Poly[penta-μ-aqua-μ6-methyl­ene­disulfonato-μ5-methyl­enedisulfonato-tetra­sodium(I)]

Cao, D.-D.; Zhang, Z.-C.

doi:10.1107/S1600536808014037

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m815

doi:10.1107/S1600536808014037

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Poly[penta-μ-aqua-μ₆-methylenedisulfonato-μ₅-methylenedisulfonato-tetrasodium(I)]

Dan-Dan Cao ^a and Zai-Chao Zhang ^a ^*

^aDepartment of Chemistry, Huaiyin Teachers College, 111 West Changjiang Road, Huaian 223300, Jiangsu, People's Republic of China
^*Correspondence e-mail: overloadzz@hotmail.com

(Received 1 May 2008; accepted 10 May 2008; online 17 May 2008)

The title compound, [Na₄(CH₂O₆S₂)₂(H₂O)₅]_n, was crystallized from an aqueous solution. The sodium ions are surrounded and bridged by O atoms from coordinated water molecules and sulfonate ions in a three-dimensional neutral network. The crystal structure is also stabilized by an intricate system of hydrogen bonds.

Related literature

The supramolecular chemistry of the sulfonate group in extended solids constructed by cooperative coordination and other weak intermolecular interactions, as well as the structural and functional properties of Ba²⁺ and Ag⁺ sulfonates, has been reviewed by Côté & Shimizu (2003 ). For a review of the structural chemistry and properties of metal arenesulfonates, see: Cai (2004 ). For related literature, see: Li et al. (2008 ); Mi et al. (2007 ); Videnova-Adrabinska (2007 ).

Experimental

Crystal data

[Na₄(CH₂O₆S₂)₂(H₂O)₅]
M_r = 530.33
Triclinic, $[P \overline 1]$
a = 8.7758 (7) Å
b = 9.5339 (7) Å
c = 10.7878 (8) Å
α = 81.425 (2)°
β = 74.545 (2)°
γ = 87.227 (2)°
V = 860.19 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 296 (2) K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker SMART APEX2 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.81, T_max = 0.84
10702 measured reflections
3321 independent reflections
3050 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.093
S = 1.00
3321 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O8ⁱ	0.97	1.93	2.868 (2)	163
O13—H13B⋯O5ⁱⁱ	0.97	1.87	2.824 (2)	166
O14—H14A⋯O9ⁱⁱⁱ	0.97	2.00	2.871 (2)	148
O15—H15B⋯O3^iv	0.97	1.97	2.877 (2)	155
O16—H16A⋯O9ⁱⁱⁱ	0.97	1.87	2.794 (2)	158
O16—H16B⋯O12	0.97	2.18	3.034 (3)	147
O17—H17A⋯O4^v	0.97	2.17	2.879 (3)	129
O17—H17B⋯O12^vi	0.97	2.10	2.918 (3)	141
Symmetry codes: (i) x-1, y, z; (ii) x, y-1, z; (iii) -x+2, -y+1, -z+1; (iv) x+1, y, z; (v) -x, -y+2, -z+2; (vi) x-1, y+1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014037/zl2114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014037/zl2114Isup2.hkl

checkCIF report

Comment top

Due to the weak coordination strength of monosulfonate ions, most metal complexes of these ligands obtained from aqueous solution are water-coordinated metal sulfonate salts, and the coordination chemistry of the sulfonate ion has been less well investigated in comparison with other organic acidato anions such as carbonates and phosfonates (Côté & Shimizu, 2003). However, by employing disulfonates, which can provide multiple potentially chelating coordination sites, stable networks sustained by sulfonate-metal interactions can be obtained with various dimensionalities (Cai, 2004; Li et al., 2008; Mi et al., 2007; Videnova-Adrabinska, 2007).

The present structral study of the title compound {Na₄(mds)₂(H₂O) ₅}_n (I) reveals the existence of sulfonate-sodium interactions. The asymmetric unit consists of four sodium ions, five coordinated µ₂-H₂O molecules and two CH₃(SO₃)₂^2- ligands (Fig. 1). Of the four sodium ions, Na1, Na2 and Na4 are six-coordinated. Na3 is coordinated by five oxygen atoms (O2^vi, O13, O14, O16 and O16^iv). The Na—O bond lengths fall in the range of 2.334 (2) to 2.5609 (18) Å. All sulfonate oxygens are deprotonated. Three sulfonate oxygen atoms (O5, O9 and O12) are not coordinated to sodium atoms and do instead act as hydrogen bonding acceptors towards coordinated water molecules. All other hydrogen bonds are from water molecules towards Na coordinated sulfonate oxygen atoms (Table 1).

