Disodium 5,5′-diamino-2,2′-ethyl­enedibenzene­sulfonate tetra­hydrate

In the title disodium salt, 2Na⁺·C₁₄H₁₂N₂O₆S₂²⁻·4H₂O, the two aryl units of the centrosymmetric anion are coplanar. The E geometric isomer was exclusively found, while the mean plane of the unsaturated group is twisted by 10.1 (2)° from the mean plane described by the two amino­benzenes. Four water mol­ecules cocrystallize and participate in inter­molecular hydrogen bonding. The anions lie in parallel planes separated by 3.367 (16) Å and their symmetry-related benzene rings are separated by 3.84 (1) Å, leading to weak inter­molecular π-stacking.

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.068
• wR factor = 0.185
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96

Author Response: ...With regard to the missing completeness of the reflection data: The structure was measured on a newly installed (July 2006) Bruker X8 Proteum four circle diffractometer with a fine-focused rotating anode source with Cu radiation. This diffractometer is equipped with a sample changing robot, which limits access of the detector at high positive theta-angles. The beam stop support limits access at high negative theta-angles. The reported completeness and two theta values are the maximum values obtainable with the instrument, already optimized by using a data collection strategy employing two different crystal detector distances and the collection of ALL accessible data.

PLAT420_ALERT_2_B D-H Without Acceptor       O4     -   H4B    ...          ?

Author Response: ...We let the proton rotate and didn't find other minimum of potential. It is the only one that has no H-bond acceptor.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?

Author Response: The molecule is on the inversion centre of the P21/c lattice. The formula is then twice the calculated one.

PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

Author Response: The molecule is on the inversion centre of the P21/c lattice. The formula is then twice the calculated one.

PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio

Author Response: The molecule is on the inversion centre of the P21/c lattice. The formula is then twice the calculated one.

PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio

Author Response: ...this is probably due to nitrogen protons. Their Ueq are fixed to 1.5Ueq of the nitrogen and the nitrogens have some libration as they are terminal in the molecule.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

Author Response: ... they are explained in the experimental refinement section.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Stilbenes are an interesting class of compounds that can be photoexcited with standard UV irradiation sources because of their high degree of conjugation. Even though diamininostilbene (I) is an extended stilbene, photoinduced conversion does not proceed resulting in high fluorescence (Zhao et al., 1996). Owing to our on-going azomethine (–N=C–) research, (Pérez Guarìn et al., 2007), we examined (I) as a novel monomer for the synthesis of unprecedented water soluble conjugated functional materials. (Dufresne et al., 2007) Its diamine residues are suitable for condensation with aryl aldehydes for preparation of the pi-conjugated compounds. During the course of this research we isolated (I), whose crystallographic study is discussed herein. This study is of importance for assigning the geometric isomer, co-planarity of the stilbene moiety, and cation exchange, all of which cannot be unequivocally confirmed by standard characterization techniques such as ¹H and ¹³C NMR.

The resulting crystal structure found for (I) confirmed that the compound contained the stilbenoid structure with the two sulfonate groups in the 2,2' positions. Of importance, the exchange of the original two H atoms with sodium cations on the two sulfonic acid groups was confirmed from the X-ray analysis. Four water molecules were found to coordinate with the sulfonic moieties to further stabilize the charges of the ionic groups. Confirmation of the amine substitution in the para position of the stilbene was also possible. The exclusive formation of the thermodynamic E isomer was also confirmed.

Even though stilbenes are generally understood to be completely planar, the structure obtained for (I) illustrates this is not the case. The mean plane described by the phenyl rings is rotated 10.14 (24) ° from the mean plane of the unsaturated alkene to which they are covalently bonded. For comparison, the angle described by similar planes for analogous unsubstituted stilbenes is much smaller ranging between 2.7 (4) ° (Wang et al., 2005) and 1.9 (3) ° (Zhang et al., 2005). The larger degree of twisting from planarity for the phenyl rings of (I) is a result of the bulky sulfonic groups that reduce the amount of intermolecular p-stacking.

Besides the cation required to counter balance the sulfonate group, three additional sodium cations were found in close proximity to the ionic group. The distance separating the sodium cations of adjacent molecules is 3.588 (1) Å. One counter cation is located 2.539 (2) Å from the anionic O3 while the two other cations are 2.399 (2) and 2.421 (2) Å from O1. All the cations are within sufficient proximity to be described as counter ions of the sulfonate group. The sodium cations are symmetry related and the negative charge is uniformly spread over all oxygen atoms of the sulfonate. There are additionally two water molecules per sodium cation (Fig. 2) that are co-crystallized within the structure. These solvate the sodium cations and are located 2.419 (2) and 2.383 (3) Å from the cation.

