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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-[kappa]O)[tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl-[kappa]S)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-[mu]-chlorido-bis­{chlorido­[tris­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl-[kappa]S)hydro­borato]bis­muth(III)}, [Bi2(C21H34BN6S3)2Cl4], (II). These complexes show {BiIIIS3Cl2O} and {BiIIIS3Cl3} coordination geometries with average BiIII-S bond lengths of 2.73 and 2.78 Å in (I) and (II), respectively. The overall BiIII coordination geometry is distorted octa­hedral due to stereochemically active lone pairs. The three BiIII-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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616010615/yp3123sup1.cif
Contains datablocks global, BiTmCl2, BiTmClm-Cl2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616010615/yp3123BiTmCl2sup2.hkl
Contains datablock BiTmCl2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616010615/yp3123BiTmClm-Cl2sup3.hkl
Contains datablock BiTmClm-Cl2

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616010615/yp3123sup4.pdf
XAS analysis

CCDC references: 1488897; 1488896

Computing details top

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) top
Crystal data top
[Bi(C21H34BN6S3)Cl2(CH4O)]Z = 2
Mr = 789.46F(000) = 780.00
Triclinic, P1Dx = 1.697 Mg m3
a = 10.2899 (5) ÅMo Kα radiation, λ = 0.71075 Å
b = 10.6653 (4) ÅCell parameters from 6399 reflections
c = 15.9818 (10) Åθ = 3.0–27.5°
α = 72.157 (6)°µ = 6.10 mm1
β = 83.838 (8)°T = 179 K
γ = 67.742 (7)°Block, orange
V = 1545.08 (16) Å30.24 × 0.16 × 0.07 mm
Data collection top
Rigaku XtaLAB P200
diffractometer
6768 reflections with F2 > 2.0σ(F2)
Detector resolution: 5.814 pixels mm-1Rint = 0.037
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: numerical
(NUMABS; Rigaku, 1999)
h = 1313
Tmin = 0.465, Tmax = 0.653k = 1313
51186 measured reflectionsl = 2020
7083 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.012Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.032H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0201P)2]
where P = (Fo2 + 2Fc2)/3
7083 reflections(Δ/σ)max = 0.008
327 parametersΔρmax = 1.03 e Å3
0 restraintsΔρmin = 0.66 e Å3
Primary atom site location: structure-invariant direct methods
Special details top

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 (Å2) top
xyzUiso*/Ueq