Each sodium atom is bridged to an equivalent neighbour, forming {Na₂O₂} dimers with inversion centers in the middle. O1 and O7 connect the dimers of Na1 and Na2 into an infinite chain. Na1-Na2 chains are joined to dimers of Na3 and Na4 through intricate bridges of oxygens from sulfonate groups and coordinated waters, and O—S—O connectivities, thus generating a three-dimensional network (Fig. 2).

Related literature top

The supramolecular chemistry of the sulfonate group in extended solids constructed by cooperative coordination and other weak intermolecular interactions, as well as the structural and functional properties of Ba²⁺ and Ag⁺ sulfonates, has been reviewed by Côté & Shimizu (2003). For a review of the structural chemistry and properties of metal arenesulfonates, see: Cai (2004).

For related literature, see: Bruker (1999); Li et al. (2008); Mi et al. (2007); Videnova-Adrabinska (2007).

Experimental top

An 1 mol L^-1 NaOH aqueous solution was droped into one of mdsH₂ (0.14 g, 1 mmol in 20 ml H₂O) until the pH value of the solution reached 7 to 9. Slow evaporation for several days yieled colorless prismlike crystals of the title compound. Anal. Calcd for C₂H₁₄O₁₇Na₄S₄ (530.34): C 4.51, H 2.69%; Found: C 4.53, H 2.66%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of I with atom labels and 50% probability displacement ellipsoids for non-H atoms. H atoms attached to carbon atoms are omitted for clarity. Symmetry codes: (i) -1+x, y, z; (ii) 1+x, y, z; (iii) -x, 2-y, 2-z. (iv) 1-x, 1-y, 1-z; (v) 1-x, 1-y, 2-z; (vi) 1-x, 2-y, 1-z; (vii) 1-x, 2-y, 2-z; (viii) 2-x, 2-y, 1-z;
	Fig. 2. Packing diagram of compound I. Na—O bond is showed by black line, H atoms are omitted for clarity.

Poly[penta-µ-aqua-µ₆-methylenedisulfonato-µ₅-methylenedisulfonato- tetrasodium(I)] top

Crystal data top

[Na₄(CH₂O₆S₂)₂(H₂O)₅]	Z = 2
M_r = 530.33	F(000) = 540
Triclinic, P1	D_x = 2.048 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7758 (7) Å	Cell parameters from 202 reflections
b = 9.5339 (7) Å	θ = 2.6–21.1°
c = 10.7878 (8) Å	µ = 0.74 mm⁻¹
α = 81.425 (2)°	T = 296 K
β = 74.545 (2)°	Prismlike, colourless
γ = 87.227 (2)°	0.30 × 0.25 × 0.25 mm
V = 860.19 (11) Å³

Data collection top

Bruker SMART APEX2 diffractometer	3321 independent reflections
Radiation source: fine-focus sealed tube	3050 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.81, T_max = 0.84	k = −11→11
10702 measured reflections	l = −13→13

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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0428P)² + 0.7023P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
3321 reflections	Δρ_max = 0.47 e Å⁻³
244 parameters	Δρ_min = −0.56 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), F*=F(1+0.002xF²(sin(2θ))^-0.25
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00025 (5)

Crystal data top

[Na₄(CH₂O₆S₂)₂(H₂O)₅]	γ = 87.227 (2)°
M_r = 530.33	V = 860.19 (11) Å³
Triclinic, P1	Z = 2
a = 8.7758 (7) Å	Mo Kα radiation
b = 9.5339 (7) Å	µ = 0.74 mm⁻¹
c = 10.7878 (8) Å	T = 296 K
α = 81.425 (2)°	0.30 × 0.25 × 0.25 mm
β = 74.545 (2)°