In addition to these ionic interactions, hydrogen bonding also occurs in an anticipated manner predicted by Etter's topological descriptors (Etter, 1990). Three such hydrogen bonds take place between the hydrogen donors of the co-crystallized water molecules and (I), represented in Fig. 3. Specifically the interactions are: O4—H4A···N1ⁱⁱ, O5—H5A···O2ⁱⁱⁱ and O5—H5B···O2^iv whose lengths are 2.818 (3), 2.942 (3), and 2.915 (3) Å, respectively. The amino groups act both as donors and acceptors via the hydrogen and its nitrogen to form N—H···O and H···N interactions, respectively. Such hydrogen bonding occurs via N1—H1A···O3^v of the sulfonate and N1—H1B···O5^v of a water molecule. The distances of these hydrogen bonds are 3.236 (3) and 3.403 (3) Å, respectively. Each hydrogen present in (I) participates in hydrogen bonds with the exception for H4B.

Overlapping of the aryl groups resulting in pi-stacking normally takes place with conjugated aromatic compounds such as stilbenes. This is not entirely the case with (I). While the distance of 3.367 (16) Å separating similarly parallel molecules of (I) is ideal for pi-stacking, such a strong interaction is not expected because the aryl units are not completely superimposed. However, there is some overlap between the symmetrically related phenyl rings C2—C7 whose distance between the ring centroids is 3.84 (1) Å. This leads to weaker pi-stacking in comparison to its unsubstituted analogue.

Related literature

For general background, see: Dufresne et al. (2007); Pérez Guarìn et al. (2007) and references therein; Zhao et al. (1996). For related literature, see: Wang et al. (2005); Zhang et al. (2005); Etter (1990).

S2. Experimental

The commercially available 4,4'-diamino-2,2'-stilbene-disulfonic acid from Aldrich was dissolved in a NaOH solution. It was then purified by successive acid and base washes. The desired water soluble product was obtained by adjusting the pH ≥ 8 with NaOH and then it was recrystallized by slow evaporation in ethanol.

S3. Refinement

H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and included in the refinement in the riding-model approximation, with U_iso(H) = 1.2 U_eq(C). Some special constraints were added for hydrogen on nitrogen (N—H = 0.87 /%A) with U_iso(H) = 1.5 U_eq(C) and for hydrogen on oxygen (O—H = 0.83 /%A) with U_iso(H) = 1.5 U_eq(C). More constraints were used on these protons to get more realistic angle for amine and water protons.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (Marris, 2004).

Figures

	Fig. 1. ORTEP representation of (I) with the numbering scheme adopted (Farrugia 1997). Ellipsoids drawn at 30% probability level. [Symmetry code: (i) -x, 1 - y, -z.]
	Fig. 2. The three-dimensional network demonstrating the well arranged ionic assembly between sulfonate group, sodium cations and water molecule. Hydrogen atoms have been omitted for clarity. [Symmetry codes: (i) -x, 1 - y, -z; (iv) x, y, 1 + z; (viii) -x, 1 - y, 1 - z; (ix) -x, -1/2 + y, 1/2 - z; (x) -x, -1/2 + y, -1/2 + z; (xi) x, y, -1 + z; (xii) x, 1.5 - y, -1/2 + z; (xiii) x, 1.5 - y, 1/2 + z.]
	Fig. 3. Supramolecular structure showing the intermolecular H-bonding giving the structural arrangement. Dashed lines indicate hydrogen bonds. Only H-bonding hydrogen atoms are shown for clarity. [Symmetry codes: (i) -x, 1 - y, -z; (ii) 1 + x, y, z; (iii) 1 - x, y, z; (iv) x, y, 1 + z; (v) 1 - x, 1 - y, 1 - z; (vi) 1 - x, 1 - y, -z; (vii) 1 + x, y, 1 + z; (viii) -x, 1 - y, 1 - z.]

