Poly[diaqua­bis­(μ₃-1H-imidazole-4,5-dicarboxyl­ato)(μ₂-sulfato)­diytterbium(III)]

Abstract

In the title compound, [Yb₂(C₅H₂N₂O₄)₂(SO₄)(H₂O)₂]_n, the Yb^III ion is eight-coordinated by four O atoms and one N atom from three imidazole-4,5-dicarboxyl­ate ligands, two O atoms from one SO₄ ²⁻ anion (site symmetry 2), as well as one O atom of a water mol­ecule, giving a bicapped trigonal–prismatic coordination geometry. The metal coordination units are connected by bridging imidazole-4,5-dicarboxyl­ate and sulfate ligands, generating a heterometallic layer. The layers are stacked along the a axis via N—H⋯O, O—H⋯O, and C—H⋯O hydrogen-bonding inter­actions, generating a three-dimensional framework.

Related literature

For the application of multifunctional organic ligands containing O- and N-donors in the design of metal-organic frameworks, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Sun et al. (2006 ▶); Zhu et al. (2010 ▶).

Experimental

Crystal data

• [Yb₂(C₅H₂N₂O₄)₂(SO₄)(H₂O)₂]

• M _r = 786.35

• Monoclinic,

• a = 21.1089 (14) Å

• b = 6.5584 (4) Å

• c = 12.8766 (9) Å

• β = 105.874 (1)°

• V = 1714.7 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 11.05 mm⁻¹

• T = 296 K

• 0.20 × 0.18 × 0.15 mm

Data collection

• Bruker APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.126, T _max = 0.191

• 4239 measured reflections

• 1534 independent reflections

• 1392 reflections with I > 2σ(I)

• R _int = 0.023

Refinement

• R[F ² > 2σ(F ²)] = 0.020

• wR(F ²) = 0.047

• S = 1.09

• 1534 reflections

• 150 parameters

• 4 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.66 e Å⁻³

• Δρ_min = −0.99 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: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O6i	0.87 (5)	2.09 (3)	2.925 (6)	161 (5)
O1W—H2W⋯O2ii	0.82 (2)	1.94 (3)	2.693 (5)	151 (5)
O1W—H1W⋯O3iii	0.82 (6)	2.24 (4)	2.896 (5)	138 (5)
O1W—H1W⋯O4iii	0.82 (6)	2.51 (6)	3.308 (5)	167 (5)
C5—H5⋯O5iv	0.93	2.52	3.347 (6)	149

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

supplementary crystallographic information

Comment

In the past few years, the application of multifunctional organic ligands containing O– and N–donors to design metal-organic frameworks are of increasing interest, not only because of their impressive topological structures, but also due to their versatile applications in ion exchange, magnetism, bimetallic catalysis and luminescent probe (Cheng et al., 2006; Kuang et al., 2007; Sun et al., 2006; Zhu et al., 2010). As an extension of this research, the structure of the title compound, a new metal-organic framework, has been determined which is presented in this artcle.

The asymmetric unite of the title compound (Fig. 1), contains a Yb^III ion, an imidazole-4,5-dicarboxylate ligand, a half SO₄^2- anion, and a coordinated water molecule. The Yb^III ion is eight-coordinated by four O atoms and a N atom from three imidazole-4,5-dicarboxylate ligands, two O atoms from a SO₄^2- anion as well as a coordinated water molecule, giving a bicapped trigonal prismatic coordination geometry. The metal coordination units are connected by bridging imidazole-4,5-dicarboxylate and sulfate ligands, generating a two-dimensional heterometallic layer. The two-dimensional layers are stacked along a axis via N—H···O, O—H···O, and C—H···O hydrogen-bonding interactions to generate the three-dimensional framework (Table 1 and Fig. 2).

Experimental

A mixture of Yb₂O₃ (0.099 g, 0.25 mmol), imidazole-4,5-dicarboxylic acid (0.156 g, 1 mmol), and H₂O (7 ml) was sealed in a 20 ml Teflon-lined reaction vessel at 443 K for 5 days then slowly cooled to room temperature. The product was collected by filtration, washed with water and air-dried. Colorless block crystals suitable for X-ray analysis were obtained.

