Sodium rubidium disaccharinate tetra­hydrate

Nazarenko, A.Y.

doi:10.1107/S2414314618008672

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180867

https://doi.org/10.1107/S2414314618008672

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Sodium rubidium disaccharinate tetrahydrate

Alexander Y. Nazarenko ^a ^*

^aChemistry Department, SUNY Buffalo State, 1300 Elmwood Ave, Buffalo, NY 14222, USA
^*Correspondence e-mail: nazareay@buffalostate.edu

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 14 May 2018; accepted 12 June 2018; online 28 June 2018)

1,2-Benzothiazol-3(2H)-one 1,1 dioxide (more commonly known under its commercial name saccharin) forms a double salt with sodium and rubidium, Na⁺·Rb⁺·2C₇H₄NO₃S⁻·4H₂O. The coordination numbers of the sodium and rubidium ions are 6 and 8, respectively; the coordination polyhedra can be described as distorted triangular and rectangular prisms. Both Rb⁺ and Na⁺ cations and flat saccharinate moieties are positioned at mirror planes parallel to the (010) crystallographic plane. Metal ions and saccharinate anions are assembled into infinite layers parallel to the (001) plane via electrostatic interactions and hydrogen-bonded networks. These layers are connected by stacking interactions and C—H⋯O hydrogen bonds into a three-dimensional structure.

Keywords: crystal structure; 1,2-benzothiazol-3(2H)-one 1,1-dioxide; saccharin; rubidium; sodium; hydrate; binary compound.

CCDC reference: 1849000

Structure description

Saccharin [1,2-benzothiazol-3(2H)-one 1,1-dioxide] is one of the most widely used sweeteners; its water-soluble sodium salt is commonly used as an artificial sweetener in food and beverages, and it is also the major component in the diet of diabetics. Saccharin has a very rich crystal chemistry: the Cambridge Structural Database (CSD version 5.39; Groom et al., 2016 ) contains several hundred different structures of its compounds. For practical purposes, most interesting are non-toxic saccharin salts with alkali metals. Crystal structures of all simple salts [Na⁺: refcode MGSACD11 (Naumov et al., 2005 ), LANBOS (Banerjee et al., 2005 ); K⁺: LANBUY (Banerjee et al., 2005); Rb⁺ and Cs⁺: FAZHAS, FAZHEW, FAZHIA and FAZHOG (Karothu et al., 2017 )] and several binary compounds [Na⁺ and K⁺: COCRIV (Malik et al., 1984 ); Li⁺ and Na⁺: MIPSUA (Bhatt & Desiraju, 2007 )] have been determined. As a continuation of a structural study of common sweeteners (Nazarenko, 2018 ), the crystal structure of sodium rubidium di-saccharinate tetrahydrate, I, is presented here.

The numbering scheme for I is shown in Fig. 1. Both the sodium and rubidium ions are located on a mirror plane. The Na⁺ ions have a distorted trigonal–prismatic environment (coordination number 6); the coordination sphere of Na1 contains bridging O atoms of water molecules (Table 1, Fig. 2). The coordination sphere of Rb1 (coordination number 8) is a distorted rectangular prism (Table 1, Fig. 2). It contains two pairs of crystallographically identical O atoms of sulfonyl groups (O3 and O6), two crystallographically identical atoms (O3) of bidentate sulfonyl groups and two crystallographically identical water molecules (O2).

Table 1
Selected bond lengths (Å)

Rb1—O3ⁱ	2.9921 (14)	Rb1—O2ⁱ	3.0473 (15)
Rb1—O3	2.9921 (14)	Na1—O1^iv	2.5123 (16)
Rb1—O3ⁱⁱ	3.1346 (14)	Na1—O1	2.4696 (16)
Rb1—O3ⁱⁱⁱ	3.1346 (14)	Na1—O1ⁱ	2.4696 (16)
Rb1—O6	3.0056 (15)	Na1—O1^v	2.5123 (16)
Rb1—O6ⁱ	3.0056 (15)	Na1—O2	2.4074 (17)
Rb1—O2	3.0473 (15)	Na1—O2ⁱ	2.4074 (16)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z]$ ; (ii) -x+2, -y+1, -z+1; (iii) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (iv) -x+1, -y+1, -z+1; (v) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Figure 1
The numbering scheme for the title compound with 50% probability displacement ellipsoids.

