Poly[di-μ4-benzene-1,4-dicarboxyl­ato-μ6-succinato-diholmium(III)]

He, Q.; Huang, B.-J.

doi:10.1107/S1600536807066950

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m237

https://doi.org/10.1107/S1600536807066950

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Poly[di-μ₄-benzene-1,4-dicarboxylato-μ₆-succinato-diholmium(III)]

Qin He ^a ^* and Bao-Jun Huang ^a

^aDepartment of Chemistry, Xuchang University, Xuchang 461000, People's Republic of China
^*Correspondence e-mail: qhe.xcu@163.com

(Received 25 October 2007; accepted 14 December 2007; online 21 December 2007)

The title compound, [Ho₂(C₄H₄O₄)(C₈H₄O₄)₂]_n, was synthesized hydrothermally. The Ho atom is coordinated by four O atoms from four benzene-1,4-dicarboxylate (BDC) anions and four O atoms from three succinate anions, in a distorted square-antiprismatic coordination geometry. The antiprisms are bridged by the benzene-1,4-dicarboxylate and succinate anions, into a three-dimensional coordination network. The succinate anions are located on centres of inversion.

Related literature

For related literature, see: Li & Wang (2005 ); Li et al. (2006 ); Wang & Li (2005 ); He et al. (2006 ).

Experimental

Crystal data

[Ho₂(C₄H₄O₄)(C₈H₄O₄)₂]
M_r = 387.08
Orthorhombic, P b c a
a = 13.8147 (3) Å
b = 6.7850 (2) Å
c = 21.7103 (5) Å
V = 2034.97 (9) Å³
Z = 8
Mo Kα radiation
μ = 7.79 mm⁻¹
T = 291 (2) K
0.18 × 0.15 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.245, T_max = 0.682
11598 measured reflections
2411 independent reflections
2140 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.042
S = 1.06
2411 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected bond lengths (Å)

Ho—O1	2.2899 (17)
Ho—O2ⁱ	2.2320 (17)
Ho—O3ⁱⁱ	2.3208 (16)
Ho—O4ⁱⁱⁱ	2.3013 (16)
Ho—O5	2.4753 (16)
Ho—O5^iv	2.4015 (18)
Ho—O6^v	2.4633 (17)
Ho—O6	2.5230 (16)
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, -y+2, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807066950/nc2068sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066950/nc2068Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is isostructural with its [M₂(C₈H₄O₄)₂(C₄H₄O₄)]_n [M = Gd (Wang & Li, 2005), Dy ((Li & Wang, 2005), Nd (Li et al., 2006) and Er (He et al., 2006)] analogues. The Ho³⁺ ion is located at the center of a distorted square antiprism and is coordinated by four oxygen atoms from four benzene-1,4-dicarboxylate anions and four oxygen atoms from three succinate anions (Fig. 1). The Ho—O bond distances ranging from 2.2851 (2) to 2.5764 (16) Å.

The succinate anions are located on centres of inversion and acts as a bis-chelating ligands for each two symmetry related Ho atoms. Each of the four oxygen atom are additionally connected by Ho atoms into layers which are parallel to the (001) plane. These layers are connected via the benzene-1,4-dicarboxylate anions into a three-dimensional coordination network.

Related literature top

For related literature, see: Li & Wang (2005); Li et al. (2006); Wang & Li (2005); He et al. (2006).

Experimental top

A mixture of HoCl₃.6H₂O (2.00 mmol, 0.74 g), benzene-1,4-dicarboxylic acid (1.0 mmol, 0.16 g), succinic acid (1.0 mmol, 0.10 g), NaOH (6.0 ml, 1 mol/L) and H₂O (20.0 ml) was heated in a 35 ml stainless steel reactor with a Teflon liner at 453 K for 48 h. The column-like crystals were filtered and washed with ethanol. Yield: 30% based on Ho.

Structure description top

For related literature, see: Li & Wang (2005); Li et al. (2006); Wang & Li (2005); He et al. (2006).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top

Fig. 1. The coordination environment of the Ho atom, with the atom-numbering scheme, showing displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) 2 - x, 2 - y, 1 - z; (ii) x, 3/2 - y, z + 1/2; (iii) 3/2 - x, 2 - y, z + 1/2; (iv) 3/2 - x, y + 1/2, z; (v) 3/2 - x, y - 1/2, z; (vi) 1 - x, 2 - y, 1 - z.