Data collection top

Bruker SMART APEX2 diffractometer	3321 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3050 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.84	R_int = 0.022
10702 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.00	Δρ_max = 0.47 e Å⁻³
3321 reflections	Δρ_min = −0.56 e Å⁻³
244 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.4436 (2)	1.0561 (2)	0.8451 (2)	0.0189 (4)
H1A	0.4297	0.9743	0.9121	0.023*
H1B	0.5440	1.0983	0.8394	0.023*
C2	0.9094 (3)	0.4391 (2)	0.8842 (2)	0.0217 (4)
H2A	1.0010	0.3786	0.8863	0.026*
H2B	0.8798	0.4796	0.9647	0.026*
Na1	0.55562 (10)	0.66480 (9)	0.86815 (9)	0.0253 (2)
Na2	0.85901 (11)	0.87496 (9)	0.59357 (9)	0.0268 (2)
Na3	0.54875 (13)	0.67712 (11)	0.52620 (12)	0.0421 (3)
Na4	0.08149 (10)	0.88263 (9)	0.88189 (8)	0.0240 (2)
O1	0.57149 (19)	0.87897 (16)	0.69116 (15)	0.0261 (4)
O2	0.5103 (2)	1.11297 (17)	0.59433 (15)	0.0278 (4)
O3	0.29960 (18)	0.94639 (19)	0.70181 (15)	0.0287 (4)
O4	0.3169 (2)	1.21026 (19)	1.01825 (16)	0.0334 (4)
O5	0.3122 (2)	1.30241 (17)	0.79628 (18)	0.0353 (4)
O6	0.13991 (19)	1.11171 (17)	0.91904 (17)	0.0290 (4)
O7	0.82527 (18)	0.65404 (17)	0.73482 (15)	0.0259 (4)
O8	1.06688 (19)	0.66657 (17)	0.80084 (17)	0.0286 (4)
O9	1.0542 (2)	0.51641 (18)	0.64174 (16)	0.0325 (4)
O10	0.6110 (2)	0.41828 (18)	0.9018 (2)	0.0366 (4)
O11	0.7435 (2)	0.21996 (18)	0.99171 (18)	0.0352 (4)
O12	0.7916 (2)	0.27615 (19)	0.75861 (17)	0.0367 (4)
O13	0.3962 (2)	0.59164 (17)	0.74448 (17)	0.0316 (4)
H13A	0.2921	0.6356	0.7642	0.038*
H13B	0.3854	0.4893	0.7581	0.038*
O14	0.8268 (2)	0.7545 (2)	0.42866 (17)	0.0361 (4)
H14A	0.8993	0.6746	0.4159	0.043*
H14B	0.8388	0.8170	0.3470	0.043*
O15	1.1401 (2)	0.88559 (19)	0.51526 (17)	0.0338 (4)
H15A	1.1832	0.8177	0.4560	0.041*
H15B	1.1927	0.8759	0.5846	0.041*
O16	0.6570 (2)	0.43211 (19)	0.54436 (17)	0.0355 (4)
H16A	0.7614	0.4243	0.4860	0.043*
H16B	0.6587	0.3945	0.6326	0.043*
O17	−0.1158 (2)	0.97729 (18)	0.77543 (16)	0.0308 (4)
H17A	−0.2173	0.9697	0.8396	0.037*
H17B	−0.0951	1.0776	0.7471	0.037*
S1	0.45658 (6)	0.99467 (5)	0.69417 (5)	0.01723 (13)
S2	0.29091 (6)	1.18145 (5)	0.89699 (5)	0.02035 (14)
S3	0.96766 (6)	0.58056 (5)	0.75349 (5)	0.01822 (14)
S4	0.75141 (6)	0.33016 (5)	0.88177 (5)	0.01945 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0163 (10)	0.0213 (10)	0.0196 (9)	−0.0008 (8)	−0.0062 (8)	−0.0015 (8)
C2	0.0201 (11)	0.0206 (10)	0.0249 (10)	−0.0059 (8)	−0.0097 (9)	0.0031 (8)
Na1	0.0236 (5)	0.0240 (5)	0.0298 (5)	−0.0020 (3)	−0.0086 (4)	−0.0049 (4)
Na2	0.0269 (5)	0.0246 (5)	0.0278 (5)	−0.0050 (4)	−0.0061 (4)	−0.0010 (4)
Na3	0.0352 (6)	0.0290 (5)	0.0592 (7)	−0.0041 (4)	−0.0151 (5)	0.0090 (5)
Na4	0.0222 (5)	0.0225 (4)	0.0275 (4)	−0.0026 (3)	−0.0064 (4)	−0.0035 (3)
O1	0.0236 (8)	0.0227 (8)	0.0298 (8)	0.0048 (6)	−0.0047 (6)	−0.0026 (6)
O2	0.0333 (9)	0.0226 (8)	0.0217 (8)	0.0005 (7)	−0.0009 (7)	0.0034 (6)
O3	0.0179 (8)	0.0449 (10)	0.0253 (8)	−0.0059 (7)	−0.0055 (6)	−0.0102 (7)
O4	0.0336 (10)	0.0408 (10)	0.0289 (9)	−0.0089 (8)	−0.0056 (7)	−0.0161 (8)
O5	0.0451 (11)	0.0193 (8)	0.0410 (10)	0.0027 (7)	−0.0139 (8)	0.0013 (7)
O6	0.0177 (8)	0.0302 (9)	0.0412 (9)	−0.0024 (7)	−0.0055 (7)	−0.0149 (7)
O7	0.0199 (8)	0.0258 (8)	0.0296 (8)	0.0012 (6)	−0.0064 (6)	0.0031 (6)
O8	0.0241 (8)	0.0224 (8)	0.0401 (9)	−0.0078 (6)	−0.0080 (7)	−0.0050 (7)
O9	0.0320 (9)	0.0296 (9)	0.0299 (9)	−0.0016 (7)	0.0049 (7)	−0.0088 (7)
O10	0.0195 (8)	0.0249 (9)	0.0626 (12)	−0.0013 (7)	−0.0085 (8)	−0.0010 (8)
O11	0.0371 (10)	0.0292 (9)	0.0376 (9)	−0.0137 (8)	−0.0151 (8)	0.0151 (7)
O12	0.0471 (11)	0.0332 (10)	0.0309 (9)	−0.0113 (8)	−0.0073 (8)	−0.0097 (7)
O13	0.0273 (9)	0.0237 (8)	0.0458 (10)	−0.0008 (7)	−0.0128 (8)	−0.0051 (7)
O14	0.0411 (11)	0.0366 (10)	0.0339 (9)	0.0084 (8)	−0.0144 (8)	−0.0096 (8)
O15	0.0280 (9)	0.0371 (10)	0.0331 (9)	0.0018 (7)	−0.0063 (7)	0.0011 (7)
O16	0.0296 (9)	0.0405 (10)	0.0330 (9)	−0.0025 (8)	−0.0060 (7)	0.0020 (8)
O17	0.0318 (9)	0.0290 (9)	0.0328 (9)	−0.0004 (7)	−0.0097 (7)	−0.0061 (7)
S1	0.0149 (3)	0.0180 (3)	0.0175 (2)	−0.00013 (19)	−0.00291 (19)	−0.00080 (19)
S2	0.0192 (3)	0.0183 (3)	0.0247 (3)	−0.0022 (2)	−0.0057 (2)	−0.0062 (2)
S3	0.0165 (3)	0.0157 (3)	0.0210 (3)	−0.00201 (19)	−0.00272 (19)	−0.00110 (19)
S4	0.0192 (3)	0.0153 (3)	0.0240 (3)	−0.00369 (19)	−0.0073 (2)	0.00080 (19)

