Poly[diaqua-μ₂-oxalato-di-μ₄-terephthalato-diytterbium(III)]

Abstract

The crystal structure of the title complex, [Yb₂(C₈H₄O₄)₂(C₂O₄)(H₂O)₂]_n, features an extended three-dimensional framework made up of Yb³⁺ ions coordinated by terephthalate ligands, oxalate ligands and water mol­ecules. The Yb³⁺ ion has a distorted square-anti­prismatic coordination formed by one aqua ligand, two O atoms from an oxalate ligand and five O atoms belonging to four terephthalate anions. Two symmetry-independent terephthalate anions, as well as the oxalate anion, occupy special positions on inversion centers. The water molecule participates in O—H⋯O hydrogen bonding with both terephthalate anions.

Related literature

For isotypic structures, derivatives of Lu and Dy, see: Li & Wang (2009 ▶) and Li et al. (2009 ▶), respectively.

Experimental

Crystal data

• [Yb₂(C₈H₄O₄)₂(C₂O₄)(H₂O)₂]

• M _r = 798.36

• Triclinic,

• a = 7.034 (2) Å

• b = 7.583 (2) Å

• c = 10.213 (3) Å

• α = 75.372 (4)°

• β = 70.851 (4)°

• γ = 88.126 (4)°

• V = 497.2 (2) ų

• Z = 1

• Mo Kα radiation

• μ = 9.43 mm⁻¹

• T = 295 K

• 0.24 × 0.15 × 0.05 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.211, T _max = 0.629

• 2630 measured reflections

• 1882 independent reflections

• 1785 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.120

• S = 1.06

• 1882 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 4.45 e Å⁻³

• Δρ_min = −4.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Yb—O1	2.790 (6)
Yb—O1i	2.315 (6)
Yb—O2	2.314 (6)
Yb—O3	2.264 (6)
Yb—O4ii	2.209 (6)
Yb—O5	2.310 (6)
Yb—O6iii	2.321 (6)
Yb—O7	2.293 (5)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O3i	0.85	1.92	2.751 (6)	167
O7—H7B⋯O2iv	0.85	1.91	2.754 (6)	178

Symmetry codes: (i) ; (iv) .

supplementary crystallographic information

Comment

The title compound is isostructural with its Lu and Dy analogues (Li & Wang, 2009; Li et al., 2009). As illustrated in Fig. 1, the Yb atoms is coordinated by two oxalate O atoms and five O atoms of four terephthalate anions; an aqua ligand completes a distorted square antiprismatic geometry. The Yb-O distances are in the range of 2.208 (6)–2.790 (6) Å, with an average Yb-O bond of 2.352 Å; these parameters are similar to M-O bonds found in the above mentioned previously reported isostructural complexes.

In the title complex, both symmetry independent terephthalate (tp) anions occupy special positions on the inversion centers; nevertheless they exhibit different modes of coordination of Yb atoms. The tp1 anion (O1 to O2, C1 to C4) functions as chelating-bridging tridentate ligand: two carboxylate oxygen atoms (O1 and O2) chelate one Yb atom; the O1 atom is additionally bonded to another Yb atom; the Yb···Yb separation is 4.232 (1) Å. Two edge-sharing [YbO₈] polyhedra are bridged by the bidentate tp2 (O3 to O4, C5 to C8) ligands thus generating chains along the [010] direction. The chains are further linked by the tp1 and tp2 ligands into three-dimensional framework. The oxalate anion is also located on the inversion center and acts as a tetradentate ligand connecting the edge-sharing [YbO₈] polyhedra along the [100] direction thus even further stabilizing the three-dimensional framework. The aqua ligand provides H-bond donors which participate in H-bonds with terephthalate oxygen atoms O2 and O3.

