An ethanol-solvated centrosymmetric dimer of bismuth(III) and thiosaccharinate resulting from `semicoordination' contacts

In the title compound, bis(μ-1,1-dioxo-1,2-benzothiazole-3-thiolato)-κ³N,S:S;κ³S:N,S-bis[(1,1-dioxo-1,2-benzothiazole-3-thiolato-κ²N,S)(ethanol-κO)bismuth(III)] ethanol hemisolvate, [Bi₂(C₇H₄NO₂S₂)₆(C₂H₅OH)₂]·0.5C₂H₅OH, three independent thio­saccharinate (tsac) anions chelate the metal centre through the endocyclic N and exocyclic S atoms. The complex also presnts two `semicoordination' contacts, one from a pendant ethanol solvent mol­ecule and a second one from an S atom of a centrosymmetrically related mol­ecule. This latter inter­action complements two π–π interactions between tsac rings to form a dimeric entity which is the elemental unit that builds up the crystal structure. These dinuclear units are connected to each other via a second type of π–π interaction, generating chains along [11]. Two ethanol mol­ecules, one of them of full occupancy at a general position and semicoordinated to the central cation, and a second one depleted and disordered around a symmetry centre, stabilize the structure. The complex was studied theoretically and the vibrational assignations were confirmed by employing theoretical density functional theory (DFT) methods.

S1. Introduction

Thio­nates, anions produced by the deprotonation of heterocyclic thio­amides, can coordinate to metals to produce a variety of structures, from simple mononuclear to complex polynuclear species. Over the years we have developed a sustained inter­est in the coordination behaviour of heterocyclic thio­nes in general, and thio­saccharine [the thione form of saccharine, 1,2-benzoiso­thia­zol-3(2H)-thione-1,1-dioxide, C₆H₄SO₂NHCS] in particular. Like other thio­amides, it is a versatile ligand. Its anion (hereinafter tsac) has the ability to coordinate to metal centres in many different ways (Dennehy et al., 2007). We have studied metal thio­saccharinates with heavy metals (Dennehy et al., 2012, 2011, and references therein). Because bis­muth compounds are known to be safe to humans, in recent decades efforts have been made to synthesize bis­muth complexes (Briand & Burford, 2000). Within the chemistry of Bi^III, bis­muth(III) thiol­ates (containing a Bi—S bond) are some of the most studied classes of bis­muth compounds. Exploring the coordination chemistry of bis­muth could be advantageous in synthesizing biologically important compounds. Therefore, the structural characterization of bis­muth complexes is inter­esting and meaningful (Andrews et al., 2011).

Despite the great number of metal–thio­nate complexes reported in the last decade or so, bis­muth(III) thio­saccharinates have not received much attention, and the only crystal structure reported so far of a bis­muth(III) thio­saccharinate complex is [Ph₂Bi(tsac)] (Andrews et al., 2011). In the same paper the authors claim to have synthesized bis­muth thio­saccharinate, Bi(tsac)₃, but they were unsuccessful in their attempts to crystallize it, so no direct crystallographic evidence of its structure is available. In spite of this, the authors presented the complex as a polymeric chain, [Bi(tsac)₃]_n, and, based on the analysis of their vibrational data, they propose a coordination mode through the exocyclic S atom. In trying to elucidate this crystal structure, we have developed a different synthetic pathway which ended up with the Bi(tsac)₃ phase reported here, (I). Accordingly, this is the first structural work on a Bi–tsac complex crystallized without the presence of any facilitator ancillary ligand.

S2. Experimental

S2.1. Synthesis and crystallization

Solid thio­saccharin (Htsac) in its α-form was prepared by the reaction of saccharin (3.00 g; Mallindkrodt Pharmaceuticals) with Lawesson's reagent (3.64 g; Fluka) in toluene (25 ml), following the technique published by Schibye et al. (1978), and characterized by melting point and IR spectroscopic analysis (Grupče et al., 1994). The title complex, (I), was synthesized by dropwise addition of a yellow solution of Htsac (15 mg, 0.075 mmol) in ethanol–acetone (1:1 v/v, 5 ml) to another solution of Bi(NO₃)₃ (10 mg, 0.025 mmol of Bi³⁺) [In what solvent?] (4 ml) with mechanical stirring. A saturated solution of the complex [In what solvent?] was allowed to evaporate slowly at room temperature, and 24 h later yellow single crystals of (I) suitable for X-ray diffraction were formed. The crystals were washed with di­ethyl ether and were air stable.

