The surprisingly elusive crystal structure of sodium metabisulfite

Carter, K.L.; Siddiquee, T.A.; Murphy, K.L.; Bennett, D.W.

doi:10.1107/S0108768104003325

The surprisingly elusive crystal structure of sodium metabisulfite

K. L. Carter, T. A. Siddiquee, K. L. Murphy and D. W. Bennett

The crystal structure of Na₂S₂O₅, a simple and common ionic compound, is reported here for the first time. The crystals form non-merohedral twins, with the twin domains related by a twofold axis which bisects the angle between the a and c axes of each unit cell. The structure was determined from a single-crystal fragment of a twinned crystal that had undergone cleavage along the twin boundary. In addition to the problems associated with twinning, space-group determination proved difficult as well, with the structure initially determined in the P2₁ space group appearing to be disordered with two rotational conformers of the metabisulfite ion occupying equivalent sites in the lattice. An analysis at low temperature provided new weak reflections which were inconsistent with the original unit cell, but indexed to the correct unit cell, allowing for space group and crystal structure determination. The apparent structure, which appeared disordered in P2₁, seems to have resulted from an apparently fortuitous superposition of two conformationally inequivalent S₂O $_5^{2-}$ anions in the asymmetric unit of the correct structure in the P2₁/n space group. The metabisulfite ions in this structure do not adopt the C_s geometry observed in previously determined crystal structures containing S₂O $_5^{2-}$ . The structures of both ions in the asymmetric unit are effectively conformational mirror images of one another with two of the O atoms on each S atom in the ion approaching an eclipsed geometry. This observation provides further evidence that the structures of sulfur-oxy anions in the solid state are dictated mainly by interionic coulombic forces rather than by intraionic bonding interactions

Keywords: metabisulfite; sulfur-oxy anions; twinning.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768104003325/bk0141sup1.cif Contains datablocks global, metabi-P21_n, metabi-P21
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104003325/bk0141metabi_P21sup2.fcf Contains datablock metabi_P21
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104003325/bk0141metabi_P21_nsup3.fcf Contains datablock metabi_P21_n

Computing details top

For both compounds, data collection: Bruker XSCANS; cell refinement: Bruker XSCANS; data reduction: Bruker XSCANS. Program(s) used to solve structure: SIR97 (Altomare A., et al., 1999) for metabi-P21_n; SHELXS97 (Sheldrick, 1997) for metabi-P21. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

(metabi-P21_n) top

Crystal data top

Na₂O₅S₂	F(000) = 752
M_r = 190.1	D_x = 2.384 Mg m⁻³ D_m = 2.35 Mg m⁻³ D_m measured by flotation
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.060 (1) Å	Cell parameters from 49 reflections
b = 5.447 (1) Å	θ = 4.5–13.1°
c = 21.560 (2) Å	µ = 1.10 mm⁻¹
β = 95.31 (1)°	T = 153 K
V = 1059.4 (2) Å³	Rectangular solid, colorless
Z = 8	0.3 × 0.2 × 0.2 × 0.25 (radius) mm

Data collection top

Bruker P4 diffractometer	2004 reflections with I > 2σ(I)
ω–2\q scans	R_int = 0.049
Absorption correction: for a cylinder mounted on the ϕ axis Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3 for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959) p.302; Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification.	θ_max = 27.5°, θ_min = 2.4°
T_min = 0.604, T_max = 0.609	h = −11→11
4568 measured reflections	k = −6→7
2419 independent reflections	l = −28→28

Refinement top

Refinement on F²	163 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.026P)² + 4.7418P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.115	(Δ/σ)_max < 0.001
S = 1.15	Δρ_max = 0.75 e Å⁻³
2419 reflections	Δρ_min = −0.78 e Å⁻³

Crystal data top

Na₂O₅S₂	V = 1059.4 (2) Å³
M_r = 190.1	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.060 (1) Å	µ = 1.10 mm⁻¹
b = 5.447 (1) Å	T = 153 K
c = 21.560 (2) Å	0.3 × 0.2 × 0.2 × 0.25 (radius) mm
β = 95.31 (1)°

Data collection top

Bruker P4 diffractometer	2419 independent reflections
Absorption correction: for a cylinder mounted on the ϕ axis Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3 for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959) p.302; Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification.	2004 reflections with I > 2σ(I)
T_min = 0.604, T_max = 0.609	R_int = 0.049
4568 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	163 parameters
wR(F²) = 0.115	0 restraints
S = 1.15	Δρ_max = 0.75 e Å⁻³
2419 reflections	Δρ_min = −0.78 e Å⁻³

Special details top

Experimental. Details of the twinning analysis for the twinned crystal reported in the manuscript:

Given that [Rt] [A1] = [A2], [Rt] = [A2][A1]-1

Twin 1 Orientation Matrix [A1]:

−0.05186 0.02711 0.03813 − 0.09713 − 0.02683 − 0.02463 0.00669 − 0.17890 0.00948 —————————————————- Twin 2 Orientation Matrix [A2]:

−0.07281 − 0.02724 0.03108 0.07941 0.02677 0.03436 − 0.02291 0.17871 − 0.00040

—————————————————- Twin Transformation matrix [Rt]:

0.92942 0.27200 0.25261 0.27251 − 0.96299 0.03566 0.25237 0.03628 − 0.96805

Since the columns of the orientation matrix are simply the Cartesian components of the reciprocal axes, the eigenvector/eigenvalue solution produces the rotation axis and rotation angles (proved in many books on Linear Algebra – e.g., Matrix theory, by Joel. N. Franklin,Dover Publications) in reciprocal Cartesian space (i.e. diffractometer space).

The advantage of leaving the vector in this form is that it is the same vector in real and reciprocal (Cartesian) space, provided that the Cartesian coordinate systems are defined consistently.

—————————————————- Eigenvectors (column vectors) of twin transformation matrix [Rt]:

0.98202 − 0.02887 − 0.18658 0.13839 0.78231 0.60732 0.12843 − 0.62222 0.77223

—————————————————- Eigenvalues of Twin Transformation matrix [Rt]:

1.00083 − 1.00195 − 1.00050

The first eigenvalue is real, the second two imaginary (giving 180 degree rotations, e^{(i*pi) and e}-(i*pi)). The eigenvector (0.98202, 0.13839, 0.12843) is the rotation vector in the diffractometer (orthonormal) coordinate system.

The real space axes for both twins in diffractometer Cartesian coordinates are ([A1]^{-1) T and ([A2]}-1) T, respectively.

Since [A1] and [A2] are the transformation matrices for reciprocal to Cartesian coordinates), [A1]^{-1 and [A2]}-1 are the transforms from Cartesian to reciprocal coordinates.

Transforming the eigenvector (rotation axis) using either of these matrices givesthe twin rotation axis in reciprocal space,

(−0.31708,-0.00006,0.94840)

Dividing each component by the smallest number gives the vector

(−1, 0, 2.991), that is −1, 0, 3.

Likewise

(([A1]^{-1) T)}-1 and (([A2]^{-1) T)}-1 = [A1}T and [A2]T, transform the rotation axis into real lattice coordinates (−0.06346,-0.00010,0.03522).

Dividing each component by the smallest gives (1.8018, 0, 1), which scales to (2,0, 1.11) if an integer is desired for the first component.

Finally for a given vector with diffractometer coordinates Z,

[A1]h1 = Z and [A2]h2 = Z.