Figure 2
Coordination polyhedra of the metal ions in I. For bond lengths and symmetry codes, see Table 1

Both saccharinate anions are planar with all atoms (except the O atoms of the sulfonyl groups) located on crystallographic mirror planes. The distribution of the Hirshfeld surface electrostatic potential of the anion shows that the negative charge is almost evenly distributed around the carboxyl and sulfonyl oxygen atoms and amide nitrogen atom: the remaining Hirshfeld surface is almost neutral electrostatically.

The coordination polyhedra of the sodium ions are bridged by two edges of a triangle (two crystallographically identical water molecules O1) with an inversion centre located at each edge. This linking forms an infinite chain of hydrated sodium cations along [010].

The coordination polyhedra of the rubidium ions are bridged via a common edge containing the sulfonyl oxygen atom O3; again, an inversion centre is located at each of these edges. Two sulfonyl groups of another saccharinate anion (O6) form a bridge to the next rubidium ion (Fig. 3) from each side of the mirror plane. All these interactions result in a zigzag-type chain along [010]. Two parallel chains of Rb⁺ and Na⁺ ions are bound by two identical water molecules (atom O2) related by mirror planes. These bridges form a layer of hydrated cations parallel to the (001) plane (Fig. 3). The hydrogen atoms of both bridging water molecules form electrostatically enhanced hydrogen bonds with the nitrogen atoms and carbonyl oxygen atoms as acceptors (Table 2, Figs. 3 and 4).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5^vi	0.79 (3)	2.02 (3)	2.801 (2)	170 (2)
O1—H1B⋯O4^v	0.84 (3)	1.99 (3)	2.819 (2)	168 (2)
O2—H2A⋯N2^vi	0.81 (3)	2.12 (3)	2.924 (2)	174 (2)
O2—H2B⋯N1	0.83 (3)	2.09 (3)	2.915 (2)	175 (3)
C5—H5⋯O4^vii	0.95	2.45	3.388 (3)	169
C13—H13⋯O5^viii	0.95	2.47	3.318 (3)	148
Symmetry codes: (v) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (vi) x, y+1, z; (vii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (viii) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 3
The infinite chains of hydrated sodium (green) and rubidium (purple) ions along the [010] direction. View along [001] vector, with 5° offset.

Figure 4
Packing of the title compound viewed along [010]. Sodium ions are green. Hydrogen bonds are shown as dashed lines with the following colour scheme: O—H⋯N: red, O—H⋯O: green and C—H⋯O: blue.

The saccharinate anions are positioned in planes parallel to (010) and are perpendicular to the layer of hydrated cations. Two C—H⋯O enhanced hydrogen bonds (Table 2, Fig. 4) connect anions from neighbouring layers. Additional interlayer binding comes from the stacking interactions. The distance between the planes of aromatic saccharin moieties is 3.2916 (2) Å (exactly half of cell dimension b). This value is short enough to expect an overall attractive interaction of benzene rings (there is no negative electrostatic potential in this area of the saccharine anion).

Synthesis and crystallization

The title compound was crystallized following the published procedure for rubidium saccharinate (Karothu et al., 2017) with a sodium salt being used instead of the acidic form and rubidium chloride instead of rubidium carbonate. Slow crystallization yielded thin needles, some of which were suitable for the single-crystal X-ray experiment. Reaction with caesium chloride under the same conditions yielded the already known caesium saccharinate (refcode FAZHOG; Karothu et al., 2017).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	Na⁺·Rb⁺·2C₇H₄NO₃S⁻·4H₂O
M_r	544.87
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	14.2754 (9), 6.5831 (4), 21.5365 (13)
V (Å³)	2023.9 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.73
Crystal size (mm)	0.79 × 0.09 × 0.05

Data collection
Diffractometer	Bruker PHOTON-100 CMOS
Absorption correction	Numerical (SADABS; Krause et al., 2015 )
T_min, T_max	0.362, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	31423, 2724, 2288
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.067, 1.05
No. of reflections	2724
No. of parameters	185
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.39
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1849000

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008672/bh4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008672/bh4037Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008672/bh4037Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: APEX2 (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Sodium rubidium bis(3-oxo-3H-1,2-benzothiazol-2-ide 1,1-dioxide) tetrahydrate top