The IR spectra were obtained in a KBr dispersion. The IR spectrum of (I) confirms the presence of thio­saccharinate anions and molecules of the crystallization solvent (Dennehy et al., 2007). Selected anion bands for (I) (ν, cm^-1): 1472 (m), 1409 (m), 1341/1326 (m), 1239 (m), 1180/1167 (s), 1016 (w), 997 (m), 794 (m), 736 (w), 627 (w), 586 (m) 557 (m), 532 (m), 425 (m). Selected anion bands for (II) [as reported by Andrews et al. (2011)] (ν, cm^-1): 1325 (m), 1419 (m), 1156 (m), 1001 (m), 805 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were identified in a difference Fourier map, but were further idealized and allowed to ride (C—H_methyl = 0.96Å and U_iso(H) = 1.5U_eq(C); C—H_arom = 0.93Å and U_iso(H) = 1.2U_eq(C). As expected, the presence of the heavy Bi³⁺ cation produced some disruptive effects, viz. large peaks in the difference maps (2.76 and 2.54 eÅ^-3) at distances slightly less than 1 Å from the metal centre, and ill-defined H_methyl, which oscillated during refinement and had finally to be kept fixed at a reasonable position. One of the solvent molecules is disordered over an inversion centre. Its occupancy was fixed at 0.25 in the refinement.

S3. Results and discussion

The monomeric unit of (I) is presented in Fig. 1(a), which shows the most relevant characteristics of the Bi coordination environment. To a first-order approximation, this is constituted by three tsac anions acting in a κN,κS chelating mode, with coordination lengths spanning the ranges 2.613 (3)–2.715 (3) Å (Bi—S) and 2.617 (9)–2.723 (8) Å (Bi—N) (for more details see Table 2), and S—Bi—N chelating angles lying between 58.18 (16) and 59.04 (18)° (for more details see Table 3). The three ligands are disposed in a rather symmetric fashion, mimicking a mirror plane relating units 1 and 2 [Please define atoms involved in each] [mean least-squares deviation for these groups = 0.14 (2)Å] and leaving tsac3 [Please define] slightly offset from its pseudo mirror image [by 0.37 (9)Å; Fig. 1b]. The three tsac ligands (O atoms excluded) are planar [maximum deviations from the least-squares plane are 0.021 (9) Å for atom C61 (tsac1), 0.021 (12) Å for atom C22 (tsac2) and 0.052 (11)Å for atom C63 (tsac3)], while the inter­planar angles in the coordination polyhedron are 4.5 (3)° (tsac1–tsac2), 97.8 (2)° (tsac1–tsac3) and 98.2 (2)° (tsac2–tsac3).

Within this picture, the formal coordination number of Bi would be 6, but there are in addition two rather long 'semicoordination' distances to be taken into account (dashed lines in Fig 2), a Bi···O one involving the fully occupied ethanol molecule [Bi1···O14 = 2.926 (9) Å] and one between two centrosymmetrically related complex molecules [Bi1···S14ⁱ = 3.364 (3) Å; symmetry code: (i) 1 - x, 2 - y, 1 - z]. Even though they are unusually long for standard Bi···(S,O) distances, simple inspection of Fig. 1(a) discloses the need to take these inter­actions into account, given the rather bizarre geometry around the metal that the chelating ligands alone give rise to; a very crude idea is given by the baricentre of the three (S,N) pairs, which lies 0.787 (2) Å from the cation. A rather more elaborate argument is provided by a bond-valence calculation (Brown, 2002), as performed with PLATON (Spek, 2003), which gives for atom Bi1, in the biased six-fold coordination, a bond valence of 2.744 valence units (v.u.) (expected value 3.00 v.u.), while the complete eight-coordination raises this value to 2.974 v.u.

