A barium complex of a phenoxazinone sulfonate dye

An aqueous reaction of barium hydroxide and 3-amino-4-hy­droxy­benzene­sulfonic acid yielded a very small amount of an unexpected product, bis­(2-amino-3-oxo-3H-phenoxazine-8-sulfonato)­tetra­aqua­barium, [Ba(C₁₂H₇N₂O₅S)₂(H₂O)₄], (I). The compound crystallizes in the triclinic space group P1 with all atoms on general positions. The barium cation is 8-coordinate with three sulfonate O atoms, one carbonyl O atom, and four water mol­ecules at Ba—O distances of 2.716 (2) to 2.807 (1) Å. The two independent anions have essentially planar phenoxazinone systems with an angle of ca 2.4° between them. The extended structure has columns of nearly parallel anions that are bridged by the hydrated barium cations so that the overall motif consists of alternating layers of inorganic cations and organic anions. The packing is reinforced by O—H⋯O and N—H⋯O hydrogen bonds involving the coordinated water mol­ecules, amine groups, and sulfonate groups. This is the first reported structure of a metal salt of a phenoxazinone sulfonate derivative. The condensation of 3-amino-4-hy­droxy­benzene­sulfonic acid to form the phenoxazinone is known to occur in an enzyme-catalyzed reaction, though how or when it occurred here is uncertain.

1. Chemical context

Organo­sulfonate anions have been an active focus as building blocks for metal–organic framework (MOF) structures for the past few decades (Zhang & Fei, 2019; Dey et al., 2014; Shimizu et al., 2009). As part of our continuing inter­est in metal organo­sulfonate salts (Bettinger et al., 2022), we recently attempted to prepare a barium 3-amino-4-hy­droxy­benzene­sulfonate compound. No crystals of the target product were obtained but a small yield of an unexpected product, bis­(2-amino-3-oxo-3H-phenoxazine-8-sulfonato)­tetra­aqua­barium, (I), was discovered and structurally characterized. We subsequently learned that the starting 3-amino-4-hy­droxy­benzene­sulfonic acid (i) can be converted to the observed 2-amino-3-oxo-3H-phenoxazine-8-sulfonic acid (ii) via an enzyme produced by a fungus (Forte et al., 2010).

The product sulfonate belongs to a class of tricyclic organic compounds that are of inter­est as dyes (Bruyneel et al., 2010) and pharmacological agents (Graf et al., 2007; Zhou et al., 2021). To our knowledge, this is the first crystal structure of a metal complex of a sulfonate derivative containing the phenoxazine ring system.

2. Structural commentary

The reaction of barium hydroxide octa­hydrate and 3-amino-4-hy­droxy­benzene­sulfonic acid monohydrate in water with gentle heating and slow evaporation to dryness at ambient temperature and pressure repeatedly produces a polycrystalline residue. In one such reaction, a couple of small clusters of red needle-shaped crystals were found. The structure determination revealed the crystals to be bis­(2-amino-3-oxo-3H-phenoxazine-8-sulfonato)­tetra­aqua­barium, Ba(C₁₂H₇N₂O₅S)₂(H₂O)₄, (I). The compound crystallizes in the triclinic space group P with the asymmetric unit consisting of one barium cation, two 2-amino-3-oxo-3H-phenoxazine-8-sulfonate anions, and four coordinated water mol­ecules, all in general positions. The barium ion has an eightfold coordination of three sulfonate O atoms from three different anions, one oxo O atom from a fourth anion, and four water mol­ecules (Fig. 1). This mix of sulfonate and water in the coordination sphere and the Ba—O distances [2.716 (2)–2.807 (1) Å] are consistent with other barium sulfonate complexes (Gunderman et al., 1997; Gao et al., 2005a; Black et al., 2019). The coordination geometry is somewhat irregular but could be described as either a triangular dodeca­hedron or a square anti­prism (Lippard & Russ, 1967). There are two trapezoids around the cation formed by the four water mol­ecules and the three sulfonate and one oxo O atoms, respectively (Fig. 2). The angle between these planes is ca. 88°. This angle for the ideal dodeca­hedron (point symmetry D_2d) is 90°, while it is 77.4° for the ideal square anti­prism (point symmetry D_4d). On this basis, the coordination environment in (I) is better described as dodeca­hedral. Barium shows a wide diversity of coordination environments in sulfonate systems with eight-, nine- and tenfold coordination being the most common (Wu et al., 2011; Gardner et al., 2020). The two independent 2-amino-3-oxo-3H-phenoxazine-8-sulfonate anions are both highly planar with C—C, C—O, and C—N distances that agree with those found in the related 2-amino-3-oxo-7-meth­oxy-3H-phenoxazine (Buckley et al., 1982). They report a fold angle across the O5⋯N10 line of 5°, however the similar angles in (I) are ca. 1° for anion 1 and 0.5° for anion 2. The angle between the two anion planes is ca. 2.4°. The main conformational difference between the anions is a roughly 30° rotation of the sulfonate group [torsion angles: anion 1 C71—C81—S81—O1S1 = 52.6 (2)°, anion 2 C72—C82—S82—O3S2 = 21.3 (2)°]. Anion 1 only bonds to the Ba²⁺ cation through one sulfonate O atom (O1S1), while each anion 2 bonds to three different cations through O32 (shown in Fig. 1) and sulfonate O atoms O1S2 and O3S2.

Figure 1 The mol­ecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are shown at the 70% probability level and hydrogen atoms are shown as small spheres of arbitrary radii. Symmetry-equivalent oxygen atoms are included to show the complete coordination environment of the cation. [Symmetry codes: (#) −x + 1, −y + 1, −z + 1; ($) x, y, z + 1.]

Figure 2 The coordination geometry of barium in (I). Barium and oxygen atoms are shown as spheres of arbitrary radii. [Symmetry codes: (#) −x + 1, −y + 1, −z + 1; ($) x, y, z + 1.]

