Poly[[tetra­aquabis­(μ-hydroxy­acetato-κ4O1,O2:O1,O1′)-μ2-sulfato-κ2O:O′-dicadmium(II)] monohydrate]

Rychlewska, U.; Warzajtis, B.; Dimitrijević, M.D.; Draskovic, N.S.; Djuran, M.I.

doi:10.1107/S1600536809017255

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m648-m649

doi:10.1107/S1600536809017255

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Poly[[tetraaquabis(μ-hydroxyacetato-κ⁴O¹,O²:O¹,O^1′)-μ₂-sulfato-κ²O:O′-dicadmium(II)] monohydrate]

Urszula Rychlewska,^a ^* Beata Warzajtis,^a Mirjana Dj. Dimitrijević,^b Nenad S. Draskovic ^b and Miloš I. Djuran ^b

^aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland, and ^bDepartment of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, PO Box 60, 34000 Kragujevac, Serbia
^*Correspondence e-mail: urszular@amu.edu.pl

(Received 28 April 2009; accepted 7 May 2009; online 14 May 2009)

The title compound, {[Cd₂(C₂H₃O₃)₂(SO₄)(H₂O)₄]·H₂O}_n, was obtained unintentionally in a transmetallation reaction. The crystal structure contains a two-dimensional metal–organic framework based on Cd^II–(μ-hydroxyacetato-κ⁴O¹,O²:O¹,O^1′)–Cd^II zigzag chains joined together by bridging SO₄ anions. The resulting layers are shifted with respect to each other and are stacked along the c axis. Their construction is supported by hydrogen bonds between water molecules and between water molecules and carboxylate or sulfate groups. Neighbouring layers are bridged by hydrogen bonds between the hydroxyl substituent and a sulfate anion. The sulfate anion and solvent water molecule are located on twofold axes. The results demonstrate that care must be taken when preparing ethylenediaminetetraacetic acid-type complexes by transmetallation, in order to avoid precipitation of metal complexes with the α-hydroxyacetate ligand.

Related literature

For examples of the successful application of transmetallation reactions in the synthesis of metal(II) complexes with hexadentate 1,3-propanediaminetetraacetate and 1,4-butanediaminetetraacetate ligands, see: Radanović et al. (2003 , 2004 , 2007 ); Rychlewska et al. (2000 , 2005 , 2007 ).

Experimental

Crystal data

[Cd₂(C₂H₃O₃)₂(SO₄)(H₂O)₄]·H₂O
M_r = 561.03
Monoclinic, C 2/c
a = 13.5750 (3) Å
b = 8.5777 (1)
c = 13.7734 (3) Å
β = 107.528 (2)°
V = 1529.34 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 295 K
0.30 × 0.30 × 0.20 mm

Data collection

Kuma KM4 CCD κ-geometry diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.388, T_max = 0.550
8842 measured reflections
1710 independent reflections
1602 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.038
S = 1.13
1710 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O1	2.3584 (14)
Cd1—O2	2.3013 (14)
Cd1—O4	2.2386 (16)
Cd1—O1W	2.2731 (15)
Cd1—O2W	2.3245 (14)
Cd1—O2ⁱ	2.5937 (14)
Cd1—O3ⁱ	2.3379 (17)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2Wⁱⁱ	0.85	1.94	2.784 (2)	170
O1W—H2w⋯O3ⁱⁱⁱ	0.85	1.88	2.723 (2)	172
O2W—H3W⋯O3W	0.85	1.88	2.720 (2)	172
O2W—H4W⋯O5ⁱ	0.85	1.82	2.648 (2)	162
O1—H1O⋯O5^iv	0.85	1.81	2.659 (2)	175
O3W—H5W⋯O4^v	0.85	2.25	2.813 (3)	124
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) x, y-1, z; (iv) $[x, -y+2, z-{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1989 ) and Mercury (Bruno et al., 2002 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017255/gk2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017255/gk2209Isup2.hkl