The above-mentioned Bi···S14ⁱ contact, together with two π–π inter­actions involving the tsac1 and tsac2 rings (Table 4, first entry), define the dimeric entities represented in Fig. 2 and which can be considered the supra­molecular unit from which the crystal structure builds up. This dimeric binding leads to a Bi···Biⁱ distance of 4.3846 (8) Å

These dimers are in turn connected by a second type of π–π bond, now involving only symmetry-related tsac3 rings (Table 4, second entry). This leads to the formation of chains running along [111], shown in Fig. 3(a).

Finally, there are a few C—H···O contacts (Table 5, entries 2–4) linking the chains into a planar array parallel to (110) (Fig. 3b). Inter­planar contacts are of a much weaker van der Waals nature. The first entry in Table 5 corresponds to an inter­action between the fully occupied ethanol molecule and the molecular core, invo ====================== Sean Conway Technical Editor (Acta C and E) E-mail: [e-mail] lving the same OH group which 'semicoordinates' to Bi1.

As mentioned above, Andrews et al. (2011) reported the synthesis of a bis­muth thio­saccharinate phase, (II), which the authors, through a spectroscopic characterization, finally formulated as a one-dimensional polymer, [Bi(tsac)₃]_n. Unfortunately, no crystallographic data (neither powder nor single-crystal X-ray diffraction) are available for this compound to be compared with the corresponding data for (I). However, comparison of the vibrational frequencies in both compounds (see Experimental section for details) suggests the weakly dimeric compound presented here, (I), to be different from the complex reported by Andrews' group, (II).

In order to check the assignments of the vibrational frequencies, quantum-mechanical calculations were performed using density functional theory (DFT) analysis at the B3LYP/Lanl2dz(Bi);6-31G**(CHNOS) level. Computations were carried out using the GAUSSIAN09 suite of programs (Frisch et al., 2010) running under Linux. The calculated parameters reproduced the crystal structure reasonably (see comparative values in Tables 2 and 3). As previously reported by Soran et al. (2010), calculated Bi—S distances undergo elongations and the Bi–N distances are correspondingly shortened. The computed bond angles are very accurate. The theoretical vibrational analysis performed with the optimized geometry of the complex at the DFT level yields vibrational spectra in good agreement with the experimental spectra (Table 6). The most inter­esting bands to be observed in these complexes are those related to the five-membered ring of the thio­saccharinate anions, located between 1500 and 400 cm^-1. The absorption band at 794 cm^-1, attributable to the ν(NS), δ(CCC) vibration (C—N stretching vibrations coupled with aromatic ring motions), has a computed value of 791 cm^-1. The experimental ν(CS), δ(CNS) at 997 (m)/1016 (w) cm^-1 has a calculated frequency at 1014/1019 cm^-1. Thus, the experimental-to-computed frequency ratio is good when compared with literature values.

Related literature

For related literature, see: Andrews et al. (2011); Briand & Burford (2000); Brown (2002); Dennehy et al. (2007, 2011, 2012); Frisch (2010); Grupče et al. (1994); Schibye et al. (1978); Soran et al. (2010); Spek (2003).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

Fig. 1. (a) A molecular view of the monomeric unit in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Dashed lines indicate the semicoordination bonds. (b) A least-squares fit of a monomer and its pseudo mirror-related image.

Fig. 2. The centrosymmetric dimeric unit of (I). Dashed lines indicate the various intermolecular interactions. Cg indicates a ring centroid; see Table 2 for definitions. [Symmetry code: (i) 1 - x, 2 - y, 1 - z.]

Fig. 3. (a) A packing view of (I). Shown between brackets and running from bottom left to upper right is one isolated [111] chain. (b) A complementary projection rotated 90° from the view in (a), showing the resulting (110) planes. Dashed lines indicate the various intermolecular interactions.

