Poly[[piperazine-1,4-dium [diaqua­tetra­kis­(μ-sulfanediyldiacetato)­dicerate(III)]] trihydrate]

Mohammad Ghadermazi; Marilyn M Olmstead; Shahideh Rostami; Jafar Attar Gharamaleki

doi:10.1107/S1600536811002923

. 2011 Feb 2;67(Pt 3):m291–m292. doi: 10.1107/S1600536811002923

Poly[[piperazine-1,4-dium [diaquatetrakis(μ-sulfanediyldiacetato)dicerate(III)]] trihydrate]

Mohammad Ghadermazi ^a,^*, Marilyn M Olmstead ^b, Shahideh Rostami ^a, Jafar Attar Gharamaleki ^c

PMCID: PMC3052029 PMID: 21522233

Abstract

The title compound, (C₄H₁₂N₂)[Ce₂(C₄H₄O₄S)₄(H₂O)₂]·3H₂O, features a polymeric anion with a centrosymmetric Ce₂O₂ core and a Ce⋯Ce distance of 4.3625 (4) Å. The anions form ribbons {[Ce₂(C₄H₄O₄S)₄(H₂O)₂]²⁻}_n extending along [100]. The doubly protonated piperazinium cations reside on centers of inversion and link the polymeric ribbons via N—H⋯O hydrogen bonding. Each Ce^III cation is ten-coordinated by an O₂S donor set from two tridentate sulfanediyldiacetate (tda) ligands, one water molecule and three other tda O donors from adjacent {Ce(tda)₂(H₂O)} units in a distorted bicapped cubic environment. Additional O—H⋯O hydrogen bonding involving the coordinated and solvent water molecules is also present. H atoms of the crystal water molecules could not be located and were not included in the refinement.

Related literature

For the structure determination of a bis-sulfanediyldiacetatonickelate(II), see: Delaunay et al. (1976 ▶). For a dinuclear sulfanediyldiacetato complex, see: Baggio et al. (1999 ▶). For an example with a solely bidentate coordination mode of the sulfanediyldiacetato ligand, see: Marek et al. (2003 ▶). For bond-valence-sum calculations, see: Zhang et al. (2004 ▶).

Experimental

Crystal data

(C₄H₁₂N₂)[Ce₂(C₄H₄O₄S)₄(H₂O)₂]·3H₂O
M _r = 1051.00
Triclinic,
a = 6.4361 (7) Å
b = 11.1135 (12) Å
c = 12.5627 (14) Å
α = 96.693 (4)°
β = 104.646 (3)°
γ = 101.192 (3)°
V = 839.76 (16) Å³
Z = 1
Mo Kα radiation
μ = 3.01 mm⁻¹
T = 90 K
0.25 × 0.22 × 0.05 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.520, T _max = 0.864
11816 measured reflections
4482 independent reflections
4433 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.056
S = 1.11
4482 reflections
229 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.79 e Å⁻³
Δρ_min = −1.81 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002923/wm2442sup1.cif

e-67-0m291-sup1.cif^{(30.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002923/wm2442Isup2.hkl

e-67-0m291-Isup2.hkl^{(219.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ce1—S1	3.2903 (6)
Ce1—S2	3.1445 (6)
Ce1—O1	2.5359 (15)
Ce1—O4	2.5069 (14)
Ce1—O5	2.4278 (14)
Ce1—O7	2.5117 (15)
Ce1—O8ⁱ	2.5024 (15)
Ce1—O3ⁱⁱ	2.6137 (16)
Ce1—O4ⁱⁱ	2.6542 (15)
Ce1—O9	2.6644 (15)

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Symmetry codes: (i) Inline graphic ; (ii) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9C⋯O7ⁱ	0.82 (2)	2.00 (2)	2.793 (2)	163 (3)
O9—H9D⋯O1ⁱⁱ	0.83 (2)	1.92 (2)	2.729 (2)	167 (3)
N1—H1A⋯O6ⁱⁱⁱ	0.92	1.84	2.732 (2)	162
N1—H1B⋯O9^iv	0.92	2.10	2.988 (2)	161

