	0.068*
C10	0.5884 (4)	0.8614 (2)	0.72301 (19)	0.0229 (7)
C11	0.6738 (4)	0.8243 (3)	0.6616 (2)	0.0365 (9)
H11A	0.6250	0.8430	0.6047	0.055*
H11B	0.6818	0.7525	0.6655	0.055*
H11C	0.7695	0.8536	0.6752	0.055*

	U11	U22	U33	U12	U13	U23
La1	0.02665 (12)	0.01320 (10)	0.01550 (10)	0.00021 (7)	0.00519 (7)	0.00054 (6)
La2	0.02568 (12)	0.01433 (10)	0.01519 (10)	−0.00034 (7)	0.00396 (7)	−0.00131 (6)
O1	0.0374 (16)	0.0368 (15)	0.0278 (13)	0.0104 (12)	0.0111 (11)	0.0146 (11)
O2	0.0411 (17)	0.0468 (17)	0.0327 (14)	0.0106 (13)	0.0172 (12)	0.0183 (12)
O3	0.0396 (18)	0.060 (2)	0.0522 (18)	0.0180 (15)	0.0222 (14)	0.0200 (14)
O4	0.067 (2)	0.084 (3)	0.0305 (16)	−0.0347 (19)	−0.0072 (14)	−0.0020 (15)
O5	0.0349 (16)	0.0358 (15)	0.0365 (15)	−0.0001 (12)	0.0004 (11)	−0.0111 (11)
O6	0.0304 (14)	0.0234 (13)	0.0297 (13)	−0.0051 (10)	0.0046 (10)	−0.0019 (10)
O7	0.0483 (16)	0.0218 (12)	0.0159 (12)	−0.0054 (11)	0.0047 (10)	−0.0012 (9)
O8	0.0405 (15)	0.0239 (12)	0.0173 (12)	−0.0002 (11)	0.0096 (10)	0.0007 (9)
O9	0.0332 (15)	0.0246 (13)	0.0314 (13)	−0.0015 (11)	0.0067 (11)	−0.0018 (10)
O10	0.0318 (15)	0.0261 (13)	0.0221 (12)	−0.0036 (11)	0.0029 (10)	−0.0047 (9)
O11	0.0561 (18)	0.0160 (12)	0.0325 (14)	0.0026 (11)	0.0183 (12)	0.0011 (10)
O12	0.0460 (16)	0.0160 (12)	0.0240 (12)	−0.0007 (11)	0.0152 (11)	−0.0013 (9)
O13	0.0280 (16)	0.072 (2)	0.0382 (15)	0.0102 (14)	0.0003 (11)	−0.0260 (14)
O14	0.0296 (18)	0.093 (3)	0.097 (3)	0.0079 (17)	0.0056 (17)	0.062 (2)
C1	0.035 (2)	0.0217 (18)	0.0212 (17)	−0.0014 (15)	0.0080 (14)	0.0011 (13)
C2	0.033 (2)	0.052 (3)	0.0205 (18)	−0.0039 (19)	0.0083 (15)	0.0007 (16)
C3	0.045 (3)	0.052 (3)	0.069 (3)	0.007 (2)	−0.009 (2)	−0.011 (2)
C4	0.029 (2)	0.0226 (18)	0.0282 (18)	−0.0024 (15)	0.0064 (15)	0.0049 (14)
C5	0.030 (3)	0.044 (3)	0.099 (4)	0.002 (2)	0.011 (2)	−0.006 (3)
C6	0.0277 (19)	0.0150 (16)	0.0190 (17)	0.0046 (13)	0.0055 (13)	−0.0003 (12)
C7	0.049 (3)	0.035 (2)	0.033 (2)	−0.0146 (19)	0.0088 (17)	−0.0027 (16)
C8	0.031 (2)	0.029 (2)	0.0175 (16)	0.0030 (16)	0.0068 (13)	−0.0052 (13)
C9	0.040 (3)	0.045 (3)	0.048 (2)	0.010 (2)	0.0007 (19)	0.0001 (19)
C10	0.034 (2)	0.0177 (17)	0.0168 (16)	0.0020 (14)	0.0047 (13)	0.0012 (12)
C11	0.044 (2)	0.032 (2)	0.040 (2)	0.0031 (18)	0.0233 (18)	0.0015 (16)

La1—O3	2.476 (3)	O8—La2v	2.739 (2)
La1—O1	2.505 (2)	O9—C8	1.273 (4)
La1—O11i	2.515 (2)	O10—C8	1.256 (4)
La1—O2ii	2.519 (2)	O11—C10	1.260 (4)
La1—O10	2.548 (2)	O11—La1iv	2.515 (2)