checkCIF report

Comment top

Research concerning metal–organic frameworks (MOF) has recently become important due to their potential application in a number of areas, including gas storage and catalysis. Prominent in this class of materials are frameworks that involve α-hydroxycarboxylate ligands spanning network nodes. We have recently obtained one such MOF by serendipity, when trying to synthesize cadmium(II) homometallic complex with 1,4-bdta ligand (1,4-bdta stands for 1,4-butanediaminetetraactetate) by the process of transmetallation. So far we have successfully used this strategy for obtaining M(II) complexes with both 1,3-pdta (1,3-propanediaminetetraacetate) (Rychlewska et al., 2000; Radanović et al., 2003; Radanović et al., 2004; Rychlewska et al., 2005, 2007) and 1,4-bdta ligands (Radanović et al., 2007). In this procedure, barium(II) cations, forming the homometallic barium 1,3-pdta or 1,4-bdta complex, are being exchanged by much smaller in size metal(II) cations. At the very first step of this reaction we synthesize the ligands by reacting 1,3-propanediamine (or 1,4-butanediamine) with sodium chloracetate. It turned out that, when trying to synthesize 1,4-bdta ligand, we have obtained, in the reaction mixture, besides the expected H₄-1,4-bdta, some amount of α-hydroxycarboxylic acid. Most probably, this α-hydroxycarboxylic acid has originated from the chloracetic acid when heated at pH > 10. Consequent addition of BaCl₂ to the solution resulted in formation of two types of barium(II) salts, one formed by H₄-1,4-bdta and the other by HOCH₂COOH. An attempt to exchange barium(II) by cadmium(II) cations by addition of CdSO₄ resulted in percipitation of two-dimensional homometallic MOF formed by Cd^II cations, hydroxyacetate and sulfate anions, instead of the expected Cd^II 1,4-bdta complex. This has been unequivocally established by the X-ray crystal structure analysis, the results of which are reported in this paper. We next attempted to verify this hypothetical synthetic route by synthesizing the very same Cd^II complex starting from (HOCH₂COO)₂Ba salt. For both samples we have performed elemental microanalyses and NMR measurements which confirmed their identity.

In the crystal the Cd^II nodes bind together by a singly deprotonated hydroxyacetate and doubly deprotonated sulfate linkers. The hydroxyacetate acts as a tetradentate ligand with α-hydroxyacetate group O1–C1–C2–O2 acting as a bidentate chelate to Cd1, and carboxylate group O2–C2–O3 acting as a bidentate chelate to Cd1 at 1/2 - x, 1/2 + y, 1/2 - z. The two Cd^II centers sharing the same (O2) carboxylate oxygen and bridged by the O2–C2–O3 carboxylate group are 4.736 (1) Å apart, and extend in a zigzag manner along the b-direction. Each Cd^II cation is chelated by a hydroxyacetate residue and a carboxylate group, and is coordinated by two water molecules, and one sulfate anion, resulting in a sevenfold coordination mode (Fig. 1). The hydroxyacetate anions and one coordinated water molecule (O1W) lie in the equatorial plane while the other water molecule (O2W) and the sulfate anion take the axial positions. Hence, the coordination polyhedron formed around Cd1 is a distorted pentagonal bipyramid with the in-plane cis bond angles in the range 52.37 (4)–83.68 (5)°, the smallest angle reflecting chelation by the carboxylate ligand, and with the out-of-plane trans angle of 170.76 (6)°. Sulfate anions lie on the twofold axis and connect the neighbouring Cd^II centers, related by this symmetry axis via O4 oxygen atoms. Separation of the two Cd^II metal centers bridged by the sulfate group measures 6.773 (1) Å. The sulfate bridges help to extend the basic structural motif in the a-direction, thus forming a (001) layer (Fig. 2). This polymeric two-dimensional construction is additionally supported by hydrogen bonds (Table 2) that involve crystalline water molecule, which also occupies the twofold axis (O3w). This water molecule acts as a double hydrogen bond donor to two coordinated sulfate O atoms (O4 and its symmetry equivalent) and a double hydrogen bond acceptor from the axially coordinated water molecule (O2W and its twofold equivalent). The equatorially coordinated water molecule (O1W) acts as a hydrogen bond donor to carboxylate O3 and the axially coordinated water O2W. The neighbouring two-dimensional layers are bridged by a hydrogen bond formed between a hydroxyl group (O1) acting as a hydrogen-bond donor and the uncoordinated oxygen atom (O5) from the sulfate anion. The hydrogen bond parameters are provided in Table 2.