Thus [A1]h1 = [A2]h2 and [A2]^{-1[A1]h1 =h2. Rh = [A2]}-1[A1], the twin law matrix:

—————————————————- Twin Law matrix [Rh]:

−0.24898 0.00090 − 0.41770 0.00043 − 1.00098 0.00005 − 2.25160 − 0.00307 0.24834

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
O22	0.3407 (3)	0.3973 (5)	−0.02508 (11)	0.0145 (5)
O12	0.4024 (3)	0.4958 (4)	−0.15472 (11)	0.0151 (5)
O11	0.2768 (3)	0.1356 (5)	−0.20098 (12)	0.0160 (5)
O42	0.0893 (3)	0.0364 (5)	0.22490 (12)	0.0146 (5)
O33	0.2679 (3)	0.3737 (5)	0.11702 (12)	0.0154 (5)
O31	0.0378 (3)	0.3270 (5)	0.05235 (12)	0.0173 (5)
O32	0.1670 (3)	−0.0373 (4)	0.09474 (12)	0.0143 (5)
O41	0.0659 (3)	0.4800 (5)	0.21246 (13)	0.0190 (6)
O21	0.3075 (3)	−0.0447 (5)	−0.04145 (13)	0.0174 (5)
O13	0.5095 (3)	0.0871 (5)	−0.13824 (13)	0.0171 (5)
S3	0.13419 (8)	0.22266 (14)	0.10345 (4)	0.00846 (19)
S2	0.25679 (9)	0.20387 (15)	−0.06309 (4)	0.00992 (19)
S1	0.37385 (8)	0.23379 (14)	−0.14869 (4)	0.00856 (19)
S4	0.01132 (9)	0.23741 (14)	0.18763 (4)	0.00987 (19)
Na3	0.17253 (15)	0.6831 (3)	0.01558 (6)	0.0119 (3)
Na2	0.51005 (15)	0.7263 (3)	−0.06784 (6)	0.0128 (3)
Na4	0.26714 (15)	−0.2658 (2)	0.18526 (6)	0.0129 (3)
Na1	0.42248 (15)	−0.2320 (2)	−0.23332 (6)	0.0128 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O22	0.0178 (12)	0.0086 (11)	0.0172 (12)	−0.0009 (10)	0.0030 (10)	−0.0028 (9)
O12	0.0258 (13)	0.0050 (11)	0.0149 (12)	−0.0037 (10)	0.0043 (10)	0.0025 (9)
O11	0.0187 (12)	0.0114 (12)	0.0181 (12)	−0.0024 (10)	0.0025 (10)	−0.0026 (10)
O42	0.0174 (12)	0.0089 (11)	0.0178 (12)	0.0008 (9)	0.0036 (9)	0.0033 (9)
O33	0.0106 (11)	0.0111 (12)	0.0255 (13)	−0.0036 (9)	0.0072 (10)	−0.0050 (10)
O31	0.0176 (12)	0.0142 (12)	0.0198 (13)	0.0006 (10)	0.0007 (10)	0.0078 (10)
O32	0.0211 (12)	0.0045 (11)	0.0175 (12)	0.0015 (9)	0.0031 (10)	−0.0027 (9)
O41	0.0243 (13)	0.0055 (11)	0.0293 (14)	−0.0030 (10)	0.0141 (11)	−0.0064 (10)
O21	0.0229 (13)	0.0051 (11)	0.0262 (13)	0.0010 (10)	0.0124 (11)	0.0053 (10)
O13	0.0129 (11)	0.0154 (13)	0.0239 (13)	0.0047 (10)	0.0069 (10)	0.0052 (10)
S3	0.0098 (4)	0.0039 (4)	0.0120 (4)	−0.0006 (3)	0.0023 (3)	0.0002 (3)
S2	0.0102 (4)	0.0054 (4)	0.0148 (4)	0.0003 (3)	0.0042 (3)	−0.0002 (3)
S1	0.0100 (4)	0.0041 (4)	0.0118 (4)	−0.0003 (3)	0.0025 (3)	0.0006 (3)
S4	0.0106 (4)	0.0051 (4)	0.0145 (4)	−0.0003 (3)	0.0043 (3)	0.0001 (3)
Na3	0.0136 (6)	0.0060 (6)	0.0167 (7)	−0.0011 (5)	0.0037 (5)	−0.0009 (5)
Na2	0.0136 (6)	0.0091 (6)	0.0157 (7)	0.0022 (5)	0.0022 (5)	0.0001 (5)
Na4	0.0150 (6)	0.0073 (6)	0.0166 (7)	−0.0007 (5)	0.0022 (5)	0.0008 (5)
Na1	0.0165 (6)	0.0060 (6)	0.0166 (7)	−0.0004 (5)	0.0049 (5)	0.0021 (5)

Geometric parameters (Å, º) top

O22—S2	1.498 (3)	S2—Na2ⁱ	3.3869 (16)
O22—Na3	2.400 (3)	S1—Na1	3.1794 (16)
O22—Na2ⁱ	2.407 (3)	S1—Na2	3.3706 (16)
O22—Na2	2.584 (3)	S4—Na4^v	3.2437 (16)
O12—S1	1.459 (2)	S4—Na1^viii	3.3262 (16)
O12—Na1ⁱⁱ	2.272 (3)	S4—Na1^iv	3.3744 (16)
O12—Na2	2.387 (3)	Na3—O32ⁱⁱ	2.291 (3)
O11—S1	1.465 (3)	Na3—O31^vi	2.294 (3)
O11—Na1ⁱⁱⁱ	2.305 (3)	Na3—O21ⁱⁱ	2.342 (3)
O11—Na1	2.531 (3)	Na3—Na4ⁱⁱ	3.690 (2)
O42—S4	1.496 (3)	Na3—Na2	3.6958 (19)
O42—Na1^iv	2.469 (3)	Na3—Na3^vi	3.717 (3)
O42—Na4^v	2.478 (3)	Na3—Na2ⁱ	3.7302 (19)
O42—Na4	2.508 (3)	Na2—O21ⁱⁱ	2.333 (3)
O33—S3	1.472 (2)	Na2—O22ⁱ	2.407 (3)
O33—Na2ⁱ	2.421 (3)	Na2—O33ⁱ	2.421 (3)
O33—Na4ⁱⁱ	2.454 (3)	Na2—O13ⁱⁱ	2.483 (3)
O33—Na3	2.832 (3)	Na2—S2ⁱ	3.3869 (16)
O31—S3	1.456 (3)	Na2—Na1ⁱⁱ	3.590 (2)
O31—Na3^vi	2.294 (3)	Na2—Na3ⁱ	3.7302 (19)
O31—Na3	2.462 (3)	Na2—Na2ⁱ	3.843 (3)
O32—S3	1.463 (2)	Na4—O41^vii	2.405 (3)
O32—Na3^vii	2.291 (3)	Na4—O33^vii	2.454 (3)
O32—Na4	2.419 (3)	Na4—O42^x	2.478 (3)
O41—S4	1.493 (3)	Na4—O13^ix	2.540 (3)
O41—Na1^viii	2.285 (3)	Na4—O41^x	2.885 (3)
O41—Na4ⁱⁱ	2.405 (3)	Na4—S4^x	3.2437 (16)
O41—Na4^v	2.885 (3)	Na4—Na3^vii	3.690 (2)
O21—S2	1.491 (3)	Na4—Na1^iv	3.7211 (19)
O21—Na2^vii	2.333 (3)	Na4—Na4^v	3.933 (2)
O21—Na3^vii	2.342 (3)	Na1—O12^vii	2.272 (3)
O13—S1	1.466 (3)	Na1—O41^xi	2.285 (3)
O13—Na2^vii	2.483 (3)	Na1—O11^xii	2.305 (3)
O13—Na4^ix	2.540 (3)	Na1—O42^xiii	2.469 (3)
O13—Na1	2.747 (3)	Na1—S4^xi	3.3262 (16)
S3—S4	2.2165 (11)	Na1—S4^xiii	3.3744 (16)
S3—Na3	3.1815 (16)	Na1—Na2^vii	3.590 (2)
S3—Na4	3.3538 (16)	Na1—Na4^xiii	3.7211 (19)
S2—S1	2.2179 (11)	Na1—Na4^ix	3.974 (2)
S2—Na3	3.2425 (16)