Geometric parameters (Å, º) top

C1—S2	1.783 (2)	Na4—O17	2.3942 (19)
C1—S1	1.785 (2)	Na4—O11ⁱⁱ	2.3972 (19)
C1—H1A	0.9700	Na4—O6^viii	2.4881 (18)
C1—H1B	0.9700	Na4—Na4^viii	3.6050 (17)
C2—S4	1.780 (2)	Na4—Na2^vii	4.1000 (13)
C2—S3	1.785 (2)	O1—S1	1.4562 (16)
C2—H2A	0.9700	O2—S1	1.4398 (16)
C2—H2B	0.9700	O2—Na3^v	2.3339 (18)
Na1—O4ⁱ	2.3382 (19)	O3—S1	1.4512 (16)
Na1—O13	2.3644 (19)	O4—S2	1.4528 (17)
Na1—O10	2.3709 (19)	O4—Na1ⁱ	2.3382 (19)
Na1—O7	2.4260 (18)	O5—S2	1.4437 (18)
Na1—O10ⁱⁱ	2.552 (2)	O6—S2	1.4577 (17)
Na1—O1	2.5607 (18)	O6—Na4^viii	2.4881 (18)
Na1—O11ⁱⁱ	2.913 (2)	O7—S3	1.4492 (16)
Na1—S4ⁱⁱ	3.2699 (10)	O8—S3	1.4569 (16)
Na1—Na3	3.6898 (15)	O8—Na4ⁱⁱⁱ	2.3763 (18)
Na1—Na2	3.7975 (13)	O9—S3	1.4460 (16)
Na1—Na1ⁱⁱ	3.8822 (18)	O10—S4	1.4432 (17)
Na2—O14	2.3389 (19)	O10—Na1ⁱⁱ	2.552 (2)
Na2—O17ⁱⁱⁱ	2.3816 (19)	O11—S4	1.4515 (17)
Na2—O15	2.3866 (19)	O11—Na4ⁱⁱ	2.3972 (19)
Na2—O7	2.3893 (18)	O11—Na1ⁱⁱ	2.913 (2)
Na2—O15^iv	2.4057 (19)	O12—S4	1.4462 (17)
Na2—O1	2.4623 (18)	O13—H13A	0.9700
Na2—Na2^iv	3.5152 (18)	O13—H13B	0.9700
Na2—Na3	3.6688 (15)	O14—H14A	0.9700
Na2—Na4ⁱⁱⁱ	4.1000 (13)	O14—H14B	0.9700
Na3—O2^v	2.3339 (18)	O15—Na2^iv	2.4057 (19)
Na3—O13	2.420 (2)	O15—H15A	0.9700
Na3—O16^vi	2.465 (2)	O15—H15B	0.9700
Na3—O16	2.479 (2)	O16—Na3^vi	2.465 (2)
Na3—O14	2.486 (2)	O16—H16A	0.9700
Na3—O1	2.856 (2)	O16—H16B	0.9700
Na3—Na3^vi	3.683 (2)	O17—Na2^vii	2.3816 (19)
Na4—O3	2.3635 (18)	O17—H17A	0.9700
Na4—O8^vii	2.3763 (18)	O17—H17B	0.9700
Na4—O6	2.3816 (18)	S4—Na1ⁱⁱ	3.2699 (10)