3. Supra­molecular features

The packing in (I) features layers of nearly parallel 2-amino-3-oxo-3H-phenoxazine-8-sulfonate anions in the ab plane with the barium cations and water mol­ecules in between (Fig. 3). These layers stack along the c-axis direction. The two independent anions (marked 1 and 2 in Fig. 3) both have their sulfonate groups oriented down relative to the stacking direction, while the anions on the other side of the cell (2′ and 1′ in Fig. 3) are flipped in keeping with the inversion symmetry. This detail is different from most arene mono­sulfonate systems we have examined, where the sulfonate groups alternate up-down-up-down and are usually all symmetry-related (Genther et al., 2007). If one looks only at the phenoxazine rings and ignores the functional groups, 1 and 2 are approximately related by inversion at the midpoint between them, while 2′ and 1′ are translationally related to 1 and 2, respectively. Thus, the approximate symmetry of the organic moieties is higher than the overall structure (Brock, 2022). This is in keeping with what is found in the neutral phenoxazine mol­ecules 2-amino-3H-phenoxazin-3-one (Nie & Xu, 2002) and 2-amino-7-meth­oxy-3H-phenoxazin-3-one (Buckley et al., 1982), both of which have four symmetry-related mol­ecules in their unit cells. The approximate symmetry in (I) is broken by the positioning of the functional groups, presumably to accommodate the coordination of the barium ions and the hydrogen bonding scheme. As can be seen in Fig. 3, anion 2 bridges two cations within a layer across the inversion center at 0.5, 0.5, 0 and bridges cations in adjacent layers via sulfonate and oxo O atom coordination. Although anion 1 is only coordinated to a single cation, it does form an N—H⋯O hydrogen bond to a coordinated water mol­ecule in the next layer (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H1N1⋯O4W^i	0.87 (1)	2.50 (2)	3.089 (3)	125 (2)
N21—H2N1⋯O2S1^ii	0.87 (1)	2.45 (2)	3.055 (2)	127 (2)
O1W—H1A⋯O1S1^iii	0.84 (1)	1.96 (1)	2.787 (2)	168 (3)
O1W—H1B⋯O2S2^i	0.84 (1)	1.95 (1)	2.757 (2)	163 (3)
O2W—H2A⋯O2S2^iv	0.84 (1)	1.95 (1)	2.756 (2)	160 (3)
O2W—H2B⋯O1S2^v	0.84 (1)	2.15 (2)	2.905 (2)	149 (3)
O3W—H3A⋯O31^vi	0.83 (1)	2.11 (1)	2.906 (2)	162 (3)
O3W—H3B⋯O3S1^vii	0.84 (1)	2.00 (1)	2.836 (2)	178 (3)
O4W—H4A⋯O2S1^vii	0.84 (1)	2.04 (2)	2.823 (2)	155 (3)
O4W—H4B⋯O3S1^viii	0.84 (1)	1.92 (1)	2.734 (2)	164 (3)
N22—H1N2⋯O2W^iii	0.88 (1)	2.33 (2)	2.939 (2)	126 (2)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Figure 3 Packing diagram of (I) with the outline of the unit cell. The alternating layers of barium cations and 2-amino-3-oxo-3H-phenoxazine-8-sulfonate anions are evident. The independent anions are marked 1 and 2, correlating with the last digit in the atom labels. O—H⋯O and N—H⋯O hydrogen bonds are shown as striped cylinders. Anions related by the inversion at the center of the cell are marked 2′ and 1′. H atoms bonded to C atoms have been omitted. Displacement ellipsoids are drawn at the 70% probability level.

The structure is reinforced by an extensive network of strong (H⋯O ca. 1.9–2.2Å) approximately linear O—H⋯O hydrogen bonds (Table 1, Fig. 4) involving the coordinated water mol­ecules and sulfonate groups. All of the water H atoms participate in such inter­actions, while five sulfonate O atoms and one oxo O atom function as hydrogen-bond acceptors. The amine groups also participate in somewhat longer N—H⋯O hydrogen bonds with water and sulfonate O atoms (Figs. 3 and 4, Table 1).

Figure 4 A portion of the hydrogen-bonding network with O—H⋯O and N—H ⋯O hydrogen bonds shown as striped cylinders. C atoms and their bonded H atoms have been omitted. Displacement ellipsoids are drawn at the 70% probability level. View is approximately onto the (001) plane. [Symmetry codes: ($) x, y, z + 1; (@) −x + 1, −y + 1, −z + 1; (#) −x + 2, −y + 1, −z + 1; (&) x + 1, y, z; (%) x + 2, y, z.]

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of November 2020; Groom et al., 2016) for the 2-amino-3H-phenoxazin-3-one core yielded 17 hits. These include 2-amino-3H-phenoxazin-3-one itself (refcode XINYUO; Nie & Xu, 2002), 2-amino-7-meth­oxy-3H-phenoxazin-3-one (refcode BAXVOL; Buckley et al., 1982) and 2-amino-1-carbamoyl-3-oxo-3H-phenoxazine-8-carb­oxy­lic acid methyl ester (refcode MOQLUA; Graf et al., 2007). Two sulfonamide derivatives were found, dimethyl 2,2′-[(3-oxo-3H-phenoxazine-1,9-di­yl)bis­(sulfonyl­imino)]di­acetate (refcode IGISOH; Bruyneel et al., 2009) and 2-amino-N,N′-bis­(3-hy­droxy­prop­yl)-3-oxo-3H-phenoxazine-1,9-disulfonamide (ref­code IGISUN; Bruyneel et al., 2009), but no sulfonates. The only metal complexes are two silver complexes (coordination through the phenoxazine N atom), catena-[(μ₃-nitrato)(2-amino-3H-phenoxazin-3-one)silver(I)] (refcode BUVZOI; Pandurangan et al., 2010) and bis­(2-amino-4a,7-dimethyl-4,4a-di­hydro-3H-phenoxazin-3-one)nitratosilver(I) (refcode ZEMYIC; Helios et al., 2017). 2-Amino-3H-phenoxazin-3-one is also found as an inclusion with a hexa­nuclear iron(III) complex with no direct inter­actions between the cation and the phenoxazine mol­ecule (refcode CUMGEX; Feltham et al., 2009).

