Mono- and binuclear tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl)hydro­borate bis­muth(III) dichloride complexes: a soft scorpionate ligand can coordinate to p-block elements

Tris(pyrazol­yl)hydro­borate ligands have been utilized in the fields of inorganic and coordination chemistry due to the ease of introduction of steric and electronic substitutions at the pyrazole rings. The development and use of the tris­(pyrazol­yl)hydro­borate ligand, called a `scorpionate', were pioneered by the late Professor Swiatoslaw Trofimenko. He developed a second generation for his ligand system by the introduction of 3-tert-butyl and 3-phenyl substituents and this new ligand system accounted for many remarkable developments in inorganic and coordination chemistry in stabilizing monomeric species while maintaining an open coordination site. Bismuth is remarkably harmless among the toxic heavy metal p-block elements and is now becoming popular as a replacement for highly toxic metal elements, such as lead. Two bis­muth(III) complexes of the anionic sulfur-containing tripod tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl)hydro­borate ligand were prepared. By recrystallization from MeOH/CH₂Cl₂, orange crystals of di­chlorido­(methanol-κO)[tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl-κS)hydro­borato]bis­muth(III), [Bi(C₂₁H₃₄BN₆S₃)Cl₂(CH₄O)], (I), were obtained, manifesting a mononuclear structure. By using a noncoordinating solvent, red crystals of the binuclear structure with bridging Cl atoms were obtained, namely di-μ-chlorido-bis­{chlorido­[tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl-κS)hydro­borato]bis­muth(III)}, [Bi₂(C₂₁H₃₄BN₆S₃)₂Cl₄], (II). These complexes show {Bi^IIIS₃Cl₂O} and {Bi^IIIS₃Cl₃} coordination geometries with average Bi^III—S bond lengths of 2.73 and 2.78 Å in (I) and (II), respectively. The overall Bi^III coordination geometry is distorted octa­hedral due to stereochemically active lone pairs. The three Bi^III—S bond lengths are almost equal in (I) but show considerable differences in (II), with one long and two shorter distances that also correlate with changes in the UV–Vis and ¹H NMR spectra. For direct measurements of the Bi—S/Cl coordination, ligand K-edge X-ray absorption measurements were carried out in combination with ground and excited-state electronic structure analyses. For p-block elements, these sulfur-containing ligands are useful for preparing the appropriate complexes due to their flexible coordination geometry.

Computing details

For both compounds, data collection: CrystalClear-SM Expert (Rigaku, 2013); cell refinement: CrystalClear-SM Expert (Rigaku, 2013); data reduction: CrystalClear-SM Expert (Rigaku, 2013). Program(s) used to solve structure: SIR2011 (Burla et al., 2012) for BiTmCl2; Il Milione (Burla et al., 2007) for BiTmClm-Cl2. For both compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: CrystalStructure (Rigaku, 2015); software used to prepare material for publication: CrystalStructure (Rigaku, 2015).

(BiTmCl2) Dichlorido(methanol-κO)[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III)

Crystal data

[Bi(C21H34BN6S3)Cl2(CH4O)]	Z = 2
Mr = 789.46	F(000) = 780.00
Triclinic, P1	Dx = 1.697 Mg m^−3
a = 10.2899 (5) Å	Mo Kα radiation, λ = 0.71075 Å
b = 10.6653 (4) Å	Cell parameters from 6399 reflections
c = 15.9818 (10) Å	θ = 3.0–27.5°
α = 72.157 (6)°	µ = 6.10 mm^−1
β = 83.838 (8)°	T = 179 K
γ = 67.742 (7)°	Block, orange
V = 1545.08 (16) Å^3	0.24 × 0.16 × 0.07 mm

Data collection

Rigaku XtaLAB P200 diffractometer	6768 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 5.814 pixels mm^-1	Rint = 0.037
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −13→13
Tmin = 0.465, Tmax = 0.653	k = −13→13
51186 measured reflections	l = −20→20
7083 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.012	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.032	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0201P)^2] where P = (Fo^2 + 2Fc^2)/3
7083 reflections	(Δ/σ)max = 0.008
327 parameters	Δρmax = 1.03 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3
Primary atom site location: structure-invariant direct methods