S2—O22—Na3	110.40 (14)	O12—Na2—S1	21.89 (6)
S2—O22—Na2ⁱ	118.43 (14)	O22ⁱ—Na2—S1	110.99 (8)
Na3—O22—Na2ⁱ	101.78 (10)	O33ⁱ—Na2—S1	82.73 (7)
S2—O22—Na2	125.49 (14)	O13ⁱⁱ—Na2—S1	109.51 (8)
Na3—O22—Na2	95.65 (10)	O22—Na2—S1	55.35 (6)
Na2ⁱ—O22—Na2	100.65 (10)	O21ⁱⁱ—Na2—S2ⁱ	100.42 (9)
S1—O12—Na1ⁱⁱ	137.08 (16)	O12—Na2—S2ⁱ	153.01 (8)
S1—O12—Na2	120.51 (14)	O22ⁱ—Na2—S2ⁱ	22.89 (6)
Na1ⁱⁱ—O12—Na2	100.78 (10)	O33ⁱ—Na2—S2ⁱ	84.89 (7)
S1—O11—Na1ⁱⁱⁱ	137.63 (16)	O13ⁱⁱ—Na2—S2ⁱ	112.74 (8)
S1—O11—Na1	102.11 (14)	O22—Na2—S2ⁱ	97.21 (7)
Na1ⁱⁱⁱ—O11—Na1	118.48 (11)	S1—Na2—S2ⁱ	133.68 (5)
S4—O42—Na1^iv	114.40 (14)	O21ⁱⁱ—Na2—Na1ⁱⁱ	95.86 (8)
S4—O42—Na4^v	106.81 (14)	O12—Na2—Na1ⁱⁱ	38.44 (6)
Na1^iv—O42—Na4^v	107.56 (10)	O22ⁱ—Na2—Na1ⁱⁱ	154.21 (8)
S4—O42—Na4	125.69 (14)	O33ⁱ—Na2—Na1ⁱⁱ	72.25 (7)
Na1^iv—O42—Na4	96.77 (10)	O13ⁱⁱ—Na2—Na1ⁱⁱ	49.80 (7)
Na4^v—O42—Na4	104.14 (10)	O22—Na2—Na1ⁱⁱ	108.33 (7)
S3—O33—Na2ⁱ	119.28 (14)	S1—Na2—Na1ⁱⁱ	59.98 (3)
S3—O33—Na4ⁱⁱ	121.24 (14)	S2ⁱ—Na2—Na1ⁱⁱ	152.21 (5)
Na2ⁱ—O33—Na4ⁱⁱ	119.43 (11)	O21ⁱⁱ—Na2—Na3	37.84 (7)
S3—O33—Na3	89.57 (12)	O12—Na2—Na3	92.98 (8)
Na2ⁱ—O33—Na3	90.13 (9)	O22ⁱ—Na2—Na3	90.20 (7)
Na4ⁱⁱ—O33—Na3	88.24 (9)	O33ⁱ—Na2—Na3	163.15 (8)
S3—O31—Na3^vi	151.42 (17)	O13ⁱⁱ—Na2—Na3	113.15 (7)
S3—O31—Na3	105.70 (14)	O22—Na2—Na3	40.26 (6)
Na3^vi—O31—Na3	102.74 (10)	S1—Na2—Na3	85.48 (4)
S3—O32—Na3^vii	139.28 (16)	S2ⁱ—Na2—Na3	94.70 (4)
S3—O32—Na4	117.38 (14)	Na1ⁱⁱ—Na2—Na3	111.78 (5)
Na3^vii—O32—Na4	103.10 (10)	O21ⁱⁱ—Na2—Na3ⁱ	148.00 (9)
S4—O41—Na1^viii	122.00 (15)	O12—Na2—Na3ⁱ	99.80 (8)
S4—O41—Na4ⁱⁱ	130.98 (15)	O22ⁱ—Na2—Na3ⁱ	39.04 (7)
Na1^viii—O41—Na4ⁱⁱ	105.00 (11)	O33ⁱ—Na2—Na3ⁱ	49.39 (7)
S4—O41—Na4^v	89.79 (13)	O13ⁱⁱ—Na2—Na3ⁱ	128.00 (8)
Na1^viii—O41—Na4^v	99.82 (11)	O22—Na2—Na3ⁱ	86.79 (7)
Na4ⁱⁱ—O41—Na4^v	95.62 (10)	S1—Na2—Na3ⁱ	85.15 (4)
S2—O21—Na2^vii	129.48 (15)	S2ⁱ—Na2—Na3ⁱ	53.94 (3)
S2—O21—Na3^vii	125.38 (15)	Na1ⁱⁱ—Na2—Na3ⁱ	115.55 (5)
Na2^vii—O21—Na3^vii	104.49 (11)	Na3—Na2—Na3ⁱ	117.67 (4)
S1—O13—Na2^vii	118.66 (14)	O21ⁱⁱ—Na2—Na2ⁱ	93.65 (8)
S1—O13—Na4^ix	114.67 (14)	O12—Na2—Na2ⁱ	102.42 (8)
Na2^vii—O13—Na4^ix	126.23 (11)	O22ⁱ—Na2—Na2ⁱ	41.36 (7)
S1—O13—Na1	92.95 (13)	O33ⁱ—Na2—Na2ⁱ	106.78 (9)
Na2^vii—O13—Na1	86.54 (9)	O13ⁱⁱ—Na2—Na2ⁱ	167.33 (9)
Na4^ix—O13—Na1	97.41 (10)	O22—Na2—Na2ⁱ	37.99 (6)
O31—S3—O32	113.28 (16)	S1—Na2—Na2ⁱ	80.91 (5)
O31—S3—O33	110.93 (15)	S2ⁱ—Na2—Na2ⁱ	60.49 (4)
O32—S3—O33	113.18 (15)	Na1ⁱⁱ—Na2—Na2ⁱ	140.84 (6)
O31—S3—S4	107.09 (11)	Na3—Na2—Na2ⁱ	59.27 (4)
O32—S3—S4	105.29 (11)	Na3ⁱ—Na2—Na2ⁱ	58.40 (4)
O33—S3—S4	106.48 (11)	O41^vii—Na4—O32	104.88 (11)
O31—S3—Na3	48.15 (11)	O41^vii—Na4—O33^vii	74.33 (9)
O32—S3—Na3	130.69 (11)	O32—Na4—O33^vii	87.11 (10)
O33—S3—Na3	62.88 (11)	O41^vii—Na4—O42^x	85.07 (10)
S4—S3—Na3	123.35 (4)	O32—Na4—O42^x	170.03 (10)
O31—S3—Na4	150.27 (12)	O33^vii—Na4—O42^x	95.18 (10)
O32—S3—Na4	39.83 (11)	O41^vii—Na4—O42	76.66 (9)
O33—S3—Na4	95.17 (11)	O32—Na4—O42	74.49 (9)
S4—S3—Na4	77.37 (4)	O33^vii—Na4—O42	140.08 (10)
Na3—S3—Na4	152.24 (4)	O42^x—Na4—O42	109.05 (7)
O21—S2—O22	109.96 (15)	O41^vii—Na4—O13^ix	165.49 (11)
O21—S2—S1	99.80 (11)	O32—Na4—O13^ix	74.57 (9)
O22—S2—S1	98.39 (10)	O33^vii—Na4—O13^ix	91.19 (9)
O21—S2—Na3	130.39 (11)	O42^x—Na4—O13^ix	95.66 (9)
O22—S2—Na3	43.94 (10)	O42—Na4—O13^ix	116.44 (10)
S1—S2—Na3	122.00 (4)	O41^vii—Na4—O41^x	115.87 (8)
O21—S2—Na2ⁱ	71.98 (11)	O32—Na4—O41^x	120.58 (9)
O22—S2—Na2ⁱ	38.68 (10)	O33^vii—Na4—O41^x	143.04 (10)
S1—S2—Na2ⁱ	112.08 (4)	O42^x—Na4—O41^x	53.43 (8)
Na3—S2—Na2ⁱ	68.44 (4)	O42—Na4—O41^x	75.11 (9)
O12—S1—O11	112.78 (15)	O13^ix—Na4—O41^x	75.32 (9)
O12—S1—O13	113.21 (16)	O41^vii—Na4—S4^x	102.76 (8)
O11—S1—O13	110.74 (16)	O32—Na4—S4^x	146.65 (8)
O12—S1—S2	104.39 (11)	O33^vii—Na4—S4^x	118.36 (8)
O11—S1—S2	108.33 (11)	O42^x—Na4—S4^x	26.20 (6)
O13—S1—S2	106.90 (11)	O42—Na4—S4^x	94.32 (7)
O12—S1—Na1	134.00 (11)	O13^ix—Na4—S4^x	83.20 (7)
O11—S1—Na1	51.12 (11)	O41^x—Na4—S4^x	27.40 (5)
O13—S1—Na1	59.63 (12)	O41^vii—Na4—S3	109.97 (8)
S2—S1—Na1	121.41 (4)	O32—Na4—S3	22.79 (6)
O12—S1—Na2	37.60 (10)	O33^vii—Na4—S3	109.89 (8)
O11—S1—Na2	148.58 (11)	O42^x—Na4—S3	153.28 (8)
O13—S1—Na2	95.33 (12)	O42—Na4—S3	56.48 (6)
S2—S1—Na2	78.96 (4)	O13^ix—Na4—S3	75.32 (7)
Na1—S1—Na2	150.27 (4)	O41^x—Na4—S3	99.85 (7)
O41—S4—O42	109.33 (15)	S4^x—Na4—S3	127.16 (5)
O41—S4—S3	98.68 (11)	O41^vii—Na4—Na3^vii	94.97 (8)
O42—S4—S3	99.52 (10)	O32—Na4—Na3^vii	37.22 (6)
O41—S4—Na4^v	62.81 (12)	O33^vii—Na4—Na3^vii	50.10 (7)
O42—S4—Na4^v	46.99 (10)	O42^x—Na4—Na3^vii	143.06 (8)
S3—S4—Na4^v	111.91 (4)	O42—Na4—Na3^vii	106.84 (7)
O41—S4—Na1^viii	35.63 (10)	O13^ix—Na4—Na3^vii	75.74 (7)
O42—S4—Na1^viii	116.24 (11)	O41^x—Na4—Na3^vii	148.21 (7)
S3—S4—Na1^viii	127.78 (4)	S4^x—Na4—Na3^vii	155.08 (5)