A search of the Cambridge Structural Database (CSD, Version 5.42, update of November 2020; Groom et al., 2016) for compounds with direct bonding between barium and an arene­sulfonate yielded 49 hits. Of these, none have three fused arene rings. Those with two fused rings and one sulfonate group include catena-(bis­{μ₂-2-[2-(2-oxido-1-naphth­yl)diazenium­yl]naphthalene-1-sulfonato}­diaqua­barium dihydrate) (refcode CAWCUA; Kennedy et al., 2012), catena-[(μ₄-8-oxy-7-iodo­quinoline-5-sulfonato)­tri­aqua­barium monohydrate] (refcode IPUSUH; Mu­thiah et al., 2003), catena-[(μ₃-8-oxyquinoline-5-sulfonato)(μ₂-aqua)­tri­aqua­barium] (ref­code NUVROM; Balasubramani et al., 2010), and catena-[bis­(μ₃-5,6-bi­hydroxy­flavone-6-sulfonato)­barium] (refcode PEHROK; Zhang et al., 2006). Fused bicyclics with two sulfonate groups include [μ₂-7-oxo-8-(phenyl­hydrazono)-7,8-di­hydro­naphthalene-1-sulfonate-3-sulfonato]­tetra­deca­aqua­dibarium dihydrate (refcode DEHMUZ; Kennedy et al., 2006), catena-[(μ₈-[2-(naphthalen-1-yl)hydrazinyl­idene]-7-oxo-7,8-di­hydro­naphthalene-1,3-di­sulfonato)­tris­(aqua)(N,N-di­methyl­formamide)­barium] (refcode EGOGUF; Black et al., 2019), catena-[(μ₆-1,5-naphthalene­disulfonato)­diaqua­barium] (refcode FOBYAX; Gao et al., 2005b), catena-[bis­(μ₇-9,10-dioxoanthracene-2,6-di­sulfonato)­barium] (refcode IWIMUX; Platero-Prats et al., 2011), bis­(6-ammonio­naphthalene-1,3-di­sulfonato)­hexa­aqua­barium tetra­hydrate (refcode NIHSIG; Gunderman et al., 1997), catena-[(μ₆-1,5-naphthalene­disulfonato)(μ₂-di­aqua)­barium] (refcode RAKZEI; Cai et al., 2001), and catena-[(μ₅-naphthalene-2,7-di­sulfonato)(μ₂-aqua)aqua­barium] (refcode YAFWEI; Huo et al., 2004)

5. Synthesis and crystallization

A 2.05 g (9.89 mmol) sample of 3-amino-4-hy­droxy­benzene­sulfonic acid monohydrate (Aldrich, 98%) was dissolved in 100 ml of water. To this solution was added a cloudy suspension of 2.09 g (6.62 mmol) of Ba(OH)₂^.8H₂O (Baker, >99%) in 50 ml of water. The resulting golden-brown cloudy mixture was stirred for about 30 minutes with gentle heating and then vacuum filtered. The resulting clear light orange–brown solution was transferred to a porcelain evaporating dish that was set out to evaporate in a fume hood. After several days, the water had completely evaporated leaving behind a polycrystalline brown crust. A few small (ca. 1 mm) clusters of red needle-shaped crystals were found and collected by hand. These were identified as (I) through the single crystal X-ray study. A powder X-ray diffraction pattern of the crust shows it to be partially crystalline with the most intense peak having a d-spacing of 15.48 Å. The 001 d-spacing for (I) is 15.79 Å, so this observation suggests another layered structure such as barium 3-amino-4-hy­droxy­benzene­sulfonate, but no single crystals of such a compound have been achieved to date. Subsequent attempts to repeat the synthesis of (I) by similar means were unsuccessful. Analysis of the starting 3-amino-4-hy­droxy­benzene­sulfonic acid by mass spectrometry yielded only a large peak at 189 amu due to 3-amino-4-hy­droxy­benzene­sulfonic acid and no evidence of 2-amino-3-oxo-3H-phenoxazine-8-sulfonic acid (292 amu). We have also attempted to perform the reaction hydro­thermally. So far, crystals of (I) have not been obtained. Mass spectral analysis of a solution obtained from such a reaction showed only the peak at 189 amu with none at 292. As a result, it remains unknown whether the tricyclic sulfonate formed in situ during the reaction or was already present in trace (i.e., undetectable) amounts in the starting material. 2-Amino-3H-phenoxazin-3-one has been reported to form in situ via oxidative condensation of 2-amino­phenol (Feltham et al., 2009).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms bonded to carbon atoms were located in difference electron-density maps, constrained on idealized positions, and included in the refinement as riding atoms with C—H = 0.95 Å and their U_iso constrained to be 1.2 times the U_eq of the bonding atom. Oxygen- and nitro­gen-bound hydrogen atoms were located in difference electron-density maps and refined with distances restrained to O—H = 0.84 (1) Å and N—H = 0.88 (1) Å and U_iso(H) = 1.5U_eq(O or N).

Table 2
Experimental details

Crystal data
Chemical formula	[Ba(C12H7N2O5S)2(H2O)4]
Mr	791.91
Crystal system, space group	Triclinic, P
Temperature (K)	130
a, b, c (Å)	6.0052 (3), 13.9739 (6), 16.0374 (7)
α, β, γ (°)	79.966 (1), 87.604 (1), 85.581 (1)
V (Å^3)	1320.72 (10)
Z	2
Radiation type	Mo Kα
μ (mm^−1)	1.75
Crystal size (mm)	0.21 × 0.11 × 0.04
Data collection
Diffractometer	Bruker duo with Photon II area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015)
Tmin, Tmax	0.670, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	49891, 8091, 7383
Rint	0.048
(sin θ/λ)max (Å^−1)	0.715
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.025, 0.056, 1.05
No. of reflections	8091
No. of parameters	442
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	1.13, −0.67
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT2014/5 (Sheldrick, 2015a), SHELXL2019/2 (Sheldrick, 2015b) and CrystalMaker (Palmer, 2014).