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.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Bi1	0.36354 (2)	1.04501 (2)	0.67383 (2)	0.01603 (2)
Cl1	0.25103 (5)	1.26183 (4)	0.53006 (3)	0.02523 (8)
Cl2	0.50213 (4)	1.17929 (5)	0.73128 (3)	0.02968 (9)
S1	0.20113 (4)	1.14394 (4)	0.79687 (3)	0.01864 (8)
S2	0.45474 (4)	0.76840 (4)	0.79180 (2)	0.02165 (8)
S3	0.15003 (4)	0.98696 (4)	0.62743 (2)	0.01790 (7)
O1	0.62244 (15)	0.89575 (17)	0.61046 (10)	0.0438 (4)
H1D	0.6395	0.8542	0.5713	0.053*
N1	−0.08146 (13)	1.24077 (14)	0.75734 (9)	0.0191 (3)
N2	0.01419 (13)	1.00946 (14)	0.81002 (9)	0.0187 (3)
N3	0.43620 (14)	0.78152 (14)	0.96219 (9)	0.0214 (3)
N4	0.23275 (15)	0.82784 (14)	0.90396 (8)	0.0202 (3)
N5	0.22948 (14)	0.69860 (13)	0.65939 (9)	0.0188 (3)
N6	0.15131 (14)	0.77211 (14)	0.77630 (8)	0.0198 (3)
C1	−0.0224 (2)	1.4371 (2)	0.65160 (12)	0.0338 (4)
H1A	−0.0408	1.5388	0.6351	0.041*
H1B	0.0776	1.3839	0.6658	0.041*
H1C	−0.0477	1.4138	0.6024	0.041*
C2	−0.2653 (2)	1.4796 (2)	0.70769 (15)	0.0388 (5)
H2A	−0.2849	1.5815	0.6909	0.047*
H2B	−0.2884	1.4551	0.6584	0.047*
H2C	−0.3224	1.4546	0.7585	0.047*
C3	−0.0764 (2)	1.4329 (2)	0.81079 (13)	0.0340 (4)
H3A	−0.0940	1.5343	0.7954	0.041*
H3B	−0.1363	1.4082	0.8600	0.041*
H3C	0.0224	1.3786	0.8278	0.041*
C4	−0.10966 (17)	1.39816 (17)	0.73153 (11)	0.0243 (3)
C5	0.04038 (15)	1.13061 (16)	0.78764 (10)	0.0166 (3)
C6	−0.18439 (17)	1.18594 (18)	0.75890 (11)	0.0226 (3)
H6	−0.2794	1.2387	0.7404	0.027*
C7	−0.12563 (17)	1.04496 (18)	0.79122 (11)	0.0228 (3)
H7	−0.1722	0.9803	0.7998	0.027*
C8	0.6598 (2)	0.57980 (19)	0.97319 (12)	0.0316 (4)
H8A	0.7612	0.5455	0.9837	0.038*
H8B	0.6190	0.5192	1.0177	0.038*
H8C	0.6429	0.5773	0.9146	0.038*
C9	0.6141 (2)	0.7329 (2)	1.07119 (13)	0.0374 (5)
H9A	0.7149	0.7009	1.0828	0.045*
H9B	0.5673	0.8292	1.0762	0.045*
H9C	0.5745	0.6693	1.1140	0.045*
C10	0.6543 (2)	0.8316 (2)	0.91306 (14)	0.0427 (5)
H10A	0.7553	0.7982	0.9245	0.051*
H10B	0.6391	0.8335	0.8531	0.051*
H10C	0.6086	0.9272	0.9195	0.051*
C11	0.59183 (18)	0.73193 (18)	0.97865 (11)	0.0243 (3)
C12	0.37182 (17)	0.79315 (16)	0.88797 (10)	0.0187 (3)
C13	0.33391 (19)	0.81150 (19)	1.02439 (11)	0.0278 (4)
H13	0.3487	0.8122	1.0819	0.033*
C14	0.20998 (19)	0.83945 (19)	0.98888 (10)	0.0267 (4)
H14	0.1216	0.8632	1.0171	0.032*
C15	0.14735 (19)	0.7795 (2)	0.50545 (11)	0.0292 (4)
H15A	0.1754	0.7766	0.4453	0.035*
H15B	0.0738	0.7396	0.5242	0.035*
H15C	0.1114	0.8778	0.5074	0.035*
C16	0.39551 (19)	0.7470 (2)	0.54034 (12)	0.0288 (4)
H16A	0.4245	0.7434	0.4804	0.035*
H16B	0.3646	0.8448	0.5427	0.035*
H16C	0.4749	0.6871	0.5809	0.035*
C17	0.3252 (2)	0.53949 (19)	0.56530 (13)	0.0338 (4)
H17A	0.3546	0.5344	0.5057	0.041*
H17B	0.4049	0.4820	0.6060	0.041*
H17C	0.2488	0.5035	0.5832	0.041*
C18	0.27423 (17)	0.69314 (17)	0.56696 (10)	0.0214 (3)
C19	0.17947 (16)	0.81433 (16)	0.68941 (10)	0.0171 (3)
C20	0.23340 (19)	0.58114 (17)	0.72914 (11)	0.0258 (4)
H20	0.2646	0.4861	0.7271	0.031*
C21	0.18492 (19)	0.62702 (17)	0.79991 (11)	0.0264 (4)
H21	0.1752	0.5694	0.8570	0.032*
C22	0.7500 (2)	0.8917 (2)	0.63949 (15)	0.0427 (5)
H22A	0.7306	0.9713	0.6633	0.051*
H22B	0.8142	0.8984	0.5899	0.051*
H22C	0.7931	0.8026	0.6853	0.051*
B1	0.1064 (2)	0.8501 (2)	0.84775 (12)	0.0208 (4)
H1	0.0452	0.8058	0.8891	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01464 (3)	0.01767 (3)	0.01733 (3)	−0.00662 (2)	0.00094 (2)	−0.00655 (2)
Cl1	0.0344 (2)	0.02018 (19)	0.02140 (18)	−0.01082 (17)	0.00152 (16)	−0.00566 (15)
Cl2	0.0225 (2)	0.0394 (2)	0.0369 (2)	−0.01774 (19)	0.00175 (17)	−0.01666 (19)
S1	0.01422 (17)	0.0227 (2)	0.02320 (18)	−0.00741 (15)	0.00018 (14)	−0.01156 (15)
S2	0.02088 (19)	0.0249 (2)	0.01456 (16)	−0.00174 (16)	−0.00040 (14)	−0.00753 (15)
S3	0.02191 (19)	0.01311 (17)	0.01865 (17)	−0.00623 (15)	−0.00488 (14)	−0.00307 (14)
O1	0.0377 (8)	0.0580 (10)	0.0466 (9)	−0.0171 (7)	0.0138 (7)	−0.0353 (8)
N1	0.0140 (6)	0.0211 (7)	0.0227 (6)	−0.0048 (5)	0.0013 (5)	−0.0097 (5)
N2	0.0154 (6)	0.0216 (7)	0.0210 (6)	−0.0076 (5)	0.0014 (5)	−0.0082 (5)
N3	0.0235 (7)	0.0213 (7)	0.0170 (6)	−0.0028 (6)	−0.0029 (5)	−0.0079 (5)
N4	0.0239 (7)	0.0206 (7)	0.0143 (6)	−0.0059 (6)	0.0016 (5)	−0.0059 (5)
N5	0.0224 (7)	0.0144 (6)	0.0207 (6)	−0.0071 (5)	−0.0036 (5)	−0.0048 (5)
N6	0.0248 (7)	0.0160 (6)	0.0191 (6)	−0.0087 (6)	−0.0022 (5)	−0.0031 (5)
C1	0.0318 (10)	0.0274 (10)	0.0328 (10)	−0.0069 (8)	0.0053 (8)	−0.0022 (8)
C2	0.0221 (9)	0.0264 (10)	0.0568 (13)	0.0016 (8)	0.0000 (9)	−0.0098 (9)
C3	0.0388 (11)	0.0251 (9)	0.0414 (11)	−0.0087 (8)	0.0064 (8)	−0.0201 (8)
C4	0.0208 (8)	0.0193 (8)	0.0307 (9)	−0.0041 (7)	0.0037 (7)	−0.0094 (7)
C5	0.0138 (7)	0.0198 (8)	0.0185 (7)	−0.0055 (6)	0.0017 (5)	−0.0099 (6)
C6	0.0134 (7)	0.0298 (9)	0.0263 (8)	−0.0078 (7)	0.0015 (6)	−0.0110 (7)
C7	0.0168 (8)	0.0305 (9)	0.0272 (8)	−0.0126 (7)	0.0032 (6)	−0.0126 (7)
C8	0.0298 (10)	0.0283 (10)	0.0304 (9)	0.0019 (8)	−0.0097 (7)	−0.0124 (8)
C9	0.0402 (11)	0.0391 (11)	0.0317 (10)	−0.0031 (9)	−0.0153 (8)	−0.0175 (9)
C10	0.0388 (11)	0.0449 (12)	0.0423 (11)	−0.0219 (10)	−0.0124 (9)	0.0028 (10)
C11	0.0248 (8)	0.0240 (9)	0.0224 (8)	−0.0049 (7)	−0.0080 (6)	−0.0067 (7)
C12	0.0225 (8)	0.0150 (7)	0.0152 (7)	−0.0031 (6)	−0.0017 (6)	−0.0040 (6)
C13	0.0345 (10)	0.0299 (9)	0.0149 (7)	−0.0050 (8)	0.0008 (7)	−0.0095 (7)
C14	0.0298 (9)	0.0299 (9)	0.0161 (7)	−0.0060 (8)	0.0058 (6)	−0.0087 (7)
C15	0.0316 (9)	0.0337 (10)	0.0250 (8)	−0.0094 (8)	−0.0067 (7)	−0.0129 (7)
C16	0.0241 (9)	0.0283 (9)	0.0361 (10)	−0.0099 (8)	0.0037 (7)	−0.0128 (8)
C17	0.0451 (11)	0.0225 (9)	0.0370 (10)	−0.0115 (8)	0.0067 (9)	−0.0160 (8)
C18	0.0243 (8)	0.0195 (8)	0.0225 (8)	−0.0071 (7)	−0.0011 (6)	−0.0097 (6)
C19	0.0174 (7)	0.0151 (7)	0.0198 (7)	−0.0066 (6)	−0.0038 (6)	−0.0043 (6)
C20	0.0352 (9)	0.0149 (8)	0.0271 (8)	−0.0102 (7)	−0.0042 (7)	−0.0029 (6)
C21	0.0383 (10)	0.0174 (8)	0.0236 (8)	−0.0131 (7)	−0.0036 (7)	−0.0008 (6)
C22	0.0408 (12)	0.0457 (13)	0.0449 (12)	−0.0117 (10)	0.0046 (9)	−0.0241 (10)
B1	0.0218 (9)	0.0207 (9)	0.0212 (8)	−0.0092 (8)	0.0022 (7)	−0.0066 (7)