Bis[tris(1,2-benzoisothiazol-3-thionato-1,1-dioxide- κN,κS)(ethanol)bismuth(III)] ethanol hemisolvate

Crystal data

[Bi(C7H4NO2S2)3(C2H6O)]2·0.5C2H6O	Z = 1
Mr = 1722.52	F(000) = 837
Triclinic, P1	Dx = 1.904 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1979 (6) Å	Cell parameters from 4557 reflections
b = 14.0424 (16) Å	θ = 3.9–26.5°
c = 14.1697 (10) Å	µ = 6.33 mm^−1
α = 70.779 (8)°	T = 295 K
β = 80.031 (6)°	Plate, light yellow
γ = 79.353 (8)°	0.18 × 0.05 × 0.05 mm
V = 1502.6 (2) Å^3

Data collection

Oxford Gemini S Ultra CCD area-detector diffractometer	7115 independent reflections
Radiation source: fine-focus sealed tube	5631 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.102
ω scans, thick slices	θmax = 29.3°, θmin = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −10→11
Tmin = 0.68, Tmax = 0.74	k = −17→18
19073 measured reflections	l = −18→18

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) = 0.189	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + (0.092P)^2] where P = (Fo^2 + 2Fc^2)/3
7115 reflections	(Δ/σ)max = 0.001
371 parameters	Δρmax = 2.75 e Å^−3
3 restraints	Δρmin = −1.38 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0.63193 (4)	0.87818 (3)	0.61397 (3)	0.03910 (16)
S11	0.4875 (4)	0.6604 (2)	0.5100 (2)	0.0485 (7)
S21	0.6864 (3)	0.92945 (19)	0.41108 (18)	0.0401 (6)
N11	0.5693 (11)	0.7601 (6)	0.5150 (6)	0.042 (2)
O11	0.3189 (11)	0.6666 (7)	0.5546 (6)	0.069 (3)
O21	0.6010 (11)	0.5696 (6)	0.5464 (7)	0.067 (3)
C11	0.5035 (13)	0.6995 (8)	0.3757 (8)	0.045 (2)
C21	0.4659 (15)	0.6529 (9)	0.3130 (9)	0.051 (3)
H21	0.4244	0.5909	0.3374	0.062*
C31	0.4931 (16)	0.7031 (9)	0.2118 (9)	0.057 (3)
H31	0.4679	0.6742	0.1666	0.068*
C41	0.5544 (14)	0.7917 (10)	0.1756 (8)	0.055 (3)
H41	0.5679	0.8235	0.1064	0.066*
C51	0.5986 (12)	0.8379 (9)	0.2394 (7)	0.046 (3)
H51	0.6425	0.8991	0.2138	0.055*
C61	0.5752 (11)	0.7898 (8)	0.3406 (7)	0.040 (2)
C71	0.6038 (12)	0.8199 (7)	0.4256 (8)	0.039 (2)
S12	0.7069 (4)	0.9237 (2)	0.88089 (19)	0.0491 (7)
S22	0.8000 (3)	1.0394 (2)	0.57304 (17)	0.0424 (6)
N12	0.7115 (11)	0.9325 (6)	0.7581 (6)	0.044 (2)
O12	0.5364 (10)	0.9355 (7)	0.9248 (6)	0.059 (2)
O22	0.8138 (12)	0.8356 (7)	0.9293 (7)	0.075 (3)
C12	0.8041 (14)	1.0351 (9)	0.8546 (8)	0.049 (3)
C22	0.8409 (16)	1.0759 (12)	0.9222 (9)	0.064 (4)
H22	0.8140	1.0491	0.9915	0.077*
C32	0.9197 (17)	1.1585 (13)	0.8795 (11)	0.072 (4)