Crystal data top

Na⁺·Rb⁺·2C₇H₄NO₃S⁻·4H₂O	D_x = 1.788 Mg m⁻³
M_r = 544.87	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 9989 reflections
a = 14.2754 (9) Å	θ = 3.0–28.1°
b = 6.5831 (4) Å	µ = 2.73 mm⁻¹
c = 21.5365 (13) Å	T = 173 K
V = 2023.9 (2) Å³	Needle, colourless
Z = 4	0.79 × 0.09 × 0.05 mm
F(000) = 1096

Data collection top

Bruker PHOTON-100 CMOS diffractometer	2288 reflections with I > 2σ(I)
Radiation source: sealedtube	R_int = 0.041
ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: numerical (SADABS; Krause et al., 2015)	h = −19→19
T_min = 0.362, T_max = 0.884	k = −8→8
31423 measured reflections	l = −28→21
2724 independent 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)] = 0.027	Hydrogen site location: mixed
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0327P)² + 1.4364P] where P = (F_o² + 2F_c²)/3
2724 reflections	(Δ/σ)_max = 0.001
185 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³
0 constraints

Special details top

Refinement. Hydrogen atoms of water molecules are refined in isotropic approximation. Aromatic hydrogen atoms are refined with riding coordinates and with U_iso (H) = 1.2U_iso (carrier C).