Poly[di-µ₄-benzene-1,4-dicarboxylato-µ₆-succinato-diholmium(III)] top

Crystal data top

[Ho₂(C₄H₄O₄)(C₈H₄O₄)₂]	F(000) = 1448
M_r = 387.08	D_x = 2.527 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 254 reflections
a = 13.8147 (3) Å	θ = 2.1–27.1°
b = 6.7850 (2) Å	µ = 7.79 mm⁻¹
c = 21.7103 (5) Å	T = 291 K
V = 2034.97 (9) Å³	Column, orange
Z = 8	0.18 × 0.15 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2411 independent reflections
Radiation source: fine-focus sealed tube	2140 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 28.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→16
T_min = 0.245, T_max = 0.682	k = −7→8
11598 measured reflections	l = −28→25

Refinement top

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)] = 0.015	H-atom parameters constrained
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0238P)² + 0.923P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
2411 reflections	Δρ_max = 0.94 e Å⁻³
155 parameters	Δρ_min = −0.60 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Bruker, 1998), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00060 (5)

Crystal data top

[Ho₂(C₄H₄O₄)(C₈H₄O₄)₂]	V = 2034.97 (9) Å³
M_r = 387.08	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.8147 (3) Å	µ = 7.79 mm⁻¹
b = 6.7850 (2) Å	T = 291 K
c = 21.7103 (5) Å	0.18 × 0.15 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2411 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2140 reflections with I > 2σ(I)
T_min = 0.245, T_max = 0.682	R_int = 0.019
11598 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	0 restraints
wR(F²) = 0.042	H-atom parameters constrained
S = 1.06	Δρ_max = 0.94 e Å⁻³
2411 reflections	Δρ_min = −0.60 e Å⁻³
155 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ho	0.830676 (8)	1.016049 (15)	0.554834 (5)	0.01275 (6)
O1	0.86282 (15)	1.0368 (2)	0.45156 (8)	0.0198 (4)
O2	1.01131 (12)	0.9282 (3)	0.43269 (7)	0.0206 (3)
C1	0.92600 (17)	0.9674 (3)	0.41630 (11)	0.0148 (4)
C2	0.89870 (17)	0.9259 (3)	0.35070 (10)	0.0177 (5)
C3	0.96527 (18)	0.8440 (4)	0.31009 (11)	0.0257 (5)
H3A	1.0274	0.8143	0.3237	0.031*
C4	0.93977 (19)	0.8064 (4)	0.24966 (11)	0.0276 (6)
H4A	0.9846	0.7510	0.2228	0.033*
C5	0.84715 (17)	0.8514 (3)	0.22885 (11)	0.0208 (5)
C6	0.81879 (18)	0.8035 (3)	0.16377 (11)	0.0213 (5)
C7	0.78017 (19)	0.9332 (4)	0.26926 (11)	0.0259 (5)
H7A	0.7181	0.9634	0.2555	0.031*
C8	0.8056 (2)	0.9698 (4)	0.32984 (13)	0.0244 (5)
H8A	0.7605	1.0240	0.3568	0.029*
O3	0.87624 (13)	0.6998 (3)	0.13253 (8)	0.0284 (4)
O4	0.73920 (13)	0.8685 (3)	0.14403 (7)	0.0265 (4)
O5	0.66712 (11)	0.8691 (3)	0.54719 (8)	0.0229 (4)
O6	0.67647 (11)	1.1742 (2)	0.51694 (8)	0.0205 (4)
C9	0.6257 (2)	1.0274 (3)	0.53160 (14)	0.0240 (6)
C10	0.5157 (2)	1.0403 (4)	0.53093 (15)	0.0313 (6)
H10A	0.4883	0.9627	0.5641	0.038*
H10B	0.4948	1.1760	0.5356	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ho	0.01198 (8)	0.01651 (7)	0.00977 (8)	−0.00044 (3)	0.00010 (4)	0.00131 (3)
O1	0.0203 (10)	0.0274 (9)	0.0118 (9)	0.0012 (7)	0.0002 (7)	−0.0009 (6)
O2	0.0158 (9)	0.0311 (8)	0.0149 (8)	−0.0020 (7)	−0.0033 (7)	−0.0017 (7)
C1	0.0166 (12)	0.0170 (10)	0.0108 (11)	−0.0019 (8)	0.0003 (9)	0.0010 (8)
C2	0.0190 (12)	0.0229 (11)	0.0112 (11)	0.0006 (9)	−0.0022 (9)	−0.0021 (8)
C3	0.0203 (13)	0.0393 (14)	0.0175 (13)	0.0050 (10)	−0.0054 (10)	−0.0067 (10)
C4	0.0250 (14)	0.0385 (14)	0.0193 (13)	0.0056 (11)	−0.0008 (10)	−0.0087 (11)
C5	0.0278 (13)	0.0224 (11)	0.0123 (12)	0.0005 (9)	−0.0051 (10)	−0.0036 (9)
C6	0.0302 (14)	0.0206 (11)	0.0131 (12)	−0.0036 (9)	−0.0049 (10)	−0.0017 (9)
C7	0.0228 (13)	0.0364 (13)	0.0186 (13)	0.0066 (11)	−0.0097 (11)	−0.0037 (11)
C8	0.0210 (13)	0.0356 (13)	0.0167 (13)	0.0063 (10)	−0.0022 (11)	−0.0065 (10)
O3	0.0338 (10)	0.0312 (9)	0.0203 (10)	0.0021 (8)	−0.0054 (8)	−0.0088 (7)
O4	0.0264 (10)	0.0378 (10)	0.0154 (8)	0.0011 (8)	−0.0072 (7)	0.0012 (7)
O5	0.0173 (9)	0.0174 (8)	0.0341 (11)	0.0002 (6)	−0.0071 (7)	0.0010 (7)
O6	0.0189 (9)	0.0188 (8)	0.0238 (10)	−0.0010 (6)	−0.0022 (7)	0.0019 (7)
C9	0.0197 (14)	0.0212 (12)	0.0310 (16)	−0.0020 (9)	−0.0089 (12)	0.0025 (10)
C10	0.0376 (18)	0.0236 (12)	0.0326 (17)	0.0037 (11)	−0.0005 (14)	−0.0019 (11)