H32	0.9513	1.1874	0.9227	0.086*
C42	0.9576 (16)	1.2038 (11)	0.7787 (11)	0.066 (3)
H42	1.0121	1.2612	0.7549	0.079*
C52	0.9115 (14)	1.1607 (10)	0.7115 (9)	0.054 (3)
H52	0.9318	1.1899	0.6422	0.065*
C62	0.8357 (12)	1.0743 (8)	0.7522 (8)	0.041 (2)
C72	0.7828 (12)	1.0133 (8)	0.7000 (7)	0.038 (2)
S13	0.6004 (4)	0.5960 (3)	0.8533 (3)	0.0616 (9)
S23	0.9197 (3)	0.7609 (2)	0.6282 (2)	0.0461 (6)
N13	0.6621 (10)	0.6911 (7)	0.7545 (7)	0.049 (2)
O13	0.4965 (13)	0.5430 (8)	0.8236 (9)	0.095 (4)
O23	0.5379 (11)	0.6350 (9)	0.9363 (8)	0.090 (4)
C13	0.7984 (14)	0.5292 (9)	0.8662 (9)	0.058 (3)
C23	0.8483 (15)	0.4371 (9)	0.9410 (10)	0.060 (3)
H23	0.7726	0.4016	0.9911	0.071*
C33	1.0180 (16)	0.4043 (9)	0.9335 (10)	0.063 (4)
H33	1.0588	0.3448	0.9807	0.075*
C43	1.1277 (15)	0.4561 (10)	0.8594 (11)	0.066 (4)
H43	1.2395	0.4276	0.8550	0.079*
C53	1.0810 (14)	0.5482 (9)	0.7911 (9)	0.054 (3)
H53	1.1587	0.5871	0.7465	0.065*
C63	0.9118 (14)	0.5793 (8)	0.7926 (8)	0.046 (2)
C73	0.8212 (13)	0.6748 (8)	0.7310 (8)	0.043 (2)
O14	0.2919 (11)	0.8258 (8)	0.6748 (7)	0.073 (3)
H14	0.2913	0.7759	0.6520	0.109*
C14	0.1947 (19)	0.8115 (14)	0.7679 (11)	0.080 (4)
H14A	0.0803	0.8413	0.7569	0.096*
H14B	0.1948	0.7392	0.8020	0.096*
C24	0.250 (2)	0.8557 (14)	0.8320 (11)	0.086 (5)
H24A	0.3704	0.8455	0.8256	0.129*
H24B	0.2071	0.8240	0.9006	0.129*
H24C	0.2107	0.9273	0.8132	0.129*
O15	1.009 (5)	0.445 (3)	0.552 (3)	0.073 (3)	0.25
H15	1.1043	0.4238	0.5257	0.109*	0.25
C15	1.016 (7)	0.536 (3)	0.566 (3)	0.080 (4)	0.25
H15A	1.1190	0.5366	0.5883	0.096*	0.25
H15B	0.9261	0.5482	0.6155	0.096*	0.25
C25	1.011 (9)	0.618 (3)	0.472 (4)	0.086 (5)	0.25
H25A	1.0124	0.6828	0.4813	0.129*	0.25
H25B	1.1013	0.6064	0.4227	0.129*	0.25
H25C	0.9066	0.6181	0.4502	0.129*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0345 (2)	0.0432 (2)	0.0314 (2)	−0.00218 (15)	0.00001 (13)	−0.00424 (15)
S11	0.0521 (16)	0.0426 (14)	0.0391 (13)	−0.0114 (12)	−0.0005 (11)	0.0032 (11)
S21	0.0401 (13)	0.0415 (13)	0.0328 (12)	−0.0099 (10)	0.0030 (9)	−0.0048 (10)
N11	0.049 (5)	0.041 (5)	0.025 (4)	−0.011 (4)	0.007 (3)	0.001 (3)
O11	0.062 (5)	0.085 (6)	0.050 (5)	−0.026 (5)	0.014 (4)	−0.009 (5)
O21	0.072 (6)	0.042 (4)	0.061 (5)	0.000 (4)	−0.003 (4)	0.011 (4)
C11	0.043 (6)	0.043 (6)	0.038 (5)	−0.004 (4)	−0.006 (4)	0.001 (4)
C21	0.054 (7)	0.039 (6)	0.058 (7)	−0.005 (5)	−0.015 (5)	−0.007 (5)