Geometric parameters (Å, º)

Bi1—S1	2.6463 (5)	C3—H3B	0.9800
Bi1—Cl1	2.6933 (5)	C3—H3C	0.9800
Bi1—S3	2.7242 (4)	C6—C7	1.340 (2)
Bi1—Cl2	2.7499 (4)	C6—H6	0.9500
Bi1—S2	2.8307 (5)	C7—H7	0.9500
Bi1—O1	2.8023 (14)	C8—C11	1.531 (2)
S1—C5	1.7381 (15)	C8—H8A	0.9800
S2—C12	1.7193 (16)	C8—H8B	0.9800
S3—C19	1.7283 (15)	C8—H8C	0.9800
O1—C22	1.419 (3)	C9—C11	1.524 (2)
O1—H1D	0.8400	C9—H9A	0.9800
N1—C5	1.361 (2)	C9—H9B	0.9800
N1—C6	1.3852 (19)	C9—H9C	0.9800
N1—C4	1.518 (2)	C10—C11	1.527 (3)
N2—C5	1.3528 (19)	C10—H10A	0.9800
N2—C7	1.383 (2)	C10—H10B	0.9800
N2—B1	1.558 (2)	C10—H10C	0.9800
N3—C12	1.3702 (19)	C13—C14	1.342 (3)
N3—C13	1.383 (2)	C13—H13	0.9500
N3—C11	1.509 (2)	C14—H14	0.9500
N4—C12	1.352 (2)	C15—C18	1.526 (2)
N4—C14	1.387 (2)	C15—H15A	0.9800
N4—B1	1.562 (2)	C15—H15B	0.9800
N5—C19	1.359 (2)	C15—H15C	0.9800
N5—C20	1.389 (2)	C16—C18	1.532 (2)
N5—C18	1.511 (2)	C16—H16A	0.9800
N6—C19	1.3580 (19)	C16—H16B	0.9800
N6—C21	1.386 (2)	C16—H16C	0.9800
N6—B1	1.545 (2)	C17—C18	1.528 (2)
C1—C4	1.524 (2)	C17—H17A	0.9800
C1—H1A	0.9800	C17—H17B	0.9800
C1—H1B	0.9800	C17—H17C	0.9800
C1—H1C	0.9800	C20—C21	1.342 (2)
C2—C4	1.529 (2)	C20—H20	0.9500
C2—H2A	0.9800	C21—H21	0.9500
C2—H2B	0.9800	C22—H22A	0.9800
C2—H2C	0.9800	C22—H22B	0.9800
C3—C4	1.528 (2)	C22—H22C	0.9800
C3—H3A	0.9800	B1—H1	1.0000
S1—Bi1—Cl1	100.115 (14)	H8A—C8—H8C	109.5
S1—Bi1—S3	88.960 (13)	H8B—C8—H8C	109.5
Cl1—Bi1—S3	76.546 (13)	C11—C9—H9A	109.5
S1—Bi1—Cl2	74.926 (13)	C11—C9—H9B	109.5
Cl1—Bi1—Cl2	95.046 (14)	H9A—C9—H9B	109.5
S3—Bi1—Cl2	160.381 (14)	C11—C9—H9C	109.5
S1—Bi1—S2	90.300 (14)	H9A—C9—H9C	109.5
Cl1—Bi1—S2	160.302 (13)	H9B—C9—H9C	109.5
S3—Bi1—S2	87.065 (14)	C11—C10—H10A	109.5
Cl2—Bi1—S2	103.836 (14)	C11—C10—H10B	109.5
S1—Bi1—O1	152.76 (4)	H10A—C10—H10B	109.5
S2—Bi1—O1	74.07 (3)	C11—C10—H10C	109.5
S3—Bi1—O1	111.80 (4)	H10A—C10—H10C	109.5
Cl1—Bi1—O1	101.73 (3)	H10B—C10—H10C	109.5
Cl2—Bi1—O1	87.10 (4)	N3—C11—C9	108.59 (14)
C5—S1—Bi1	106.38 (5)	N3—C11—C10	110.33 (14)
C12—S2—Bi1	103.20 (5)	C9—C11—C10	108.58 (16)
C19—S3—Bi1	104.44 (5)	N3—C11—C8	108.13 (14)
C22—O1—H1D	109.5	C9—C11—C8	108.76 (14)
C5—N1—C6	108.00 (13)	C10—C11—C8	112.36 (17)
C5—N1—C4	128.36 (13)	N4—C12—N3	107.91 (13)
C6—N1—C4	123.51 (13)	N4—C12—S2	126.54 (12)
C5—N2—C7	107.75 (13)	N3—C12—S2	125.54 (12)
C5—N2—B1	133.83 (13)	C14—C13—N3	107.66 (14)
C7—N2—B1	118.40 (13)	C14—C13—H13	126.2
C12—N3—C13	108.05 (14)	N3—C13—H13	126.2
C12—N3—C11	127.23 (14)	C13—C14—N4	108.47 (15)
C13—N3—C11	124.50 (13)	C13—C14—H14	125.8
C12—N4—C14	107.90 (13)	N4—C14—H14	125.8
C12—N4—B1	132.50 (13)	C18—C15—H15A	109.5
C14—N4—B1	119.57 (14)	C18—C15—H15B	109.5
C19—N5—C20	108.25 (13)	H15A—C15—H15B	109.5
C19—N5—C18	127.58 (13)	C18—C15—H15C	109.5
C20—N5—C18	124.16 (13)	H15A—C15—H15C	109.5
C19—N6—C21	107.34 (13)	H15B—C15—H15C	109.5
C19—N6—B1	132.76 (13)	C18—C16—H16A	109.5
C21—N6—B1	119.59 (13)	C18—C16—H16B	109.5
C4—C1—H1A	109.5	H16A—C16—H16B	109.5
C4—C1—H1B	109.5	C18—C16—H16C	109.5
H1A—C1—H1B	109.5	H16A—C16—H16C	109.5
C4—C1—H1C	109.5	H16B—C16—H16C	109.5
H1A—C1—H1C	109.5	C18—C17—H17A	109.5
H1B—C1—H1C	109.5	C18—C17—H17B	109.5
C4—C2—H2A	109.5	H17A—C17—H17B	109.5