Experimental

A mixture of YbCl₃.6H₂O (1.00 mmol, 0.39 g), oxalic acid (0.50 mmol, 0.05 g), terephthalic acid (0.50 mmol, 0.09 g), NaOH (2.00 mmol, 0.08 g) and H₂O (10.0 ml) was heated in a 23 ml stainless steel reactor with a Teflon liner at 453 K for 72 h. A small amount of colorless plate-like crystals were filtered and washed with water and acetone.

Refinement

H atoms attached to C atoms were included at calculated positions and treated as riding atoms [C–H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. Water H atoms were located in difference Fourier maps placed at the idealized positions with O-H distance of 0.85 Å and included in the final refinement as fixed contribution with U_iso(H) = 1.5U_eq(O). The highest density peak and deepest hole are located at 0.87 Å and 1.09 Å from the Yb atom respectively.

Figures

Fig. 1.

The fragment of the structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small circles of arbitrary radii. Symmetry codes: (i) 1 -x, -y, 2 - z; (ii) 1 - x, 1 - y, 2 - z; (iii) -x, 1 - y, 2 - z; (iv) 1 - x, -y, 1 - z; (v) 2 - x, 1 - y, 1 - z.

Crystal data

[Yb2(C8H4O4)2(C2O4)(H2O)2]	Z = 1
Mr = 798.36	F(000) = 372
Triclinic, P1	Dx = 2.666 Mg m−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.034 (2) Å	Cell parameters from 196 reflections
b = 7.583 (2) Å	θ = 2.1–27.3°
c = 10.213 (3) Å	µ = 9.43 mm−1
α = 75.372 (4)°	T = 295 K
β = 70.851 (4)°	Plate, colorless
γ = 88.126 (4)°	0.24 × 0.15 × 0.05 mm
V = 497.2 (2) Å3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1882 independent reflections
Radiation source: fine-focus sealed tube	1785 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.211, Tmax = 0.629	k = −8→9
2630 measured reflections	l = −7→12