La1—O5	2.565 (3)	O12—C10	1.261 (4)
La1—O12	2.572 (2)	O13—H13B	0.8200
La1—O7iii	2.578 (2)	O13—H13A	0.8200
La1—O6	2.727 (2)	O14—H14B	0.8733
La2—O4iv	2.427 (3)	O14—H14A	0.8611
La2—O6	2.469 (2)	C1—C1ii	1.542 (7)
La2—O13	2.517 (3)	C2—C3	1.490 (6)
La2—O8	2.561 (2)	C3—H3A	0.9600
La2—O9	2.598 (3)	C3—H3B	0.9600
La2—O7v	2.636 (2)	C3—H3C	0.9600
La2—O12	2.655 (2)	C4—C5	1.484 (5)
La2—O8v	2.739 (2)	C5—H5A	0.9600
La2—O11	2.771 (2)	C5—H5B	0.9600
La2—O10	2.802 (2)	C5—H5C	0.9600
O1—C1	1.254 (4)	C6—C7	1.491 (5)
O2—C1	1.247 (4)	C7—H7A	0.9600
O2—La1ii	2.519 (2)	C7—H7B	0.9600
O3—C2	1.258 (5)	C7—H7C	0.9600
O4—C2	1.244 (5)	C8—C9	1.498 (5)
O4—La2i	2.427 (3)	C9—H9A	0.9600
O5—C4	1.250 (4)	C9—H9B	0.9600
O6—C4	1.272 (4)	C9—H9C	0.9600
O7—C6	1.263 (4)	C10—C11	1.491 (5)
O7—La1vi	2.578 (2)	C11—H11A	0.9600
O7—La2v	2.636 (2)	C11—H11B	0.9600
O8—C6	1.255 (4)	C11—H11C	0.9600
O3—La1—O1	133.67 (9)	C4—O5—La1	99.7 (2)
O3—La1—O11i	95.29 (10)	C4—O6—La2	142.5 (2)
O1—La1—O11i	83.53 (8)	C4—O6—La1	91.4 (2)
O3—La1—O2ii	70.52 (9)	La2—O6—La1	105.00 (8)
O1—La1—O2ii	63.98 (8)	C6—O7—La1vi	152.2 (2)
O11i—La1—O2ii	77.69 (9)	C6—O7—La2v	98.07 (18)
O3—La1—O10	81.21 (10)	La1vi—O7—La2v	109.26 (8)
O1—La1—O10	83.72 (8)	C6—O8—La2	146.7 (2)
O11i—La1—O10	158.48 (8)	C6—O8—La2v	93.35 (18)
O2ii—La1—O10	81.16 (9)	La2—O8—La2v	118.52 (8)
O3—La1—O5	151.38 (9)	C8—O9—La2	100.4 (2)
O1—La1—O5	73.70 (9)	C8—O10—La1	134.3 (2)
O11i—La1—O5	77.68 (8)	C8—O10—La2	91.1 (2)
O2ii—La1—O5	132.77 (9)	La1—O10—La2	100.79 (8)
O10—La1—O5	114.99 (8)	C10—O11—La1iv	149.3 (2)
O3—La1—O12	78.93 (9)	C10—O11—La2	93.83 (19)
O1—La1—O12	131.63 (8)	La1iv—O11—La2	106.98 (8)
O11i—La1—O12	135.50 (7)	C10—O12—La1	153.9 (2)
O2ii—La1—O12	137.28 (9)	C10—O12—La2	99.38 (18)
O10—La1—O12	64.94 (7)	La1—O12—La2	104.19 (8)
O5—La1—O12	86.80 (8)	La2—O13—H13B	109.5
O3—La1—O7iii	78.23 (9)	La2—O13—H13A	139.9
O1—La1—O7iii	137.68 (9)	H13B—O13—H13A	110.2
O11i—La1—O7iii	63.59 (7)	H14B—O14—H14A	123.3
O2ii—La1—O7iii	127.01 (8)	O2—C1—O1	126.8 (3)
O10—La1—O7iii	135.05 (8)	O2—C1—C1ii	116.8 (4)
O5—La1—O7iii	73.79 (9)	O1—C1—C1ii	116.4 (4)
O12—La1—O7iii	72.09 (7)	O4—C2—O3	124.0 (4)
O3—La1—O6	138.55 (9)	O4—C2—C3	117.1 (4)
O1—La1—O6	69.50 (7)	O3—C2—C3	118.9 (4)
O11i—La1—O6	124.24 (8)	C2—C3—H3A	109.5
O2ii—La1—O6	125.26 (8)	C2—C3—H3B	109.5
O10—La1—O6	66.35 (7)	H3A—C3—H3B	109.5
O5—La1—O6	48.66 (7)	C2—C3—H3C	109.5
O12—La1—O6	64.57 (7)	H3A—C3—H3C	109.5
O7iii—La1—O6	106.60 (7)	H3B—C3—H3C	109.5
O4iv—La2—O6	78.42 (11)	O5—C4—O6	120.1 (3)