Bi10.36354 (2)1.04501 (2)0.67383 (2)0.01603 (2)
Cl10.25103 (5)1.26183 (4)0.53006 (3)0.02523 (8)
Cl20.50213 (4)1.17929 (5)0.73128 (3)0.02968 (9)
S10.20113 (4)1.14394 (4)0.79687 (3)0.01864 (8)
S20.45474 (4)0.76840 (4)0.79180 (2)0.02165 (8)
S30.15003 (4)0.98696 (4)0.62743 (2)0.01790 (7)
O10.62244 (15)0.89575 (17)0.61046 (10)0.0438 (4)
H1D0.63950.85420.57130.053*
N10.08146 (13)1.24077 (14)0.75734 (9)0.0191 (3)
N20.01419 (13)1.00946 (14)0.81002 (9)0.0187 (3)
N30.43620 (14)0.78152 (14)0.96219 (9)0.0214 (3)
N40.23275 (15)0.82784 (14)0.90396 (8)0.0202 (3)
N50.22948 (14)0.69860 (13)0.65939 (9)0.0188 (3)
N60.15131 (14)0.77211 (14)0.77630 (8)0.0198 (3)
C10.0224 (2)1.4371 (2)0.65160 (12)0.0338 (4)
H1A0.04081.53880.63510.041*
H1B0.07761.38390.66580.041*
H1C0.04771.41380.60240.041*
C20.2653 (2)1.4796 (2)0.70769 (15)0.0388 (5)
H2A0.28491.58150.69090.047*
H2B0.28841.45510.65840.047*
H2C0.32241.45460.75850.047*
C30.0764 (2)1.4329 (2)0.81079 (13)0.0340 (4)
H3A0.09401.53430.79540.041*
H3B0.13631.40820.86000.041*
H3C0.02241.37860.82780.041*
C40.10966 (17)1.39816 (17)0.73153 (11)0.0243 (3)
C50.04038 (15)1.13061 (16)0.78764 (10)0.0166 (3)
C60.18439 (17)1.18594 (18)0.75890 (11)0.0226 (3)
H60.27941.23870.74040.027*
C70.12563 (17)1.04496 (18)0.79122 (11)0.0228 (3)
H70.17220.98030.79980.027*
C80.6598 (2)0.57980 (19)0.97319 (12)0.0316 (4)
H8A0.76120.54550.98370.038*
H8B0.61900.51921.01770.038*
H8C0.64290.57730.91460.038*
C90.6141 (2)0.7329 (2)1.07119 (13)0.0374 (5)
H9A0.71490.70091.08280.045*
H9B0.56730.82921.07620.045*
H9C0.57450.66931.11400.045*
C100.6543 (2)0.8316 (2)0.91306 (14)0.0427 (5)
H10A0.75530.79820.92450.051*
H10B0.63910.83350.85310.051*
H10C0.60860.92720.91950.051*
C110.59183 (18)0.73193 (18)0.97865 (11)0.0243 (3)
C120.37182 (17)0.79315 (16)0.88797 (10)0.0187 (3)
C130.33391 (19)0.81150 (19)1.02439 (11)0.0278 (4)
H130.34870.81221.08190.033*
C140.20998 (19)0.83945 (19)0.98888 (10)0.0267 (4)
H140.12160.86321.01710.032*
C150.14735 (19)0.7795 (2)0.50545 (11)0.0292 (4)
H15A0.17540.77660.44530.035*
H15B0.07380.73960.52420.035*
H15C0.11140.87780.50740.035*
C160.39551 (19)0.7470 (2)0.54034 (12)0.0288 (4)
H16A0.42450.74340.48040.035*
H16B0.36460.84480.54270.035*
H16C0.47490.68710.58090.035*
C170.3252 (2)0.53949 (19)0.56530 (13)0.0338 (4)
H17A0.35460.53440.50570.041*
H17B0.40490.48200.60600.041*
H17C0.24880.50350.58320.041*
C180.27423 (17)0.69314 (17)0.56696 (10)0.0214 (3)
C190.17947 (16)0.81433 (16)0.68941 (10)0.0171 (3)