Disodium 5,5'-diamino-2,2'-ethylenedibenzenesulfonate tetrahydrate

Crystal data

2Na^+·C14H12N2O6S2^2^−·4H2O	F(000) = 504
Mr = 486.43	Dx = 1.704 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2942 reflections
a = 8.1415 (6) Å	θ = 4.7–72.1°
b = 18.6885 (15) Å	µ = 3.56 mm^−1
c = 6.3230 (5) Å	T = 220 K
β = 99.860 (4)°	Block, orange
V = 947.85 (13) Å^3	0.18 × 0.18 × 0.07 mm
Z = 2

Data collection

Bruker SMART 2000 diffractometer	1778 independent reflections
Radiation source: X-ray Sealed Tube	1617 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 5.5 pixels mm^-1	θmax = 72.1°, θmin = 4.7°
ω scans	h = −8→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −23→21
Tmin = 0.560, Tmax = 0.779	l = −7→7
4637 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1547P)^2] where P = (Fo^2 + 2Fc^2)/3
1778 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.79 e Å^−3
9 restraints	Δρmin = −0.77 e Å^−3

Special details

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.47929 (13)	0.70461 (6)	0.82314 (16)	0.0220 (3)
S1	0.31622 (6)	0.63408 (3)	0.27575 (8)	0.0134 (3)
O1	0.4039 (2)	0.68007 (10)	0.4429 (3)	0.0235 (5)
O2	0.4037 (2)	0.56729 (10)	0.2570 (3)	0.0233 (5)
O3	0.2760 (2)	0.67132 (12)	0.0699 (3)	0.0249 (5)
O4	0.6775 (2)	0.78332 (11)	0.6530 (3)	0.0232 (5)
H4A	0.759 (2)	0.7566 (12)	0.688 (5)	0.035*
H4B	0.697 (4)	0.8187 (10)	0.733 (4)	0.035*
O5	0.5550 (3)	0.58184 (12)	0.8734 (4)	0.0391 (6)
H5A	0.527 (6)	0.5482 (13)	0.789 (4)	0.059*
H5B	0.522 (5)	0.5698 (19)	0.985 (3)	0.059*
N1	−0.0974 (3)	0.67174 (14)	0.7935 (3)	0.0226 (5)
H1A	−0.010 (2)	0.6876 (17)	0.879 (3)	0.034*
H1B	−0.168 (3)	0.6459 (17)	0.849 (4)	0.034*
C1	0.0441 (3)	0.52710 (13)	0.0485 (4)	0.0160 (5)
H1	0.1357	0.5430	−0.0112	0.019*
C2	0.0102 (3)	0.56404 (12)	0.2411 (4)	0.0138 (5)
C3	−0.1390 (3)	0.55170 (14)	0.3206 (4)	0.0179 (5)
H3	−0.2168	0.5190	0.2484	0.021*
C4	−0.1748 (3)	0.58591 (14)	0.5005 (4)	0.0188 (6)
H4	−0.2759	0.5766	0.5481	0.023*
C5	−0.0613 (3)	0.63444 (13)	0.6121 (4)	0.0158 (6)
C6	0.0858 (3)	0.64861 (14)	0.5362 (4)	0.0165 (5)
H6	0.1616	0.6823	0.6071	0.020*
C7	0.1217 (3)	0.61327 (13)	0.3559 (3)	0.0126 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0202 (6)	0.0241 (6)	0.0203 (6)	−0.0008 (4)	−0.0003 (4)	−0.0023 (4)
S1	0.0093 (4)	0.0144 (4)	0.0157 (4)	−0.00317 (18)	−0.0002 (3)	−0.00306 (18)
O1	0.0183 (9)	0.0256 (10)	0.0263 (10)	−0.0104 (8)	0.0035 (8)	−0.0093 (7)
O2	0.0164 (9)	0.0205 (10)	0.0337 (10)	0.0007 (7)	0.0066 (8)	−0.0051 (7)
O3	0.0194 (9)	0.0303 (11)	0.0246 (10)	−0.0028 (8)	0.0032 (8)	0.0092 (8)
O4	0.0189 (9)	0.0234 (10)	0.0242 (10)	0.0016 (7)	−0.0051 (7)	−0.0037 (7)
O5	0.0607 (16)	0.0227 (11)	0.0404 (12)	0.0024 (10)	0.0267 (12)	−0.0028 (9)
N1	0.0217 (11)	0.0282 (12)	0.0179 (11)	0.0057 (9)	0.0029 (9)	−0.0026 (8)
C1	0.0125 (11)	0.0186 (11)	0.0163 (11)	−0.0034 (9)	0.0007 (9)	−0.0018 (9)
C2	0.0128 (11)	0.0137 (11)	0.0134 (11)	−0.0010 (8)	−0.0023 (9)	0.0014 (8)
C3	0.0103 (11)	0.0206 (12)	0.0210 (12)	−0.0045 (9)	−0.0019 (9)	0.0005 (9)
C4	0.0116 (11)	0.0232 (14)	0.0215 (12)	0.0000 (9)	0.0022 (10)	0.0028 (10)
C5	0.0146 (12)	0.0177 (13)	0.0143 (12)	0.0060 (8)	0.0002 (9)	0.0031 (8)
C6	0.0132 (11)	0.0179 (11)	0.0162 (12)	0.0011 (9)	−0.0036 (9)	−0.0029 (9)
C7	0.0093 (10)	0.0133 (11)	0.0140 (11)	−0.0001 (8)	−0.0012 (8)	0.0010 (8)