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

	x	y	z	U_iso*/U_eq
Rb1	0.88342 (2)	0.250000	0.53575 (2)	0.02062 (8)
S1	0.87768 (4)	0.750000	0.41360 (3)	0.01658 (14)
O3	0.91761 (9)	0.5667 (2)	0.43872 (6)	0.0250 (3)
O4	0.63582 (12)	0.750000	0.35725 (9)	0.0205 (4)
N1	0.76426 (15)	0.750000	0.42033 (10)	0.0190 (5)
C1	0.72184 (18)	0.750000	0.36403 (12)	0.0156 (5)
C2	0.78955 (18)	0.750000	0.31096 (12)	0.0154 (5)
C3	0.76969 (19)	0.750000	0.24776 (12)	0.0193 (5)
H3	0.706937	0.750000	0.233074	0.023*
C4	0.8449 (2)	0.750000	0.20690 (13)	0.0235 (6)
H4	0.833394	0.750000	0.163452	0.028*
C5	0.9367 (2)	0.750000	0.22833 (13)	0.0266 (6)
H5	0.986743	0.750000	0.199277	0.032*
C6	0.95660 (19)	0.750000	0.29150 (13)	0.0224 (6)
H6	1.019247	0.750000	0.306375	0.027*
C7	0.88137 (18)	0.750000	0.33154 (12)	0.0169 (5)
S2	0.82267 (5)	−0.250000	0.65317 (3)	0.02080 (15)
O5	0.56611 (13)	−0.250000	0.66279 (9)	0.0219 (4)
O6	0.87003 (10)	−0.0638 (3)	0.63672 (7)	0.0330 (4)
N2	0.71624 (16)	−0.250000	0.62557 (10)	0.0203 (5)
C8	0.65226 (19)	−0.250000	0.67156 (12)	0.0166 (5)
C9	0.69418 (18)	−0.250000	0.73533 (11)	0.0157 (5)
C10	0.6489 (2)	−0.250000	0.79189 (12)	0.0189 (5)
H10	0.582487	−0.250000	0.794381	0.023*
C11	0.7040 (2)	−0.250000	0.84519 (12)	0.0237 (6)
H11	0.674624	−0.250000	0.884767	0.028*
C12	0.8011 (2)	−0.250000	0.84165 (13)	0.0252 (6)
H12	0.836769	−0.250000	0.878906	0.030*
C13	0.8475 (2)	−0.250000	0.78489 (13)	0.0224 (6)
H13	0.913937	−0.250000	0.782258	0.027*
C14	0.79153 (18)	−0.250000	0.73245 (12)	0.0177 (5)
Na1	0.56939 (7)	0.250000	0.50765 (5)	0.0186 (2)
O1	0.48492 (10)	0.4992 (2)	0.57256 (6)	0.0215 (3)
O2	0.69978 (10)	0.4792 (2)	0.51854 (7)	0.0241 (3)
H1A	0.5133 (17)	0.561 (4)	0.5976 (11)	0.033 (7)*
H1B	0.4428 (17)	0.437 (4)	0.5921 (11)	0.032 (7)*
H2A	0.7002 (18)	0.553 (4)	0.5485 (12)	0.037 (7)*
H2B	0.7148 (19)	0.558 (5)	0.4902 (12)	0.046 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.01761 (14)	0.02122 (14)	0.02303 (14)	0.000	−0.00236 (10)	0.000
S1	0.0138 (3)	0.0200 (3)	0.0159 (3)	0.000	−0.0008 (2)	0.000
O3	0.0222 (7)	0.0272 (7)	0.0256 (7)	0.0031 (6)	−0.0034 (6)	0.0056 (6)
O4	0.0138 (9)	0.0230 (10)	0.0246 (10)	0.000	0.0016 (7)	0.000
N1	0.0162 (11)	0.0258 (12)	0.0151 (10)	0.000	0.0039 (8)	0.000
C1	0.0176 (13)	0.0104 (11)	0.0189 (12)	0.000	0.0024 (10)	0.000
C2	0.0164 (12)	0.0099 (11)	0.0199 (13)	0.000	0.0014 (10)	0.000
C3	0.0233 (14)	0.0139 (12)	0.0206 (13)	0.000	−0.0008 (11)	0.000
C4	0.0372 (16)	0.0161 (13)	0.0170 (13)	0.000	0.0032 (12)	0.000
C5	0.0310 (16)	0.0214 (14)	0.0274 (15)	0.000	0.0152 (12)	0.000
C6	0.0167 (13)	0.0206 (13)	0.0299 (15)	0.000	0.0048 (11)	0.000
C7	0.0170 (13)	0.0148 (12)	0.0189 (12)	0.000	0.0018 (10)	0.000
S2	0.0174 (3)	0.0257 (3)	0.0193 (3)	0.000	0.0009 (2)	0.000
O5	0.0179 (10)	0.0241 (10)	0.0238 (10)	0.000	−0.0061 (8)	0.000
O6	0.0280 (8)	0.0393 (9)	0.0318 (8)	−0.0114 (7)	0.0021 (6)	0.0078 (7)
N2	0.0196 (12)	0.0258 (12)	0.0156 (11)	0.000	−0.0028 (9)	0.000
C8	0.0191 (13)	0.0140 (12)	0.0167 (12)	0.000	−0.0037 (10)	0.000
C9	0.0208 (13)	0.0098 (11)	0.0166 (12)	0.000	−0.0026 (10)	0.000
C10	0.0216 (13)	0.0124 (12)	0.0228 (13)	0.000	0.0027 (11)	0.000
C11	0.0414 (17)	0.0143 (13)	0.0154 (12)	0.000	−0.0005 (12)	0.000
C12	0.0364 (17)	0.0173 (13)	0.0218 (14)	0.000	−0.0126 (12)	0.000
C13	0.0202 (13)	0.0195 (13)	0.0274 (14)	0.000	−0.0073 (11)	0.000
C14	0.0180 (13)	0.0137 (12)	0.0213 (13)	0.000	−0.0029 (10)	0.000
Na1	0.0193 (5)	0.0170 (5)	0.0194 (5)	0.000	0.0012 (4)	0.000
O1	0.0223 (7)	0.0213 (7)	0.0207 (7)	−0.0049 (6)	0.0012 (6)	−0.0017 (6)
O2	0.0278 (8)	0.0195 (7)	0.0249 (7)	−0.0051 (6)	0.0006 (6)	0.0005 (6)