C31	0.074 (8)	0.060 (7)	0.048 (6)	−0.009 (6)	−0.004 (5)	−0.034 (6)
C41	0.042 (6)	0.080 (9)	0.033 (5)	−0.006 (6)	0.003 (4)	−0.010 (5)
C51	0.031 (5)	0.057 (6)	0.033 (5)	0.004 (4)	0.003 (4)	−0.001 (5)
C61	0.026 (5)	0.050 (6)	0.030 (5)	−0.005 (4)	−0.001 (3)	0.005 (4)
C71	0.033 (5)	0.032 (5)	0.043 (5)	0.002 (4)	−0.003 (4)	−0.004 (4)
S12	0.0577 (17)	0.0513 (16)	0.0298 (12)	−0.0062 (12)	−0.0047 (11)	−0.0021 (11)
S22	0.0474 (15)	0.0490 (14)	0.0277 (11)	−0.0116 (11)	0.0024 (9)	−0.0088 (10)
N12	0.055 (5)	0.037 (5)	0.034 (4)	−0.006 (4)	−0.004 (4)	−0.005 (4)
O12	0.049 (5)	0.081 (6)	0.042 (4)	−0.025 (4)	0.016 (3)	−0.014 (4)
O22	0.078 (6)	0.072 (6)	0.059 (5)	0.003 (5)	−0.031 (5)	0.004 (5)
C12	0.051 (6)	0.065 (7)	0.035 (5)	−0.015 (5)	−0.011 (4)	−0.015 (5)
C22	0.056 (8)	0.093 (10)	0.038 (6)	−0.021 (7)	0.001 (5)	−0.010 (6)
C32	0.052 (8)	0.101 (11)	0.071 (9)	−0.012 (8)	−0.027 (6)	−0.027 (8)
C42	0.059 (8)	0.071 (9)	0.071 (9)	−0.024 (6)	−0.006 (6)	−0.017 (7)
C52	0.047 (7)	0.065 (8)	0.051 (6)	−0.010 (5)	−0.006 (5)	−0.017 (6)
C62	0.033 (5)	0.042 (5)	0.046 (6)	0.000 (4)	0.007 (4)	−0.019 (5)
C72	0.040 (5)	0.040 (5)	0.030 (5)	0.001 (4)	−0.007 (4)	−0.011 (4)
S13	0.0325 (14)	0.0606 (18)	0.0632 (19)	−0.0031 (13)	0.0008 (12)	0.0139 (15)
S23	0.0346 (13)	0.0455 (14)	0.0448 (14)	−0.0035 (11)	0.0042 (10)	−0.0018 (11)
N13	0.025 (4)	0.046 (5)	0.055 (5)	0.003 (4)	−0.003 (4)	0.005 (4)
O13	0.072 (7)	0.090 (7)	0.104 (8)	−0.038 (6)	−0.018 (6)	0.016 (6)
O23	0.049 (5)	0.101 (8)	0.073 (6)	0.015 (5)	0.017 (4)	0.009 (6)
C13	0.045 (6)	0.046 (6)	0.060 (7)	−0.010 (5)	0.001 (5)	0.012 (5)
C23	0.053 (7)	0.042 (6)	0.064 (8)	0.004 (5)	−0.009 (6)	0.005 (6)
C33	0.054 (7)	0.047 (7)	0.070 (8)	0.001 (5)	−0.019 (6)	0.007 (6)
C43	0.040 (7)	0.066 (8)	0.078 (9)	0.012 (6)	−0.009 (6)	−0.011 (7)
C53	0.036 (6)	0.047 (6)	0.064 (7)	0.006 (5)	−0.003 (5)	−0.006 (5)
C63	0.049 (6)	0.035 (5)	0.052 (6)	0.009 (4)	−0.005 (5)	−0.020 (5)
C73	0.037 (6)	0.039 (5)	0.049 (6)	−0.013 (4)	−0.005 (4)	−0.004 (5)
O14	0.059 (6)	0.084 (6)	0.079 (6)	−0.020 (5)	0.006 (4)	−0.032 (5)
C14	0.070 (9)	0.126 (13)	0.063 (8)	−0.048 (9)	0.001 (6)	−0.040 (9)
C24	0.093 (11)	0.102 (12)	0.057 (8)	−0.009 (9)	0.005 (7)	−0.026 (8)
O15	0.059 (6)	0.084 (6)	0.079 (6)	−0.020 (5)	0.006 (4)	−0.032 (5)
C15	0.070 (9)	0.126 (13)	0.063 (8)	−0.048 (9)	0.001 (6)	−0.040 (9)
C25	0.093 (11)	0.102 (12)	0.057 (8)	−0.009 (9)	0.005 (7)	−0.026 (8)