Na4^v—S4—Na1^viii	74.43 (4)	S3—Na4—Na3^vii	59.95 (3)
O41—S4—Na1^iv	128.88 (12)	O41^vii—Na4—Na1^iv	36.38 (7)
O42—S4—Na1^iv	41.78 (10)	O32—Na4—Na1^iv	96.54 (8)
S3—S4—Na1^iv	123.05 (4)	O33^vii—Na4—Na1^iv	109.23 (7)
Na4^v—S4—Na1^iv	74.14 (4)	O42^x—Na4—Na1^iv	91.87 (7)
Na1^viii—S4—Na1^iv	108.76 (5)	O42—Na4—Na1^iv	41.21 (6)
O32ⁱⁱ—Na3—O31^vi	114.67 (11)	O13^ix—Na4—Na1^iv	157.51 (8)
O32ⁱⁱ—Na3—O21ⁱⁱ	91.07 (10)	O41^x—Na4—Na1^iv	92.54 (7)
O31^vi—Na3—O21ⁱⁱ	97.07 (11)	S4^x—Na4—Na1^iv	94.71 (4)
O32ⁱⁱ—Na3—O22	139.59 (11)	S3—Na4—Na1^iv	88.54 (4)
O31^vi—Na3—O22	105.62 (10)	Na3^vii—Na4—Na1^iv	109.84 (5)
O21ⁱⁱ—Na3—O22	80.73 (9)	O41^vii—Na4—Na4^v	96.56 (8)
O32ⁱⁱ—Na3—O31	103.78 (10)	O32—Na4—Na4^v	99.67 (7)
O31^vi—Na3—O31	77.26 (10)	O33^vii—Na4—Na4^v	169.89 (8)
O21ⁱⁱ—Na3—O31	165.14 (11)	O42^x—Na4—Na4^v	79.43 (8)
O22—Na3—O31	87.54 (10)	O42—Na4—Na4^v	37.65 (6)
O32ⁱⁱ—Na3—O33	81.16 (9)	O13^ix—Na4—Na4^v	97.82 (7)
O31^vi—Na3—O33	130.92 (10)	O41^x—Na4—Na4^v	37.48 (6)
O21ⁱⁱ—Na3—O33	130.20 (10)	S4^x—Na4—Na4^v	58.66 (4)
O22—Na3—O33	74.78 (9)	S3—Na4—Na4^v	77.04 (3)
O31—Na3—O33	53.66 (8)	Na3^vii—Na4—Na4^v	136.85 (5)
O32ⁱⁱ—Na3—S3	93.97 (8)	Na1^iv—Na4—Na4^v	62.78 (4)
O31^vi—Na3—S3	103.38 (8)	O12^vii—Na1—O41^xi	149.59 (12)
O21ⁱⁱ—Na3—S3	154.55 (9)	O12^vii—Na1—O11^xii	98.16 (10)
O22—Na3—S3	79.29 (7)	O41^xi—Na1—O11^xii	108.89 (11)
O31—Na3—S3	26.15 (6)	O12^vii—Na1—O42^xiii	85.86 (10)
O33—Na3—S3	27.55 (5)	O41^xi—Na1—O42^xiii	79.66 (10)
O32ⁱⁱ—Na3—S2	161.29 (9)	O11^xii—Na1—O42^xiii	92.11 (10)
O31^vi—Na3—S2	82.45 (8)	O12^vii—Na1—O11	103.36 (10)
O21ⁱⁱ—Na3—S2	94.33 (8)	O41^xi—Na1—O11	90.08 (10)
O22—Na3—S2	25.66 (6)	O11^xii—Na1—O11	91.03 (8)
O31—Na3—S2	71.45 (7)	O42^xiii—Na1—O11	169.73 (10)
O33—Na3—S2	81.67 (6)	O12^vii—Na1—O13	83.88 (9)
S3—Na3—S2	73.79 (4)	O41^xi—Na1—O13	82.19 (10)
O32ⁱⁱ—Na3—Na4ⁱⁱ	39.69 (7)	O11^xii—Na1—O13	144.19 (10)
O31^vi—Na3—Na4ⁱⁱ	137.55 (9)	O42^xiii—Na1—O13	123.64 (9)
O21ⁱⁱ—Na3—Na4ⁱⁱ	112.84 (9)	O11—Na1—O13	54.19 (8)
O22—Na3—Na4ⁱⁱ	108.29 (8)	O12^vii—Na1—S1	93.88 (8)
O31—Na3—Na4ⁱⁱ	79.44 (7)	O41^xi—Na1—S1	85.98 (8)
O33—Na3—Na4ⁱⁱ	41.66 (6)	O11^xii—Na1—S1	117.38 (8)
S3—Na3—Na4ⁱⁱ	59.82 (3)	O42^xiii—Na1—S1	150.14 (8)
S2—Na3—Na4ⁱⁱ	122.35 (5)	O11—Na1—S1	26.77 (6)
O32ⁱⁱ—Na3—Na2	113.34 (8)	O13—Na1—S1	27.42 (5)
O31^vi—Na3—Na2	111.51 (8)	O12^vii—Na1—S4^xi	161.94 (9)
O21ⁱⁱ—Na3—Na2	37.67 (7)	O41^xi—Na1—S4^xi	22.37 (7)
O22—Na3—Na2	44.09 (7)	O11^xii—Na1—S4^xi	98.71 (8)
O31—Na3—Na2	131.62 (8)	O42^xiii—Na1—S4^xi	99.88 (7)
O33—Na3—Na2	101.92 (6)	O11—Na1—S4^xi	69.97 (7)
S3—Na3—Na2	118.74 (5)	O13—Na1—S4^xi	78.68 (7)
S2—Na3—Na2	63.34 (3)	S1—Na1—S4^xi	72.59 (4)
Na4ⁱⁱ—Na3—Na2	110.54 (5)	O12^vii—Na1—S4^xiii	83.32 (8)
O32ⁱⁱ—Na3—Na3^vi	114.54 (9)	O41^xi—Na1—S4^xiii	93.33 (8)
O31^vi—Na3—Na3^vi	40.24 (7)	O11^xii—Na1—S4^xiii	69.17 (7)
O21ⁱⁱ—Na3—Na3^vi	135.74 (10)	O42^xiii—Na1—S4^xiii	23.82 (6)
O22—Na3—Na3^vi	97.92 (8)	O11—Na1—S4^xiii	159.95 (8)
O31—Na3—Na3^vi	37.02 (6)	O13—Na1—S4^xiii	145.87 (7)
O33—Na3—Na3^vi	90.67 (7)	S1—Na1—S4^xiii	173.27 (5)
S3—Na3—Na3^vi	63.14 (4)	S4^xi—Na1—S4^xiii	108.76 (5)
S2—Na3—Na3^vi	73.03 (4)	O12^vii—Na1—Na2^vii	40.79 (7)
Na4ⁱⁱ—Na3—Na3^vi	109.51 (6)	O41^xi—Na1—Na2^vii	117.56 (9)
Na2—Na3—Na3^vi	131.77 (6)	O11^xii—Na1—Na2^vii	132.80 (8)
O32ⁱⁱ—Na3—Na2ⁱ	103.99 (8)	O42^xiii—Na1—Na2^vii	103.52 (8)
O31^vi—Na3—Na2ⁱ	138.61 (9)	O11—Na1—Na2^vii	81.32 (7)
O21ⁱⁱ—Na3—Na2ⁱ	96.42 (8)	O13—Na1—Na2^vii	43.66 (6)
O22—Na3—Na2ⁱ	39.17 (7)	S1—Na1—Na2^vii	60.64 (4)
O31—Na3—Na2ⁱ	79.80 (7)	S4^xi—Na1—Na2^vii	121.25 (5)
O33—Na3—Na2ⁱ	40.48 (5)	S4^xiii—Na1—Na2^vii	114.16 (5)
S3—Na3—Na2ⁱ	58.16 (3)	O12^vii—Na1—Na4^xiii	118.59 (9)
S2—Na3—Na2ⁱ	57.61 (3)	O41^xi—Na1—Na4^xiii	38.62 (7)
Na4ⁱⁱ—Na3—Na2ⁱ	69.13 (4)	O11^xii—Na1—Na4^xiii	110.67 (8)
Na2—Na3—Na2ⁱ	62.33 (4)	O42^xiii—Na1—Na4^xiii	42.02 (7)
Na3^vi—Na3—Na2ⁱ	110.23 (6)	O11—Na1—Na4^xiii	127.89 (8)
O21ⁱⁱ—Na2—O12	101.48 (11)	O13—Na1—Na4^xiii	99.13 (7)
O21ⁱⁱ—Na2—O22ⁱ	109.92 (11)	S1—Na1—Na4^xiii	116.12 (5)
O12—Na2—O22ⁱ	131.54 (10)	S4^xi—Na1—Na4^xiii	60.49 (3)
O21ⁱⁱ—Na2—O33ⁱ	158.67 (11)	S4^xiii—Na1—Na4^xiii	60.61 (3)
O12—Na2—O33ⁱ	80.42 (10)	Na2^vii—Na1—Na4^xiii	110.53 (5)
O22ⁱ—Na2—O33ⁱ	82.88 (10)	O12^vii—Na1—Na4^ix	110.76 (8)
O21ⁱⁱ—Na2—O13ⁱⁱ	76.64 (9)	O41^xi—Na1—Na4^ix	45.68 (8)
O12—Na2—O13ⁱⁱ	87.65 (10)	O11^xii—Na1—Na4^ix	150.32 (8)
O22ⁱ—Na2—O13ⁱⁱ	134.39 (11)	O42^xiii—Na1—Na4^ix	96.38 (7)
O33ⁱ—Na2—O13ⁱⁱ	82.25 (9)	O11—Na1—Na4^ix	76.28 (7)
O21ⁱⁱ—Na2—O22	77.14 (9)	O13—Na1—Na4^ix	39.32 (6)
O12—Na2—O22	72.67 (9)	S1—Na1—Na4^ix	55.82 (3)
O22ⁱ—Na2—O22	79.35 (10)	S4^xi—Na1—Na4^ix	51.84 (3)
O33ⁱ—Na2—O22	123.01 (10)	S4^xiii—Na1—Na4^ix	119.49 (4)
O13ⁱⁱ—Na2—O22	143.08 (10)	Na2^vii—Na1—Na4^ix	72.43 (4)
O21ⁱⁱ—Na2—S1	107.04 (8)	Na4^xiii—Na1—Na4^ix	61.37 (3)