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0995P)2] where P = (Fo2 + 2Fc2)/3
1882 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 4.45 e Å−3
0 restraints	Δρmin = −4.21 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Yb	0.31071 (4)	0.22186 (3)	1.01498 (3)	0.01504 (19)
C1	0.3854 (12)	0.0294 (11)	0.7912 (9)	0.0203 (16)
C2	0.4409 (12)	0.0093 (11)	0.6438 (9)	0.0202 (16)
C3	0.3229 (16)	0.0805 (15)	0.5592 (11)	0.033 (2)
H3	0.2048	0.1355	0.5976	0.039*
C4	0.6198 (14)	−0.0700 (13)	0.5823 (10)	0.030 (2)
H4	0.7015	−0.1163	0.6370	0.036*
C5	0.7144 (12)	0.4806 (10)	0.7821 (9)	0.0189 (16)
C6	0.8607 (13)	0.4930 (11)	0.6352 (10)	0.0211 (18)
C7	0.8292 (13)	0.3852 (12)	0.5521 (10)	0.0282 (19)
H7	0.7149	0.3066	0.5875	0.034*
C8	1.0353 (13)	0.6070 (12)	0.5820 (10)	0.0275 (19)
H8	1.0602	0.6780	0.6374	0.033*
C9	−0.0833 (11)	0.4309 (10)	1.0574 (9)	0.0194 (16)
O1	0.4818 (8)	−0.0459 (8)	0.8752 (6)	0.0228 (12)
O2	0.2462 (9)	0.1353 (8)	0.8314 (6)	0.0228 (12)
O3	0.6140 (8)	0.3311 (8)	0.8501 (6)	0.0224 (12)
O4	0.6994 (9)	0.6187 (8)	0.8296 (7)	0.0248 (13)
O5	−0.0295 (9)	0.2697 (8)	1.0944 (7)	0.0246 (12)
O6	−0.2511 (8)	0.4911 (8)	1.1074 (7)	0.0254 (13)
O7	0.1351 (8)	−0.0452 (7)	1.1590 (7)	0.0242 (13)
H7B	0.0166	−0.0740	1.1644	0.036*
H7A	0.1979	−0.1429	1.1672	0.036*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Yb	0.0191 (3)	0.0156 (3)	0.0129 (3)	0.00119 (15)	−0.00688 (17)	−0.00586 (17)
C1	0.024 (4)	0.017 (4)	0.023 (5)	−0.008 (3)	−0.009 (3)	−0.007 (3)
C2	0.026 (4)	0.020 (4)	0.016 (4)	0.003 (3)	−0.008 (3)	−0.004 (3)
C3	0.036 (5)	0.043 (6)	0.023 (5)	0.015 (4)	−0.014 (4)	−0.012 (4)
C4	0.032 (4)	0.039 (5)	0.025 (5)	0.015 (4)	−0.015 (4)	−0.015 (4)
C5	0.026 (4)	0.017 (4)	0.013 (4)	0.001 (3)	−0.007 (3)	−0.002 (3)
C6	0.026 (4)	0.017 (4)	0.020 (5)	−0.001 (3)	−0.006 (4)	−0.007 (3)
C7	0.030 (4)	0.028 (4)	0.024 (5)	−0.015 (3)	0.000 (4)	−0.010 (4)
C8	0.034 (4)	0.024 (4)	0.028 (5)	−0.014 (3)	−0.007 (4)	−0.014 (4)
C9	0.022 (4)	0.017 (3)	0.021 (4)	0.004 (3)	−0.009 (3)	−0.006 (3)
O1	0.025 (3)	0.031 (3)	0.018 (3)	0.002 (2)	−0.014 (2)	−0.008 (2)
O2	0.029 (3)	0.028 (3)	0.015 (3)	0.007 (2)	−0.008 (3)	−0.013 (2)
O3	0.024 (3)	0.022 (3)	0.020 (3)	0.002 (2)	−0.004 (2)	−0.007 (2)
O4	0.032 (3)	0.026 (3)	0.019 (3)	−0.003 (2)	−0.005 (3)	−0.016 (3)
O5	0.030 (3)	0.020 (3)	0.023 (3)	0.004 (2)	−0.011 (3)	−0.003 (2)
O6	0.023 (3)	0.026 (3)	0.019 (3)	0.007 (2)	−0.004 (2)	0.003 (2)
O7	0.020 (3)	0.017 (3)	0.029 (3)	−0.001 (2)	−0.004 (3)	−0.001 (2)

Geometric parameters (Å, °)

