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

Ghadermazi, M.; Olmstead, M.M.; Rostami, S.; Attar Gharamaleki, J.

doi:10.1107/S1600536811002923

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Pages m291-m292

doi:10.1107/S1600536811002923

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

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

^aDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran, ^bDepartment of Chemistry, One Shields Ave., University of California, Davis, CA, USA, and ^cFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
^*Correspondence e-mail: mghadermazi@yahoo.com

(Received 17 December 2010; accepted 21 January 2011; online 2 February 2011)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.021
wR(F²) = 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

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)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z.

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

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compound at the 50% probability level. Hydrogen atoms are removed for clarity except those bonded to the piperazine N atoms and the coordinated water molecule. Hydrogen atoms are drawn as spheres of arbitrary radius. Atoms that indicate the propagation of the coordination polymer are shown. Symmetry codes: i = 1 - x, 1 - y, -z; ii = x - 1, y z; iii = 1 + x, y, z; iv = -x, 1 - y, -z; v = -x, 2 - y, -z.

Fig. 2. A view down [100] of the polymeric structure.

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

Crystal data top

(C₄H₁₂N₂)[Ce₂(C₄H₄O₄S)₄(H₂O)₂]·3H₂O	Z = 1
M_r = 1051.00	F(000) = 520
Triclinic, P1	D_x = 2.078 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4361 (7) Å	Cell parameters from 9880 reflections
b = 11.1135 (12) Å	θ = 2.7–31.5°
c = 12.5627 (14) Å	µ = 3.01 mm⁻¹
α = 96.693 (4)°	T = 90 K
β = 104.646 (3)°	Plate, colourless
γ = 101.192 (3)°	0.25 × 0.22 × 0.05 mm
V = 839.76 (16) Å³

Data collection top

Bruker SMART APEXII diffractometer	4482 independent reflections
Radiation source: fine-focus sealed tube	4433 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.3 pixels mm^-1	θ_max = 29.1°, θ_min = 2.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.520, T_max = 0.864	l = −17→17
11816 measured reflections

Refinement top

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0319P)² + 0.9355P] where P = (F_o² + 2F_c²)/3
4482 reflections	(Δ/σ)_max = 0.002
229 parameters	Δρ_max = 1.79 e Å⁻³
3 restraints	Δρ_min = −1.81 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Ce₂(C₄H₄O₄S)₄(H₂O)₂]·3H₂O	γ = 101.192 (3)°
M_r = 1051.00	V = 839.76 (16) Å³
Triclinic, P1	Z = 1
a = 6.4361 (7) Å	Mo Kα radiation
b = 11.1135 (12) Å	µ = 3.01 mm⁻¹
c = 12.5627 (14) Å	T = 90 K
α = 96.693 (4)°	0.25 × 0.22 × 0.05 mm
β = 104.646 (3)°