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

(metabi-P21) top

Crystal data top

Na₂O₅S₂	F(000) = 188
M_r = 190.1	D_x = 2.346 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.073 (1) Å	Cell parameters from 39 reflections
b = 5.470 (1) Å	θ = 4.5–19.9°
c = 8.318 (1) Å	µ = 1.08 mm⁻¹
β = 103.16 (1)°	T = 293 K
V = 269.06 (7) Å³	Rectangular solid, colorless
Z = 2	0.25 × 0.2 × 0.15 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.030
ω–2\q scans	θ_max = 30.0°, θ_min = 2.5°
1831 measured reflections	h = −8→8
1559 independent reflections	k = −7→7
1349 reflections with I > 2σ(I)	l = −11→11

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0555P)² + 0.3072P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.04	(Δ/σ)_max = 0.001
wR(F²) = 0.110	Δρ_max = 0.56 e Å⁻³
S = 1.07	Δρ_min = −0.50 e Å⁻³
1559 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
111 parameters	Absolute structure parameter: 0.3 (3)

Crystal data top

Na₂O₅S₂	V = 269.06 (7) Å³
M_r = 190.1	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.073 (1) Å	µ = 1.08 mm⁻¹
b = 5.470 (1) Å	T = 293 K
c = 8.318 (1) Å	0.25 × 0.2 × 0.15 mm
β = 103.16 (1)°