C4—C2—H2B	109.5	C18—C17—H17C	109.5
H2A—C2—H2B	109.5	H17A—C17—H17C	109.5
C4—C2—H2C	109.5	H17B—C17—H17C	109.5
H2A—C2—H2C	109.5	N5—C18—C15	108.87 (13)
H2B—C2—H2C	109.5	N5—C18—C17	108.59 (13)
C4—C3—H3A	109.5	C15—C18—C17	108.52 (14)
C4—C3—H3B	109.5	N5—C18—C16	109.45 (13)
H3A—C3—H3B	109.5	C15—C18—C16	112.53 (14)
C4—C3—H3C	109.5	C17—C18—C16	108.80 (15)
H3A—C3—H3C	109.5	N6—C19—N5	108.29 (13)
H3B—C3—H3C	109.5	N6—C19—S3	125.46 (12)
N1—C4—C1	109.70 (14)	N5—C19—S3	126.22 (12)
N1—C4—C3	108.27 (14)	C21—C20—N5	107.17 (14)
C1—C4—C3	112.34 (15)	C21—C20—H20	126.4
N1—C4—C2	108.68 (14)	N5—C20—H20	126.4
C1—C4—C2	108.85 (15)	C20—C21—N6	108.95 (14)
C3—C4—C2	108.92 (15)	C20—C21—H21	125.5
N2—C5—N1	108.14 (13)	N6—C21—H21	125.5
N2—C5—S1	126.07 (12)	O1—C22—H22A	109.5
N1—C5—S1	125.79 (12)	O1—C22—H22B	109.5
C7—C6—N1	107.55 (14)	H22A—C22—H22B	109.5
C7—C6—H6	126.2	O1—C22—H22C	109.5
N1—C6—H6	126.2	H22A—C22—H22C	109.5
C6—C7—N2	108.53 (14)	H22B—C22—H22C	109.5
C6—C7—H7	125.7	N6—B1—N2	112.52 (13)
N2—C7—H7	125.7	N6—B1—N4	112.92 (14)
C11—C8—H8A	109.5	N2—B1—N4	112.23 (13)
C11—C8—H8B	109.5	N6—B1—H1	106.2
H8A—C8—H8B	109.5	N2—B1—H1	106.2
C11—C8—H8C	109.5	N4—B1—H1	106.2
C5—N1—C4—C1	65.0 (2)	C11—N3—C13—C14	−174.35 (15)
C6—N1—C4—C1	−119.63 (17)	N3—C13—C14—N4	−0.2 (2)
C5—N1—C4—C3	−57.9 (2)	C12—N4—C14—C13	−0.3 (2)
C6—N1—C4—C3	117.46 (17)	B1—N4—C14—C13	177.98 (15)
C5—N1—C4—C2	−176.10 (16)	C19—N5—C18—C15	−62.95 (19)
C6—N1—C4—C2	−0.7 (2)	C20—N5—C18—C15	116.96 (17)
C7—N2—C5—N1	1.47 (17)	C19—N5—C18—C17	179.07 (15)
B1—N2—C5—N1	179.71 (15)	C20—N5—C18—C17	−1.0 (2)
C7—N2—C5—S1	−179.10 (12)	C19—N5—C18—C16	60.4 (2)
B1—N2—C5—S1	−0.9 (2)	C20—N5—C18—C16	−119.66 (16)
C6—N1—C5—N2	−1.59 (17)	C21—N6—C19—N5	−0.02 (17)
C4—N1—C5—N2	174.36 (14)	B1—N6—C19—N5	173.38 (15)
C6—N1—C5—S1	178.98 (12)	C21—N6—C19—S3	177.76 (12)
C4—N1—C5—S1	−5.1 (2)	B1—N6—C19—S3	−8.8 (2)
Bi1—S1—C5—N2	71.57 (14)	C20—N5—C19—N6	−0.30 (17)
Bi1—S1—C5—N1	−109.10 (13)	C18—N5—C19—N6	179.63 (14)
C5—N1—C6—C7	1.10 (18)	C20—N5—C19—S3	−178.05 (12)
C4—N1—C6—C7	−175.09 (14)	C18—N5—C19—S3	1.9 (2)
N1—C6—C7—N2	−0.20 (19)	Bi1—S3—C19—N6	76.69 (13)
C5—N2—C7—C6	−0.78 (18)	Bi1—S3—C19—N5	−105.93 (13)
B1—N2—C7—C6	−179.34 (14)	C19—N5—C20—C21	0.51 (19)
C12—N3—C11—C9	−178.53 (16)	C18—N5—C20—C21	−179.42 (14)
C13—N3—C11—C9	−4.6 (2)	N5—C20—C21—N6	−0.5 (2)
C12—N3—C11—C10	62.6 (2)	C19—N6—C21—C20	0.34 (19)
C13—N3—C11—C10	−123.47 (18)	B1—N6—C21—C20	−174.09 (15)
C12—N3—C11—C8	−60.7 (2)	C19—N6—B1—N2	31.8 (2)
C13—N3—C11—C8	113.28 (18)	C21—N6—B1—N2	−155.42 (14)
C14—N4—C12—N3	0.63 (18)	C19—N6—B1—N4	−96.48 (19)
B1—N4—C12—N3	−177.31 (15)	C21—N6—B1—N4	76.27 (18)
C14—N4—C12—S2	−179.10 (13)	C5—N2—B1—N6	−100.67 (19)
B1—N4—C12—S2	3.0 (3)	C7—N2—B1—N6	77.43 (17)
C13—N3—C12—N4	−0.75 (18)	C5—N2—B1—N4	28.0 (2)
C11—N3—C12—N4	174.00 (14)	C7—N2—B1—N4	−153.90 (13)
C13—N3—C12—S2	178.99 (12)	C12—N4—B1—N6	23.5 (2)
C11—N3—C12—S2	−6.3 (2)	C14—N4—B1—N6	−154.27 (14)
Bi1—S2—C12—N4	70.01 (14)	C12—N4—B1—N2	−104.98 (19)
Bi1—S2—C12—N3	−109.68 (13)	C14—N4—B1—N2	77.27 (18)
C12—N3—C13—C14	0.58 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···Cl1^i	0.84	2.28	3.0969 (18)	164