S2—C1—S1	117.32 (11)	O13—Na3—Na2	100.89 (6)
S2—C1—H1A	108.0	O16^vi—Na3—Na2	172.47 (6)
S1—C1—H1A	108.0	O16—Na3—Na2	101.22 (6)
S2—C1—H1B	108.0	O14—Na3—Na2	39.03 (5)
S1—C1—H1B	108.0	O1—Na3—Na2	42.08 (4)
H1A—C1—H1B	107.2	O2^v—Na3—Na3^vi	123.29 (7)
S4—C2—S3	117.32 (12)	O13—Na3—Na3^vi	81.18 (5)
S4—C2—H2A	108.0	O16^vi—Na3—Na3^vi	41.99 (5)
S3—C2—H2A	108.0	O16—Na3—Na3^vi	41.70 (5)
S4—C2—H2B	108.0	O14—Na3—Na3^vi	116.43 (7)
S3—C2—H2B	108.0	O1—Na3—Na3^vi	151.94 (6)
H2A—C2—H2B	107.2	Na2—Na3—Na3^vi	142.60 (5)
O4ⁱ—Na1—O13	166.18 (8)	O2^v—Na3—Na1	121.20 (6)
O4ⁱ—Na1—O10	111.23 (8)	O13—Na3—Na1	38.99 (5)
O13—Na1—O10	82.42 (7)	O16^vi—Na3—Na1	124.37 (6)
O4ⁱ—Na1—O7	80.23 (6)	O16—Na3—Na1	85.67 (5)
O13—Na1—O7	105.45 (7)	O14—Na3—Na1	96.42 (5)
O10—Na1—O7	78.58 (6)	O1—Na3—Na1	43.79 (4)
O4ⁱ—Na1—O10ⁱⁱ	81.40 (7)	Na2—Na3—Na1	62.14 (3)
O13—Na1—O10ⁱⁱ	100.65 (7)	Na3^vi—Na3—Na1	109.09 (4)
O10—Na1—O10ⁱⁱ	75.97 (7)	O3—Na4—O8^vii	88.53 (6)
O7—Na1—O10ⁱⁱ	140.45 (7)	O3—Na4—O6	78.83 (6)
O4ⁱ—Na1—O1	91.18 (7)	O8^vii—Na4—O6	167.28 (7)
O13—Na1—O1	78.18 (6)	O3—Na4—O17	95.65 (7)
O10—Na1—O1	142.97 (7)	O8^vii—Na4—O17	87.86 (6)
O7—Na1—O1	76.66 (6)	O6—Na4—O17	92.01 (6)
O10ⁱⁱ—Na1—O1	138.45 (6)	O3—Na4—O11ⁱⁱ	90.43 (7)
O4ⁱ—Na1—O11ⁱⁱ	88.36 (6)	O8^vii—Na4—O11ⁱⁱ	92.18 (7)
O13—Na1—O11ⁱⁱ	82.51 (6)	O6—Na4—O11ⁱⁱ	89.29 (7)
O10—Na1—O11ⁱⁱ	120.57 (6)	O17—Na4—O11ⁱⁱ	173.92 (7)
O7—Na1—O11ⁱⁱ	160.46 (6)	O3—Na4—O6^viii	163.22 (7)
O10ⁱⁱ—Na1—O11ⁱⁱ	51.33 (5)	O8^vii—Na4—O6^viii	108.07 (6)
O1—Na1—O11ⁱⁱ	87.86 (5)	O6—Na4—O6^viii	84.51 (6)
O4ⁱ—Na1—S4ⁱⁱ	85.44 (5)	O17—Na4—O6^viii	82.85 (6)
O13—Na1—S4ⁱⁱ	90.84 (5)	O11ⁱⁱ—Na4—O6^viii	91.36 (7)
O10—Na1—S4ⁱⁱ	97.33 (5)	O3—Na4—Na4^viii	122.20 (6)
O7—Na1—S4ⁱⁱ	162.36 (5)	O8^vii—Na4—Na4^viii	149.15 (6)
O10ⁱⁱ—Na1—S4ⁱⁱ	25.03 (4)	O6—Na4—Na4^viii	43.39 (4)
O1—Na1—S4ⁱⁱ	114.07 (5)	O17—Na4—Na4^viii	86.40 (5)
O11ⁱⁱ—Na1—S4ⁱⁱ	26.35 (3)	O11ⁱⁱ—Na4—Na4^viii	90.47 (6)
O4ⁱ—Na1—Na3	135.93 (6)	O6^viii—Na4—Na4^viii	41.12 (4)
O13—Na1—Na3	40.08 (5)	O3—Na4—Na2^vii	81.93 (5)
O10—Na1—Na3	95.38 (6)	O8^vii—Na4—Na2^vii	60.20 (5)
O7—Na1—Na3	71.14 (5)	O6—Na4—Na2^vii	115.90 (5)
O10ⁱⁱ—Na1—Na3	140.70 (6)	O17—Na4—Na2^vii	30.76 (4)