Geometric parameters (Å, º) top

Ho—O1	2.2899 (17)	C4—C5	1.391 (3)
Ho—O2ⁱ	2.2320 (17)	C4—H4A	0.9300
Ho—O3ⁱⁱ	2.3208 (16)	C5—C7	1.391 (3)
Ho—O4ⁱⁱⁱ	2.3013 (16)	C5—C6	1.502 (3)
Ho—O5	2.4753 (16)	C6—O3	1.259 (3)
Ho—O5^iv	2.4015 (18)	C6—O4	1.260 (3)
Ho—O6^v	2.4633 (17)	C7—C8	1.384 (4)
Ho—O6	2.5230 (16)	C7—H7A	0.9300
O1—C1	1.253 (3)	C8—H8A	0.9300
O2—C1	1.259 (3)	O5—C9	1.263 (3)
C1—C2	1.500 (3)	O6—C9	1.259 (3)
C2—C3	1.390 (3)	C9—C10	1.523 (4)
C2—C8	1.395 (4)	C10—C10^vi	1.514 (6)
C3—C4	1.382 (3)	C10—H10A	0.9700
C3—H3A	0.9300	C10—H10B	0.9700

O2ⁱ—Ho—O1	85.34 (7)	C3—C2—C8	119.3 (2)
O2ⁱ—Ho—O4ⁱⁱⁱ	104.50 (6)	C3—C2—C1	120.7 (2)
O1—Ho—O4ⁱⁱⁱ	152.17 (6)	C8—C2—C1	120.0 (2)
O2ⁱ—Ho—O3ⁱⁱ	75.73 (6)	C4—C3—C2	120.5 (2)
O1—Ho—O3ⁱⁱ	134.25 (7)	C4—C3—H3A	119.8
O4ⁱⁱⁱ—Ho—O3ⁱⁱ	73.56 (7)	C2—C3—H3A	119.8
O2ⁱ—Ho—O5^iv	80.03 (6)	C3—C4—C5	120.2 (2)
O1—Ho—O5^iv	82.44 (6)	C3—C4—H4A	119.9
O4ⁱⁱⁱ—Ho—O5^iv	73.97 (6)	C5—C4—H4A	119.9
O3ⁱⁱ—Ho—O5^iv	132.55 (6)	C7—C5—C4	119.7 (2)
O2ⁱ—Ho—O6^v	103.85 (6)	C7—C5—C6	120.4 (2)
O1—Ho—O6^v	74.86 (6)	C4—C5—C6	119.9 (2)
O4ⁱⁱⁱ—Ho—O6^v	125.79 (6)	O3—C6—O4	124.2 (2)
O3ⁱⁱ—Ho—O6^v	70.08 (6)	O3—C6—C5	117.6 (2)
O5^iv—Ho—O6^v	156.47 (6)	O4—C6—C5	118.2 (2)
O2ⁱ—Ho—O5	165.74 (6)	C8—C7—C5	120.1 (2)
O1—Ho—O5	97.82 (7)	C8—C7—H7A	119.9
O4ⁱⁱⁱ—Ho—O5	79.09 (6)	C5—C7—H7A	119.9
O3ⁱⁱ—Ho—O5	92.42 (6)	C7—C8—C2	120.3 (2)
O5^iv—Ho—O5	114.12 (5)	C7—C8—H8A	119.9
O6^v—Ho—O5	64.00 (6)	C2—C8—H8A	119.9
O2ⁱ—Ho—O6	142.50 (6)	C6—O3—Ho^vii	124.97 (15)
O1—Ho—O6	79.54 (6)	C6—O4—Ho^viii	140.49 (16)
O4ⁱⁱⁱ—Ho—O6	77.02 (6)	C9—O5—Ho^v	150.76 (16)
O3ⁱⁱ—Ho—O6	137.25 (6)	C9—O5—Ho	95.09 (15)
O5^iv—Ho—O6	64.15 (5)	Ho^v—O5—Ho	112.68 (6)
O6^v—Ho—O6	104.93 (5)	C9—O6—Ho^iv	129.67 (17)
O5—Ho—O6	51.58 (6)	C9—O6—Ho	92.94 (15)
O2ⁱ—Ho—C9	168.32 (6)	Ho^iv—O6—Ho	108.99 (6)