C200.23340 (19)0.58114 (17)0.72914 (11)0.0258 (4)
H200.26460.48610.72710.031*
C210.18492 (19)0.62702 (17)0.79991 (11)0.0264 (4)
H210.17520.56940.85700.032*
C220.7500 (2)0.8917 (2)0.63949 (15)0.0427 (5)
H22A0.73060.97130.66330.051*
H22B0.81420.89840.58990.051*
H22C0.79310.80260.68530.051*
B10.1064 (2)0.8501 (2)0.84775 (12)0.0208 (4)
H10.04520.80580.88910.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.01464 (3)0.01767 (3)0.01733 (3)0.00662 (2)0.00094 (2)0.00655 (2)
Cl10.0344 (2)0.02018 (19)0.02140 (18)0.01082 (17)0.00152 (16)0.00566 (15)
Cl20.0225 (2)0.0394 (2)0.0369 (2)0.01774 (19)0.00175 (17)0.01666 (19)
S10.01422 (17)0.0227 (2)0.02320 (18)0.00741 (15)0.00018 (14)0.01156 (15)
S20.02088 (19)0.0249 (2)0.01456 (16)0.00174 (16)0.00040 (14)0.00753 (15)
S30.02191 (19)0.01311 (17)0.01865 (17)0.00623 (15)0.00488 (14)0.00307 (14)
O10.0377 (8)0.0580 (10)0.0466 (9)0.0171 (7)0.0138 (7)0.0353 (8)
N10.0140 (6)0.0211 (7)0.0227 (6)0.0048 (5)0.0013 (5)0.0097 (5)
N20.0154 (6)0.0216 (7)0.0210 (6)0.0076 (5)0.0014 (5)0.0082 (5)
N30.0235 (7)0.0213 (7)0.0170 (6)0.0028 (6)0.0029 (5)0.0079 (5)
N40.0239 (7)0.0206 (7)0.0143 (6)0.0059 (6)0.0016 (5)0.0059 (5)
N50.0224 (7)0.0144 (6)0.0207 (6)0.0071 (5)0.0036 (5)0.0048 (5)
N60.0248 (7)0.0160 (6)0.0191 (6)0.0087 (6)0.0022 (5)0.0031 (5)
C10.0318 (10)0.0274 (10)0.0328 (10)0.0069 (8)0.0053 (8)0.0022 (8)
C20.0221 (9)0.0264 (10)0.0568 (13)0.0016 (8)0.0000 (9)0.0098 (9)
C30.0388 (11)0.0251 (9)0.0414 (11)0.0087 (8)0.0064 (8)0.0201 (8)
C40.0208 (8)0.0193 (8)0.0307 (9)0.0041 (7)0.0037 (7)0.0094 (7)
C50.0138 (7)0.0198 (8)0.0185 (7)0.0055 (6)0.0017 (5)0.0099 (6)
C60.0134 (7)0.0298 (9)0.0263 (8)0.0078 (7)0.0015 (6)0.0110 (7)
C70.0168 (8)0.0305 (9)0.0272 (8)0.0126 (7)0.0032 (6)0.0126 (7)
C80.0298 (10)0.0283 (10)0.0304 (9)0.0019 (8)0.0097 (7)0.0124 (8)
C90.0402 (11)0.0391 (11)0.0317 (10)0.0031 (9)0.0153 (8)0.0175 (9)
C100.0388 (11)0.0449 (12)0.0423 (11)0.0219 (10)0.0124 (9)0.0028 (10)
C110.0248 (8)0.0240 (9)0.0224 (8)0.0049 (7)0.0080 (6)0.0067 (7)
C120.0225 (8)0.0150 (7)0.0152 (7)0.0031 (6)0.0017 (6)0.0040 (6)
C130.0345 (10)0.0299 (9)0.0149 (7)0.0050 (8)0.0008 (7)0.0095 (7)
C140.0298 (9)0.0299 (9)0.0161 (7)0.0060 (8)0.0058 (6)0.0087 (7)
C150.0316 (9)0.0337 (10)0.0250 (8)0.0094 (8)0.0067 (7)0.0129 (7)
C160.0241 (9)0.0283 (9)0.0361 (10)0.0099 (8)0.0037 (7)0.0128 (8)
C170.0451 (11)0.0225 (9)0.0370 (10)0.0115 (8)0.0067 (9)0.0160 (8)
C180.0243 (8)0.0195 (8)0.0225 (8)0.0071 (7)0.0011 (6)0.0097 (6)