O1—Na1—Na3	50.52 (4)	O11ⁱⁱ—Na4—Na2^vii	151.34 (6)
O11ⁱⁱ—Na1—Na3	108.04 (5)	O6^viii—Na4—Na2^vii	103.86 (5)
S4ⁱⁱ—Na1—Na3	126.48 (3)	Na4^viii—Na4—Na2^vii	117.00 (4)
O4ⁱ—Na1—Na2	78.15 (5)	S1—O1—Na2	131.01 (10)
O13—Na1—Na2	98.51 (5)	S1—O1—Na1	125.55 (9)
O10—Na1—Na2	114.45 (6)	Na2—O1—Na1	98.21 (6)
O7—Na1—Na2	37.60 (4)	S1—O1—Na3	114.45 (9)
O10ⁱⁱ—Na1—Na2	159.32 (5)	Na2—O1—Na3	86.90 (5)
O1—Na1—Na2	39.92 (4)	Na1—O1—Na3	85.68 (5)
O11ⁱⁱ—Na1—Na2	124.52 (4)	S1—O2—Na3^v	148.85 (11)
S4ⁱⁱ—Na1—Na2	147.72 (3)	S1—O3—Na4	131.30 (9)
Na3—Na1—Na2	58.66 (3)	S2—O4—Na1ⁱ	150.62 (11)
O4ⁱ—Na1—Na1ⁱⁱ	97.06 (6)	S2—O6—Na4	130.70 (10)
O13—Na1—Na1ⁱⁱ	92.35 (5)	S2—O6—Na4^viii	123.77 (9)
O10—Na1—Na1ⁱⁱ	39.63 (5)	Na4—O6—Na4^viii	95.49 (6)
O7—Na1—Na1ⁱⁱ	112.71 (5)	S3—O7—Na2	116.86 (9)
O10ⁱⁱ—Na1—Na1ⁱⁱ	36.33 (4)	S3—O7—Na1	134.13 (9)
O1—Na1—Na1ⁱⁱ	168.41 (6)	Na2—O7—Na1	104.11 (6)
O11ⁱⁱ—Na1—Na1ⁱⁱ	84.25 (4)	S3—O8—Na4ⁱⁱⁱ	144.64 (11)
S4ⁱⁱ—Na1—Na1ⁱⁱ	58.81 (2)	S4—O10—Na1	135.88 (11)
Na3—Na1—Na1ⁱⁱ	124.47 (4)	S4—O10—Na1ⁱⁱ	106.52 (10)
Na2—Na1—Na1ⁱⁱ	150.21 (4)	Na1—O10—Na1ⁱⁱ	104.03 (7)
O14—Na2—O17ⁱⁱⁱ	174.53 (8)	S4—O11—Na4ⁱⁱ	136.83 (11)
O14—Na2—O15	94.48 (7)	S4—O11—Na1ⁱⁱ	90.67 (9)
O17ⁱⁱⁱ—Na2—O15	87.48 (7)	Na4ⁱⁱ—O11—Na1ⁱⁱ	117.01 (7)
O14—Na2—O7	88.36 (7)	Na1—O13—Na3	100.93 (7)
O17ⁱⁱⁱ—Na2—O7	86.24 (6)	Na1—O13—H13A	111.6
O15—Na2—O7	101.40 (7)	Na3—O13—H13A	111.6
O14—Na2—O15^iv	99.06 (7)	Na1—O13—H13B	111.6
O17ⁱⁱⁱ—Na2—O15^iv	86.17 (7)	Na3—O13—H13B	111.6
O15—Na2—O15^iv	85.64 (7)	H13A—O13—H13B	109.4
O7—Na2—O15^iv	169.40 (7)	Na2—O14—Na3	98.94 (7)
O14—Na2—O1	91.38 (7)	Na2—O14—H14A	112.0
O17ⁱⁱⁱ—Na2—O1	86.73 (6)	Na3—O14—H14A	112.0
O15—Na2—O1	174.12 (7)	Na2—O14—H14B	112.0
O7—Na2—O1	79.24 (6)	Na3—O14—H14B	112.0
O15^iv—Na2—O1	92.95 (6)	H14A—O14—H14B	109.7
O14—Na2—Na2^iv	99.26 (6)	Na2—O15—Na2^iv	94.36 (7)
O17ⁱⁱⁱ—Na2—Na2^iv	85.67 (6)	Na2—O15—H15A	112.9
O15—Na2—Na2^iv	43.03 (5)	Na2^iv—O15—H15A	112.9
O7—Na2—Na2^iv	143.79 (6)	Na2—O15—H15B	112.9
O15^iv—Na2—Na2^iv	42.61 (5)	Na2^iv—O15—H15B	112.9
O1—Na2—Na2^iv	135.28 (6)	H15A—O15—H15B	110.3
O14—Na2—Na3	42.03 (5)	Na3^vi—O16—Na3	96.30 (7)
O17ⁱⁱⁱ—Na2—Na3	134.64 (6)	Na3^vi—O16—H16A	112.5