Data collection top

Bruker P4 diffractometer	1349 reflections with I > 2σ(I)
1831 measured reflections	R_int = 0.030
1559 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.04	1 restraint
wR(F²) = 0.110	Δρ_max = 0.56 e Å⁻³
S = 1.07	Δρ_min = −0.50 e Å⁻³
1559 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
111 parameters	Absolute structure parameter: 0.3 (3)

Special details top

Experimental. This structure, determined in the P21 space group, is correctly solved in the p21/n space group. Because of a fortuitous overlap and pseudo 21 symmetry between elements of the asymmetric unit in the p21/n lattice, a structure arises which superpositions the two anions in the asymmetric P21/n unit cell into a single "apparently" disorderd anion in P21.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.17866 (9)	0.7510 (6)	0.26907 (7)	0.02189 (17)
S2	0.55190 (10)	0.7542 (7)	0.30265 (8)	0.0308 (2)
Na3	0.71380 (18)	0.7516 (9)	−0.05186 (14)	0.0296 (3)
Na2	0.8752 (2)	1.2576 (16)	0.31210 (17)	0.0506 (4)
O4	0.5752 (12)	0.9922 (14)	0.2157 (12)	0.077 (3)
O5	0.5785 (14)	0.5554 (16)	0.1949 (10)	0.0618 (17)
O3A	0.126 (2)	0.481 (2)	0.2477 (17)	0.031 (3)	0.471 (15)
O1B	0.123 (2)	1.0099 (19)	0.2399 (17)	0.040 (3)	0.554 (15)
O1A	0.0843 (19)	0.893 (2)	0.1232 (13)	0.033 (4)	0.471 (15)
O2B	0.076 (2)	0.611 (2)	0.1219 (15)	0.042 (3)	0.554 (15)
O2A	0.121 (2)	0.840 (3)	0.4151 (16)	0.035 (3)	0.471 (15)
O3B	0.121 (2)	0.653 (2)	0.4198 (15)	0.041 (3)	0.554 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0151 (3)	0.0290 (3)	0.0225 (3)	0.0027 (8)	0.00627 (19)	0.0027 (9)
S2	0.0150 (3)	0.0512 (4)	0.0251 (3)	0.0005 (10)	0.0024 (2)	0.0049 (10)
Na3	0.0249 (5)	0.0342 (6)	0.0310 (5)	0.0040 (18)	0.0093 (4)	0.0018 (18)
Na2	0.0208 (6)	0.0990 (13)	0.0333 (6)	0.002 (2)	0.0091 (5)	−0.002 (3)
O4	0.019 (2)	0.093 (5)	0.106 (6)	−0.025 (3)	−0.012 (3)	0.058 (4)
O5	0.029 (3)	0.102 (5)	0.054 (3)	0.010 (3)	0.008 (2)	−0.037 (3)
O3A	0.023 (5)	0.030 (6)	0.046 (6)	−0.002 (4)	0.020 (5)	0.009 (5)
O1B	0.038 (6)	0.027 (5)	0.057 (7)	0.001 (4)	0.016 (5)	0.004 (4)
O1A	0.022 (5)	0.047 (8)	0.022 (5)	−0.008 (4)	−0.015 (3)	0.018 (5)
O2B	0.026 (5)	0.045 (7)	0.058 (7)	0.002 (4)	0.014 (4)	−0.021 (6)
O2A	0.031 (6)	0.045 (8)	0.033 (6)	−0.009 (5)	0.017 (5)	−0.014 (5)
O3B	0.039 (6)	0.052 (9)	0.036 (5)	−0.017 (5)	0.016 (4)	−0.004 (5)

Geometric parameters (Å, º) top

S1—O2A	1.425 (12)	Na2—O3B^vii	2.665 (15)
S1—O1A	1.445 (10)	Na2—O2A^v	2.756 (17)
S1—O2B	1.460 (12)	Na2—O2B^vii	2.930 (15)
S1—O1B	1.464 (11)	Na2—O1A^v	2.994 (16)
S1—O3B	1.477 (12)	Na2—S1^vii	3.333 (7)
S1—O3A	1.512 (12)	Na2—S2^ix	3.342 (7)
S1—S2	2.2199 (9)	O4—Na3^iv	2.422 (8)
S1—Na2ⁱ	3.333 (7)	O5—Na2ⁱⁱ	2.460 (10)
S2—O5	1.441 (8)	O5—Na3ⁱⁱⁱ	2.523 (9)
S2—O4	1.511 (8)	O3A—O2B	1.242 (18)
S2—Na3	3.3140 (13)	O3A—O3B	1.719 (19)
S2—Na2ⁱⁱ	3.342 (7)	O3A—Na2ⁱ	2.115 (12)
S2—Na2	3.372 (7)	O3A—Na3ⁱⁱⁱ	2.429 (13)
Na3—O4ⁱⁱⁱ	2.422 (8)	O1B—O1A	1.141 (17)
Na3—O1Bⁱⁱⁱ	2.427 (12)	O1B—O2A	1.73 (2)
Na3—O3A^iv	2.429 (13)	O1B—Na2^x	2.205 (13)
Na3—O1Aⁱⁱⁱ	2.457 (12)	O1B—Na3^iv	2.427 (12)
Na3—O2B^v	2.463 (13)	O1A—O2B	1.546 (7)
Na3—O2B^iv	2.484 (11)	O1A—Na3^iv	2.457 (12)
Na3—O1A^v	2.508 (11)	O1A—Na3^x	2.508 (11)
Na3—O5^iv	2.523 (9)	O1A—Na2^x	2.994 (16)
Na3—O5	2.609 (10)	O2B—Na3^x	2.463 (12)
Na3—O4	2.872 (11)	O2B—Na3ⁱⁱⁱ	2.484 (11)
Na3—Na2^vi	3.6574 (17)	O2B—Na2ⁱ	2.930 (14)
Na2—O3A^vii	2.115 (12)	O2A—O3B	1.022 (8)
Na2—O1B^v	2.205 (13)	O2A—Na2^xi	2.308 (13)
Na2—O3B^viii	2.297 (12)	O2A—Na2^x	2.756 (17)
Na2—O2A^viii	2.308 (13)	O3B—Na2^xi	2.297 (12)
Na2—O4	2.325 (9)	O3B—Na2ⁱ	2.665 (15)
Na2—O5^ix	2.460 (10)