Data collection top

Bruker SMART APEXII diffractometer	4482 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4433 reflections with I > 2σ(I)
T_min = 0.520, T_max = 0.864	R_int = 0.021
11816 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	3 restraints
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 1.79 e Å⁻³
4482 reflections	Δρ_min = −1.81 e Å⁻³
229 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	Occ. (<1)
Ce1	0.572270 (15)	0.396056 (9)	0.136487 (8)	0.00772 (4)
S1	0.50618 (8)	0.61593 (5)	0.31570 (4)	0.01299 (10)
S2	0.81761 (8)	0.37549 (4)	0.38182 (4)	0.01047 (9)
O1	0.8397 (2)	0.60785 (14)	0.18806 (12)	0.0126 (3)
O2	0.9817 (3)	0.81191 (14)	0.24661 (13)	0.0155 (3)
O3	0.4131 (3)	0.75180 (14)	0.03785 (13)	0.0150 (3)
O4	0.3790 (2)	0.55553 (13)	0.05890 (12)	0.0116 (3)
O5	0.5613 (2)	0.18686 (13)	0.17676 (12)	0.0121 (3)
O6	0.5126 (3)	0.02205 (15)	0.25991 (14)	0.0204 (3)
O7	0.9607 (2)	0.36963 (14)	0.16697 (12)	0.0128 (3)
O8	1.2946 (2)	0.33740 (14)	0.24070 (12)	0.0118 (3)
O9	0.1631 (2)	0.30107 (14)	0.00472 (12)	0.0118 (3)
H9C	0.092 (5)	0.329 (3)	0.043 (2)	0.024 (8)*
H9D	0.146 (6)	0.332 (3)	−0.052 (2)	0.034 (9)*
N1	0.1458 (3)	0.94944 (16)	0.08009 (15)	0.0121 (3)
H1A	0.2761	0.9585	0.1349	0.015*
H1B	0.0661	0.8687	0.0701	0.015*
C1	0.7895 (4)	0.7018 (2)	0.35817 (17)	0.0144 (4)
H1C	0.8004	0.7868	0.3965	0.017*
H1D	0.8795	0.6601	0.4116	0.017*
C2	0.8790 (3)	0.70996 (19)	0.25730 (16)	0.0117 (3)
C3	0.3913 (4)	0.7073 (2)	0.21616 (18)	0.0174 (4)
H3A	0.2354	0.7020	0.2151	0.021*
H3B	0.4716	0.7955	0.2429	0.021*
C4	0.3986 (3)	0.67031 (19)	0.09779 (16)	0.0114 (3)
C5	0.6813 (4)	0.2163 (2)	0.37811 (18)	0.0164 (4)
H5A	0.7899	0.1761	0.4223	0.020*
H5B	0.5635	0.2172	0.4156	0.020*
C6	0.5786 (3)	0.13566 (19)	0.26210 (17)	0.0126 (4)
C7	1.0804 (3)	0.3580 (2)	0.36422 (17)	0.0159 (4)
H7A	1.1962	0.4274	0.4151	0.019*
H7B	1.1077	0.2799	0.3895	0.019*
C8	1.1111 (3)	0.35473 (17)	0.24746 (16)	0.0100 (3)
C9	0.0173 (3)	1.03697 (19)	0.11667 (17)	0.0134 (4)
H9A	0.1071	1.1235	0.1328	0.016*
H9B	−0.0169	1.0173	0.1861	0.016*
C10	−0.1952 (3)	1.02600 (19)	0.02648 (17)	0.0133 (4)
H10A	−0.2903	0.9413	0.0146	0.016*
H10B	−0.2757	1.0867	0.0502	0.016*
O10	0.0974 (4)	0.0278 (2)	0.41702 (19)	0.0388 (5)
O11	0.4926 (7)	0.0607 (4)	0.5455 (3)	0.0312 (8)*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.00901 (6)	0.00557 (6)	0.00889 (6)	0.00190 (4)	0.00262 (4)	0.00197 (4)
S1	0.0153 (2)	0.0122 (2)	0.0120 (2)	0.00179 (17)	0.00535 (18)	0.00315 (17)
S2	0.0117 (2)	0.0087 (2)	0.0111 (2)	0.00170 (16)	0.00410 (16)	0.00140 (16)
O1	0.0135 (7)	0.0103 (6)	0.0125 (6)	0.0009 (5)	0.0036 (5)	−0.0009 (5)
O2	0.0177 (7)	0.0109 (7)	0.0174 (7)	0.0011 (5)	0.0058 (6)	0.0022 (5)
O3	0.0214 (7)	0.0108 (7)	0.0148 (7)	0.0063 (6)	0.0060 (6)	0.0038 (5)
O4	0.0133 (6)	0.0093 (6)	0.0130 (6)	0.0045 (5)	0.0034 (5)	0.0028 (5)
O5	0.0146 (7)	0.0089 (6)	0.0132 (6)	0.0033 (5)	0.0038 (5)	0.0032 (5)
O6	0.0244 (8)	0.0098 (7)	0.0199 (8)	−0.0015 (6)	−0.0035 (6)	0.0060 (6)
O7	0.0130 (6)	0.0150 (7)	0.0124 (6)	0.0052 (5)	0.0045 (5)	0.0045 (5)
O8	0.0112 (6)	0.0116 (6)	0.0135 (6)	0.0029 (5)	0.0045 (5)	0.0030 (5)
O9	0.0143 (7)	0.0103 (6)	0.0115 (6)	0.0027 (5)	0.0048 (5)	0.0023 (5)
N1	0.0129 (8)	0.0080 (7)	0.0144 (8)	0.0024 (6)	0.0016 (6)	0.0027 (6)
C1	0.0165 (9)	0.0130 (9)	0.0118 (9)	0.0006 (7)	0.0033 (7)	0.0007 (7)
C2	0.0108 (8)	0.0120 (9)	0.0112 (8)	0.0022 (7)	0.0018 (7)	0.0015 (7)
C3	0.0234 (10)	0.0202 (10)	0.0123 (9)	0.0137 (8)	0.0049 (8)	0.0025 (7)
C4	0.0103 (8)	0.0123 (9)	0.0118 (8)	0.0047 (7)	0.0020 (7)	0.0021 (7)
C5	0.0209 (10)	0.0105 (9)	0.0132 (9)	−0.0015 (7)	−0.0010 (8)	0.0056 (7)
C6	0.0114 (8)	0.0096 (8)	0.0160 (9)	0.0026 (7)	0.0015 (7)	0.0036 (7)
C7	0.0112 (9)	0.0255 (11)	0.0114 (9)	0.0052 (8)	0.0033 (7)	0.0031 (8)
C8	0.0123 (8)	0.0048 (8)	0.0128 (8)	0.0011 (6)	0.0041 (7)	0.0010 (6)
C9	0.0172 (9)	0.0098 (8)	0.0132 (9)	0.0041 (7)	0.0037 (7)	0.0014 (7)
C10	0.0144 (9)	0.0114 (9)	0.0154 (9)	0.0039 (7)	0.0055 (7)	0.0027 (7)
O10	0.0566 (14)	0.0248 (10)	0.0376 (11)	0.0073 (9)	0.0213 (10)	0.0010 (8)