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

Acknowledgments

MMO thanks the University of California, Davis, for the purchase of the X-ray diffractometer. Financial support from University of Kurdistan, Sanandaj, is gratefully acknowledged.

supplementary crystallographic information

Comment

Thiodiacetic acid is one class of dicarboxylic acid ligands that has been used for construction of coordination polymers. It is a versatile complexing agent with one sulfur and two oxygen donor atoms and can strongly complex metal ions. Although the structural study of sulfanediyldiacetate-transition metal compounds was initiated several decades ago (Delaunay, et al., 1976), interest in the structural aspects of sulfanediyldiacetate compounds has remarkably increased in recent years, and many structures with d- and f-block metals are known to date. The ligand is usually tridentate, but at least one Mn(II) complex has been reported in which it is solely bidentate where the thioether S atom is not involved in bonding to the metal (Marek et al., 2003). The ligand can be simply chelating or is involved in both bridging and chelating modes to give rise to dinuclear complexes (Baggio et al., 1999).

The crystal structure of {(C₄H₁₂N₂)[Ce(C₄H₄O₄S)₂(H₂O)]₂^.3H₂O}_n or {[(pipzH₂)[Ce(tda)₂(H₂O)]₂.3H₂O}_n, where tda = [S(CH₂COO)₂]^2-, sulfanediyldiacetate, and pipzH₂ is doubly protonated piperazine, is composed of a polymeric dinuclear anion [Ce(tda)₂(H₂O)]₂^2-, [pipzH₂]²⁺ cations, and three water molecules of hydration. The components of the structure are shown in Fig. 1. The sulfanediyldiacetate group involving S1 behaves as both a tridentate chelating ligand and a bridging ligand to form a centrosymmetric dimer. The Ce1···Ce1ⁱ (i = 1 - x, 1 - y, -z) distance is 4.3625 (4) Å. The sulfanediyldiacetate ligand involving S2 is also a tridentate chelating ligand while its oxygen, O8, coordinates to the Ce of an adjoining dimer and propagates the structure as a coordination polymer parallel to [100] (Fig. 2). The more distant Ce1ⁱⁱⁱ (iii = 1 + x, y, z) is 6.4361 (7) Å away from Ce1. The local coordination of the Ce^III cations consists of two thioethers (S1 and S2) and four O atoms (O1, O4, O5 and O7) from two chelating sulfanediyldiacetate groups, three oxygen atoms (O3, O4 and O8) of the carboxylate moieties from other sulfanediyldiacetate groups, and one oxygen atom from the coordinated water molecule (O9), resulting in an S₂O₈ distorted bicapped cubic environment. The Ce—O and Ce—S distances are normal and are gathered in Table 1. Bond valence sum calculations (Zhang et al., 2004) yield a value of 2.9, in agreement with the oxidation state +III for the cerium atom. The [pipzH₂]²⁺ cations and water molecules are further engaged in hydrogen bonding between polymeric units (Table 2). Although the H atoms of the uncoordinated water molecules could not be located, O···O contacts between 2.58 and 2.86 Å suggest that these molecules also participate in O—H···O hydrogen bonding.

Experimental

The title compound was prepared by mixing two solutions containing 1.5 g (10 mmol) of 2,2'-thiodiacetic acid in 10 ml THF and 0.86 g (10 mmol) piperazine in 10 ml THF. A white precipitate was obtained after evaporating the solvent. An aqueous solution containing 0.34 g (1.5 mmol) of the obtained ion pair in 20 ml water was added dropwise to 0.21 g (0.5 mmol) Ce(NO₃)₃^.6H₂O in 15 ml water. After 60 min stirring and heating to 303 K, the solution became clear. Yellow crystals of the title compound were obtained after allowing the mixture to stand for 3 weeks at room temperature to evaporate the solvent.