Yb—O1	2.790 (6)	C3—H3	0.9300
Yb—O1i	2.315 (6)	C4—H4	0.9300
Yb—O2	2.314 (6)	C5—O4	1.249 (10)
Yb—O3	2.264 (6)	C5—O3	1.264 (10)
Yb—O4ii	2.209 (6)	C5—C6	1.497 (12)
Yb—O5	2.310 (6)	C6—C7	1.387 (13)
Yb—O6iii	2.321 (6)	C6—C8	1.395 (11)
Yb—O7	2.293 (5)	C7—C8v	1.377 (12)
Yb—Ybi	4.2315 (10)	C7—H7	0.9300
C1—O2	1.274 (10)	C8—H8	0.9300
C1—O1	1.277 (10)	C9—O6	1.245 (10)
C1—C2	1.473 (12)	C9—O5	1.269 (9)
C2—C3	1.390 (13)	C9—C9iii	1.550 (15)
C2—C4	1.401 (12)	O7—H7B	0.85
C3—C4iv	1.390 (13)	O7—H7A	0.85
O4ii—Yb—O3	98.9 (2)	O1—Yb—Ybi	30.57 (12)
O4ii—Yb—O7	102.6 (2)	C9iii—Yb—Ybi	163.60 (15)
O3—Yb—O7	141.9 (2)	O2—C1—O1	119.6 (8)
O4ii—Yb—O5	79.5 (2)	O2—C1—C2	118.4 (8)
O3—Yb—O5	145.4 (2)	O1—C1—C2	121.8 (7)
O7—Yb—O5	70.19 (19)	C3—C2—C4	118.5 (8)
O4ii—Yb—O2	159.4 (3)	C3—C2—C1	120.3 (8)
O3—Yb—O2	85.5 (2)	C4—C2—C1	121.1 (8)
O7—Yb—O2	85.2 (2)	C4iv—C3—C2	120.5 (9)
O5—Yb—O2	85.5 (2)	C4iv—C3—H3	119.8
O4ii—Yb—O1i	82.5 (2)	C2—C3—H3	119.8
O3—Yb—O1i	80.7 (2)	C3iv—C4—C2	121.0 (8)
O7—Yb—O1i	71.5 (2)	C3iv—C4—H4	119.5
O5—Yb—O1i	132.4 (2)	C2—C4—H4	119.5
O2—Yb—O1i	118.1 (2)	O4—C5—O3	124.2 (7)
O4ii—Yb—O6iii	79.2 (2)	O4—C5—C6	117.8 (7)
O3—Yb—O6iii	75.4 (2)	O3—C5—C6	118.0 (7)
O7—Yb—O6iii	139.4 (2)	C7—C6—C8	118.8 (8)
O5—Yb—O6iii	70.34 (19)	C7—C6—C5	120.4 (8)
O2—Yb—O6iii	82.5 (2)	C8—C6—C5	120.7 (8)
O1i—Yb—O6iii	147.1 (2)	C8v—C7—C6	121.0 (7)
O4ii—Yb—O1	150.1 (2)	C8v—C7—H7	119.5
O3—Yb—O1	70.77 (19)	C6—C7—H7	119.5
O7—Yb—O1	74.9 (2)	C7v—C8—C6	120.2 (9)
O5—Yb—O1	125.1 (2)	C7v—C8—H8	119.9
O2—Yb—O1	50.14 (19)	C6—C8—H8	119.9
O1i—Yb—O1	68.4 (2)	O6—C9—O5	127.2 (8)
O6iii—Yb—O1	122.4 (2)	O6—C9—C9iii	117.0 (8)
O4ii—Yb—C9iii	72.4 (2)	O5—C9—C9iii	115.7 (8)
O3—Yb—C9iii	96.2 (2)	O5—C9—Ybiii	166.7 (6)
O7—Yb—C9iii	120.2 (2)	C9iii—C9—Ybiii	76.1 (5)
O5—Yb—C9iii	50.05 (19)	C1—O1—Ybi	165.8 (6)
O2—Yb—C9iii	87.2 (2)	C1—O1—Yb	82.4 (5)
O1i—Yb—C9iii	154.0 (2)	Ybi—O1—Yb	111.6 (2)
O6iii—Yb—C9iii	21.0 (2)	C1—O2—Yb	104.7 (5)
O1—Yb—C9iii	135.19 (19)	C5—O3—Yb	140.5 (5)
O4ii—Yb—Ybi	120.04 (17)	C5—O4—Ybii	157.0 (6)
O3—Yb—Ybi	72.20 (14)	C9—O5—Yb	117.5 (5)
O7—Yb—Ybi	69.81 (14)	C9—O6—Ybiii	117.0 (5)