Geometric parameters (Å, º) top

Ce1—S1	3.2903 (6)	O9—H9D	0.825 (18)
Ce1—S2	3.1445 (6)	N1—C10ⁱⁱⁱ	1.495 (3)
Ce1—O1	2.5359 (15)	N1—C9	1.497 (3)
Ce1—O4	2.5069 (14)	N1—H1A	0.9200
Ce1—O5	2.4278 (14)	N1—H1B	0.9200
Ce1—O7	2.5117 (15)	C1—C2	1.524 (3)
Ce1—O8ⁱ	2.5024 (15)	C1—H1C	0.9900
Ce1—O3ⁱⁱ	2.6137 (16)	C1—H1D	0.9900
Ce1—O4ⁱⁱ	2.6542 (15)	C3—C4	1.511 (3)
Ce1—O9	2.6644 (15)	C3—H3A	0.9900
S1—C1	1.798 (2)	C3—H3B	0.9900
S1—C3	1.806 (2)	C5—C6	1.531 (3)
S2—C7	1.804 (2)	C5—H5A	0.9900
S2—C5	1.805 (2)	C5—H5B	0.9900
O1—C2	1.287 (2)	C7—C8	1.526 (3)
O2—C2	1.236 (3)	C7—H7A	0.9900
O3—C4	1.248 (2)	C7—H7B	0.9900
O4—C4	1.282 (2)	C9—C10	1.513 (3)
O5—C6	1.262 (2)	C9—H9A	0.9900
O6—C6	1.246 (3)	C9—H9B	0.9900
O7—C8	1.262 (2)	C10—H10A	0.9900
O8—C8	1.255 (2)	C10—H10B	0.9900
O9—H9C	0.817 (17)