Symmetry code: (i) −x+1, −y+2, −z+1.

(BiTmClm-Cl2) Di-µ-chlorido-bis{chlorido[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III)}

Crystal data

[Bi2(C21H34BN6S3)2Cl4]	Z = 1
Mr = 1514.83	F(000) = 744.00
Triclinic, P1	Dx = 1.759 Mg m^−3
a = 10.8009 (11) Å	Mo Kα radiation, λ = 0.71075 Å
b = 11.3698 (14) Å	Cell parameters from 6052 reflections
c = 11.8690 (13) Å	θ = 3.0–27.5°
α = 95.125 (4)°	µ = 6.58 mm^−1
β = 91.947 (4)°	T = 179 K
γ = 99.549 (3)°	Block, orange
V = 1429.9 (3) Å^3	0.23 × 0.15 × 0.15 mm

Data collection

Rigaku XtaLAB P200 diffractometer	5816 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 5.814 pixels mm^-1	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −14→14
Tmin = 0.270, Tmax = 0.373	k = −14→14
39709 measured reflections	l = −14→15
6115 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.013	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.033	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.019P)^2] where P = (Fo^2 + 2Fc^2)/3
6115 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.85 e Å^−3
Primary atom site location: structure-invariant direct methods

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.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Bi1	0.39969 (2)	0.41301 (2)	0.85362 (2)	0.01774 (3)
Cl1	0.37944 (5)	0.61914 (5)	1.01595 (4)	0.03186 (11)
Cl2	0.54822 (4)	0.56134 (4)	0.74438 (5)	0.02943 (11)
S1	0.18081 (4)	0.26572 (4)	0.93598 (4)	0.02185 (10)
S2	0.45110 (4)	0.20689 (4)	0.74473 (4)	0.01891 (9)
S3	0.24933 (4)	0.44487 (4)	0.67720 (4)	0.02081 (10)
N1	0.22072 (14)	0.03193 (13)	0.93270 (12)	0.0190 (3)
N2	0.16688 (14)	0.08266 (13)	0.76597 (12)	0.0181 (3)
N3	0.43753 (14)	0.20501 (13)	0.51162 (12)	0.0184 (3)
N4	0.25221 (14)	0.17310 (13)	0.58613 (12)	0.0190 (3)
N5	0.00025 (13)	0.41876 (13)	0.73377 (13)	0.0206 (3)
N6	0.06462 (13)	0.24855 (13)	0.68614 (12)	0.0189 (3)
C1	0.3749 (2)	0.1261 (2)	1.08680 (19)	0.0363 (5)
H1A	0.3979	0.1279	1.1676	0.044*
H1B	0.4434	0.1038	1.0420	0.044*
H1C	0.3598	0.2055	1.0700	0.044*
C2	0.1451 (2)	0.06199 (19)	1.12597 (17)	0.0303 (5)
H2A	0.1674	0.0635	1.2069	0.036*
H2B	0.1258	0.1402	1.1099	0.036*
H2C	0.0713	0.0000	1.1053	0.036*
C3	0.2806 (2)	−0.0901 (2)	1.08051 (18)	0.0344 (5)
H3A	0.3033	−0.0900	1.1612	0.041*
H3B	0.2047	−0.1495	1.0601	0.041*
H3C	0.3497	−0.1103	1.0354	0.041*
C4	0.25550 (17)	0.03418 (17)	1.05699 (15)	0.0231 (4)
C5	0.19061 (16)	0.12427 (15)	0.87656 (15)	0.0174 (4)
C6	0.21619 (19)	−0.06658 (16)	0.85467 (16)	0.0250 (4)
H6	0.2336	−0.1429	0.8703	0.030*
C7	0.18299 (18)	−0.03572 (16)	0.75342 (16)	0.0237 (4)
H7	0.1723	−0.0865	0.6845	0.028*
C8	0.6337 (2)	0.35132 (18)	0.54280 (18)	0.0300 (5)
H8A	0.7244	0.3657	0.5323	0.036*
H8B	0.5942	0.4089	0.5036	0.036*
H8C	0.6187	0.3610	0.6238	0.036*
C9	0.63882 (18)	0.13017 (18)	0.54876 (17)	0.0268 (4)
H9A	0.7292	0.1440	0.5368	0.032*
H9B	0.6254	0.1357	0.6302	0.032*
H9C	0.6010	0.0502	0.5142	0.032*
C10	0.59799 (19)	0.21018 (19)	0.36664 (16)	0.0287 (4)
H10A	0.6883	0.2227	0.3543	0.034*
H10B	0.5595	0.1293	0.3351	0.034*
H10C	0.5591	0.2693	0.3291	0.034*
C11	0.57765 (17)	0.22470 (17)	0.49425 (15)	0.0216 (4)
C12	0.37782 (16)	0.19445 (15)	0.61077 (14)	0.0170 (3)
C13	0.34632 (18)	0.19420 (18)	0.42468 (16)	0.0241 (4)
H13	0.3609	0.1999	0.3467	0.029*
C14	0.23349 (18)	0.17415 (18)	0.47038 (15)	0.0243 (4)
H14	0.1543	0.1627	0.4300	0.029*