O1—Ho—C9	91.01 (8)	O6—C9—O5	119.2 (2)
O4ⁱⁱⁱ—Ho—C9	74.08 (8)	O6—C9—C10	120.5 (2)
O3ⁱⁱ—Ho—C9	114.28 (7)	O5—C9—C10	120.2 (2)
O5^iv—Ho—C9	88.50 (6)	O6—C9—Ho	61.15 (13)
O6^v—Ho—C9	85.82 (6)	O5—C9—Ho	58.99 (13)
O5—Ho—C9	25.92 (6)	C10—C9—Ho	170.3 (2)
O6—Ho—C9	25.91 (6)	C10^vi—C10—C9	105.9 (3)
C1—O1—Ho	135.25 (16)	C10^vi—C10—H10A	110.6
C1—O2—Hoⁱ	156.02 (15)	C9—C10—H10A	110.6
O1—C1—O2	124.0 (2)	C10^vi—C10—H10B	110.6
O1—C1—C2	118.4 (2)	C9—C10—H10B	110.6
O2—C1—C2	117.6 (2)	H10A—C10—H10B	108.7

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

Experimental details

Crystal data
Chemical formula	[Ho₂(C₄H₄O₄)(C₈H₄O₄)₂]
M_r	387.08
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	291
a, b, c (Å)	13.8147 (3), 6.7850 (2), 21.7103 (5)
V (Å³)	2034.97 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	7.79
Crystal size (mm)	0.18 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.245, 0.682
No. of measured, independent and observed [I > 2σ(I)] reflections	11598, 2411, 2140
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.042, 1.06
No. of reflections	2411
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.60

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Selected bond lengths (Å) top

Ho—O1	2.2899 (17)	Ho—O5	2.4753 (16)
Ho—O2ⁱ	2.2320 (17)	Ho—O5^iv	2.4015 (18)
Ho—O3ⁱⁱ	2.3208 (16)	Ho—O6^v	2.4633 (17)
Ho—O4ⁱⁱⁱ	2.3013 (16)	Ho—O6	2.5230 (16)

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

References

Bruker (1998). SMART (Version 5.16), SAINT (Version 6.01) and SHELXTL (Version 6.14). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Li, Z.-F., Wang, C.-X., Li, Y., Cai, D.-J. & Xiao, Y.-J. (2006). Acta Cryst. E62, m251–m252. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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