Geometric parameters (Å, º) top

Rb1—S1ⁱ	3.5807 (7)	S2—O6^v	1.4438 (15)
Rb1—O3ⁱⁱ	2.9921 (14)	S2—N2	1.632 (2)
Rb1—O3	2.9921 (14)	S2—C14	1.764 (3)
Rb1—O3ⁱ	3.1346 (14)	O5—C8	1.244 (3)
Rb1—O3ⁱⁱⁱ	3.1346 (14)	N2—C8	1.347 (3)
Rb1—O6	3.0056 (15)	C8—C9	1.498 (3)
Rb1—O6ⁱⁱ	3.0056 (15)	C9—C10	1.379 (4)
Rb1—O2	3.0473 (15)	C9—C14	1.391 (4)
Rb1—O2ⁱⁱ	3.0473 (15)	C10—H10	0.9500
S1—O3^iv	1.4399 (14)	C10—C11	1.392 (4)
S1—O3	1.4399 (14)	C11—H11	0.9500
S1—N1	1.626 (2)	C11—C12	1.389 (4)
S1—C7	1.768 (3)	C12—H12	0.9500
O4—C1	1.237 (3)	C12—C13	1.390 (4)
N1—C1	1.355 (3)	C13—H13	0.9500
C1—C2	1.497 (3)	C13—C14	1.384 (4)
C2—C3	1.390 (4)	Na1—O1^vi	2.5123 (16)
C2—C7	1.384 (4)	Na1—O1	2.4696 (16)
C3—H3	0.9500	Na1—O1ⁱⁱ	2.4696 (16)
C3—C4	1.388 (4)	Na1—O1^vii	2.5123 (16)
C4—H4	0.9500	Na1—O2	2.4074 (17)
C4—C5	1.389 (4)	Na1—O2ⁱⁱ	2.4074 (16)
C5—H5	0.9500	O1—H1A	0.79 (3)
C5—C6	1.390 (4)	O1—H1B	0.84 (3)
C6—H6	0.9500	O2—H2A	0.81 (3)
C6—C7	1.377 (4)	O2—H2B	0.83 (3)
S2—O6	1.4438 (15)