O5—Ce1—O8ⁱ	69.44 (5)	C8—O7—Ce1	136.54 (13)
O5—Ce1—O4	150.35 (5)	C8—O8—Ce1^iv	140.41 (13)
O8ⁱ—Ce1—O4	91.13 (5)	Ce1—O9—H9C	101 (2)
O5—Ce1—O7	74.48 (5)	Ce1—O9—H9D	109 (3)
O8ⁱ—Ce1—O7	131.20 (5)	H9C—O9—H9D	108 (3)
O4—Ce1—O7	133.20 (5)	C10ⁱⁱⁱ—N1—C9	111.17 (15)
O5—Ce1—O1	138.75 (5)	C10ⁱⁱⁱ—N1—H1A	109.4
O8ⁱ—Ce1—O1	121.49 (5)	C9—N1—H1A	109.4
O4—Ce1—O1	70.37 (5)	C10ⁱⁱⁱ—N1—H1B	109.4
O7—Ce1—O1	70.20 (5)	C9—N1—H1B	109.4
O5—Ce1—O3ⁱⁱ	69.93 (5)	H1A—N1—H1B	108.0
O8ⁱ—Ce1—O3ⁱⁱ	121.93 (5)	C2—C1—S1	110.59 (14)
O4—Ce1—O3ⁱⁱ	105.26 (5)	C2—C1—H1C	109.5
O7—Ce1—O3ⁱⁱ	71.75 (5)	S1—C1—H1C	109.5
O1—Ce1—O3ⁱⁱ	116.48 (5)	C2—C1—H1D	109.5
O5—Ce1—O4ⁱⁱ	119.23 (5)	S1—C1—H1D	109.5
O8ⁱ—Ce1—O4ⁱⁱ	144.10 (5)	H1C—C1—H1D	108.1
O4—Ce1—O4ⁱⁱ	64.63 (6)	O2—C2—O1	124.50 (19)
O7—Ce1—O4ⁱⁱ	82.62 (5)	O2—C2—C1	119.06 (18)
O1—Ce1—O4ⁱⁱ	76.75 (5)	O1—C2—C1	116.43 (18)
O3ⁱⁱ—Ce1—O4ⁱⁱ	49.44 (5)	C4—C3—S1	115.90 (15)
O5—Ce1—O9	85.38 (5)	C4—C3—H3A	108.3
O8ⁱ—Ce1—O9	66.23 (5)	S1—C3—H3A	108.3
O4—Ce1—O9	65.95 (5)	C4—C3—H3B	108.3
O7—Ce1—O9	141.72 (5)	S1—C3—H3B	108.3
O1—Ce1—O9	135.87 (5)	H3A—C3—H3B	107.4
O3ⁱⁱ—Ce1—O9	70.84 (5)	O3—C4—O4	121.12 (19)
O4ⁱⁱ—Ce1—O9	79.35 (5)	O3—C4—C3	119.05 (19)
O5—Ce1—S2	63.64 (4)	O4—C4—C3	119.73 (18)
O8ⁱ—Ce1—S2	70.54 (4)	C6—C5—S2	116.14 (15)
O4—Ce1—S2	132.01 (3)	C6—C5—H5A	108.3
O7—Ce1—S2	64.42 (3)	S2—C5—H5A	108.3
O1—Ce1—S2	82.04 (4)	C6—C5—H5B	108.3
O3ⁱⁱ—Ce1—S2	122.24 (4)	S2—C5—H5B	108.3
O4ⁱⁱ—Ce1—S2	145.36 (3)	H5A—C5—H5B	107.4
O9—Ce1—S2	133.47 (3)	O6—C6—O5	124.6 (2)
C4ⁱⁱ—Ce1—S2	139.09 (4)	O6—C6—C5	116.06 (18)
O5—Ce1—S1	120.96 (4)	O5—C6—C5	119.27 (18)
O8ⁱ—Ce1—S1	62.01 (4)	C8—C7—S2	117.92 (15)
O4—Ce1—S1	62.43 (4)	C8—C7—H7A	107.8
O7—Ce1—S1	115.38 (4)	S2—C7—H7A	107.8
O1—Ce1—S1	60.23 (4)	C8—C7—H7B	107.8
O3ⁱⁱ—Ce1—S1	167.65 (3)	S2—C7—H7B	107.8
O4ⁱⁱ—Ce1—S1	119.75 (3)	H7A—C7—H7B	107.2
O9—Ce1—S1	102.88 (3)	O8—C8—O7	124.80 (19)
C4ⁱⁱ—Ce1—S1	144.33 (4)	O8—C8—C7	114.35 (17)
S2—Ce1—S1	69.898 (14)	O7—C8—C7	120.85 (18)
C1—S1—C3	99.14 (11)	N1—C9—C10	110.34 (16)
C1—S1—Ce1	95.72 (7)	N1—C9—H9A	109.6
C3—S1—Ce1	97.65 (7)	C10—C9—H9A	109.6
C7—S2—C5	101.63 (11)	N1—C9—H9B	109.6
C7—S2—Ce1	100.18 (7)	C10—C9—H9B	109.6
C5—S2—Ce1	97.24 (7)	H9A—C9—H9B	108.1
C2—O1—Ce1	138.15 (13)	N1ⁱⁱⁱ—C10—C9	110.03 (17)
C4—O3—Ce1ⁱⁱ	95.97 (12)	N1ⁱⁱⁱ—C10—H10A	109.7
C4—O4—Ce1	131.30 (13)	C9—C10—H10A	109.7
C4—O4—Ce1ⁱⁱ	93.20 (12)	N1ⁱⁱⁱ—C10—H10B	109.7
Ce1—O4—Ce1ⁱⁱ	115.37 (5)	C9—C10—H10B	109.7
C6—O5—Ce1	136.68 (13)	H10A—C10—H10B	108.2