C15	0.0832 (2)	0.6027 (2)	0.8588 (2)	0.0394 (5)
H15A	0.0791	0.6879	0.8752	0.047*
H15B	0.0593	0.5604	0.9252	0.047*
H15C	0.1691	0.5935	0.8405	0.047*
C16	0.0232 (2)	0.61294 (19)	0.6516 (2)	0.0388 (5)
H16A	0.0189	0.6983	0.6667	0.047*
H16B	0.1079	0.6038	0.6294	0.047*
H16C	−0.0380	0.5771	0.5901	0.047*
C17	−0.1409 (2)	0.5614 (2)	0.7884 (2)	0.0424 (6)
H17A	−0.1470	0.6462	0.8046	0.051*
H17B	−0.1991	0.5261	0.7245	0.051*
H17C	−0.1626	0.5191	0.8553	0.051*
C18	−0.00674 (17)	0.55006 (17)	0.75832 (18)	0.0262 (4)
C19	0.10116 (16)	0.36878 (16)	0.70073 (15)	0.0182 (4)
C20	−0.09990 (17)	0.32700 (18)	0.74195 (17)	0.0263 (4)
H20	−0.1817	0.3358	0.7646	0.032*
C21	−0.06013 (17)	0.22343 (17)	0.71200 (17)	0.0250 (4)
H21	−0.1095	0.1458	0.7091	0.030*
B1	0.13545 (19)	0.14250 (19)	0.65828 (17)	0.0199 (4)
H1	0.0750	0.0805	0.6102	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01588 (4)	0.01547 (4)	0.02072 (4)	0.00196 (3)	−0.00091 (3)	−0.00250 (3)
Cl1	0.0333 (3)	0.0311 (3)	0.0322 (3)	0.0143 (2)	−0.0045 (2)	−0.0054 (2)
Cl2	0.0192 (2)	0.0237 (2)	0.0458 (3)	0.00227 (18)	0.0058 (2)	0.0070 (2)
S1	0.0284 (2)	0.0156 (2)	0.0213 (2)	0.00477 (18)	0.00527 (19)	−0.00240 (18)
S2	0.0203 (2)	0.0211 (2)	0.0155 (2)	0.00582 (18)	−0.00146 (17)	−0.00098 (17)
S3	0.0129 (2)	0.0214 (2)	0.0285 (2)	0.00180 (17)	0.00229 (18)	0.00610 (19)
N1	0.0211 (8)	0.0175 (8)	0.0191 (8)	0.0043 (6)	0.0044 (6)	0.0016 (6)
N2	0.0201 (8)	0.0158 (7)	0.0181 (8)	0.0032 (6)	0.0033 (6)	−0.0007 (6)
N3	0.0189 (7)	0.0209 (8)	0.0164 (7)	0.0070 (6)	0.0012 (6)	0.0006 (6)
N4	0.0192 (7)	0.0214 (8)	0.0167 (7)	0.0060 (6)	−0.0002 (6)	−0.0003 (6)
N5	0.0128 (7)	0.0205 (8)	0.0280 (8)	0.0025 (6)	0.0004 (6)	0.0003 (6)
N6	0.0147 (7)	0.0192 (8)	0.0225 (8)	0.0020 (6)	0.0007 (6)	0.0026 (6)
C1	0.0299 (11)	0.0471 (14)	0.0296 (12)	−0.0004 (10)	−0.0033 (9)	0.0063 (10)
C2	0.0334 (11)	0.0360 (12)	0.0245 (10)	0.0101 (9)	0.0109 (9)	0.0074 (9)
C3	0.0416 (12)	0.0369 (12)	0.0303 (11)	0.0172 (10)	0.0049 (9)	0.0126 (9)
C4	0.0243 (10)	0.0261 (10)	0.0198 (9)	0.0057 (8)	0.0026 (8)	0.0047 (8)
C5	0.0156 (8)	0.0153 (9)	0.0208 (9)	0.0011 (7)	0.0045 (7)	0.0003 (7)
C6	0.0319 (11)	0.0150 (9)	0.0292 (11)	0.0067 (8)	0.0057 (8)	0.0007 (8)
C7	0.0293 (10)	0.0159 (9)	0.0249 (10)	0.0033 (8)	0.0057 (8)	−0.0045 (8)
C8	0.0295 (11)	0.0245 (10)	0.0340 (12)	−0.0007 (8)	0.0105 (9)	−0.0006 (9)
C9	0.0199 (9)	0.0291 (11)	0.0329 (11)	0.0080 (8)	0.0010 (8)	0.0033 (9)
C10	0.0265 (10)	0.0378 (12)	0.0246 (10)	0.0134 (9)	0.0075 (8)	0.0013 (9)
C11	0.0195 (9)	0.0244 (10)	0.0218 (10)	0.0058 (8)	0.0044 (7)	0.0011 (8)
C12	0.0191 (9)	0.0144 (8)	0.0177 (9)	0.0051 (7)	0.0002 (7)	−0.0013 (7)
C13	0.0262 (10)	0.0325 (11)	0.0153 (9)	0.0095 (8)	0.0001 (8)	0.0027 (8)
C14	0.0241 (10)	0.0336 (11)	0.0159 (9)	0.0091 (8)	−0.0034 (7)	−0.0001 (8)
C15	0.0335 (12)	0.0329 (12)	0.0480 (14)	0.0044 (10)	−0.0063 (10)	−0.0128 (10)
C16	0.0380 (12)	0.0279 (12)	0.0550 (15)	0.0147 (10)	0.0028 (11)	0.0102 (10)
C17	0.0238 (11)	0.0320 (12)	0.0696 (17)	0.0077 (9)	0.0081 (11)	−0.0139 (11)
C18	0.0180 (9)	0.0203 (10)	0.0397 (12)	0.0050 (7)	0.0001 (8)	−0.0035 (8)
C19	0.0137 (8)	0.0215 (9)	0.0191 (9)	0.0028 (7)	−0.0004 (7)	0.0018 (7)
C20	0.0122 (9)	0.0283 (10)	0.0377 (12)	0.0010 (8)	0.0043 (8)	0.0022 (9)
C21	0.0149 (9)	0.0235 (10)	0.0351 (11)	−0.0014 (7)	0.0016 (8)	0.0043 (8)
B1	0.0191 (10)	0.0196 (10)	0.0195 (10)	0.0015 (8)	−0.0012 (8)	−0.0015 (8)