Refinement

H atoms bonded to C atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å and U_iso(H) = 1.2 U_eq(C). H atoms bonded to N atoms water molecules were found from difference Fourier maps and refined isotropically with a restraint of N—H = 0.87 Å, O—H = 0.82 Å and U_iso(H) = 1.5 U_eq(N, O).

Figures

Fig. 1.

The molecular structure of the title comples showing atomic-numbering scheme and displacement ellipsoids drawn at 30% probability level. Symmetry codes: A = 1 - x, y, 1.5 - z; B = x, 1 - y, -1/2 + z; C = x, -y, -1/2 + z.

Fig. 2.

A view of the three-dimensional structure of the title compound, the hydrogen bonding interactions have been drawn as broken lines.

Crystal data

[Yb2(C5H2N2O4)2(SO4)(H2O)2]	F(000) = 1456
Mr = 786.35	Dx = 3.046 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2574 reflections
a = 21.1089 (14) Å	θ = 3.3–28.0°
b = 6.5584 (4) Å	µ = 11.05 mm−1
c = 12.8766 (9) Å	T = 296 K
β = 105.874 (1)°	Block, colorless
V = 1714.7 (2) Å3	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	1534 independent reflections
Radiation source: fine-focus sealed tube	1392 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scan	θmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→22
Tmin = 0.126, Tmax = 0.191	k = −7→7
4239 measured reflections	l = −14→15

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0216P)2 + 5.6648P] where P = (Fo2 + 2Fc2)/3
1534 reflections	(Δ/σ)max = 0.001
150 parameters	Δρmax = 0.66 e Å−3
4 restraints	Δρmin = −0.99 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
Yb1	0.355312 (10)	0.07841 (3)	0.714967 (16)	0.01086 (9)
S1	0.5000	0.0299 (3)	0.7500	0.0182 (4)
C1	0.3390 (2)	0.0272 (7)	0.9554 (4)	0.0134 (10)
C2	0.3697 (2)	0.2318 (7)	0.9654 (4)	0.0148 (10)
C3	0.3764 (2)	0.3838 (7)	1.0402 (4)	0.0145 (10)
C4	0.3492 (2)	0.4128 (7)	1.1340 (4)	0.0128 (10)
C5	0.4168 (2)	0.4805 (8)	0.9077 (4)	0.0179 (11)
H5	0.4371	0.5603	0.8664	0.022*
N1	0.3942 (2)	0.2930 (6)	0.8817 (3)	0.0165 (9)
N2	0.4065 (2)	0.5391 (6)	1.0009 (3)	0.0183 (10)
H1	0.420 (3)	0.648 (6)	1.039 (4)	0.027*
O1	0.32418 (19)	−0.0583 (5)	1.0318 (3)	0.0220 (9)
O2	0.32955 (18)	−0.0546 (5)	0.8633 (3)	0.0192 (8)
O3	0.33204 (18)	0.2591 (5)	1.1767 (3)	0.0219 (8)
O4	0.34067 (19)	0.5917 (5)	1.1620 (3)	0.0219 (8)
O5	0.45816 (18)	−0.0925 (5)	0.7997 (3)	0.0304 (10)
O6	0.45308 (19)	0.1572 (6)	0.6710 (3)	0.0349 (10)
O1W	0.24374 (18)	0.1038 (6)	0.6799 (3)	0.0250 (9)
H2W	0.224 (2)	0.201 (6)	0.646 (4)	0.037*
H1W	0.221 (3)	0.075 (8)	0.720 (4)	0.037*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Yb1	0.01712 (13)	0.00743 (13)	0.00944 (13)	0.00016 (8)	0.00604 (9)	0.00022 (8)
S1	0.0156 (9)	0.0145 (9)	0.0250 (10)	0.000	0.0063 (8)	0.000
C1	0.017 (2)	0.010 (2)	0.012 (3)	0.0000 (19)	0.001 (2)	0.001 (2)
C2	0.021 (2)	0.012 (3)	0.011 (2)	−0.003 (2)	0.0040 (19)	0.000 (2)
C3	0.021 (3)	0.013 (2)	0.011 (2)	0.002 (2)	0.006 (2)	0.001 (2)
C4	0.017 (2)	0.010 (3)	0.010 (2)	−0.0018 (19)	0.002 (2)	−0.0017 (19)
C5	0.025 (3)	0.015 (3)	0.015 (3)	−0.005 (2)	0.008 (2)	0.003 (2)
N1	0.024 (2)	0.012 (2)	0.016 (2)	−0.0023 (17)	0.0082 (18)	−0.0010 (17)
N2	0.027 (2)	0.014 (2)	0.016 (2)	−0.0064 (19)	0.0084 (19)	−0.0018 (18)
O1	0.042 (2)	0.0151 (19)	0.0107 (19)	−0.0090 (16)	0.0095 (17)	−0.0001 (15)
O2	0.033 (2)	0.0155 (19)	0.0110 (18)	−0.0084 (15)	0.0090 (15)	−0.0058 (15)
O3	0.037 (2)	0.0144 (19)	0.0182 (18)	0.0042 (16)	0.0134 (16)	0.0061 (16)
O4	0.039 (2)	0.0103 (19)	0.018 (2)	0.0028 (16)	0.0105 (17)	−0.0009 (14)
O5	0.021 (2)	0.030 (2)	0.041 (3)	0.0019 (16)	0.0104 (18)	0.0155 (19)
O6	0.023 (2)	0.044 (2)	0.041 (3)	0.0071 (19)	0.0135 (19)	0.027 (2)
O1W	0.024 (2)	0.023 (2)	0.031 (2)	0.0066 (17)	0.0129 (18)	0.0083 (17)