The reported X-ray analysis allowed us to identify and structurally characterize the unintentionally synthesized two-dimensional MOF and to demonstrate that care must be taken when preparing the edta-type complexes by transmetallation to avoid precipitation of metal complexes with α-hydroxyacetate bridges. To remove the excess of Ba(II) α-hydroxyacetate, a water washing procedure should be repeated several times.

Related literature top

For examples of the successful application of transmetallation reactions in the synthesis of metal(II) complexes with hexadentate 1,3-propanediaminetetraacetate and 1,4-butanediaminetetraacetate ligands, see: Radanović et al. (2003, 2004, 2007); Rychlewska et al. (2000, 2005, 2007).

Experimental top

2.56 g (0.003 mol) of CdSO₄.8H₂O were dissolved in 50 cm³ of distilled water at 70°C. To this solution, 6.27 g of solid Ba[Ba(1,4-bdta)].2H₂O containing Ba(HOCH₂COO)₂ in ratio 3:1, respectively, was added and the reaction mixture was heated at 90°C with stirring for 6 h. The precipitated BaSO₄ was removed by filtration and the filtrate was evaporated to ca 10 cm³ and then left in a refrigerator for several days. Colorless crystals of the title compound were collected, washed with ethanol, and air-dried. Yield 0.98 g (59.5%). The complex was recrystallized from hot water while cooling in a refrigerator. Analysis calculated for C₄H₁₄Cd₂O₁₄S.H₂O (FW = 561.03; m. p. 416 K): C 8.84, H 2.87, S 5.90%; found: C 8.93, H 2.83, S 6.28%.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1989) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Basic supramolecular motif showing pentagonal bipyramidal coordination around Cd^II. Displacement ellipsoids are drawn at the 40% probability level. Symmetry codes: i = -x + 1/2, y - 1/2, -z + 1/2; ii= -x + 1/2, y + 1/2, -z + 1/2; iii= -x, y, -z + 1/2.
	Fig. 2. View down the monoclinic c-direction showing hydrogen bonding (dashed lines), water channels and two-dimensional structure of the complex.

Poly[[tetraaquabis(µ₂-hydroxyacetato- κ⁴O¹,O²:O¹,O^1')-µ₂-sulfato- κ²O:O'-dicadmium(II)] monohydrate] top

Crystal data top

[Cd₂(C₂H₃O₃)₂(SO₄)(H₂O)₄]·H₂O	F(000) = 1088
M_r = 561.03	D_x = 2.437 Mg m⁻³
Monoclinic, C2/c	Melting point: 416 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 13.5750 (3) Å	Cell parameters from 5972 reflections
b = 8.5777 (1) Å	θ = 2.9–28.0°
c = 13.7734 (3) Å	µ = 2.99 mm⁻¹
β = 107.528 (2)°	T = 295 K
V = 1529.34 (5) Å³	Prismatic, colourless
Z = 4	0.30 × 0.30 × 0.20 mm

Data collection top

Kuma KM4 CCD κ-geometry diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1602 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω and ϕ scans	θ_max = 28.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	h = −17→17
T_min = 0.388, T_max = 0.550	k = −10→10
8842 measured reflections	l = −17→17

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) = 0.038	w = 1/[σ²(F_o²) + (0.0212P)² + 0.9781P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
1710 reflections	Δρ_max = 0.46 e Å⁻³
102 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00703 (18)

Crystal data top

[Cd₂(C₂H₃O₃)₂(SO₄)(H₂O)₄]·H₂O	V = 1529.34 (5) Å³
M_r = 561.03	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.5750 (3) Å	µ = 2.99 mm⁻¹
b = 8.5777 (1) Å	T = 295 K
c = 13.7734 (3) Å	0.30 × 0.30 × 0.20 mm
β = 107.528 (2)°