O3ⁱⁱ—Rb1—S1ⁱ	93.29 (3)	C6—C5—H5	119.4
O3ⁱ—Rb1—S1ⁱ	23.58 (3)	C5—C6—H6	121.5
O3—Rb1—S1ⁱ	93.29 (3)	C7—C6—C5	117.0 (3)
O3ⁱⁱⁱ—Rb1—S1ⁱ	23.58 (3)	C7—C6—H6	121.5
O3—Rb1—O3ⁱⁱⁱ	104.06 (3)	C2—C7—S1	106.98 (18)
O3—Rb1—O3ⁱ	72.93 (4)	C6—C7—S1	130.5 (2)
O3ⁱⁱ—Rb1—O3ⁱⁱⁱ	72.93 (4)	C6—C7—C2	122.5 (2)
O3ⁱ—Rb1—O3ⁱⁱⁱ	45.28 (5)	O6—S2—O6^v	116.16 (13)
O3ⁱⁱ—Rb1—O3ⁱ	104.06 (3)	O6—S2—N2	110.28 (7)
O3ⁱⁱ—Rb1—O3	88.35 (5)	O6^v—S2—N2	110.28 (7)
O3ⁱⁱ—Rb1—O6	92.10 (4)	O6—S2—C14	110.83 (8)
O3—Rb1—O6	174.09 (4)	O6^v—S2—C14	110.83 (8)
O3ⁱⁱ—Rb1—O6ⁱⁱ	174.09 (4)	N2—S2—C14	96.77 (12)
O3—Rb1—O6ⁱⁱ	92.10 (4)	S2—O6—Rb1	142.26 (9)
O3—Rb1—O2ⁱⁱ	113.60 (4)	C8—N2—S2	111.31 (17)
O3ⁱⁱ—Rb1—O2ⁱⁱ	73.16 (4)	O5—C8—N2	124.0 (2)
O3—Rb1—O2	73.16 (4)	O5—C8—C9	122.3 (2)
O3ⁱⁱ—Rb1—O2	113.60 (4)	N2—C8—C9	113.8 (2)
O6ⁱⁱ—Rb1—S1ⁱ	80.80 (3)	C10—C9—C8	128.5 (2)
O6—Rb1—S1ⁱ	80.80 (3)	C10—C9—C14	120.5 (2)
O6ⁱⁱ—Rb1—O3ⁱⁱⁱ	101.26 (4)	C14—C9—C8	111.0 (2)
O6—Rb1—O3ⁱ	101.26 (4)	C9—C10—H10	121.2
O6—Rb1—O3ⁱⁱⁱ	70.50 (4)	C9—C10—C11	117.6 (3)
O6ⁱⁱ—Rb1—O3ⁱ	70.50 (4)	C11—C10—H10	121.2
O6ⁱⁱ—Rb1—O6	86.85 (6)	C10—C11—H11	119.4
O6ⁱⁱ—Rb1—O2ⁱⁱ	111.94 (4)	C12—C11—C10	121.3 (3)
O6—Rb1—O2	111.94 (4)	C12—C11—H11	119.4
O6ⁱⁱ—Rb1—O2	72.12 (4)	C11—C12—H12	119.2
O6—Rb1—O2ⁱⁱ	72.12 (4)	C11—C12—C13	121.6 (3)
O2ⁱⁱ—Rb1—S1ⁱ	148.92 (3)	C13—C12—H12	119.2
O2—Rb1—S1ⁱ	148.92 (3)	C12—C13—H13	121.9
O2ⁱⁱ—Rb1—O3ⁱⁱⁱ	127.61 (4)	C14—C13—C12	116.3 (3)
O2—Rb1—O3ⁱⁱⁱ	172.50 (4)	C14—C13—H13	121.9
O2—Rb1—O3ⁱ	127.61 (4)	C9—C14—S2	107.16 (19)
O2ⁱⁱ—Rb1—O3ⁱ	172.50 (4)	C13—C14—S2	130.1 (2)
O2ⁱⁱ—Rb1—O2	59.35 (5)	C13—C14—C9	122.7 (3)
O3^iv—S1—Rb1ⁱ	60.56 (6)	O1^vii—Na1—O1^vi	82.18 (7)
O3—S1—Rb1ⁱ	60.56 (6)	O1ⁱⁱ—Na1—O1^vi	132.46 (5)
O3—S1—O3^iv	113.84 (12)	O1—Na1—O1^vi	78.58 (5)
O3^iv—S1—N1	111.15 (7)	O1—Na1—O1ⁱⁱ	83.25 (8)
O3—S1—N1	111.15 (7)	O1ⁱⁱ—Na1—O1^vii	78.58 (5)
O3—S1—C7	111.33 (7)	O1—Na1—O1^vii	132.46 (5)
O3^iv—S1—C7	111.33 (7)	O2ⁱⁱ—Na1—O1	137.62 (7)
N1—S1—Rb1ⁱ	157.14 (8)	O2—Na1—O1^vi	83.90 (5)
N1—S1—C7	96.83 (11)	O2—Na1—O1ⁱⁱ	137.62 (7)
C7—S1—Rb1ⁱ	106.03 (9)	O2ⁱⁱ—Na1—O1ⁱⁱ	84.61 (5)
Rb1—O3—Rb1ⁱ	107.07 (4)	O2—Na1—O1	84.61 (5)
S1—O3—Rb1ⁱ	95.86 (7)	O2—Na1—O1^vii	135.84 (7)
S1—O3—Rb1	141.42 (8)	O2ⁱⁱ—Na1—O1^vii	83.90 (5)
C1—N1—S1	111.42 (17)	O2ⁱⁱ—Na1—O1^vi	135.84 (7)
O4—C1—N1	123.3 (2)	O2—Na1—O2ⁱⁱ	77.61 (8)
O4—C1—C2	123.4 (2)	Na1—O1—Na1^vi	101.42 (5)
N1—C1—C2	113.2 (2)	Na1^vi—O1—H1A	106.7 (18)
C3—C2—C1	128.0 (2)	Na1—O1—H1A	118.8 (18)
C7—C2—C1	111.5 (2)	Na1—O1—H1B	107.9 (17)
C7—C2—C3	120.5 (2)	Na1^vi—O1—H1B	116.4 (16)
C2—C3—H3	121.2	H1A—O1—H1B	106 (2)
C4—C3—C2	117.6 (3)	Rb1—O2—H2A	101.2 (18)
C4—C3—H3	121.2	Rb1—O2—H2B	100.2 (19)
C3—C4—H4	119.4	Na1—O2—Rb1	111.51 (5)
C3—C4—C5	121.3 (3)	Na1—O2—H2A	117.3 (18)
C5—C4—H4	119.4	Na1—O2—H2B	121.4 (19)
C4—C5—H5	119.4	H2A—O2—H2B	102 (3)
C4—C5—C6	121.2 (3)