Geometric parameters (Å, °)

Yb1—O4i	2.264 (3)	C1—C2	1.481 (6)
Yb1—O1ii	2.272 (3)	C2—C3	1.367 (7)
Yb1—O1W	2.280 (4)	C2—N1	1.377 (6)
Yb1—O3ii	2.291 (3)	C3—N2	1.369 (6)
Yb1—O2	2.297 (3)	C3—C4	1.485 (7)
Yb1—O6	2.342 (4)	C4—O3	1.249 (6)
Yb1—O5	2.421 (4)	C4—O4	1.255 (5)
Yb1—N1	2.510 (4)	C5—N1	1.328 (6)
Yb1—S1	2.9798 (3)	C5—N2	1.334 (7)
S1—O5iii	1.464 (4)	C5—H5	0.9300
S1—O5	1.464 (4)	N2—H1	0.87 (5)
S1—O6iii	1.470 (4)	O1—Yb1iv	2.272 (3)
S1—O6	1.470 (4)	O3—Yb1iv	2.291 (3)
S1—Yb1iii	2.9798 (3)	O4—Yb1v	2.264 (3)
C1—O1	1.244 (6)	O1W—H2W	0.82 (2)
C1—O2	1.266 (6)	O1W—H1W	0.82 (6)
O4i—Yb1—O1ii	76.46 (12)	O6iii—S1—O6	110.8 (4)
O4i—Yb1—O1W	79.74 (14)	O5iii—S1—Yb1	135.09 (15)
O1ii—Yb1—O1W	78.99 (15)	O5—S1—Yb1	53.75 (14)
O4i—Yb1—O3ii	148.74 (13)	O6iii—S1—Yb1	120.86 (16)
O1ii—Yb1—O3ii	74.75 (12)	O6—S1—Yb1	50.65 (15)
O1W—Yb1—O3ii	83.05 (14)	O5iii—S1—Yb1iii	53.75 (14)
O4i—Yb1—O2	124.73 (12)	O5—S1—Yb1iii	135.09 (15)
O1ii—Yb1—O2	140.73 (13)	O6iii—S1—Yb1iii	50.65 (15)
O1W—Yb1—O2	74.07 (14)	O6—S1—Yb1iii	120.86 (16)
O3ii—Yb1—O2	74.10 (12)	Yb1—S1—Yb1iii	167.75 (7)
O4i—Yb1—O6	76.89 (14)	O1—C1—O2	122.7 (4)
O1ii—Yb1—O6	77.64 (14)	O1—C1—C2	122.6 (4)
O1W—Yb1—O6	150.11 (14)	O2—C1—C2	114.7 (4)
O3ii—Yb1—O6	108.21 (14)	C3—C2—N1	110.6 (4)
O2—Yb1—O6	135.20 (13)	C3—C2—C1	132.9 (5)
O4i—Yb1—O5	127.57 (13)	N1—C2—C1	116.5 (4)
O1ii—Yb1—O5	114.21 (14)	C2—C3—N2	104.5 (4)
O1W—Yb1—O5	150.85 (13)	C2—C3—C4	132.8 (4)
O3ii—Yb1—O5	76.28 (13)	N2—C3—C4	121.8 (4)