C190.0174 (7)0.0151 (7)0.0198 (7)0.0066 (6)0.0038 (6)0.0043 (6)
C200.0352 (9)0.0149 (8)0.0271 (8)0.0102 (7)0.0042 (7)0.0029 (6)
C210.0383 (10)0.0174 (8)0.0236 (8)0.0131 (7)0.0036 (7)0.0008 (6)
C220.0408 (12)0.0457 (13)0.0449 (12)0.0117 (10)0.0046 (9)0.0241 (10)
B10.0218 (9)0.0207 (9)0.0212 (8)0.0092 (8)0.0022 (7)0.0066 (7)
Geometric parameters (Å, º) top
Bi1—S12.6463 (5)C3—H3B0.9800
Bi1—Cl12.6933 (5)C3—H3C0.9800
Bi1—S32.7242 (4)C6—C71.340 (2)
Bi1—Cl22.7499 (4)C6—H60.9500
Bi1—S22.8307 (5)C7—H70.9500
Bi1—O12.8023 (14)C8—C111.531 (2)
S1—C51.7381 (15)C8—H8A0.9800
S2—C121.7193 (16)C8—H8B0.9800
S3—C191.7283 (15)C8—H8C0.9800
O1—C221.419 (3)C9—C111.524 (2)
O1—H1D0.8400C9—H9A0.9800
N1—C51.361 (2)C9—H9B0.9800
N1—C61.3852 (19)C9—H9C0.9800
N1—C41.518 (2)C10—C111.527 (3)
N2—C51.3528 (19)C10—H10A0.9800
N2—C71.383 (2)C10—H10B0.9800
N2—B11.558 (2)C10—H10C0.9800
N3—C121.3702 (19)C13—C141.342 (3)
N3—C131.383 (2)C13—H130.9500
N3—C111.509 (2)C14—H140.9500
N4—C121.352 (2)C15—C181.526 (2)
N4—C141.387 (2)C15—H15A0.9800
N4—B11.562 (2)C15—H15B0.9800
N5—C191.359 (2)C15—H15C0.9800
N5—C201.389 (2)C16—C181.532 (2)
N5—C181.511 (2)C16—H16A0.9800
N6—C191.3580 (19)C16—H16B0.9800
N6—C211.386 (2)C16—H16C0.9800
N6—B11.545 (2)C17—C181.528 (2)
C1—C41.524 (2)C17—H17A0.9800
C1—H1A0.9800C17—H17B0.9800
C1—H1B0.9800C17—H17C0.9800
C1—H1C0.9800C20—C211.342 (2)
C2—C41.529 (2)C20—H200.9500
C2—H2A0.9800C21—H210.9500
C2—H2B0.9800C22—H22A0.9800
C2—H2C0.9800C22—H22B0.9800
C3—C41.528 (2)C22—H22C0.9800
C3—H3A0.9800B1—H11.0000
S1—Bi1—Cl1100.115 (14)H8A—C8—H8C109.5
S1—Bi1—S388.960 (13)H8B—C8—H8C109.5
Cl1—Bi1—S376.546 (13)C11—C9—H9A109.5
S1—Bi1—Cl274.926 (13)C11—C9—H9B109.5
Cl1—Bi1—Cl295.046 (14)H9A—C9—H9B109.5
S3—Bi1—Cl2160.381 (14)C11—C9—H9C109.5
S1—Bi1—S290.300 (14)H9A—C9—H9C109.5
Cl1—Bi1—S2160.302 (13)H9B—C9—H9C109.5
S3—Bi1—S287.065 (14)C11—C10—H10A109.5
Cl2—Bi1—S2103.836 (14)C11—C10—H10B109.5
S1—Bi1—O1152.76 (4)H10A—C10—H10B109.5
S2—Bi1—O174.07 (3)C11—C10—H10C109.5
S3—Bi1—O1111.80 (4)H10A—C10—H10C109.5
Cl1—Bi1—O1101.73 (3)H10B—C10—H10C109.5
Cl2—Bi1—O187.10 (4)N3—C11—C9108.59 (14)
C5—S1—Bi1106.38 (5)N3—C11—C10110.33 (14)
C12—S2—Bi1103.20 (5)C9—C11—C10108.58 (16)
C19—S3—Bi1104.44 (5)N3—C11—C8108.13 (14)
C22—O1—H1D109.5C9—C11—C8108.76 (14)
C5—N1—C6108.00 (13)C10—C11—C8112.36 (17)
C5—N1—C4128.36 (13)N4—C12—N3107.91 (13)
C6—N1—C4123.51 (13)N4—C12—S2126.54 (12)
C5—N2—C7107.75 (13)N3—C12—S2125.54 (12)
C5—N2—B1133.83 (13)C14—C13—N3107.66 (14)
C7—N2—B1118.40 (13)C14—C13—H13126.2