Geometric parameters (Å, º)

Na1—O5	2.383 (3)	N1—H1a	0.87 (2)
Na1—O1	2.421 (2)	N1—H1b	0.87 (3)
Na1—O4	2.553 (2)	C1—C2	1.467 (3)
C1—C1^i	1.329 (3)	C1—H1	0.94
S1—O1	1.4516 (18)	C2—C7	1.404 (3)
S1—O2	1.452 (2)	C2—C3	1.411 (3)
S1—O3	1.4627 (19)	C3—C4	1.378 (4)
S1—C7	1.787 (2)	C3—H3	0.94
O4—H4a	0.83 (2)	C4—C5	1.397 (4)
O4—H4b	0.83 (2)	C4—H4	0.94
O5—H5a	0.83 (2)	C5—C6	1.390 (4)
O5—H5b	0.83 (3)	C6—C7	1.391 (3)
N1—C5	1.415 (3)	C6—H6	0.94
O5—NA1—O1^ii	153.80 (8)	O3—S1—C7	106.35 (11)
O5—NA1—O4^ii	81.70 (9)	O2—S1—NA1^iv	126.86 (8)
O1^ii—NA1—O4^ii	79.22 (7)	O3—S1—NA1^iv	70.74 (9)
O5—NA1—O1	88.05 (8)	C7—S1—NA1^iv	122.52 (8)
O1^ii—NA1—O1	116.66 (8)	S1—O1—NA1^iv	115.00 (11)
O4^ii—NA1—O1	153.13 (8)	S1—O1—NA1	147.64 (12)
O5—NA1—O3^iii	82.13 (8)	NA1^iv—O1—NA1	96.21 (7)
O1^ii—NA1—O3^iii	78.29 (8)	S1—O3—NA1^v	126.38 (11)
O4^ii—NA1—O3^iii	84.37 (7)	NA1^iv—O4—NA1	92.32 (7)
O1—NA1—O3^iii	118.86 (7)	NA1^iv—O4—H4A	132 (2)
O5—NA1—O4	116.31 (8)	NA1—O4—H4A	94 (2)
O1^ii—NA1—O4	80.20 (7)	NA1^iv—O4—H4B	118.70 (19)
O4^ii—NA1—O4	86.16 (7)	NA1—O4—H4B	106 (3)
O1—NA1—O4	76.22 (7)	H4A—O4—H4B	105 (3)
O3^iii—NA1—O4	157.77 (8)	NA1—O5—H5A	127 (3)
O5—NA1—S1^ii	170.56 (7)	NA1—O5—H5B	105 (3)
O1^ii—NA1—S1^ii	23.59 (5)	H5A—O5—H5B	104 (3)
O4^ii—NA1—S1^ii	101.10 (6)	C5—N1—H1A	114 (2)
O1—NA1—S1^ii	93.06 (6)	C5—N1—H1B	107 (2)
O3^iii—NA1—S1^ii	89.15 (6)	H1A—N1—H1B	118 (2)
O4—NA1—S1^ii	73.01 (5)	C1^i—C1—C2	125.3 (3)
O5—NA1—NA1^iv	122.26 (6)	C1^i—C1—H1	117.3
O1^ii—NA1—NA1^iv	83.80 (6)	C2—C1—H1	117.3
O4^ii—NA1—NA1^iv	127.95 (6)	C7—C2—C3	116.3 (2)
O1—NA1—NA1^iv	41.65 (5)	C7—C2—C1	122.8 (2)
O3^iii—NA1—NA1^iv	139.09 (5)	C3—C2—C1	121.0 (2)
O4—NA1—NA1^iv	42.36 (5)	C4—C3—C2	122.3 (2)
S1^ii—NA1—NA1^iv	63.06 (3)	C4—C3—H3	118.9
O5—NA1—NA1^ii	112.13 (6)	C2—C3—H3	118.9
O1^ii—NA1—NA1^ii	42.13 (5)	C3—C4—C5	120.2 (2)
O4^ii—NA1—NA1^ii	45.32 (5)	C3—C4—H4	119.9
O1—NA1—NA1^ii	157.86 (7)	C5—C4—H4	119.9
O3^iii—NA1—NA1^ii	58.39 (5)	C6—C5—C4	119.0 (2)
O4—NA1—NA1^ii	101.20 (6)	C6—C5—N1	119.8 (2)
S1^ii—NA1—NA1^ii	65.53 (3)	C4—C5—N1	121.2 (2)