Data collection top

Kuma KM4 CCD κ-geometry diffractometer	1710 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1602 reflections with I > 2σ(I)
T_min = 0.388, T_max = 0.550	R_int = 0.018
8842 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	0 restraints
wR(F²) = 0.038	H-atom parameters constrained
S = 1.13	Δρ_max = 0.46 e Å⁻³
1710 reflections	Δρ_min = −0.31 e Å⁻³
102 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.215433 (10)	0.885016 (14)	0.174423 (9)	0.02516 (7)
O1W	0.15455 (14)	0.67573 (17)	0.07284 (12)	0.0463 (4)
H1W	0.1546	0.6610	0.0118	0.056*
H2W	0.1641	0.5894	0.1046	0.056*
O2W	0.36889 (11)	0.85773 (16)	0.13399 (12)	0.0344 (3)
H3W	0.4134	0.9233	0.1669	0.041*
H4W	0.3970	0.7714	0.1573	0.041*
O1	0.14443 (14)	1.02774 (17)	0.02309 (11)	0.0499 (4)
H1O	0.1128	1.0004	−0.0376	0.060*
C1	0.12548 (16)	1.1879 (2)	0.03179 (14)	0.0323 (4)
H1A	0.0528	1.2052	0.0191	0.039*
H1B	0.1474	1.2454	−0.0178	0.039*
C2	0.18369 (14)	1.2435 (2)	0.13702 (13)	0.0254 (4)
O2	0.23446 (11)	1.14930 (16)	0.20257 (11)	0.0310 (3)
O4	0.07190 (15)	0.87150 (18)	0.22208 (19)	0.0617 (6)
S1	0.0000	0.97501 (7)	0.2500	0.02325 (13)
O5	0.05131 (16)	1.0737 (2)	0.33543 (12)	0.0570 (5)
O3W	0.5000	1.0723 (3)	0.2500	0.0749 (10)
H5W	0.5380	1.1144	0.2183	0.090*
O3	0.17860 (15)	1.38542 (15)	0.15667 (12)	0.0396 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03149 (10)	0.02054 (9)	0.02099 (9)	0.00182 (4)	0.00418 (6)	−0.00095 (5)
O1W	0.0858 (12)	0.0209 (7)	0.0251 (7)	−0.0006 (7)	0.0062 (7)	−0.0006 (6)
O2W	0.0402 (8)	0.0289 (7)	0.0334 (8)	0.0051 (6)	0.0098 (6)	0.0019 (6)
O1	0.0872 (12)	0.0260 (8)	0.0193 (7)	0.0107 (7)	−0.0098 (7)	−0.0061 (6)
C1	0.0445 (11)	0.0231 (9)	0.0224 (9)	0.0022 (8)	−0.0001 (8)	0.0011 (7)
C2	0.0323 (9)	0.0211 (9)	0.0218 (8)	−0.0040 (7)	0.0067 (7)	0.0000 (7)
O2	0.0416 (7)	0.0226 (6)	0.0214 (6)	−0.0032 (5)	−0.0018 (6)	0.0001 (5)
O3	0.0629 (10)	0.0208 (7)	0.0274 (8)	−0.0011 (6)	0.0021 (7)	−0.0030 (5)
O4	0.0565 (11)	0.0353 (9)	0.1112 (18)	0.0121 (7)	0.0524 (13)	0.0067 (9)
S1	0.0263 (3)	0.0186 (3)	0.0233 (3)	0.000	0.0051 (2)	0.000
O5	0.0940 (15)	0.0310 (8)	0.0250 (8)	−0.0193 (8)	−0.0139 (8)	0.0032 (7)
O3W	0.0500 (15)	0.0271 (12)	0.140 (3)	0.000	0.0168 (17)	0.000