Geometric parameters (Å, º)

Bi1—S23	2.613 (3)	C42—H42	0.9300
Bi1—N12	2.617 (9)	C52—C62	1.373 (16)
Bi1—N11	2.661 (9)	C52—H52	0.9300
Bi1—S21	2.701 (2)	C62—C72	1.461 (15)
Bi1—S22	2.715 (3)	S13—O13	1.423 (12)
Bi1—N13	2.723 (8)	S13—O23	1.434 (12)
Bi1—S21^i	3.364 (3)	S13—N13	1.664 (9)
Bi1—O14	2.926 (9)	S13—C13	1.725 (12)
S11—O11	1.417 (9)	S23—C73	1.740 (10)
S11—O21	1.432 (8)	N13—C73	1.286 (13)
S11—N11	1.685 (10)	C13—C63	1.368 (15)
S11—C11	1.787 (11)	C13—C23	1.420 (15)
S21—C71	1.731 (11)	C23—C33	1.379 (17)
N11—C71	1.286 (12)	C23—H23	0.9300
C11—C21	1.366 (17)	C33—C43	1.360 (18)
C11—C61	1.400 (15)	C33—H33	0.9300
C21—C31	1.373 (16)	C43—C53	1.371 (16)
C21—H21	0.9300	C43—H43	0.9300
C31—C41	1.337 (17)	C53—C63	1.374 (15)
C31—H31	0.9300	C53—H53	0.9300
C41—C51	1.398 (17)	C63—C73	1.482 (14)
C41—H41	0.9300	O14—C14	1.391 (16)
C51—C61	1.365 (13)	O14—H14	0.8638
C51—H51	0.9300	C14—C24	1.43 (2)
C61—C71	1.467 (15)	C14—H14A	0.9700
S12—O22	1.421 (8)	C14—H14B	0.9700
S12—O12	1.432 (8)	C24—H24A	0.9600
S12—N12	1.697 (9)	C24—H24B	0.9600
S12—C12	1.787 (12)	C24—H24C	0.9600
S22—C72	1.699 (9)	O15—C15	1.37 (2)
N12—C72	1.331 (13)	O15—H15	0.8500
C12—C22	1.365 (18)	C15—C25	1.45 (3)
C12—C62	1.368 (14)	C15—H15A	0.9600
C22—C32	1.34 (2)	C15—H15B	0.9600
C22—H22	0.9300	C25—H25A	0.9601
C32—C42	1.365 (19)	C25—H25B	0.9601
C32—H32	0.9300	C25—H25C	0.9600
C42—C52	1.416 (19)
S23—Bi1—N12	84.7 (2)	C52—C42—H42	121.1
S23—Bi1—N11	83.9 (2)	C62—C52—C42	117.8 (11)
N12—Bi1—N11	160.0 (3)	C62—C52—H52	121.1
S23—Bi1—S21	90.68 (8)	C42—C52—H52	121.1
N12—Bi1—S21	138.42 (19)	C12—C62—C52	119.3 (11)
N11—Bi1—S21	58.18 (16)	C12—C62—C72	112.2 (9)
S23—Bi1—S22	88.00 (9)	C52—C62—C72	128.4 (10)
N12—Bi1—S22	58.57 (19)	N12—C72—C62	116.1 (8)
N11—Bi1—S22	137.17 (16)	N12—C72—S22	118.4 (8)
S21—Bi1—S22	80.01 (8)	C62—C72—S22	125.5 (8)
S23—Bi1—N13	59.04 (18)	O13—S13—O23	118.8 (7)
N12—Bi1—N13	82.0 (3)	O13—S13—N13	109.4 (6)
N11—Bi1—N13	78.0 (3)	O23—S13—N13	108.5 (6)
S21—Bi1—N13	129.7 (2)	O13—S13—C13	111.4 (7)
S22—Bi1—N13	131.4 (2)	O23—S13—C13	111.2 (7)
O11—S11—O21	119.6 (5)	N13—S13—C13	94.8 (5)
O11—S11—N11	108.5 (5)	C73—S23—Bi1	87.4 (4)
O21—S11—N11	108.4 (5)	C73—N13—S13	110.1 (7)
O11—S11—C11	111.9 (5)	C73—N13—Bi1	93.1 (6)
O21—S11—C11	110.5 (5)	S13—N13—Bi1	156.4 (5)