C12—N3—C13108.05 (14)N3—C13—H13126.2
C12—N3—C11127.23 (14)C13—C14—N4108.47 (15)
C13—N3—C11124.50 (13)C13—C14—H14125.8
C12—N4—C14107.90 (13)N4—C14—H14125.8
C12—N4—B1132.50 (13)C18—C15—H15A109.5
C14—N4—B1119.57 (14)C18—C15—H15B109.5
C19—N5—C20108.25 (13)H15A—C15—H15B109.5
C19—N5—C18127.58 (13)C18—C15—H15C109.5
C20—N5—C18124.16 (13)H15A—C15—H15C109.5
C19—N6—C21107.34 (13)H15B—C15—H15C109.5
C19—N6—B1132.76 (13)C18—C16—H16A109.5
C21—N6—B1119.59 (13)C18—C16—H16B109.5
C4—C1—H1A109.5H16A—C16—H16B109.5
C4—C1—H1B109.5C18—C16—H16C109.5
H1A—C1—H1B109.5H16A—C16—H16C109.5
C4—C1—H1C109.5H16B—C16—H16C109.5
H1A—C1—H1C109.5C18—C17—H17A109.5
H1B—C1—H1C109.5C18—C17—H17B109.5
C4—C2—H2A109.5H17A—C17—H17B109.5
C4—C2—H2B109.5C18—C17—H17C109.5
H2A—C2—H2B109.5H17A—C17—H17C109.5
C4—C2—H2C109.5H17B—C17—H17C109.5
H2A—C2—H2C109.5N5—C18—C15108.87 (13)
H2B—C2—H2C109.5N5—C18—C17108.59 (13)
C4—C3—H3A109.5C15—C18—C17108.52 (14)
C4—C3—H3B109.5N5—C18—C16109.45 (13)
H3A—C3—H3B109.5C15—C18—C16112.53 (14)
C4—C3—H3C109.5C17—C18—C16108.80 (15)
H3A—C3—H3C109.5N6—C19—N5108.29 (13)
H3B—C3—H3C109.5N6—C19—S3125.46 (12)
N1—C4—C1109.70 (14)N5—C19—S3126.22 (12)
N1—C4—C3108.27 (14)C21—C20—N5107.17 (14)
C1—C4—C3112.34 (15)C21—C20—H20126.4
N1—C4—C2108.68 (14)N5—C20—H20126.4
C1—C4—C2108.85 (15)C20—C21—N6108.95 (14)
C3—C4—C2108.92 (15)C20—C21—H21125.5
N2—C5—N1108.14 (13)N6—C21—H21125.5
N2—C5—S1126.07 (12)O1—C22—H22A109.5
N1—C5—S1125.79 (12)O1—C22—H22B109.5
C7—C6—N1107.55 (14)H22A—C22—H22B109.5
C7—C6—H6126.2O1—C22—H22C109.5
N1—C6—H6126.2H22A—C22—H22C109.5
C6—C7—N2108.53 (14)H22B—C22—H22C109.5
C6—C7—H7125.7N6—B1—N2112.52 (13)
N2—C7—H7125.7N6—B1—N4112.92 (14)
C11—C8—H8A109.5N2—B1—N4112.23 (13)
C11—C8—H8B109.5N6—B1—H1106.2
H8A—C8—H8B109.5N2—B1—H1106.2
C11—C8—H8C109.5N4—B1—H1106.2
C5—N1—C4—C165.0 (2)C11—N3—C13—C14174.35 (15)
C6—N1—C4—C1119.63 (17)N3—C13—C14—N40.2 (2)
C5—N1—C4—C357.9 (2)C12—N4—C14—C130.3 (2)
C6—N1—C4—C3117.46 (17)B1—N4—C14—C13177.98 (15)
C5—N1—C4—C2176.10 (16)C19—N5—C18—C1562.95 (19)
C6—N1—C4—C20.7 (2)C20—N5—C18—C15116.96 (17)
C7—N2—C5—N11.47 (17)C19—N5—C18—C17179.07 (15)
B1—N2—C5—N1179.71 (15)C20—N5—C18—C171.0 (2)
C7—N2—C5—S1179.10 (12)C19—N5—C18—C1660.4 (2)
B1—N2—C5—S10.9 (2)C20—N5—C18—C16119.66 (16)
C6—N1—C5—N21.59 (17)C21—N6—C19—N50.02 (17)
C4—N1—C5—N2174.36 (14)B1—N6—C19—N5173.38 (15)
C6—N1—C5—S1178.98 (12)C21—N6—C19—S3177.76 (12)
C4—N1—C5—S15.1 (2)B1—N6—C19—S38.8 (2)
Bi1—S1—C5—N271.57 (14)C20—N5—C19—N60.30 (17)
Bi1—S1—C5—N1109.10 (13)C18—N5—C19—N6179.63 (14)