Geometric parameters (Å, º) top

Cd1—O1	2.3584 (14)	O1—H1O	0.8500
Cd1—O2	2.3013 (14)	C1—C2	1.504 (3)
Cd1—O4	2.2386 (16)	C1—H1A	0.9601
Cd1—O1W	2.2731 (15)	C1—H1B	0.9599
Cd1—O2W	2.3245 (14)	C2—O2	1.252 (2)
Cd1—O2ⁱ	2.5937 (14)	C2—O3	1.253 (2)
Cd1—O3ⁱ	2.3379 (17)	O2—Cd1ⁱⁱ	2.5937 (14)
O1W—H1W	0.8500	O4—S1	1.4543 (16)
O1W—H2W	0.8500	S1—O5	1.4468 (16)
O2W—H3W	0.8500	O3W—H5W	0.8500
O2W—H4W	0.8500	O3—Cd1ⁱⁱ	2.3379 (17)
O1—C1	1.410 (2)

O4—Cd1—O1W	87.27 (7)	Cd1—O2W—H3W	110.5
O4—Cd1—O2	93.73 (5)	H4W—O2W—H3W	102.0
O1W—Cd1—O2	152.03 (5)	C1—O1—Cd1	117.86 (11)
O4—Cd1—O2W	170.76 (6)	C1—O1—H1O	107.6
O1W—Cd1—O2W	87.65 (6)	Cd1—O1—H1O	132.6
O2—Cd1—O2W	94.38 (5)	O1—C1—C2	109.54 (15)
O4—Cd1—O3ⁱ	92.14 (8)	O1—C1—H1A	109.8
O1W—Cd1—O3ⁱ	127.91 (5)	C2—C1—H1A	109.8
O2—Cd1—O3ⁱ	80.02 (5)	O1—C1—H1B	109.7
O2W—Cd1—O3ⁱ	84.91 (6)	C2—C1—H1B	109.8
O4—Cd1—O1	97.23 (7)	H1A—C1—H1B	108.2
O1W—Cd1—O1	83.68 (5)	O2—C2—O3	121.68 (18)
O2—Cd1—O1	68.45 (5)	O2—C2—C1	120.37 (17)
O2W—Cd1—O1	89.87 (6)	O3—C2—C1	117.95 (17)
O3ⁱ—Cd1—O1	147.55 (5)	C2—O2—Cd1	120.32 (12)
O4—Cd1—O2ⁱ	81.27 (6)	C2—O2—Cd1ⁱⁱ	86.96 (11)
O1W—Cd1—O2ⁱ	76.21 (5)	Cd1—O2—Cd1ⁱⁱ	150.69 (6)
O2—Cd1—O2ⁱ	131.594 (18)	S1—O4—Cd1	139.34 (10)
O2W—Cd1—O2ⁱ	90.02 (5)	O5—S1—O5ⁱⁱⁱ	108.34 (13)
O3ⁱ—Cd1—O2ⁱ	52.37 (4)	O5—S1—O4ⁱⁱⁱ	109.84 (12)
O1—Cd1—O2ⁱ	159.88 (5)	O5ⁱⁱⁱ—S1—O4ⁱⁱⁱ	112.05 (13)
Cd1—O1W—H2W	113.6	O5—S1—O4	112.05 (13)
Cd1—O1W—H1W	128.1	O5ⁱⁱⁱ—S1—O4	109.84 (12)
H2W—O1W—H1W	109.5	O4ⁱⁱⁱ—S1—O4	104.74 (14)
Cd1—O2W—H4W	109.2	C2—O3—Cd1ⁱⁱ	98.98 (12)