O4iv—La2—O13	72.15 (10)	O5—C4—C5	119.9 (3)
O6—La2—O13	84.84 (9)	O6—C4—C5	120.0 (3)
O4iv—La2—O8	140.15 (10)	O5—C4—La1	56.36 (18)
O6—La2—O8	88.45 (8)	O6—C4—La1	63.83 (18)
O13—La2—O8	69.29 (9)	C5—C4—La1	175.4 (3)
O4iv—La2—O9	143.46 (10)	C4—C5—H5A	109.5
O6—La2—O9	113.47 (8)	C4—C5—H5B	109.5
O13—La2—O9	140.44 (8)	H5A—C5—H5B	109.5
O8—La2—O9	76.21 (8)	C4—C5—H5C	109.5
O4iv—La2—O7v	82.21 (11)	H5A—C5—H5C	109.5
O6—La2—O7v	160.30 (7)	H5B—C5—H5C	109.5
O13—La2—O7v	92.65 (9)	O8—C6—O7	118.7 (3)
O8—La2—O7v	108.97 (7)	O8—C6—C7	120.8 (3)
O9—La2—O7v	80.56 (8)	O7—C6—C7	120.5 (3)
O4iv—La2—O12	80.35 (9)	O8—C6—La2v	62.63 (16)
O6—La2—O12	67.02 (7)	O7—C6—La2v	57.95 (16)
O13—La2—O12	144.06 (8)	C7—C6—La2v	163.9 (2)
O8—La2—O12	128.57 (7)	C6—C7—H7A	109.5
O9—La2—O12	74.00 (8)	C6—C7—H7B	109.5
O7v—La2—O12	106.28 (7)	H7A—C7—H7B	109.5
O4iv—La2—O8v	117.51 (10)	C6—C7—H7C	109.5
O6—La2—O8v	148.30 (7)	H7A—C7—H7C	109.5
O13—La2—O8v	75.62 (8)	H7B—C7—H7C	109.5
O8—La2—O8v	61.48 (8)	O10—C8—O9	120.6 (3)
O9—La2—O8v	71.19 (8)	O10—C8—C9	120.1 (3)
O7v—La2—O8v	47.50 (7)	O9—C8—C9	119.2 (3)
O12—La2—O8v	139.14 (7)	O10—C8—La2	64.91 (18)
O4iv—La2—O11	70.01 (10)	O9—C8—La2	55.73 (17)
O6—La2—O11	109.68 (7)	C9—C8—La2	174.4 (3)
O13—La2—O11	135.23 (9)	C8—C9—H9A	109.5
O8—La2—O11	148.94 (8)	C8—C9—H9B	109.5
O9—La2—O11	73.48 (8)	H9A—C9—H9B	109.5
O7v—La2—O11	59.48 (7)	C8—C9—H9C	109.5
O12—La2—O11	47.18 (7)	H9A—C9—H9C	109.5
O8v—La2—O11	101.74 (7)	H9B—C9—H9C	109.5
O4iv—La2—O10	134.52 (9)	O11—C10—O12	119.2 (3)
O6—La2—O10	66.16 (7)	O11—C10—C11	120.4 (3)
O13—La2—O10	128.54 (9)	O12—C10—C11	120.4 (3)
O8—La2—O10	68.43 (7)	O11—C10—La2	62.41 (17)
O9—La2—O10	47.82 (7)	O12—C10—La2	57.11 (16)
O7v—La2—O10	128.13 (8)	C11—C10—La2	173.2 (2)
O12—La2—O10	60.43 (7)	C10—C11—H11A	109.5
O8v—La2—O10	107.45 (7)	C10—C11—H11B	109.5
O11—La2—O10	95.38 (7)	H11A—C11—H11B	109.5
C1—O1—La1	121.6 (2)	C10—C11—H11C	109.5
C1—O2—La1ii	121.1 (2)	H11A—C11—H11C	109.5
C2—O3—La1	117.3 (3)	H11B—C11—H11C	109.5
C2—O4—La2i	144.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O14	0.82	1.84	2.654 (4)	176.
O13—H13B···O9v	0.82	2.01	2.831 (3)	176.
O14—H14B···O9vii	0.87	2.12	2.921 (4)	152.9
O14—H14A···O5viii	0.86	1.90	2.761 (4)	174.3

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O14	0.82	1.84	2.654 (4)	176
O13—H13B⋯O9i	0.82	2.01	2.831 (3)	176
O14—H14B⋯O9ii	0.87	2.12	2.921 (4)	152.9
O14—H14A⋯O5iii	0.86	1.90	2.761 (4)	174.3

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