O5—Ce1—S1—C1	108.05 (8)	O1—Ce1—O4—Ce1ⁱⁱ	84.25 (6)
O8ⁱ—Ce1—S1—C1	146.53 (8)	O3ⁱⁱ—Ce1—O4—Ce1ⁱⁱ	−28.92 (7)
O4—Ce1—S1—C1	−105.85 (8)	O4ⁱⁱ—Ce1—O4—Ce1ⁱⁱ	0.0
O7—Ce1—S1—C1	21.53 (8)	O9—Ce1—O4—Ce1ⁱⁱ	−89.30 (6)
O1—Ce1—S1—C1	−23.78 (8)	S2—Ce1—O4—Ce1ⁱⁱ	142.97 (3)
O3ⁱⁱ—Ce1—S1—C1	−101.58 (18)	S1—Ce1—O4—Ce1ⁱⁱ	150.14 (7)
O4ⁱⁱ—Ce1—S1—C1	−74.64 (8)	O8ⁱ—Ce1—O5—C6	−53.69 (19)
O9—Ce1—S1—C1	−159.61 (8)	O4—Ce1—O5—C6	−105.6 (2)
S2—Ce1—S1—C1	68.49 (7)	O7—Ce1—O5—C6	92.87 (19)
O5—Ce1—S1—C3	−151.90 (9)	O1—Ce1—O5—C6	61.1 (2)
O8ⁱ—Ce1—S1—C3	−113.42 (9)	O3ⁱⁱ—Ce1—O5—C6	168.7 (2)
O4—Ce1—S1—C3	−5.79 (9)	O4ⁱⁱ—Ce1—O5—C6	164.92 (18)
O7—Ce1—S1—C3	121.59 (9)	O9—Ce1—O5—C6	−120.01 (19)
O1—Ce1—S1—C3	76.28 (9)	S2—Ce1—O5—C6	24.12 (18)
O3ⁱⁱ—Ce1—S1—C3	−1.53 (19)	S1—Ce1—O5—C6	−17.8 (2)
O4ⁱⁱ—Ce1—S1—C3	25.42 (9)	O5—Ce1—O7—C8	−65.42 (18)
O9—Ce1—S1—C3	−59.56 (9)	O8ⁱ—Ce1—O7—C8	−22.1 (2)
S2—Ce1—S1—C3	168.54 (8)	O4—Ce1—O7—C8	127.01 (18)
O5—Ce1—S2—C7	84.51 (9)	O1—Ce1—O7—C8	92.90 (19)
O8ⁱ—Ce1—S2—C7	160.59 (9)	O3ⁱⁱ—Ce1—O7—C8	−138.95 (19)
O4—Ce1—S2—C7	−126.28 (9)	O4ⁱⁱ—Ce1—O7—C8	171.42 (19)
O7—Ce1—S2—C7	−0.10 (9)	O9—Ce1—O7—C8	−126.28 (18)
O1—Ce1—S2—C7	−71.91 (9)	S2—Ce1—O7—C8	2.38 (17)
O3ⁱⁱ—Ce1—S2—C7	44.46 (9)	S1—Ce1—O7—C8	51.92 (19)
O4ⁱⁱ—Ce1—S2—C7	−19.46 (10)	C3—S1—C1—C2	−56.27 (16)
O9—Ce1—S2—C7	138.09 (9)	Ce1—S1—C1—C2	42.45 (15)
S1—Ce1—S2—C7	−133.04 (8)	Ce1—O1—C2—O2	−159.61 (15)
O5—Ce1—S2—C5	−18.75 (9)	Ce1—O1—C2—C1	20.0 (3)
O8ⁱ—Ce1—S2—C5	57.33 (9)	S1—C1—C2—O2	132.49 (17)
O4—Ce1—S2—C5	130.46 (9)	S1—C1—C2—O1	−47.1 (2)
O7—Ce1—S2—C5	−103.36 (9)	C1—S1—C3—C4	87.74 (18)
O1—Ce1—S2—C5	−175.16 (9)	Ce1—S1—C3—C4	−9.35 (18)
O3ⁱⁱ—Ce1—S2—C5	−58.80 (9)	Ce1ⁱⁱ—O3—C4—O4	−5.3 (2)
O4ⁱⁱ—Ce1—S2—C5	−122.72 (10)	Ce1ⁱⁱ—O3—C4—C3	178.13 (16)
O9—Ce1—S2—C5	34.83 (9)	Ce1—O4—C4—O3	133.58 (17)
S1—Ce1—S2—C5	123.70 (8)	Ce1ⁱⁱ—O4—C4—O3	5.2 (2)
O5—Ce1—O1—C2	−97.7 (2)	Ce1—O4—C4—C3	−49.9 (3)
O8ⁱ—Ce1—O1—C2	−3.5 (2)	Ce1ⁱⁱ—O4—C4—C3	−178.26 (17)
O4—Ce1—O1—C2	75.31 (19)	Ce1—O4—C4—Ce1ⁱⁱ	128.35 (15)
O7—Ce1—O1—C2	−130.4 (2)	S1—C3—C4—O3	−150.05 (17)
O3ⁱⁱ—Ce1—O1—C2	173.03 (18)	S1—C3—C4—O4	33.4 (3)
O4ⁱⁱ—Ce1—O1—C2	142.8 (2)	C7—S2—C5—C6	−79.97 (18)
O9—Ce1—O1—C2	83.8 (2)	Ce1—S2—C5—C6	22.04 (17)
S2—Ce1—O1—C2	−64.81 (19)	Ce1—O5—C6—O6	160.71 (16)
S1—Ce1—O1—C2	6.54 (18)	Ce1—O5—C6—C5	−17.5 (3)
O5—Ce1—O4—C4	135.03 (17)	S2—C5—C6—O6	170.16 (17)
O8ⁱ—Ce1—O4—C4	87.52 (17)	S2—C5—C6—O5	−11.5 (3)
O7—Ce1—O4—C4	−69.76 (19)	C5—S2—C7—C8	98.32 (18)
O1—Ce1—O4—C4	−35.69 (17)	Ce1—S2—C7—C8	−1.33 (17)
O3ⁱⁱ—Ce1—O4—C4	−148.85 (17)	Ce1^iv—O8—C8—O7	32.5 (3)
O4ⁱⁱ—Ce1—O4—C4	−119.94 (19)	Ce1^iv—O8—C8—C7	−146.95 (16)
O9—Ce1—O4—C4	150.77 (18)	Ce1—O7—C8—O8	176.41 (13)
S2—Ce1—O4—C4	23.04 (19)	Ce1—O7—C8—C7	−4.1 (3)
S1—Ce1—O4—C4	30.20 (16)	S2—C7—C8—O8	−177.31 (15)
O5—Ce1—O4—Ce1ⁱⁱ	−105.03 (10)	S2—C7—C8—O7	3.2 (3)
O8ⁱ—Ce1—O4—Ce1ⁱⁱ	−152.54 (6)	C10ⁱⁱⁱ—N1—C9—C10	57.6 (2)
O7—Ce1—O4—Ce1ⁱⁱ	50.18 (9)	N1—C9—C10—N1ⁱⁱⁱ	−57.0 (2)