N11—S11—C11	94.9 (5)	C63—C13—C23	121.6 (11)
C71—S21—Bi1	85.6 (4)	C63—C13—S13	110.0 (8)
C71—N11—S11	110.2 (8)	C23—C13—S13	128.3 (9)
C71—N11—Bi1	97.0 (7)	C33—C23—C13	114.7 (11)
S11—N11—Bi1	151.9 (4)	C33—C23—H23	122.7
C21—C11—C61	123.0 (10)	C13—C23—H23	122.7
C21—C11—S11	130.2 (8)	C43—C33—C23	122.3 (11)
C61—C11—S11	106.7 (8)	C43—C33—H33	118.9
C11—C21—C31	116.0 (10)	C23—C33—H33	118.9
C11—C21—H21	122.0	C33—C43—C53	123.0 (11)
C31—C21—H21	122.0	C33—C43—H43	118.5
C41—C31—C21	122.6 (11)	C53—C43—H43	118.5
C41—C31—H31	118.7	C43—C53—C63	115.6 (11)
C21—C31—H31	118.7	C43—C53—H53	122.2
C31—C41—C51	121.5 (10)	C63—C53—H53	122.2
C31—C41—H41	119.3	C13—C63—C53	122.2 (10)
C51—C41—H41	119.3	C13—C63—C73	108.1 (9)
C61—C51—C41	117.7 (11)	C53—C63—C73	129.1 (10)
C61—C51—H51	121.1	N13—C73—C63	117.0 (9)
C41—C51—H51	121.1	N13—C73—S23	120.1 (8)
C51—C61—C11	119.0 (11)	C63—C73—S23	122.9 (8)
C51—C61—C71	130.6 (10)	C14—O14—H14	110.4
C11—C61—C71	110.3 (8)	O14—C14—C24	113.4 (12)
N11—C71—C61	117.8 (9)	O14—C14—H14A	108.6
N11—C71—S21	118.8 (9)	C24—C14—H14A	108.9
C61—C71—S21	123.3 (7)	O14—C14—H14B	109.5
O22—S12—O12	117.7 (6)	C24—C14—H14B	108.6
O22—S12—N12	110.0 (5)	H14A—C14—H14B	107.6
O12—S12—N12	109.0 (5)	C14—C24—H24A	109.8
O22—S12—C12	110.2 (6)	C14—C24—H24B	109.3
O12—S12—C12	112.8 (6)	H24A—C24—H24B	109.5
N12—S12—C12	94.8 (5)	C14—C24—H24C	109.3
C72—S22—Bi1	85.5 (4)	H24A—C24—H24C	109.5
C72—N12—S12	109.4 (7)	H24B—C24—H24C	109.5
C72—N12—Bi1	97.5 (6)	C15—O15—H15	108.6
S12—N12—Bi1	152.8 (5)	O15—C15—C25	111 (3)
C22—C12—C62	125.0 (11)	O15—C15—H15A	112.4
C22—C12—S12	127.6 (9)	C25—C15—H15A	104.0
C62—C12—S12	107.4 (8)	O15—C15—H15B	109.8
C32—C22—C12	113.8 (12)	C25—C15—H15B	111.2
C32—C22—H22	123.1	H15A—C15—H15B	109.0
C12—C22—H22	123.1	C15—C25—H25A	112.4
C22—C32—C42	126.1 (15)	C15—C25—H25B	111.5
C22—C32—H32	116.9	H25A—C25—H25B	109.5
C42—C32—H32	116.9	C15—C25—H25C	104.3
C32—C42—C52	117.9 (12)	H25A—C25—H25C	109.5
C32—C42—H42	121.1	H25B—C25—H25C	109.5

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14···O11	0.86	2.34	3.185 (14)	166
C21—H21···O21^ii	0.93	2.33	3.192 (16)	153
C33—H33···O22^iii	0.93	2.55	3.454 (17)	165
C41—H41···O12^iv	0.93	2.56	3.475 (14)	166

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