O5—Yb—Ybi	138.46 (14)	Yb—O7—H7B	123.8
O2—Yb—Ybi	80.49 (15)	Yb—O7—H7A	118.8
O1i—Yb—Ybi	37.81 (15)	H7B—O7—H7A	107.3
O6iii—Yb—Ybi	144.33 (15)
O2—C1—C2—C3	−10.1 (13)	C2—C1—O2—Yb	−155.3 (6)
O1—C1—C2—C3	174.7 (9)	O4ii—Yb—O2—C1	161.8 (6)
O2—C1—C2—C4	165.3 (8)	O3—Yb—O2—C1	58.4 (5)
O1—C1—C2—C4	−9.8 (12)	O7—Yb—O2—C1	−84.5 (5)
C4—C2—C3—C4iv	1.1 (16)	O5—Yb—O2—C1	−155.0 (5)
C1—C2—C3—C4iv	176.7 (8)	O1i—Yb—O2—C1	−18.5 (6)
C3—C2—C4—C3iv	−1.1 (16)	O6iii—Yb—O2—C1	134.3 (5)
C1—C2—C4—C3iv	−176.7 (8)	O1—Yb—O2—C1	−10.2 (5)
O4—C5—C6—C7	−152.4 (9)	C9iii—Yb—O2—C1	154.9 (5)
O3—C5—C6—C7	27.6 (12)	Ybi—Yb—O2—C1	−14.2 (5)
O4—C5—C6—C8	30.4 (13)	O4—C5—O3—Yb	30.8 (14)
O3—C5—C6—C8	−149.6 (9)	C6—C5—O3—Yb	−149.2 (7)
C8—C6—C7—C8v	−1.5 (16)	O4ii—Yb—O3—C5	−46.7 (9)
C5—C6—C7—C8v	−178.8 (8)	O7—Yb—O3—C5	−170.7 (8)
C7—C6—C8—C7v	1.5 (16)	O5—Yb—O3—C5	37.6 (11)
C5—C6—C8—C7v	178.8 (8)	O2—Yb—O3—C5	113.0 (9)
O2—C1—O1—Ybi	171.7 (17)	O1i—Yb—O3—C5	−127.6 (9)
C2—C1—O1—Ybi	−13 (3)	O6iii—Yb—O3—C5	29.6 (9)
O2—C1—O1—Yb	−16.0 (7)	O1—Yb—O3—C5	162.2 (9)
C2—C1—O1—Yb	159.1 (7)	C9iii—Yb—O3—C5	26.3 (9)
O4ii—Yb—O1—C1	−164.4 (5)	Ybi—Yb—O3—C5	−165.5 (9)
O3—Yb—O1—C1	−90.6 (5)	O3—C5—O4—Ybii	50.2 (19)
O7—Yb—O1—C1	106.3 (5)	C6—C5—O4—Ybii	−129.7 (12)
O5—Yb—O1—C1	54.5 (5)	O6—C9—O5—Yb	−166.9 (7)
O2—Yb—O1—C1	9.9 (4)	C9iii—C9—O5—Yb	9.8 (12)
O1i—Yb—O1—C1	−178.0 (6)	Ybiii—C9—O5—Yb	160 (2)
O6iii—Yb—O1—C1	−33.1 (5)	O4ii—Yb—O5—C9	69.9 (6)
C9iii—Yb—O1—C1	−11.5 (6)	O3—Yb—O5—C9	−20.5 (8)
Ybi—Yb—O1—C1	−178.0 (6)	O7—Yb—O5—C9	177.6 (7)
O4ii—Yb—O1—Ybi	13.6 (5)	O2—Yb—O5—C9	−95.9 (6)
O3—Yb—O1—Ybi	87.4 (3)	O1i—Yb—O5—C9	139.5 (6)
O7—Yb—O1—Ybi	−75.7 (3)	O6iii—Yb—O5—C9	−12.3 (6)
O5—Yb—O1—Ybi	−127.5 (2)	O1—Yb—O5—C9	−128.6 (6)
O2—Yb—O1—Ybi	−172.1 (4)	C9iii—Yb—O5—C9	−5.8 (7)
O1i—Yb—O1—Ybi	0.000 (2)	Ybi—Yb—O5—C9	−166.1 (5)
O6iii—Yb—O1—Ybi	144.9 (2)	O5—C9—O6—Ybiii	−169.3 (7)
C9iii—Yb—O1—Ybi	166.5 (2)	C9iii—C9—O6—Ybiii	14.1 (12)
O1—C1—O2—Yb	19.9 (9)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3i	0.85	1.92	2.751 (6)	167
O7—H7B···O2vi	0.85	1.91	2.754 (6)	178

Symmetry codes: (i) −x+1, −y, −z+2; (vi) −x, −y, −z+2.