O4—Cd1—O1—C1	74.77 (15)	O2ⁱ—Cd1—O2—C2	−163.19 (14)
O1W—Cd1—O1—C1	161.19 (16)	O4—Cd1—O2—Cd1ⁱⁱ	74.85 (14)
O2—Cd1—O1—C1	−16.41 (14)	O1W—Cd1—O2—Cd1ⁱⁱ	166.05 (11)
O2W—Cd1—O1—C1	−111.16 (15)	O2W—Cd1—O2—Cd1ⁱⁱ	−100.72 (13)
O3ⁱ—Cd1—O1—C1	−30.9 (2)	O3ⁱ—Cd1—O2—Cd1ⁱⁱ	−16.67 (13)
O2ⁱ—Cd1—O1—C1	159.13 (13)	O1—Cd1—O2—Cd1ⁱⁱ	171.15 (15)
Cd1—O1—C1—C2	16.3 (2)	O2ⁱ—Cd1—O2—Cd1ⁱⁱ	−6.79 (12)
O1—C1—C2—O2	−3.4 (2)	O1W—Cd1—O4—S1	−144.9 (2)
O1—C1—C2—O3	177.33 (17)	O2—Cd1—O4—S1	7.1 (2)
O3—C2—O2—Cd1	167.52 (14)	O3ⁱ—Cd1—O4—S1	87.2 (2)
C1—C2—O2—Cd1	−11.7 (2)	O1—Cd1—O4—S1	−61.6 (2)
O3—C2—O2—Cd1ⁱⁱ	−1.16 (18)	O2ⁱ—Cd1—O4—S1	138.6 (2)
C1—C2—O2—Cd1ⁱⁱ	179.64 (15)	Cd1—O4—S1—O5	−57.4 (2)
O4—Cd1—O2—C2	−81.55 (15)	Cd1—O4—S1—O5ⁱⁱⁱ	63.0 (2)
O1W—Cd1—O2—C2	9.6 (2)	Cd1—O4—S1—O4ⁱⁱⁱ	−176.5 (3)
O2W—Cd1—O2—C2	102.89 (14)	O2—C2—O3—Cd1ⁱⁱ	1.3 (2)
O3ⁱ—Cd1—O2—C2	−173.07 (15)	C1—C2—O3—Cd1ⁱⁱ	−179.48 (13)
O1—Cd1—O2—C2	14.76 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2W^iv	0.85	1.94	2.784 (2)	170
O1W—H2w···O3^v	0.85	1.88	2.723 (2)	172
O2W—H3W···O3W	0.85	1.88	2.720 (2)	172
O2W—H4W···O5ⁱ	0.85	1.82	2.648 (2)	162
O1—H1O···O5^vi	0.85	1.81	2.659 (2)	175
O3W—H5W···O4^vii	0.85	2.25	2.813 (3)	124

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

Experimental details

Crystal data
Chemical formula	[Cd₂(C₂H₃O₃)₂(SO₄)(H₂O)₄]·H₂O
M_r	561.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	13.5750 (3), 8.5777 (1), 13.7734 (3)
β (°)	107.528 (2)
V (Å³)	1529.34 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.99
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Kuma KM4 CCD κ-geometry diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.388, 0.550
No. of measured, independent and observed [I > 2σ(I)] reflections	8842, 1710, 1602
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.038, 1.13
No. of reflections	1710
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1989) and Mercury (Bruno et al., 2002).

Selected bond lengths (Å) top

Cd1—O1	2.3584 (14)	Cd1—O2W	2.3245 (14)
Cd1—O2	2.3013 (14)	Cd1—O2ⁱ	2.5937 (14)
Cd1—O4	2.2386 (16)	Cd1—O3ⁱ	2.3379 (17)
Cd1—O1W	2.2731 (15)

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2Wⁱⁱ	0.85	1.94	2.784 (2)	170
O1W—H2w···O3ⁱⁱⁱ	0.85	1.88	2.723 (2)	172
O2W—H3W···O3W	0.85	1.88	2.720 (2)	172
O2W—H4W···O5ⁱ	0.85	1.82	2.648 (2)	162
O1—H1O···O5^iv	0.85	1.81	2.659 (2)	175
O3W—H5W···O4^v	0.85	2.25	2.813 (3)	124

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

Acknowledgements

This work was funded in part by the Ministry of Science and Technological Development of the Republic of Serbia (Project No. 142008). The authors are grateful to Dr Dušanka D. Radanović (Institute of Chemistry, Technology and Metallurgy, University of Belgrade) for her valuable suggestions.

References

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