O2A—S1—O1A	113.9 (9)	O5^ix—Na2—O3B^vii	84.2 (5)
O2A—S1—O2B	138.8 (7)	O3A^vii—Na2—O2A^v	100.9 (4)
O1A—S1—O2B	64.3 (3)	O1B^v—Na2—O2A^v	38.9 (4)
O2A—S1—O1B	73.6 (8)	O3B^viii—Na2—O2A^v	66.8 (4)
O1A—S1—O1B	46.2 (7)	O2A^viii—Na2—O2A^v	88.4 (4)
O2B—S1—O1B	109.3 (7)	O4—Na2—O2A^v	85.2 (5)
O2A—S1—O3B	41.2 (3)	O5^ix—Na2—O2A^v	165.4 (4)
O1A—S1—O3B	141.4 (7)	O3B^vii—Na2—O2A^v	110.29 (16)
O2B—S1—O3B	112.4 (7)	O3A^vii—Na2—O2B^vii	21.7 (5)
O1B—S1—O3B	113.6 (7)	O1B^v—Na2—O2B^vii	82.3 (4)
O2A—S1—O3A	110.3 (8)	O3B^viii—Na2—O2B^vii	140.7 (5)
O1A—S1—O3A	113.1 (7)	O2A^viii—Na2—O2B^vii	119.3 (5)
O2B—S1—O3A	49.4 (7)	O4—Na2—O2B^vii	127.9 (3)
O1B—S1—O3A	152.8 (3)	O5^ix—Na2—O2B^vii	72.9 (4)
O3B—S1—O3A	70.2 (7)	O3B^vii—Na2—O2B^vii	51.5 (4)
O2A—S1—S2	109.5 (5)	O2A^v—Na2—O2B^vii	116.9 (3)
O1A—S1—S2	107.5 (5)	O3A^vii—Na2—O1A^v	80.6 (4)
O2B—S1—S2	109.9 (4)	O1B^v—Na2—O1A^v	18.5 (4)
O1B—S1—S2	101.9 (5)	O3B^viii—Na2—O1A^v	115.6 (5)
O3B—S1—S2	109.2 (5)	O2A^viii—Na2—O1A^v	137.3 (4)
O3A—S1—S2	101.9 (5)	O4—Na2—O1A^v	78.2 (4)
O2A—S1—Na2ⁱ	86.3 (5)	O5^ix—Na2—O1A^v	126.4 (2)
O1A—S1—Na2ⁱ	113.7 (5)	O3B^vii—Na2—O1A^v	116.4 (4)
O2B—S1—Na2ⁱ	61.4 (5)	O2A^v—Na2—O1A^v	49.2 (3)
O1B—S1—Na2ⁱ	133.4 (5)	O2B^vii—Na2—O1A^v	82.98 (12)
O3B—S1—Na2ⁱ	51.0 (5)	O3A^vii—Na2—S1^vii	19.4 (3)
O3A—S1—Na2ⁱ	27.7 (4)	O1B^v—Na2—S1^vii	92.3 (3)
S2—S1—Na2ⁱ	124.51 (13)	O3B^viii—Na2—S1^vii	115.0 (4)
O5—S2—O4	108.4 (3)	O2A^viii—Na2—S1^vii	93.7 (4)
O5—S2—S1	99.9 (3)	O4—Na2—S1^vii	151.4 (2)
O4—S2—S1	98.7 (3)	O5^ix—Na2—S1^vii	78.1 (3)
O5—S2—Na3	49.1 (4)	O3B^vii—Na2—S1^vii	25.5 (3)
O4—S2—Na3	59.9 (4)	O2A^v—Na2—S1^vii	115.6 (3)
S1—S2—Na3	112.91 (3)	O2B^vii—Na2—S1^vii	25.9 (2)
O5—S2—Na2ⁱⁱ	41.7 (4)	O1A^v—Na2—S1^vii	99.9 (2)
O4—S2—Na2ⁱⁱ	126.4 (4)	O3A^vii—Na2—S2^ix	88.7 (4)
S1—S2—Na2ⁱⁱ	125.04 (14)	O1B^v—Na2—S2^ix	157.8 (4)
Na3—S2—Na2ⁱⁱ	74.08 (10)	O3B^viii—Na2—S2^ix	95.8 (3)
O5—S2—Na2	118.9 (4)	O2A^viii—Na2—S2^ix	74.9 (4)
O4—S2—Na2	35.9 (3)	O4—Na2—S2^ix	95.1 (3)
S1—S2—Na2	125.58 (14)	O5^ix—Na2—S2^ix	22.93 (18)
Na3—S2—Na2	74.64 (10)	O3B^vii—Na2—S2^ix	68.2 (4)
Na2ⁱⁱ—S2—Na2	109.10 (4)	O2A^v—Na2—S2^ix	162.6 (3)
O4ⁱⁱⁱ—Na3—O1Bⁱⁱⁱ	70.6 (4)	O2B^vii—Na2—S2^ix	76.4 (3)
O4ⁱⁱⁱ—Na3—O3A^iv	106.0 (4)	O1A^v—Na2—S2^ix	147.8 (2)
O1Bⁱⁱⁱ—Na3—O3A^iv	64.15 (17)	S1^vii—Na2—S2^ix	71.07 (16)
O4ⁱⁱⁱ—Na3—O1Aⁱⁱⁱ	74.6 (3)	S2—O4—Na2	121.6 (5)
O1Bⁱⁱⁱ—Na3—O1Aⁱⁱⁱ	27.0 (4)	S2—O4—Na3^iv	129.7 (4)
O3A^iv—Na3—O1Aⁱⁱⁱ	87.3 (4)	Na2—O4—Na3^iv	103.8 (3)
O4ⁱⁱⁱ—Na3—O2B^v	125.6 (4)	S2—O4—Na3	93.0 (5)
O1Bⁱⁱⁱ—Na3—O2B^v	76.5 (4)	Na2—O4—Na3	102.0 (3)
O3A^iv—Na3—O2B^v	96.6 (4)	Na3^iv—O4—Na3	97.8 (3)
O1Aⁱⁱⁱ—Na3—O2B^v	57.6 (2)	S2—O5—Na2ⁱⁱ	115.4 (5)
O4ⁱⁱⁱ—Na3—O2B^iv	132.6 (4)	S2—O5—Na3ⁱⁱⁱ	128.6 (5)
O1Bⁱⁱⁱ—Na3—O2B^iv	88.3 (4)	Na2ⁱⁱ—O5—Na3ⁱⁱⁱ	97.1 (4)
O3A^iv—Na3—O2B^iv	29.3 (4)	S2—O5—Na3	106.2 (6)
O1Aⁱⁱⁱ—Na3—O2B^iv	105.21 (18)	Na2ⁱⁱ—O5—Na3	104.5 (3)
O2B^v—Na3—O2B^iv	87.0 (3)	Na3ⁱⁱⁱ—O5—Na3	102.3 (3)
O4ⁱⁱⁱ—Na3—O1A^v	161.3 (4)	O2B—O3A—S1	63.1 (8)
O1Bⁱⁱⁱ—Na3—O1A^v	95.6 (5)	O2B—O3A—O3B	110.0 (11)
O3A^iv—Na3—O1A^v	77.7 (4)	S1—O3A—O3B	53.9 (6)
O1Aⁱⁱⁱ—Na3—O1A^v	87.4 (3)	O2B—O3A—Na2ⁱ	119.3 (10)
O2B^v—Na3—O1A^v	36.22 (16)	S1—O3A—Na2ⁱ	132.9 (7)
O2B^iv—Na3—O1A^v	56.7 (3)	O3B—O3A—Na2ⁱ	87.4 (6)
O4ⁱⁱⁱ—Na3—O5^iv	77.20 (16)	O2B—O3A—Na3ⁱⁱⁱ	77.8 (8)
O1Bⁱⁱⁱ—Na3—O5^iv	113.7 (4)	S1—O3A—Na3ⁱⁱⁱ	118.5 (6)
O3A^iv—Na3—O5^iv	71.9 (3)	O3B—O3A—Na3ⁱⁱⁱ	158.0 (8)
O1Aⁱⁱⁱ—Na3—O5^iv	138.4 (3)	Na2ⁱ—O3A—Na3ⁱⁱⁱ	107.0 (5)
O2B^v—Na3—O5^iv	157.1 (4)	O1A—O1B—S1	66.0 (8)
O2B^iv—Na3—O5^iv	73.3 (4)	O1A—O1B—O2A	112.1 (11)
O1A^v—Na3—O5^iv	120.8 (4)	S1—O1B—O2A	52.2 (6)
O4ⁱⁱⁱ—Na3—O5	83.3 (3)	O1A—O1B—Na2^x	123.8 (11)
O1Bⁱⁱⁱ—Na3—O5	122.1 (4)	S1—O1B—Na2^x	134.1 (8)
O3A^iv—Na3—O5	170.5 (4)	O2A—O1B—Na2^x	88.0 (7)
O1Aⁱⁱⁱ—Na3—O5	97.2 (4)	O1A—O1B—Na3^iv	77.9 (9)
O2B^v—Na3—O5	78.9 (3)	S1—O1B—Na3^iv	121.3 (7)
O2B^iv—Na3—O5	141.3 (3)	O2A—O1B—Na3^iv	156.6 (8)
O1A^v—Na3—O5	94.1 (3)	Na2^x—O1B—Na3^iv	104.2 (5)
O5^iv—Na3—O5	109.2 (2)	O1B—O1A—S1	67.8 (8)
O4ⁱⁱⁱ—Na3—O4	113.7 (2)	O1B—O1A—O2B	124.5 (13)
O1Bⁱⁱⁱ—Na3—O4	169.9 (4)	S1—O1A—O2B	58.3 (7)
O3A^iv—Na3—O4	121.1 (3)	O1B—O1A—Na3^iv	75.0 (9)
O1Aⁱⁱⁱ—Na3—O4	143.5 (3)	S1—O1A—Na3^iv	120.5 (6)
O2B^v—Na3—O4	93.9 (3)	O2B—O1A—Na3^iv	144.5 (11)
O2B^iv—Na3—O4	94.4 (3)	O1B—O1A—Na3^x	130.5 (10)
O1A^v—Na3—O4	77.9 (4)	S1—O1A—Na3^x	117.0 (6)
O5^iv—Na3—O4	76.4 (3)	O2B—O1A—Na3^x	70.3 (8)
O5—Na3—O4	51.57 (13)	Na3^iv—O1A—Na3^x	122.5 (4)
O4ⁱⁱⁱ—Na3—S2	100.3 (2)	O1B—O1A—Na2^x	37.7 (8)
O1Bⁱⁱⁱ—Na3—S2	145.5 (3)	S1—O1A—Na2^x	93.0 (6)
O3A^iv—Na3—S2	147.1 (3)	O2B—O1A—Na2^x	130.6 (10)
O1Aⁱⁱⁱ—Na3—S2	118.9 (3)	Na3^iv—O1A—Na2^x	83.7 (4)
O2B^v—Na3—S2	83.4 (3)	Na3^x—O1A—Na2^x	94.5 (4)
O2B^iv—Na3—S2	118.6 (3)	O3A—O2B—S1	67.5 (9)
O1A^v—Na3—S2	83.7 (3)	O3A—O2B—O1A	124.2 (14)
O5^iv—Na3—S2	95.6 (2)	S1—O2B—O1A	57.4 (7)
O5—Na3—S2	24.69 (19)	O3A—O2B—Na3^x	133.5 (9)
O4—Na3—S2	27.09 (15)	S1—O2B—Na3^x	118.8 (6)
O4ⁱⁱⁱ—Na3—Na2^vi	100.2 (3)	O1A—O2B—Na3^x	73.5 (8)
O1Bⁱⁱⁱ—Na3—Na2^vi	35.8 (3)	O3A—O2B—Na3ⁱⁱⁱ	72.9 (8)
O3A^iv—Na3—Na2^vi	33.6 (3)	S1—O2B—Na3ⁱⁱⁱ	117.8 (7)
O1Aⁱⁱⁱ—Na3—Na2^vi	54.5 (4)	O1A—O2B—Na3ⁱⁱⁱ	140.6 (11)
O2B^v—Na3—Na2^vi	73.3 (3)	Na3^x—O2B—Na3ⁱⁱⁱ	123.2 (5)
O2B^iv—Na3—Na2^vi	52.9 (3)	O3A—O2B—Na2ⁱ	39.0 (7)
O1A^v—Na3—Na2^vi	72.4 (3)	S1—O2B—Na2ⁱ	92.6 (6)
O5^iv—Na3—Na2^vi	102.5 (2)	O1A—O2B—Na2ⁱ	132.3 (9)
O5—Na3—Na2^vi	148.1 (2)	Na3^x—O2B—Na2ⁱ	95.7 (4)
O4—Na3—Na2^vi	144.5 (2)	Na3ⁱⁱⁱ—O2B—Na2ⁱ	84.6 (4)
S2—Na3—Na2^vi	155.14 (4)	O3B—O2A—S1	72.1 (12)
O3A^vii—Na2—O1B^v	73.27 (19)	O3B—O2A—O1B	124.6 (16)
O3A^vii—Na2—O3B^viii	122.7 (5)	S1—O2A—O1B	54.2 (6)
O1B^v—Na2—O3B^viii	104.7 (5)	O3B—O2A—Na2^xi	76.6 (14)
O3A^vii—Na2—O2A^viii	106.8 (5)	S1—O2A—Na2^xi	145.3 (10)
O1B^v—Na2—O2A^viii	122.1 (5)	O1B—O2A—Na2^xi	158.7 (9)
O3B^viii—Na2—O2A^viii	25.66 (19)	O3B—O2A—Na2^x	146.7 (16)
O3A^vii—Na2—O4	145.7 (5)	S1—O2A—Na2^x	103.8 (8)
O1B^v—Na2—O4	92.9 (6)	O1B—O2A—Na2^x	53.1 (6)
O3B^viii—Na2—O4	90.8 (4)	Na2^xi—O2A—Na2^x	110.6 (5)
O2A^viii—Na2—O4	107.0 (4)	O2A—O3B—S1	66.7 (12)
O3A^vii—Na2—O5^ix	91.2 (5)	O2A—O3B—O3A	121.0 (16)
O1B^v—Na2—O5^ix	141.4 (4)	S1—O3B—O3A	55.9 (6)
O3B^viii—Na2—O5^ix	113.2 (4)	O2A—O3B—Na2^xi	77.8 (13)
O2A^viii—Na2—O5^ix	95.9 (4)	S1—O3B—Na2^xi	141.4 (8)
O4—Na2—O5^ix	80.28 (16)	O3A—O3B—Na2^xi	161.2 (9)
O3A^vii—Na2—O3B^vii	40.1 (5)	O2A—O3B—Na2ⁱ	143.4 (16)
O1B^v—Na2—O3B^vii	103.1 (4)	S1—O3B—Na2ⁱ	103.4 (6)
O3B^viii—Na2—O3B^vii	89.7 (4)	O3A—O3B—Na2ⁱ	52.4 (5)
O2A^viii—Na2—O3B^vii	68.4 (4)	Na2^xi—O3B—Na2ⁱ	114.2 (5)
O4—Na2—O3B^vii	163.3 (5)

