Heptaaqua­(3,4,5,6-tetra­chloro­phthalato-κO 1)erbium(III) 2-carb­oxy-3,4,5,6-tetra­chloro­benzoate–3,4,5,6-tetra­chloro­phthalic acid–water (1/1/1)

Yan Ouyang; Jia Shao; Lanfang Hao; Jixin Lu

doi:10.1107/S1600536812016923

. 2012 Apr 25;68(Pt 5):m662–m663. doi: 10.1107/S1600536812016923

Heptaaqua(3,4,5,6-tetrachlorophthalato-κO ¹)erbium(III) 2-carboxy-3,4,5,6-tetrachlorobenzoate–3,4,5,6-tetrachlorophthalic acid–water (1/1/1)

Yan Ouyang ^a,^*, Jia Shao ^a, Lanfang Hao ^a, Jixin Lu ^a

PMCID: PMC3344381 PMID: 22590147

Abstract

In the three-dimensional tetrachlorophthalate-bridged title complex [Er(C₈Cl₄O₄)(H₂O)₇](C₈HCl₄O₄)·C₈H₂Cl₄O₄·H₂O, the Er^III ion is coordinated in form of a distorted square antiprism by an O atom of a tetrachlorophthalate ligand and by seven water O atoms. Extensive hydrogen bonds establish a layered network structure extending parallel to (001).

Related literature

For transition metal tetrachlorophthalato complexes, see: Ma et al. (2009 ▶). For lanthanide tetrachlorophthalato complexes, see: Liang et al. (2004 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

[Er(C₈Cl₄O₄)(H₂O)₇](C₈HCl₄O₄)·C₈H₂Cl₄O₄·H₂O
M _r = 1220.05
Triclinic,
a = 6.865 (2) Å
b = 16.229 (5) Å
c = 19.019 (7) Å
α = 67.430 (8)°
β = 86.597 (13)°
γ = 81.626 (14)°
V = 1935.9 (11) Å³
Z = 2
Mo Kα radiation
μ = 3.08 mm⁻¹
T = 294 K
0.16 × 0.08 × 0.08 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 1999 ▶) T _min = 0.639, T _max = 0.791
14352 measured reflections
8732 independent reflections
7423 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.063
S = 1.00
8732 reflections
527 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −1.29 e Å⁻³

Data collection: CrystalClear (Rigaku, 1999 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 1999 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016923/bt5856sup1.cif

e-68-0m662-sup1.cif^{(40.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016923/bt5856Isup2.hkl

e-68-0m662-Isup2.hkl^{(427.1KB, hkl)}

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
O7—H7⋯O6ⁱ	0.82 (2)	1.77 (2)	2.566 (3)	162 (3)
O10—H10⋯O4ⁱⁱ	0.82 (3)	1.77 (3)	2.566 (3)	164 (3)
O12—H12⋯O5ⁱⁱⁱ	0.82 (3)	1.77 (2)	2.583 (3)	174 (5)
O13—H13A⋯O9^iv	0.84	2.57	2.969 (3)	110
O13—H13A⋯O2^v	0.84	2.03	2.814 (3)	155
O13—H13B⋯O20^vi	0.84	1.93	2.733 (3)	159
O14—H14A⋯O2^v	0.85	1.82	2.663 (3)	169
O14—H14B⋯O3^vii	0.85	1.92	2.724 (3)	157
O15—H15A⋯O3	0.84	2.03	2.868 (3)	169
O15—H15B⋯O4^viii	0.85	1.90	2.738 (3)	168
O16—H16A⋯O8^ix	0.85	1.95	2.774 (3)	166
O16—H16B⋯O3^vii	0.85	1.98	2.764 (3)	153
O17—H17A⋯O6^ix	0.84	1.92	2.750 (3)	168
O17—H17B⋯Cl5ⁱⁱ	0.84	2.83	3.614 (3)	157
O18—H18A⋯O20^vi	0.84	1.93	2.741 (4)	161
O18—H18B⋯O5^x	0.84	2.30	2.809 (4)	119
O19—H19A⋯O11^iv	0.84	2.09	2.909 (3)	167
O19—H19B⋯O5^xi	0.84	2.51	3.119 (3)	131
O19—H19B⋯O8^ix	0.84	2.31	3.010 (3)	141
O20—H20A⋯O11^vii	0.85	2.04	2.781 (3)	146
O20—H20B⋯O10	0.85	2.17	2.834 (3)	134
O20—H20B⋯O12	0.85	2.59	3.080 (3)	118

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 20971099, 10904111).

supplementary crystallographic information

Comment

As a versatile bridge ligand, tcph₂ anion (H₂tcph=tetrachlorophthalic acid) with versatility of coordination modes was successfully used as bridge for the design and synthesis of a wide variety of polynuclear species, often having both interesting structures and properties. To date, most of the published work concerns transition metal tetrachlorophthalato complexes (Ma et al., 2009). In order to provide more examples of lanthanide–tetrachlorophthalate complexes with novel structure in this study, we selected Erbium(III) ion to obtain the title complex.

Single crystal X-ray diffraction analysis reveals that complex (I) consists of a [Er(tcph)(H₂O)₇]⁺ cation(Figure 1), a neutral (H₂tcph) molecule, an (Htcph)^- anion and an uncoordinated water molecule. Selected bond lengths and angles are presented in Table 1. The Er^III ion is coordinated by eight O atoms, one from a tcph ligand and others from coordinated water molecular. The Er–O band distances range from 2.291 (2) Å to 2.382 (2) Å. It is interesting that the complex contains several kinds of hydrogen bonds. The oxygen atoms from carboxylate act as acceptors and the coordinated water molecules as donors. Thus along a axis neighbouring mononuclear structural units form an unusual dimer by means of two short hydrogen bonds (O2–O13=2.814 (3) Å, O2–O14 = 2.663 (3) Å) between uncoordinated carboxylate O atom and coordinated water molecule (Figure 2), and Er–Er distance is 6.218 Å. Along b axis,two adjacent [Er(tcph)(H₂O)₇]⁺ cation are linked by short hydrogen bonds (O3–O16 = 2.732 (3) Å, O3–O14 = 2.764 (3) Å) (Figure 3), and Er–Er distance is 6.865 Å. Furthermore, there are some hydrogen bonds between [Er(tcph)(H₂O)₇]⁺ cations and (Htcph)^- anions. A two-dimensional network is constructed via a series of extensive hydrogen bonds. (Figure. 4) There are many hydrogen bonds owing to the presence of fully deprotonated carboxylate groups and a significant number of water molecules. Hydrogen bonding distances and angles are presented in Table 2. For clarity the conventional description of hydrogen bonding structural parameters has been adopted: D–A indicates the distance between a donor D atom and acceptor A atom, H–A the distance between a donor hydrogen atom bound to D and acceptor, while DHA indicates the angle.

IR spectra of the title complex exhibit the bands expected for the carbonyl stretching (1721 cm_-1), the bands for water stretching (3200–3100 cm_-1) and the bands for benzene (1500–1410 cm_-1). The absorption bands in the spectrum of the title complex were red-shifted relative to strong hydrogen bonds.

Experimental

A solution of Er(NO₃)₃.6H₂O(0.5 mmol) in H₂O (10 ml) was added to a suspension of a suspension of H₂tcph (0.5 mmol) in H₂O (30 ml). The mixture was stirred at room temperature for 30 min. After filtration,the solution was left undisturbed and white crystal was obtain after 15 days.analysis, calculated for C₁₂H₈Cl₁₂ErO₂₀: C 23.63, H 1.57%; found: C 23.55, H 1.50%.