Supporting information

Computing details

Bis(2-amino-3-oxo-3H-phenoxazine-8-sulfonato)tetraaquabarium

Crystal data

[Ba(C12H7N2O5S)2(H2O)4]	Z = 2
Mr = 791.91	F(000) = 788
Triclinic, P1	Dx = 1.991 Mg m^−3
a = 6.0052 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.9739 (6) Å	Cell parameters from 7993 reflections
c = 16.0374 (7) Å	θ = 2.6–28.3°
α = 79.966 (1)°	µ = 1.75 mm^−1
β = 87.604 (1)°	T = 130 K
γ = 85.581 (1)°	Needle, red
V = 1320.72 (10) Å^3	0.21 × 0.11 × 0.04 mm

Data collection

Bruker duo with Photon II area detector diffractometer	7383 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
phi and ω scans	θmax = 30.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
Tmin = 0.670, Tmax = 0.746	k = −19→19
49891 measured reflections	l = −22→22
8091 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: mixed
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0203P)^2 + 1.027P] where P = (Fo^2 + 2Fc^2)/3
8091 reflections	(Δ/σ)max = 0.002
442 parameters	Δρmax = 1.13 e Å^−3
12 restraints	Δρmin = −0.67 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
O51	0.3303 (2)	0.16808 (10)	1.38758 (8)	0.0164 (3)
C11	0.6916 (3)	0.08226 (14)	1.57101 (12)	0.0175 (4)
H11	0.836095	0.052057	1.584032	0.021*
C21	0.5515 (3)	0.10563 (13)	1.63518 (12)	0.0181 (4)
C31	0.3199 (3)	0.14981 (14)	1.61698 (12)	0.0179 (4)
C41	0.2540 (3)	0.16875 (14)	1.53044 (12)	0.0177 (4)
H41	0.108218	0.196792	1.516586	0.021*
C61	0.3969 (3)	0.16690 (14)	1.24208 (12)	0.0168 (3)
H61	0.251059	0.196706	1.231089	0.020*
C4A1	0.3980 (3)	0.14693 (13)	1.46868 (11)	0.0151 (3)
C71	0.5352 (3)	0.14400 (14)	1.17708 (12)	0.0174 (4)
H71	0.484532	0.157255	1.120621	0.021*
C5A1	0.4733 (3)	0.14589 (13)	1.32389 (12)	0.0149 (3)
C81	0.7500 (3)	0.10127 (13)	1.19368 (12)	0.0152 (3)
C91	0.8266 (3)	0.08138 (13)	1.27518 (12)	0.0163 (3)
H91	0.973489	0.052561	1.285600	0.020*
C9A1	0.6876 (3)	0.10366 (13)	1.34277 (11)	0.0145 (3)
C101	0.6252 (3)	0.10227 (13)	1.48543 (12)	0.0149 (3)
N21	0.6038 (3)	0.09329 (14)	1.71724 (11)	0.0239 (4)
H1N1	0.505 (4)	0.113 (2)	1.7532 (14)	0.036*
H2N1	0.741 (2)	0.075 (2)	1.7318 (18)	0.036*
N101	0.7649 (3)	0.08222 (12)	1.42448 (10)	0.0157 (3)
O1S1	0.9154 (2)	0.15587 (10)	1.04338 (9)	0.0191 (3)
O2S1	1.1371 (2)	0.03763 (11)	1.14120 (9)	0.0222 (3)
O3S1	0.8110 (3)	−0.01000 (11)	1.08025 (9)	0.0223 (3)
O31	0.1938 (3)	0.16867 (11)	1.67576 (9)	0.0249 (3)
O1W	0.2716 (3)	0.27323 (12)	1.00024 (10)	0.0251 (3)
H1A	0.179 (4)	0.2309 (16)	1.0151 (18)	0.038*
H1B	0.255 (5)	0.3095 (18)	1.0367 (14)	0.038*
O2W	0.9735 (2)	0.43513 (12)	0.89003 (10)	0.0231 (3)
H2A	0.913 (4)	0.4902 (11)	0.8951 (18)	0.035*
H2B	1.097 (3)	0.433 (2)	0.9129 (16)	0.035*
O3W	1.0267 (3)	0.19924 (11)	0.84245 (10)	0.0258 (3)
H3A	1.069 (5)	0.204 (2)	0.7922 (8)	0.039*
H3B	1.075 (5)	0.1428 (11)	0.8641 (17)	0.039*
O4W	0.5649 (3)	0.11088 (12)	0.90674 (12)	0.0283 (3)
H4A	0.675 (3)	0.0709 (17)	0.905 (2)	0.042*
H4B	0.453 (3)	0.079 (2)	0.9212 (19)	0.042*
S81	0.91727 (8)	0.06830 (3)	1.10817 (3)	0.01487 (8)
Ba1	0.68488 (2)	0.28977 (2)	0.92392 (2)	0.01472 (3)
O32	0.5473 (3)	0.33725 (11)	0.75905 (9)	0.0261 (3)
N22	0.1310 (3)	0.40900 (14)	0.71889 (12)	0.0258 (4)
H2N2	−0.006 (2)	0.434 (2)	0.7089 (19)	0.039*
H1N2	0.176 (5)	0.397 (2)	0.7711 (9)	0.039*
C102	0.3854 (3)	0.39552 (13)	0.50872 (11)	0.0143 (3)
C12	0.2266 (3)	0.41550 (14)	0.57226 (12)	0.0171 (3)
H12	0.082655	0.444023	0.556221	0.021*
C22	0.2758 (3)	0.39472 (14)	0.65600 (12)	0.0176 (4)
C32	0.5032 (4)	0.35245 (14)	0.68288 (12)	0.0193 (4)
C42	0.6625 (3)	0.33122 (14)	0.61839 (12)	0.0177 (4)
H42	0.807115	0.302586	0.633441	0.021*
C4A2	0.6067 (3)	0.35204 (13)	0.53611 (11)	0.0142 (3)
C5A2	0.7075 (3)	0.35155 (13)	0.39284 (11)	0.0136 (3)
C62	0.8696 (3)	0.33028 (14)	0.33357 (12)	0.0154 (3)
H62	1.012769	0.301945	0.350928	0.019*
C72	0.8195 (3)	0.35103 (13)	0.24865 (11)	0.0146 (3)
H72	0.928616	0.337478	0.206867	0.018*