Geometric parameters (Å, º)

Bi1—Cl2	2.5949 (5)	C3—H3A	0.9800
Bi1—S3	2.6931 (5)	C3—H3B	0.9800
Bi1—S2	2.7222 (5)	C3—H3C	0.9800
Bi1—Cl1^i	2.8915 (5)	C6—C7	1.336 (3)
Bi1—S1	2.9128 (5)	C6—H6	0.9500
Bi1—Cl1	2.9401 (6)	C7—H7	0.9500
Cl1—Bi1^i	2.8915 (5)	C8—C11	1.520 (3)
S1—C5	1.7188 (18)	C8—H8A	0.9800
S2—C12	1.7354 (18)	C8—H8B	0.9800
S3—C19	1.7326 (18)	C8—H8C	0.9800
N1—C5	1.369 (2)	C9—C11	1.530 (3)
N1—C6	1.381 (2)	C9—H9A	0.9800
N1—C4	1.507 (2)	C9—H9B	0.9800
N2—C5	1.356 (2)	C9—H9C	0.9800
N2—C7	1.381 (2)	C10—C11	1.536 (3)
N2—B1	1.554 (2)	C10—H10A	0.9800
N3—C12	1.366 (2)	C10—H10B	0.9800
N3—C13	1.385 (2)	C10—H10C	0.9800
N3—C11	1.517 (2)	C13—C14	1.344 (3)
N4—C12	1.355 (2)	C13—H13	0.9500
N4—C14	1.383 (2)	C14—H14	0.9500
N4—B1	1.558 (2)	C15—C18	1.525 (3)
N5—C19	1.364 (2)	C15—H15A	0.9800
N5—C20	1.385 (2)	C15—H15B	0.9800
N5—C18	1.510 (2)	C15—H15C	0.9800
N6—C19	1.352 (2)	C16—C18	1.528 (3)
N6—C21	1.381 (2)	C16—H16A	0.9800
N6—B1	1.549 (2)	C16—H16B	0.9800
C1—C4	1.529 (3)	C16—H16C	0.9800
C1—H1A	0.9800	C17—C18	1.527 (3)
C1—H1B	0.9800	C17—H17A	0.9800
C1—H1C	0.9800	C17—H17B	0.9800
C2—C4	1.529 (3)	C17—H17C	0.9800
C2—H2A	0.9800	C20—C21	1.342 (3)
C2—H2B	0.9800	C20—H20	0.9500
C2—H2C	0.9800	C21—H21	0.9500
C3—C4	1.529 (3)	B1—H1	1.0000
Cl2—Bi1—S3	77.787 (16)	C11—C8—H8B	109.5
Cl2—Bi1—S2	97.312 (17)	H8A—C8—H8B	109.5
S3—Bi1—S2	91.074 (15)	C11—C8—H8C	109.5
Cl2—Bi1—Cl1^i	87.108 (17)	H8A—C8—H8C	109.5
S3—Bi1—Cl1^i	160.787 (15)	H8B—C8—H8C	109.5
S2—Bi1—Cl1^i	79.020 (15)	C11—C9—H9A	109.5
Cl2—Bi1—S1	164.283 (15)	C11—C9—H9B	109.5
S3—Bi1—S1	86.949 (15)	H9A—C9—H9B	109.5
S2—Bi1—S1	86.582 (15)	C11—C9—H9C	109.5
Cl1^i—Bi1—S1	108.598 (16)	H9A—C9—H9C	109.5
Cl2—Bi1—Cl1	86.939 (18)	H9B—C9—H9C	109.5
S3—Bi1—Cl1	102.541 (15)	C11—C10—H10A	109.5
S2—Bi1—Cl1	166.327 (14)	C11—C10—H10B	109.5
Cl1^i—Bi1—Cl1	88.262 (15)	H10A—C10—H10B	109.5
S1—Bi1—Cl1	92.814 (16)	C11—C10—H10C	109.5
Bi1^i—Cl1—Bi1	91.738 (15)	H10A—C10—H10C	109.5
C5—S1—Bi1	103.01 (6)	H10B—C10—H10C	109.5
C12—S2—Bi1	105.95 (6)	N3—C11—C8	108.35 (15)
C19—S3—Bi1	106.11 (6)	N3—C11—C9	110.42 (14)
C5—N1—C6	108.04 (15)	C8—C11—C9	112.19 (16)
C5—N1—C4	127.44 (15)	N3—C11—C10	108.72 (15)
C6—N1—C4	124.51 (14)	C8—C11—C10	109.60 (16)
C5—N2—C7	108.25 (14)	C9—C11—C10	107.50 (15)
C5—N2—B1	133.29 (15)	N4—C12—N3	108.17 (15)
C7—N2—B1	118.34 (15)	N4—C12—S2	126.23 (13)
C12—N3—C13	107.79 (14)	N3—C12—S2	125.59 (13)
C12—N3—C11	128.24 (14)	C14—C13—N3	107.74 (16)
C13—N3—C11	123.97 (14)	C14—C13—H13	126.1
C12—N4—C14	107.80 (15)	N3—C13—H13	126.1
C12—N4—B1	133.49 (15)	C13—C14—N4	108.45 (16)
C14—N4—B1	118.60 (15)	C13—C14—H14	125.8
C19—N5—C20	108.11 (15)	N4—C14—H14	125.8
C19—N5—C18	127.96 (15)	C18—C15—H15A	109.5
C20—N5—C18	123.93 (15)	C18—C15—H15B	109.5
C19—N6—C21	107.90 (15)	H15A—C15—H15B	109.5
C19—N6—B1	133.39 (15)	C18—C15—H15C	109.5
C21—N6—B1	118.46 (15)	H15A—C15—H15C	109.5
C4—C1—H1A	109.5	H15B—C15—H15C	109.5
C4—C1—H1B	109.5	C18—C16—H16A	109.5
H1A—C1—H1B	109.5	C18—C16—H16B	109.5
C4—C1—H1C	109.5	H16A—C16—H16B	109.5
H1A—C1—H1C	109.5	C18—C16—H16C	109.5