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

Hydrogen-bond geometry (Å, º) top

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···O6^v	0.92	1.84	2.732 (2)	162
N1—H1B···O9^vi	0.92	2.10	2.988 (2)	161

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[Ce₂(C₄H₄O₄S)₄(H₂O)₂]·3H₂O
M_r	1051.00
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	6.4361 (7), 11.1135 (12), 12.5627 (14)
α, β, γ (°)	96.693 (4), 104.646 (3), 101.192 (3)
V (Å³)	839.76 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.01
Crystal size (mm)	0.25 × 0.22 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.520, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	11816, 4482, 4433
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.056, 1.11
No. of reflections	4482
No. of parameters	229
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.79, −1.81

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

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

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9C···O7ⁱ	0.817 (17)	2.001 (18)	2.793 (2)	163 (3)
O9—H9D···O1ⁱⁱ	0.825 (18)	1.918 (18)	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

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

Acknowledgements

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.

References

Baggio, R., Garland, M. T., Manzur, J., Peña, O., Perec, M., Spodine, E. & Vega, A. (1999). Inorg. Chim. Acta, 286, 74–79. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Delaunay, J., Kappenstein, C. & Hugel, R. (1976). Acta Cryst. B32, 2341–2345. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Marek, J., Trávníček, Z. & Kopel, P. (2003). Acta Cryst. C59, m429–m431. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, C., Howell, R. C., Scotland, K. B., Perez, F. G., Todaro, L. & Francesconi, L. C. (2004). Inorg. Chem. 43, 7691–7701. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 67| Part 3| March 2011| Pages m291-m292

doi:10.1107/S1600536811002923

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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