C82	0.6071 (3)	0.39209 (12)	0.22473 (11)	0.0121 (3)
C92	0.4462 (3)	0.41247 (13)	0.28428 (11)	0.0129 (3)
H92	0.302611	0.439961	0.266712	0.015*
C9A2	0.4937 (3)	0.39287 (12)	0.37015 (11)	0.0127 (3)
O52	0.7609 (2)	0.33062 (10)	0.47675 (8)	0.0154 (2)
N102	0.3316 (3)	0.41509 (11)	0.42864 (10)	0.0145 (3)
O1S2	0.5607 (2)	0.52893 (9)	0.09565 (8)	0.0154 (2)
O2S2	0.3090 (2)	0.39942 (10)	0.11252 (8)	0.0164 (3)
O3S2	0.6984 (2)	0.36779 (10)	0.07087 (8)	0.0169 (3)
S82	0.54016 (7)	0.42413 (3)	0.11675 (3)	0.01149 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0168 (6)	0.0182 (6)	0.0130 (6)	0.0024 (5)	−0.0002 (5)	−0.0011 (5)
C11	0.0214 (9)	0.0167 (8)	0.0138 (8)	−0.0003 (7)	−0.0027 (7)	−0.0007 (7)
C21	0.0259 (9)	0.0124 (8)	0.0158 (8)	0.0003 (7)	−0.0037 (7)	−0.0022 (7)
C31	0.0242 (9)	0.0127 (8)	0.0165 (9)	0.0003 (7)	0.0012 (7)	−0.0024 (7)
C41	0.0194 (9)	0.0151 (8)	0.0176 (9)	0.0007 (7)	0.0005 (7)	−0.0012 (7)
C61	0.0165 (8)	0.0160 (8)	0.0166 (8)	0.0006 (7)	−0.0016 (7)	−0.0003 (7)
C4A1	0.0188 (8)	0.0120 (8)	0.0140 (8)	−0.0005 (6)	−0.0016 (7)	−0.0011 (6)
C71	0.0203 (9)	0.0166 (8)	0.0146 (8)	−0.0004 (7)	−0.0008 (7)	−0.0011 (7)
C5A1	0.0167 (8)	0.0129 (8)	0.0147 (8)	−0.0014 (6)	0.0019 (7)	−0.0013 (6)
C81	0.0185 (8)	0.0132 (8)	0.0140 (8)	−0.0009 (7)	0.0021 (7)	−0.0030 (6)
C91	0.0176 (8)	0.0134 (8)	0.0173 (9)	0.0011 (7)	−0.0005 (7)	−0.0019 (7)
C9A1	0.0174 (8)	0.0121 (8)	0.0136 (8)	−0.0011 (6)	−0.0005 (6)	−0.0007 (6)
C101	0.0175 (8)	0.0109 (8)	0.0157 (8)	−0.0006 (6)	−0.0014 (7)	−0.0010 (6)
N21	0.0321 (10)	0.0252 (9)	0.0140 (8)	0.0056 (8)	−0.0037 (7)	−0.0050 (7)
N101	0.0171 (7)	0.0158 (7)	0.0136 (7)	0.0009 (6)	−0.0011 (6)	−0.0014 (6)
O1S1	0.0239 (7)	0.0155 (6)	0.0164 (6)	−0.0005 (5)	0.0021 (5)	0.0009 (5)
O2S1	0.0197 (7)	0.0268 (7)	0.0197 (7)	0.0048 (6)	−0.0012 (5)	−0.0057 (6)
O3S1	0.0263 (7)	0.0184 (7)	0.0238 (7)	−0.0041 (6)	0.0005 (6)	−0.0077 (6)
O31	0.0316 (8)	0.0260 (8)	0.0161 (7)	0.0042 (6)	0.0041 (6)	−0.0047 (6)
O1W	0.0302 (8)	0.0252 (8)	0.0229 (8)	−0.0105 (6)	0.0029 (6)	−0.0096 (6)
O2W	0.0166 (7)	0.0255 (8)	0.0279 (8)	0.0009 (6)	0.0011 (6)	−0.0075 (6)
O3W	0.0371 (9)	0.0190 (7)	0.0187 (7)	0.0069 (6)	0.0078 (6)	−0.0015 (6)
O4W	0.0225 (8)	0.0208 (8)	0.0437 (10)	−0.0013 (6)	0.0011 (7)	−0.0117 (7)
S81	0.0181 (2)	0.01306 (19)	0.0133 (2)	0.00013 (16)	0.00076 (16)	−0.00253 (15)
Ba1	0.02297 (6)	0.01131 (5)	0.00926 (5)	0.00232 (4)	0.00072 (4)	−0.00182 (3)
O32	0.0432 (9)	0.0251 (8)	0.0099 (6)	0.0014 (7)	−0.0047 (6)	−0.0035 (6)
N22	0.0343 (10)	0.0275 (9)	0.0158 (8)	−0.0036 (8)	0.0084 (7)	−0.0060 (7)
C102	0.0189 (8)	0.0112 (8)	0.0129 (8)	−0.0025 (6)	0.0000 (6)	−0.0014 (6)
C12	0.0214 (9)	0.0153 (8)	0.0148 (8)	−0.0008 (7)	0.0012 (7)	−0.0032 (7)
C22	0.0260 (9)	0.0134 (8)	0.0138 (8)	−0.0031 (7)	0.0028 (7)	−0.0031 (7)
C32	0.0321 (10)	0.0135 (8)	0.0124 (8)	−0.0036 (7)	−0.0015 (7)	−0.0019 (7)
C42	0.0246 (9)	0.0152 (8)	0.0128 (8)	−0.0005 (7)	−0.0034 (7)	−0.0005 (7)
C4A2	0.0185 (8)	0.0115 (8)	0.0124 (8)	−0.0027 (6)	0.0007 (6)	−0.0007 (6)
C5A2	0.0185 (8)	0.0118 (8)	0.0099 (7)	−0.0009 (6)	−0.0021 (6)	−0.0002 (6)
C62	0.0144 (8)	0.0168 (8)	0.0142 (8)	0.0021 (6)	−0.0009 (6)	−0.0013 (7)
C72	0.0157 (8)	0.0153 (8)	0.0121 (8)	0.0010 (6)	0.0013 (6)	−0.0017 (6)
C82	0.0154 (8)	0.0105 (7)	0.0104 (7)	−0.0002 (6)	−0.0009 (6)	−0.0015 (6)
C92	0.0140 (8)	0.0132 (8)	0.0110 (8)	0.0009 (6)	−0.0009 (6)	−0.0012 (6)
C9A2	0.0158 (8)	0.0106 (7)	0.0117 (8)	−0.0009 (6)	0.0002 (6)	−0.0020 (6)
O52	0.0177 (6)	0.0186 (6)	0.0088 (6)	0.0018 (5)	−0.0017 (5)	−0.0008 (5)
N102	0.0167 (7)	0.0136 (7)	0.0130 (7)	−0.0005 (6)	0.0007 (6)	−0.0023 (6)
O1S2	0.0186 (6)	0.0123 (6)	0.0144 (6)	0.0001 (5)	−0.0009 (5)	−0.0004 (5)
O2S2	0.0158 (6)	0.0189 (6)	0.0149 (6)	−0.0024 (5)	−0.0024 (5)	−0.0028 (5)
O3S2	0.0222 (7)	0.0188 (6)	0.0098 (6)	0.0049 (5)	0.0004 (5)	−0.0058 (5)
S82	0.01439 (19)	0.01129 (18)	0.00859 (18)	0.00041 (15)	−0.00066 (14)	−0.00169 (14)