O15—Na2—Na3	134.80 (6)	Na3—O16—H16A	112.5
O7—Na2—Na3	71.87 (5)	Na3^vi—O16—H16B	112.5
O15^iv—Na2—Na3	108.79 (6)	Na3—O16—H16B	112.5
O1—Na2—Na3	51.02 (5)	H16A—O16—H16B	110.0
Na2^iv—Na2—Na3	134.34 (4)	Na2^vii—O17—Na4	118.30 (8)
O14—Na2—Na1	96.33 (6)	Na2^vii—O17—H17A	107.7
O17ⁱⁱⁱ—Na2—Na1	78.85 (5)	Na4—O17—H17A	107.7
O15—Na2—Na1	137.49 (5)	Na2^vii—O17—H17B	107.7
O7—Na2—Na1	38.29 (4)	Na4—O17—H17B	107.7
O15^iv—Na2—Na1	132.48 (5)	H17A—O17—H17B	107.1
O1—Na2—Na1	41.87 (4)	O2—S1—O3	113.99 (10)
Na2^iv—Na2—Na1	164.30 (4)	O2—S1—O1	113.19 (9)
Na3—Na2—Na1	59.20 (3)	O3—S1—O1	112.55 (10)
O14—Na2—Na4ⁱⁱⁱ	146.42 (6)	O2—S1—C1	106.32 (10)
O17ⁱⁱⁱ—Na2—Na4ⁱⁱⁱ	30.94 (5)	O3—S1—C1	106.12 (9)
O15—Na2—Na4ⁱⁱⁱ	66.79 (5)	O1—S1—C1	103.62 (10)
O7—Na2—Na4ⁱⁱⁱ	69.72 (5)	O5—S2—O4	114.42 (11)
O15^iv—Na2—Na4ⁱⁱⁱ	106.56 (5)	O5—S2—O6	112.59 (11)
O1—Na2—Na4ⁱⁱⁱ	108.29 (5)	O4—S2—O6	111.20 (10)
Na2^iv—Na2—Na4ⁱⁱⁱ	85.84 (3)	O5—S2—C1	107.49 (10)
Na3—Na2—Na4ⁱⁱⁱ	139.39 (3)	O4—S2—C1	102.79 (10)
Na1—Na2—Na4ⁱⁱⁱ	82.22 (3)	O6—S2—C1	107.57 (10)
O2^v—Na3—O13	123.40 (7)	O9—S3—O7	113.00 (10)
O2^v—Na3—O16^vi	86.03 (7)	O9—S3—O8	112.97 (10)
O13—Na3—O16^vi	85.41 (7)	O7—S3—O8	112.99 (10)
O2^v—Na3—O16	152.16 (8)	O9—S3—C2	106.55 (10)
O13—Na3—O16	81.48 (6)	O7—S3—C2	107.55 (10)
O16^vi—Na3—O16	83.70 (7)	O8—S3—C2	102.91 (10)
O2^v—Na3—O14	83.66 (7)	O10—S4—O12	113.60 (12)
O13—Na3—O14	134.23 (8)	O10—S4—O11	111.27 (11)
O16^vi—Na3—O14	136.85 (8)	O12—S4—O11	113.07 (11)
O16—Na3—O14	86.32 (7)	O10—S4—C2	106.45 (10)
O2^v—Na3—O1	79.21 (6)	O12—S4—C2	107.98 (11)
O13—Na3—O1	71.68 (6)	O11—S4—C2	103.70 (10)
O16^vi—Na3—O1	138.69 (7)	O10—S4—Na1ⁱⁱ	48.45 (8)
O16—Na3—O1	124.33 (7)	O12—S4—Na1ⁱⁱ	137.74 (8)
O14—Na3—O1	79.74 (6)	O11—S4—Na1ⁱⁱ	62.98 (8)
O2^v—Na3—Na2	87.04 (5)	C2—S4—Na1ⁱⁱ	113.81 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O8^vii	0.97	1.93	2.868 (2)	163
O13—H13B···O5^ix	0.97	1.87	2.824 (2)	166
O14—H14A···O9^x	0.97	2.00	2.871 (2)	148
O15—H15B···O3ⁱⁱⁱ	0.97	1.97	2.877 (2)	155
O16—H16A···O9^x	0.97	1.87	2.794 (2)	158
O16—H16B···O12	0.97	2.18	3.034 (3)	147
O17—H17A···O4^viii	0.97	2.17	2.879 (3)	129
O17—H17B···O12^xi	0.97	2.10	2.918 (3)	141