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

Experimental details

	(metabi-P21_n)	(metabi-P21)
Crystal data
Chemical formula	Na₂O₅S₂	Na₂O₅S₂
M_r	190.1	190.1
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁
Temperature (K)	153	293
a, b, c (Å)	9.060 (1), 5.447 (1), 21.560 (2)	6.073 (1), 5.470 (1), 8.318 (1)
β (°)	95.31 (1)	103.16 (1)
V (Å³)	1059.4 (2)	269.06 (7)
Z	8	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	1.10	1.08
Crystal size (mm)	0.3 × 0.2 × 0.2 × 0.25 (radius)	0.25 × 0.2 × 0.15

Data collection
Diffractometer	Bruker P4 diffractometer	Bruker P4 diffractometer
Absorption correction	For a cylinder mounted on the ϕ axis Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3 for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959) p.302; Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification.	–
T_min, T_max	0.604, 0.609	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4568, 2419, 2004	1831, 1559, 1349
R_int	0.049	0.030
(sin θ/λ)_max (Å⁻¹)	0.649	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.15	0.04, 0.110, 1.07
No. of reflections	2419	1559
No. of parameters	163	111
No. of restraints	0	1
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.78	0.56, −0.50
Absolute structure	?	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	?	0.3 (3)

Computer programs: Bruker XSCANS, SIR97 (Altomare A., et al., 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

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