Geometric parameters (Å, º)

O51—C4A1	1.355 (2)	O3W—H3A	0.828 (10)
O51—C5A1	1.369 (2)	O3W—H3B	0.838 (10)
C11—C21	1.370 (3)	O4W—Ba1	2.7162 (16)
C11—C101	1.420 (3)	O4W—H4A	0.835 (10)
C11—H11	0.9500	O4W—H4B	0.838 (10)
C21—N21	1.344 (2)	Ba1—O32	2.7571 (14)
C21—C31	1.497 (3)	Ba1—O3S2^i	2.7702 (13)
C31—O31	1.236 (2)	Ba1—O1S2^ii	2.8067 (13)
C31—C41	1.433 (3)	O32—C32	1.239 (2)
C41—C4A1	1.347 (3)	N22—C22	1.335 (3)
C41—H41	0.9500	N22—H2N2	0.878 (10)
C61—C71	1.372 (3)	N22—H1N2	0.875 (10)
C61—C5A1	1.383 (3)	C102—N102	1.314 (2)
C61—H61	0.9500	C102—C12	1.415 (3)
C4A1—C101	1.471 (3)	C102—C4A2	1.469 (3)
C71—C81	1.395 (3)	C12—C22	1.363 (3)
C71—H71	0.9500	C12—H12	0.9500
C5A1—C9A1	1.396 (3)	C22—C32	1.495 (3)
C81—C91	1.379 (3)	C32—C42	1.433 (3)
C81—S81	1.7706 (19)	C42—C4A2	1.352 (2)
C91—C9A1	1.404 (3)	C42—H42	0.9500
C91—H91	0.9500	C4A2—O52	1.355 (2)
C9A1—N101	1.384 (2)	C5A2—O52	1.372 (2)
C101—N101	1.315 (2)	C5A2—C62	1.384 (2)
N21—H1N1	0.873 (10)	C5A2—C9A2	1.402 (2)
N21—H2N1	0.872 (10)	C62—C72	1.383 (2)
O1S1—S81	1.4605 (14)	C62—H62	0.9500
O1S1—Ba1	2.7678 (14)	C72—C82	1.398 (2)
O2S1—S81	1.4487 (15)	C72—H72	0.9500
O3S1—S81	1.4515 (15)	C82—C92	1.379 (2)
O1W—Ba1	2.7291 (16)	C82—S82	1.7667 (18)
O1W—H1A	0.840 (10)	C92—C9A2	1.394 (2)
O1W—H1B	0.836 (10)	C92—H92	0.9500
O2W—Ba1	2.7394 (16)	C9A2—N102	1.380 (2)
O2W—H2A	0.840 (10)	O1S2—S82	1.4580 (13)
O2W—H2B	0.839 (10)	O2S2—S82	1.4632 (14)
O3W—Ba1	2.7337 (15)	O3S2—S82	1.4464 (13)
C4A1—O51—C5A1	119.21 (15)	O2W—Ba1—O32	88.93 (5)
C21—C11—C101	121.32 (18)	O4W—Ba1—O1S1	73.21 (5)
C21—C11—H11	119.3	O1W—Ba1—O1S1	97.06 (5)
C101—C11—H11	119.3	O3W—Ba1—O1S1	71.77 (4)
N21—C21—C11	125.30 (19)	O2W—Ba1—O1S1	101.52 (4)
N21—C21—C31	114.17 (18)	O32—Ba1—O1S1	146.96 (4)
C11—C21—C31	120.52 (17)	O4W—Ba1—O3S2^i	128.27 (5)
O31—C31—C41	122.58 (18)	O1W—Ba1—O3S2^i	73.73 (4)
O31—C31—C21	119.80 (18)	O3W—Ba1—O3S2^i	128.33 (5)
C41—C31—C21	117.62 (17)	O2W—Ba1—O3S2^i	73.68 (4)
C4A1—C41—C31	120.26 (18)	O32—Ba1—O3S2^i	141.30 (4)
C4A1—C41—H41	119.9	O1S1—Ba1—O3S2^i	71.52 (4)
C31—C41—H41	119.9	O4W—Ba1—O1S2^ii	130.98 (4)
C71—C61—C5A1	118.90 (17)	O1W—Ba1—O1S2^ii	69.03 (4)
C71—C61—H61	120.6	O3W—Ba1—O1S2^ii	138.33 (4)
C5A1—C61—H61	120.6	O2W—Ba1—O1S2^ii	70.80 (4)
C41—C4A1—O51	118.24 (17)	O32—Ba1—O1S2^ii	71.44 (4)
C41—C4A1—C101	122.92 (17)	O1S1—Ba1—O1S2^ii	141.60 (4)
O51—C4A1—C101	118.84 (16)	O3S2^i—Ba1—O1S2^ii	70.24 (4)
C61—C71—C81	120.16 (18)	C32—O32—Ba1	173.60 (15)
C61—C71—H71	119.9	C22—N22—H2N2	122 (2)
C81—C71—H71	119.9	C22—N22—H1N2	119 (2)
O51—C5A1—C61	117.58 (16)	H2N2—N22—H1N2	119 (3)
O51—C5A1—C9A1	119.94 (16)	N102—C102—C12	119.91 (17)
C61—C5A1—C9A1	122.48 (17)	N102—C102—C4A2	122.50 (17)
C91—C81—C71	120.80 (17)	C12—C102—C4A2	117.59 (16)