Rb1ⁱ—S1—O3—Rb1	127.00 (13)	C7—S1—O3—Rb1ⁱ	96.89 (9)
Rb1ⁱ—S1—N1—C1	180.000 (1)	C7—S1—N1—C1	0.000 (1)
Rb1ⁱ—S1—C7—C2	180.000 (1)	C7—C2—C3—C4	0.000 (1)
Rb1ⁱ—S1—C7—C6	0.000 (1)	S2—N2—C8—O5	180.000 (1)
S1—N1—C1—O4	180.000 (1)	S2—N2—C8—C9	0.000 (1)
S1—N1—C1—C2	0.000 (1)	O5—C8—C9—C10	0.000 (1)
O3^iv—S1—O3—Rb1	97.06 (14)	O5—C8—C9—C14	180.000 (1)
O3^iv—S1—O3—Rb1ⁱ	−29.94 (12)	O6^v—S2—O6—Rb1	92.86 (16)
O3—S1—N1—C1	−116.05 (7)	O6^v—S2—N2—C8	115.19 (8)
O3^iv—S1—N1—C1	116.05 (7)	O6—S2—N2—C8	−115.19 (8)
O3^iv—S1—C7—C2	−115.91 (7)	O6^v—S2—C14—C9	−114.75 (8)
O3—S1—C7—C2	115.91 (7)	O6—S2—C14—C9	114.75 (8)
O3^iv—S1—C7—C6	64.09 (7)	O6^v—S2—C14—C13	65.25 (8)
O3—S1—C7—C6	−64.09 (7)	O6—S2—C14—C13	−65.25 (8)
O4—C1—C2—C3	0.000 (1)	N2—S2—O6—Rb1	−33.53 (17)
O4—C1—C2—C7	180.000 (1)	N2—S2—C14—C9	0.000 (1)
N1—S1—O3—Rb1	−29.37 (15)	N2—S2—C14—C13	180.000 (1)
N1—S1—O3—Rb1ⁱ	−156.38 (8)	N2—C8—C9—C10	180.000 (1)
N1—S1—C7—C2	0.000 (1)	N2—C8—C9—C14	0.000 (1)
N1—S1—C7—C6	180.000 (1)	C8—C9—C10—C11	180.000 (1)
N1—C1—C2—C3	180.000 (1)	C8—C9—C14—S2	0.000 (1)
N1—C1—C2—C7	0.000 (1)	C8—C9—C14—C13	180.000 (1)
C1—C2—C3—C4	180.000 (1)	C9—C10—C11—C12	0.000 (1)
C1—C2—C7—S1	0.000 (1)	C10—C9—C14—S2	180.000 (1)
C1—C2—C7—C6	180.000 (1)	C10—C9—C14—C13	0.000 (1)
C2—C3—C4—C5	0.000 (1)	C10—C11—C12—C13	0.000 (1)
C3—C2—C7—S1	180.000 (1)	C11—C12—C13—C14	0.000 (1)
C3—C2—C7—C6	0.000 (1)	C12—C13—C14—S2	180.000 (1)
C3—C4—C5—C6	0.000 (1)	C12—C13—C14—C9	0.000 (1)
C4—C5—C6—C7	0.000 (1)	C14—S2—O6—Rb1	−139.50 (14)
C5—C6—C7—S1	180.000 (1)	C14—S2—N2—C8	0.000 (1)
C5—C6—C7—C2	0.000 (1)	C14—C9—C10—C11	0.000 (1)
C7—S1—O3—Rb1	−136.11 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5^viii	0.79 (3)	2.02 (3)	2.801 (2)	170 (2)
O1—H1B···O4^vii	0.84 (3)	1.99 (3)	2.819 (2)	168 (2)
O2—H2A···N2^viii	0.81 (3)	2.12 (3)	2.924 (2)	174 (2)
O2—H2B···N1	0.83 (3)	2.09 (3)	2.915 (2)	175 (3)
C5—H5···O4^ix	0.95	2.45	3.388 (3)	169
C13—H13···O5^x	0.95	2.47	3.318 (3)	148

Symmetry codes: (vii) −x+1, y−1/2, −z+1; (viii) x, y+1, z; (ix) x+1/2, −y+3/2, −z+1/2; (x) x+1/2, −y−1/2, −z+3/2.

Funding information

Financial support from the State University of New York for the acquisition and maintenance of the X-ray diffractometer is gratefully acknowledged.

References

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