C5—N1—C6—C71.10 (18)C20—N5—C19—S3178.05 (12)
C4—N1—C6—C7175.09 (14)C18—N5—C19—S31.9 (2)
N1—C6—C7—N20.20 (19)Bi1—S3—C19—N676.69 (13)
C5—N2—C7—C60.78 (18)Bi1—S3—C19—N5105.93 (13)
B1—N2—C7—C6179.34 (14)C19—N5—C20—C210.51 (19)
C12—N3—C11—C9178.53 (16)C18—N5—C20—C21179.42 (14)
C13—N3—C11—C94.6 (2)N5—C20—C21—N60.5 (2)
C12—N3—C11—C1062.6 (2)C19—N6—C21—C200.34 (19)
C13—N3—C11—C10123.47 (18)B1—N6—C21—C20174.09 (15)
C12—N3—C11—C860.7 (2)C19—N6—B1—N231.8 (2)
C13—N3—C11—C8113.28 (18)C21—N6—B1—N2155.42 (14)
C14—N4—C12—N30.63 (18)C19—N6—B1—N496.48 (19)
B1—N4—C12—N3177.31 (15)C21—N6—B1—N476.27 (18)
C14—N4—C12—S2179.10 (13)C5—N2—B1—N6100.67 (19)
B1—N4—C12—S23.0 (3)C7—N2—B1—N677.43 (17)
C13—N3—C12—N40.75 (18)C5—N2—B1—N428.0 (2)
C11—N3—C12—N4174.00 (14)C7—N2—B1—N4153.90 (13)
C13—N3—C12—S2178.99 (12)C12—N4—B1—N623.5 (2)
C11—N3—C12—S26.3 (2)C14—N4—B1—N6154.27 (14)
Bi1—S2—C12—N470.01 (14)C12—N4—B1—N2104.98 (19)
Bi1—S2—C12—N3109.68 (13)C14—N4—B1—N277.27 (18)
C12—N3—C13—C140.58 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1D···Cl1i0.842.283.0969 (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)} top
Crystal data top
[Bi2(C21H34BN6S3)2Cl4]Z = 1
Mr = 1514.83F(000) = 744.00
Triclinic, P1Dx = 1.759 Mg m3
a = 10.8009 (11) ÅMo Kα radiation, λ = 0.71075 Å
b = 11.3698 (14) ÅCell parameters from 6052 reflections
c = 11.8690 (13) Åθ = 3.0–27.5°
α = 95.125 (4)°µ = 6.58 mm1
β = 91.947 (4)°T = 179 K
γ = 99.549 (3)°Block, orange
V = 1429.9 (3) Å30.23 × 0.15 × 0.15 mm
Data collection top
Rigaku XtaLAB P200
diffractometer
5816 reflections with F2 > 2.0σ(F2)
Detector resolution: 5.814 pixels mm-1Rint = 0.034
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: numerical
(NUMABS; Rigaku, 1999)
h = 1414
Tmin = 0.270, Tmax = 0.373k = 1414
39709 measured reflectionsl = 1415
6115 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.013Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.033H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.019P)2]
where P = (Fo2 + 2Fc2)/3
6115 reflections(Δ/σ)max = 0.001
307 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.85 e Å3
Primary atom site location: structure-invariant direct methods
Special details top

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 (Å2) top
xyzUiso*/Ueq
Bi10.39969 (2)0.41301 (2)0.85362 (2)0.01774 (3)
Cl10.37944 (5)0.61914 (5)1.01595 (4)0.03186 (11)
Cl20.54822 (4)0.56134 (4)0.74438 (5)0.02943 (11)
S10.18081 (4)0.26572 (4)0.93598 (4)0.02185 (10)