C91—C81—S81	120.81 (14)	C22—C12—C102	121.45 (18)
C71—C81—S81	118.33 (14)	C22—C12—H12	119.3
C81—C91—C9A1	120.05 (17)	C102—C12—H12	119.3
C81—C91—H91	120.0	N22—C22—C12	124.2 (2)
C9A1—C91—H91	120.0	N22—C22—C32	115.40 (18)
N101—C9A1—C5A1	122.79 (17)	C12—C22—C32	120.40 (17)
N101—C9A1—C91	119.61 (17)	O32—C32—C42	122.58 (19)
C5A1—C9A1—C91	117.60 (17)	O32—C32—C22	119.49 (18)
N101—C101—C11	120.34 (17)	C42—C32—C22	117.93 (16)
N101—C101—C4A1	122.32 (17)	C4A2—C42—C32	119.84 (18)
C11—C101—C4A1	117.33 (17)	C4A2—C42—H42	120.1
C21—N21—H1N1	118.4 (19)	C32—C42—H42	120.1
C21—N21—H2N1	119.4 (19)	C42—C4A2—O52	118.35 (17)
H1N1—N21—H2N1	121 (3)	C42—C4A2—C102	122.75 (17)
C101—N101—C9A1	116.88 (16)	O52—C4A2—C102	118.89 (15)
S81—O1S1—Ba1	149.36 (8)	O52—C5A2—C62	117.87 (16)
Ba1—O1W—H1A	139 (2)	O52—C5A2—C9A2	119.60 (16)
Ba1—O1W—H1B	110 (2)	C62—C5A2—C9A2	122.53 (16)
H1A—O1W—H1B	104 (3)	C72—C62—C5A2	118.83 (17)
Ba1—O2W—H2A	113 (2)	C72—C62—H62	120.6
Ba1—O2W—H2B	124 (2)	C5A2—C62—H62	120.6
H2A—O2W—H2B	104 (3)	C62—C72—C82	119.51 (16)
Ba1—O3W—H3A	133 (2)	C62—C72—H72	120.2
Ba1—O3W—H3B	119 (2)	C82—C72—H72	120.2
H3A—O3W—H3B	104 (3)	C92—C82—C72	121.23 (16)
Ba1—O4W—H4A	113 (2)	C92—C82—S82	117.84 (13)
Ba1—O4W—H4B	135 (2)	C72—C82—S82	120.88 (13)
H4A—O4W—H4B	107 (3)	C82—C92—C9A2	120.21 (16)
O2S1—S81—O3S1	112.57 (9)	C82—C92—H92	119.9
O2S1—S81—O1S1	113.16 (9)	C9A2—C92—H92	119.9
O3S1—S81—O1S1	112.03 (9)	N102—C9A2—C92	119.32 (16)
O2S1—S81—C81	106.37 (9)	N102—C9A2—C5A2	122.99 (16)
O3S1—S81—C81	106.52 (9)	C92—C9A2—C5A2	117.69 (16)
O1S1—S81—C81	105.54 (8)	C4A2—O52—C5A2	119.19 (14)
O4W—Ba1—O1W	74.44 (5)	C102—N102—C9A2	116.82 (16)
O4W—Ba1—O3W	71.44 (5)	S82—O1S2—Ba1^ii	143.33 (8)
O1W—Ba1—O3W	145.84 (5)	S82—O3S2—Ba1^iii	134.57 (8)
O4W—Ba1—O2W	150.67 (5)	O3S2—S82—O1S2	113.65 (8)
O1W—Ba1—O2W	134.67 (5)	O3S2—S82—O2S2	113.53 (8)
O3W—Ba1—O2W	79.48 (5)	O1S2—S82—O2S2	111.77 (8)
O4W—Ba1—O32	82.35 (5)	O3S2—S82—C82	106.38 (8)
O1W—Ba1—O32	97.41 (5)	O1S2—S82—C82	105.30 (8)
O3W—Ba1—O32	79.65 (5)	O2S2—S82—C82	105.34 (8)
C101—C11—C21—N21	−176.93 (19)	C102—C12—C22—N22	−177.79 (19)
C101—C11—C21—C31	2.3 (3)	C102—C12—C22—C32	1.8 (3)
N21—C21—C31—O31	−2.2 (3)	N22—C22—C32—O32	−3.0 (3)
C11—C21—C31—O31	178.51 (19)	C12—C22—C32—O32	177.45 (18)
N21—C21—C31—C41	177.72 (18)	N22—C22—C32—C42	177.13 (18)
C11—C21—C31—C41	−1.6 (3)	C12—C22—C32—C42	−2.4 (3)
O31—C31—C41—C4A1	179.92 (19)	O32—C32—C42—C4A2	−178.08 (19)
C21—C31—C41—C4A1	0.0 (3)	C22—C32—C42—C4A2	1.8 (3)
C31—C41—C4A1—O51	−178.56 (16)	C32—C42—C4A2—O52	−179.69 (16)
C31—C41—C4A1—C101	0.8 (3)	C32—C42—C4A2—C102	−0.5 (3)
C5A1—O51—C4A1—C41	−179.53 (17)	N102—C102—C4A2—C42	−179.59 (18)
C5A1—O51—C4A1—C101	1.1 (2)	C12—C102—C4A2—C42	−0.2 (3)
C5A1—C61—C71—C81	−0.7 (3)	N102—C102—C4A2—O52	−0.4 (3)