NA1^iv—NA1—NA1^ii	123.56 (6)	C5—C6—C7	120.4 (2)
O1—S1—O2	112.45 (12)	C5—C6—H6	119.8
O1—S1—O3	111.93 (13)	C7—C6—H6	119.8
O2—S1—O3	112.00 (12)	C6—C7—C2	121.8 (2)
O1—S1—C7	105.75 (11)	C6—C7—S1	116.73 (18)
O2—S1—C7	107.88 (11)	C2—C7—S1	121.45 (17)
O2—S1—O1—NA1^iv	120.85 (12)	O4^ii—NA1—O4—NA1^iv	−171.25 (9)
O3—S1—O1—NA1^iv	−6.25 (16)	O1—NA1—O4—NA1^iv	29.20 (7)
C7—S1—O1—NA1^iv	−121.64 (11)	O3^iii—NA1—O4—NA1^iv	−106.34 (19)
O2—S1—O1—NA1	−75.6 (2)	S1^ii—NA1—O4—NA1^iv	−68.41 (5)
O3—S1—O1—NA1	157.3 (2)	NA1^ii—NA1—O4—NA1^iv	−128.27 (6)
C7—S1—O1—NA1	41.9 (3)	C1^i—C1—C2—C7	169.8 (3)
NA1^iv—S1—O1—NA1	163.5 (3)	C1^i—C1—C2—C3	−10.4 (5)
O5—NA1—O1—S1	47.6 (2)	C7—C2—C3—C4	0.1 (4)
O1^ii—NA1—O1—S1	−123.28 (18)	C1—C2—C3—C4	−179.6 (2)
O4^ii—NA1—O1—S1	114.9 (2)	C2—C3—C4—C5	−0.4 (4)
O3^iii—NA1—O1—S1	−32.3 (3)	C3—C4—C5—C6	1.3 (4)
O4—NA1—O1—S1	165.3 (2)	C3—C4—C5—N1	178.2 (2)
S1^ii—NA1—O1—S1	−123.0 (2)	C4—C5—C6—C7	−2.0 (4)
NA1^iv—NA1—O1—S1	−165.0 (3)	N1—C5—C6—C7	−178.9 (2)
NA1^ii—NA1—O1—S1	−108.8 (3)	C5—C6—C7—C2	1.8 (4)
O5—NA1—O1—NA1^iv	−147.35 (8)	C5—C6—C7—S1	−178.65 (18)
O1^ii—NA1—O1—NA1^iv	41.75 (14)	C3—C2—C7—C6	−0.8 (3)
O4^ii—NA1—O1—NA1^iv	−80.11 (18)	C1—C2—C7—C6	178.9 (2)
O3^iii—NA1—O1—NA1^iv	132.75 (8)	C3—C2—C7—S1	179.65 (18)
O4—NA1—O1—NA1^iv	−29.64 (7)	C1—C2—C7—S1	−0.6 (3)
S1^ii—NA1—O1—NA1^iv	42.03 (7)	O1—S1—C7—C6	6.5 (2)
NA1^ii—NA1—O1—NA1^iv	56.23 (19)	O2—S1—C7—C6	127.03 (19)
O1—S1—O3—NA1^v	73.67 (18)	O3—S1—C7—C6	−112.6 (2)
O2—S1—O3—NA1^v	−53.67 (17)	NA1^iv—S1—C7—C6	−35.4 (2)
C7—S1—O3—NA1^v	−171.30 (13)	O1—S1—C7—C2	−173.98 (19)
NA1^iv—S1—O3—NA1^v	69.30 (12)	O2—S1—C7—C2	−53.4 (2)
O5—NA1—O4—NA1^iv	109.98 (9)	O3—S1—C7—C2	66.9 (2)
O1^ii—NA1—O4—NA1^iv	−91.53 (7)	NA1^iv—S1—C7—C2	144.13 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N1^vi	0.83 (2)	2.02 (1)	2.818 (3)	163 (3)
O5—H5A···O2^vii	0.83 (2)	2.26 (3)	2.942 (3)	139 (4)
O5—H5B···O2^iii	0.83 (3)	2.11 (3)	2.915 (3)	164 (4)
N1—H1A···O3^iii	0.87 (2)	2.45 (2)	3.236 (3)	151 (3)
N1—H1B···O5^viii	0.87 (3)	2.58 (3)	3.403 (3)	158 (2)

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