S20.45110 (4)0.20689 (4)0.74473 (4)0.01891 (9)
S30.24933 (4)0.44487 (4)0.67720 (4)0.02081 (10)
N10.22072 (14)0.03193 (13)0.93270 (12)0.0190 (3)
N20.16688 (14)0.08266 (13)0.76597 (12)0.0181 (3)
N30.43753 (14)0.20501 (13)0.51162 (12)0.0184 (3)
N40.25221 (14)0.17310 (13)0.58613 (12)0.0190 (3)
N50.00025 (13)0.41876 (13)0.73377 (13)0.0206 (3)
N60.06462 (13)0.24855 (13)0.68614 (12)0.0189 (3)
C10.3749 (2)0.1261 (2)1.08680 (19)0.0363 (5)
H1A0.39790.12791.16760.044*
H1B0.44340.10381.04200.044*
H1C0.35980.20551.07000.044*
C20.1451 (2)0.06199 (19)1.12597 (17)0.0303 (5)
H2A0.16740.06351.20690.036*
H2B0.12580.14021.10990.036*
H2C0.07130.00001.10530.036*
C30.2806 (2)0.0901 (2)1.08051 (18)0.0344 (5)
H3A0.30330.09001.16120.041*
H3B0.20470.14951.06010.041*
H3C0.34970.11031.03540.041*
C40.25550 (17)0.03418 (17)1.05699 (15)0.0231 (4)
C50.19061 (16)0.12427 (15)0.87656 (15)0.0174 (4)
C60.21619 (19)0.06658 (16)0.85467 (16)0.0250 (4)
H60.23360.14290.87030.030*
C70.18299 (18)0.03572 (16)0.75342 (16)0.0237 (4)
H70.17230.08650.68450.028*
C80.6337 (2)0.35132 (18)0.54280 (18)0.0300 (5)
H8A0.72440.36570.53230.036*
H8B0.59420.40890.50360.036*
H8C0.61870.36100.62380.036*
C90.63882 (18)0.13017 (18)0.54876 (17)0.0268 (4)
H9A0.72920.14400.53680.032*
H9B0.62540.13570.63020.032*
H9C0.60100.05020.51420.032*
C100.59799 (19)0.21018 (19)0.36664 (16)0.0287 (4)
H10A0.68830.22270.35430.034*
H10B0.55950.12930.33510.034*
H10C0.55910.26930.32910.034*
C110.57765 (17)0.22470 (17)0.49425 (15)0.0216 (4)
C120.37782 (16)0.19445 (15)0.61077 (14)0.0170 (3)
C130.34632 (18)0.19420 (18)0.42468 (16)0.0241 (4)
H130.36090.19990.34670.029*
C140.23349 (18)0.17415 (18)0.47038 (15)0.0243 (4)
H140.15430.16270.43000.029*
C150.0832 (2)0.6027 (2)0.8588 (2)0.0394 (5)
H15A0.07910.68790.87520.047*
H15B0.05930.56040.92520.047*
H15C0.16910.59350.84050.047*
C160.0232 (2)0.61294 (19)0.6516 (2)0.0388 (5)
H16A0.01890.69830.66670.047*
H16B0.10790.60380.62940.047*
H16C0.03800.57710.59010.047*
C170.1409 (2)0.5614 (2)0.7884 (2)0.0424 (6)
H17A0.14700.64620.80460.051*
H17B0.19910.52610.72450.051*
H17C0.16260.51910.85530.051*
C180.00674 (17)0.55006 (17)0.75832 (18)0.0262 (4)
C190.10116 (16)0.36878 (16)0.70073 (15)0.0182 (4)
C200.09990 (17)0.32700 (18)0.74195 (17)0.0263 (4)
H200.18170.33580.76460.032*
C210.06013 (17)0.22343 (17)0.71200 (17)0.0250 (4)
H210.10950.14580.70910.030*
B10.13545 (19)0.14250 (19)0.65828 (17)0.0199 (4)