C4A1—O51—C5A1—C61	178.84 (16)	C12—C102—C4A2—O52	178.92 (16)
C4A1—O51—C5A1—C9A1	−1.2 (3)	O52—C5A2—C62—C72	−179.83 (16)
C71—C61—C5A1—O51	−178.93 (17)	C9A2—C5A2—C62—C72	0.3 (3)
C71—C61—C5A1—C9A1	1.1 (3)	C5A2—C62—C72—C82	−0.5 (3)
C61—C71—C81—C91	0.1 (3)	C62—C72—C82—C92	0.1 (3)
C61—C71—C81—S81	177.28 (15)	C62—C72—C82—S82	177.45 (14)
C71—C81—C91—C9A1	0.3 (3)	C72—C82—C92—C9A2	0.4 (3)
S81—C81—C91—C9A1	−176.85 (14)	S82—C82—C92—C9A2	−177.02 (13)
O51—C5A1—C9A1—N101	0.2 (3)	C82—C92—C9A2—N102	179.08 (16)
C61—C5A1—C9A1—N101	−179.84 (18)	C82—C92—C9A2—C5A2	−0.5 (3)
O51—C5A1—C9A1—C91	179.30 (16)	O52—C5A2—C9A2—N102	0.7 (3)
C61—C5A1—C9A1—C91	−0.8 (3)	C62—C5A2—C9A2—N102	−179.44 (17)
C81—C91—C9A1—N101	179.15 (17)	O52—C5A2—C9A2—C92	−179.67 (16)
C81—C91—C9A1—C5A1	0.0 (3)	C62—C5A2—C9A2—C92	0.1 (3)
C21—C11—C101—N101	177.72 (18)	C42—C4A2—O52—C5A2	−179.77 (16)
C21—C11—C101—C4A1	−1.4 (3)	C102—C4A2—O52—C5A2	1.0 (2)
C41—C4A1—C101—N101	−179.31 (18)	C62—C5A2—O52—C4A2	178.98 (16)
O51—C4A1—C101—N101	0.0 (3)	C9A2—C5A2—O52—C4A2	−1.2 (2)
C41—C4A1—C101—C11	−0.2 (3)	C12—C102—N102—C9A2	−179.38 (16)
O51—C4A1—C101—C11	179.20 (16)	C4A2—C102—N102—C9A2	0.0 (3)
C11—C101—N101—C9A1	179.86 (17)	C92—C9A2—N102—C102	−179.70 (16)
C4A1—C101—N101—C9A1	−1.0 (3)	C5A2—C9A2—N102—C102	−0.1 (3)
C5A1—C9A1—N101—C101	0.9 (3)	Ba1^iii—O3S2—S82—O1S2	−95.22 (12)
C91—C9A1—N101—C101	−178.17 (17)	Ba1^iii—O3S2—S82—O2S2	34.00 (14)
Ba1—O1S1—S81—O2S1	174.88 (14)	Ba1^iii—O3S2—S82—C82	149.39 (10)
Ba1—O1S1—S81—O3S1	46.32 (18)	Ba1^ii—O1S2—S82—O3S2	145.61 (11)
Ba1—O1S1—S81—C81	−69.19 (17)	Ba1^ii—O1S2—S82—O2S2	15.51 (15)
C91—C81—S81—O2S1	−9.72 (18)	Ba1^ii—O1S2—S82—C82	−98.36 (13)
C71—C81—S81—O2S1	173.06 (15)	C92—C82—S82—O3S2	−161.27 (14)
C91—C81—S81—O3S1	110.57 (16)	C72—C82—S82—O3S2	21.27 (17)
C71—C81—S81—O3S1	−66.65 (17)	C92—C82—S82—O1S2	77.81 (15)
C91—C81—S81—O1S1	−130.19 (16)	C72—C82—S82—O1S2	−99.65 (16)
C71—C81—S81—O1S1	52.58 (17)	C92—C82—S82—O2S2	−40.47 (16)
N102—C102—C12—C22	178.97 (18)	C72—C82—S82—O2S2	142.07 (15)
C4A2—C102—C12—C22	−0.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H1N1···O4W^i	0.87 (1)	2.50 (2)	3.089 (3)	125 (2)
N21—H2N1···O2S1^iv	0.87 (1)	2.45 (2)	3.055 (2)	127 (2)
O1W—H1A···O1S1^v	0.84 (1)	1.96 (1)	2.787 (2)	168 (3)
O1W—H1B···O2S2^i	0.84 (1)	1.95 (1)	2.757 (2)	163 (3)
O2W—H2A···O2S2^ii	0.84 (1)	1.95 (1)	2.756 (2)	160 (3)
O2W—H2B···O1S2^vi	0.84 (1)	2.15 (2)	2.905 (2)	149 (3)
O3W—H3A···O31^vii	0.83 (1)	2.11 (1)	2.906 (2)	162 (3)
O3W—H3B···O3S1^viii	0.84 (1)	2.00 (1)	2.836 (2)	178 (3)
O4W—H4A···O2S1^viii	0.84 (1)	2.04 (2)	2.823 (2)	155 (3)
O4W—H4B···O3S1^ix	0.84 (1)	1.92 (1)	2.734 (2)	164 (3)
N22—H1N2···O2W^v	0.88 (1)	2.33 (2)	2.939 (2)	126 (2)

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