O2—Yb1—O5	80.58 (13)	O3—C4—O4	123.2 (5)
O6—Yb1—O5	58.02 (13)	O3—C4—C3	118.5 (4)
O4i—Yb1—N1	72.99 (13)	O4—C4—C3	118.1 (4)
O1ii—Yb1—N1	148.68 (12)	N1—C5—N2	111.0 (4)
O1W—Yb1—N1	101.95 (14)	N1—C5—H5	124.5
O3ii—Yb1—N1	136.57 (13)	N2—C5—H5	124.5
O2—Yb1—N1	66.31 (12)	C5—N1—C2	105.0 (4)
O6—Yb1—N1	88.79 (15)	C5—N1—Yb1	138.2 (3)
O5—Yb1—N1	80.25 (14)	C2—N1—Yb1	113.6 (3)
O4i—Yb1—S1	101.39 (10)	C5—N2—C3	109.0 (4)
O1ii—Yb1—S1	98.30 (10)	C5—N2—H1	130 (4)
O1W—Yb1—S1	176.78 (11)	C3—N2—H1	121 (4)
O3ii—Yb1—S1	94.59 (10)	C1—O1—Yb1iv	141.5 (3)
O2—Yb1—S1	107.44 (9)	C1—O2—Yb1	127.3 (3)
O6—Yb1—S1	29.03 (9)	C4—O3—Yb1iv	143.5 (3)
O5—Yb1—S1	29.18 (9)	C4—O4—Yb1v	164.1 (3)
N1—Yb1—S1	81.27 (10)	S1—O5—Yb1	97.06 (18)
O5iii—S1—O5	113.5 (3)	S1—O6—Yb1	100.32 (19)
O5iii—S1—O6iii	103.9 (2)	Yb1—O1W—H2W	121 (4)
O5—S1—O6iii	112.4 (2)	Yb1—O1W—H1W	128 (4)
O5iii—S1—O6	112.4 (2)	H2W—O1W—H1W	102 (3)
O5—S1—O6	103.9 (2)

Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y, z−1/2; (iii) −x+1, y, −z+3/2; (iv) x, −y, z+1/2; (v) x, −y+1, z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O6v	0.87 (5)	2.09 (3)	2.925 (6)	161 (5)
O1W—H2W···O2vi	0.82 (2)	1.94 (3)	2.693 (5)	151 (5)
O1W—H1W···O3vii	0.82 (6)	2.24 (4)	2.896 (5)	138 (5)
O1W—H1W···O4vii	0.82 (6)	2.51 (6)	3.308 (5)	167 (5)
C5—H5···O5viii	0.93	2.52	3.347 (6)	149.

Symmetry codes: (v) x, −y+1, z+1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) −x+1/2, −y+1/2, −z+2; (viii) x, y+1, z.