H1B—C1—H1C	109.5	H16A—C16—H16C	109.5
C4—C2—H2A	109.5	H16B—C16—H16C	109.5
C4—C2—H2B	109.5	C18—C17—H17A	109.5
H2A—C2—H2B	109.5	C18—C17—H17B	109.5
C4—C2—H2C	109.5	H17A—C17—H17B	109.5
H2A—C2—H2C	109.5	C18—C17—H17C	109.5
H2B—C2—H2C	109.5	H17A—C17—H17C	109.5
C4—C3—H3A	109.5	H17B—C17—H17C	109.5
C4—C3—H3B	109.5	N5—C18—C15	109.08 (15)
H3A—C3—H3B	109.5	N5—C18—C16	108.88 (16)
C4—C3—H3C	109.5	C15—C18—C16	112.63 (18)
H3A—C3—H3C	109.5	N5—C18—C17	108.47 (16)
H3B—C3—H3C	109.5	C15—C18—C17	109.27 (18)
N1—C4—C1	109.13 (15)	C16—C18—C17	108.43 (17)
N1—C4—C3	108.54 (16)	N6—C19—N5	107.98 (15)
C1—C4—C3	109.24 (17)	N6—C19—S3	125.53 (13)
N1—C4—C2	109.24 (15)	N5—C19—S3	126.47 (14)
C1—C4—C2	112.29 (18)	C21—C20—N5	107.37 (16)
C3—C4—C2	108.33 (16)	C21—C20—H20	126.3
N2—C5—N1	107.40 (15)	N5—C20—H20	126.3
N2—C5—S1	126.30 (13)	C20—C21—N6	108.63 (16)
N1—C5—S1	126.29 (14)	C20—C21—H21	125.7
C7—C6—N1	107.97 (16)	N6—C21—H21	125.7
C7—C6—H6	126.0	N6—B1—N2	111.95 (15)
N1—C6—H6	126.0	N6—B1—N4	114.25 (15)
C6—C7—N2	108.34 (16)	N2—B1—N4	112.26 (14)
C6—C7—H7	125.8	N6—B1—H1	105.9
N2—C7—H7	125.8	N2—B1—H1	105.9
C11—C8—H8A	109.5	N4—B1—H1	105.9
C5—N1—C4—C1	−61.3 (2)	C11—N3—C13—C14	178.21 (16)
C6—N1—C4—C1	117.48 (19)	N3—C13—C14—N4	0.5 (2)
C5—N1—C4—C3	179.70 (17)	C12—N4—C14—C13	0.9 (2)
C6—N1—C4—C3	−1.5 (2)	B1—N4—C14—C13	−175.76 (16)
C5—N1—C4—C2	61.8 (2)	C19—N5—C18—C15	−63.0 (2)
C6—N1—C4—C2	−119.41 (19)	C20—N5—C18—C15	117.0 (2)
C7—N2—C5—N1	−0.31 (19)	C19—N5—C18—C16	60.3 (2)
B1—N2—C5—N1	−176.07 (17)	C20—N5—C18—C16	−119.7 (2)
C7—N2—C5—S1	−178.81 (13)	C19—N5—C18—C17	178.08 (18)
B1—N2—C5—S1	5.4 (3)	C20—N5—C18—C17	−1.9 (3)
C6—N1—C5—N2	0.53 (19)	C21—N6—C19—N5	−0.84 (19)
C4—N1—C5—N2	179.50 (15)	B1—N6—C19—N5	−174.81 (17)
C6—N1—C5—S1	179.03 (14)	C21—N6—C19—S3	−179.12 (14)
C4—N1—C5—S1	−2.0 (3)	B1—N6—C19—S3	6.9 (3)
Bi1—S1—C5—N2	−72.74 (15)	C20—N5—C19—N6	1.25 (19)
Bi1—S1—C5—N1	109.03 (15)	C18—N5—C19—N6	−178.75 (16)
C5—N1—C6—C7	−0.6 (2)	C20—N5—C19—S3	179.52 (14)
C4—N1—C6—C7	−179.56 (16)	C18—N5—C19—S3	−0.5 (3)
N1—C6—C7—N2	0.4 (2)	Bi1—S3—C19—N6	−75.54 (16)
C5—N2—C7—C6	0.0 (2)	Bi1—S3—C19—N5	106.49 (15)
B1—N2—C7—C6	176.46 (16)	C19—N5—C20—C21	−1.2 (2)
C12—N3—C11—C8	−70.0 (2)	C18—N5—C20—C21	178.81 (17)
C13—N3—C11—C8	110.14 (19)	N5—C20—C21—N6	0.7 (2)
C12—N3—C11—C9	53.2 (2)	C19—N6—C21—C20	0.1 (2)
C13—N3—C11—C9	−126.62 (18)	B1—N6—C21—C20	175.12 (16)
C12—N3—C11—C10	170.92 (16)	C19—N6—B1—N2	99.4 (2)
C13—N3—C11—C10	−8.9 (2)	C21—N6—B1—N2	−74.0 (2)
C14—N4—C12—N3	−1.89 (19)	C19—N6—B1—N4	−29.6 (3)
B1—N4—C12—N3	174.02 (17)	C21—N6—B1—N4	156.96 (16)
C14—N4—C12—S2	177.92 (14)	C5—N2—B1—N6	−29.7 (3)
B1—N4—C12—S2	−6.2 (3)	C7—N2—B1—N6	154.84 (15)
C13—N3—C12—N4	2.19 (19)	C5—N2—B1—N4	100.3 (2)
C11—N3—C12—N4	−177.66 (15)	C7—N2—B1—N4	−75.1 (2)
C13—N3—C12—S2	−177.62 (13)	C12—N4—B1—N6	104.3 (2)
C11—N3—C12—S2	2.5 (3)	C14—N4—B1—N6	−80.2 (2)
Bi1—S2—C12—N4	−68.38 (16)	C12—N4—B1—N2	−24.6 (3)
Bi1—S2—C12—N3	111.39 (14)	C14—N4—B1—N2	150.95 (16)
C12—N3—C13—C14	−1.6 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.