Symmetry codes: (iii) x+1, y, z; (vii) x−1, y, z; (viii) −x, −y+2, −z+2; (ix) x, y−1, z; (x) −x+2, −y+1, −z+1; (xi) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	[Na₄(CH₂O₆S₂)₂(H₂O)₅]
M_r	530.33
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.7758 (7), 9.5339 (7), 10.7878 (8)
α, β, γ (°)	81.425 (2), 74.545 (2), 87.227 (2)
V (Å³)	860.19 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Bruker SMART APEX2 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.81, 0.84
No. of measured, independent and observed [I > 2σ(I)] reflections	10702, 3321, 3050
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.093, 1.00
No. of reflections	3321
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.56

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O8ⁱ	0.97	1.93	2.868 (2)	162.8
O13—H13B···O5ⁱⁱ	0.97	1.87	2.824 (2)	166.1
O14—H14A···O9ⁱⁱⁱ	0.97	2.00	2.871 (2)	148.2
O15—H15B···O3^iv	0.97	1.97	2.877 (2)	154.8
O16—H16A···O9ⁱⁱⁱ	0.97	1.87	2.794 (2)	157.8
O16—H16B···O12	0.97	2.18	3.034 (3)	146.6
O17—H17A···O4^v	0.97	2.17	2.879 (3)	128.9
O17—H17B···O12^vi	0.97	2.10	2.918 (3)	140.9

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

References

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