H10.07500.08050.61020.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.01588 (4)0.01547 (4)0.02072 (4)0.00196 (3)0.00091 (3)0.00250 (3)
Cl10.0333 (3)0.0311 (3)0.0322 (3)0.0143 (2)0.0045 (2)0.0054 (2)
Cl20.0192 (2)0.0237 (2)0.0458 (3)0.00227 (18)0.0058 (2)0.0070 (2)
S10.0284 (2)0.0156 (2)0.0213 (2)0.00477 (18)0.00527 (19)0.00240 (18)
S20.0203 (2)0.0211 (2)0.0155 (2)0.00582 (18)0.00146 (17)0.00098 (17)
S30.0129 (2)0.0214 (2)0.0285 (2)0.00180 (17)0.00229 (18)0.00610 (19)
N10.0211 (8)0.0175 (8)0.0191 (8)0.0043 (6)0.0044 (6)0.0016 (6)
N20.0201 (8)0.0158 (7)0.0181 (8)0.0032 (6)0.0033 (6)0.0007 (6)
N30.0189 (7)0.0209 (8)0.0164 (7)0.0070 (6)0.0012 (6)0.0006 (6)
N40.0192 (7)0.0214 (8)0.0167 (7)0.0060 (6)0.0002 (6)0.0003 (6)
N50.0128 (7)0.0205 (8)0.0280 (8)0.0025 (6)0.0004 (6)0.0003 (6)
N60.0147 (7)0.0192 (8)0.0225 (8)0.0020 (6)0.0007 (6)0.0026 (6)
C10.0299 (11)0.0471 (14)0.0296 (12)0.0004 (10)0.0033 (9)0.0063 (10)
C20.0334 (11)0.0360 (12)0.0245 (10)0.0101 (9)0.0109 (9)0.0074 (9)
C30.0416 (12)0.0369 (12)0.0303 (11)0.0172 (10)0.0049 (9)0.0126 (9)
C40.0243 (10)0.0261 (10)0.0198 (9)0.0057 (8)0.0026 (8)0.0047 (8)
C50.0156 (8)0.0153 (9)0.0208 (9)0.0011 (7)0.0045 (7)0.0003 (7)
C60.0319 (11)0.0150 (9)0.0292 (11)0.0067 (8)0.0057 (8)0.0007 (8)
C70.0293 (10)0.0159 (9)0.0249 (10)0.0033 (8)0.0057 (8)0.0045 (8)
C80.0295 (11)0.0245 (10)0.0340 (12)0.0007 (8)0.0105 (9)0.0006 (9)
C90.0199 (9)0.0291 (11)0.0329 (11)0.0080 (8)0.0010 (8)0.0033 (9)
C100.0265 (10)0.0378 (12)0.0246 (10)0.0134 (9)0.0075 (8)0.0013 (9)
C110.0195 (9)0.0244 (10)0.0218 (10)0.0058 (8)0.0044 (7)0.0011 (8)
C120.0191 (9)0.0144 (8)0.0177 (9)0.0051 (7)0.0002 (7)0.0013 (7)
C130.0262 (10)0.0325 (11)0.0153 (9)0.0095 (8)0.0001 (8)0.0027 (8)
C140.0241 (10)0.0336 (11)0.0159 (9)0.0091 (8)0.0034 (7)0.0001 (8)
C150.0335 (12)0.0329 (12)0.0480 (14)0.0044 (10)0.0063 (10)0.0128 (10)
C160.0380 (12)0.0279 (12)0.0550 (15)0.0147 (10)0.0028 (11)0.0102 (10)
C170.0238 (11)0.0320 (12)0.0696 (17)0.0077 (9)0.0081 (11)0.0139 (11)
C180.0180 (9)0.0203 (10)0.0397 (12)0.0050 (7)0.0001 (8)0.0035 (8)
C190.0137 (8)0.0215 (9)0.0191 (9)0.0028 (7)0.0004 (7)0.0018 (7)
C200.0122 (9)0.0283 (10)0.0377 (12)0.0010 (8)0.0043 (8)0.0022 (9)
C210.0149 (9)0.0235 (10)0.0351 (11)0.0014 (7)0.0016 (8)0.0043 (8)
B10.0191 (10)0.0196 (10)0.0195 (10)0.0015 (8)0.0012 (8)0.0015 (8)
Geometric parameters (Å, º) top
Bi1—Cl22.5949 (5)C3—H3A0.9800
Bi1—S32.6931 (5)C3—H3B0.9800
Bi1—S22.7222 (5)C3—H3C0.9800
Bi1—Cl1i2.8915 (5)C6—C71.336 (3)
Bi1—S12.9128 (5)C6—H60.9500
Bi1—Cl12.9401 (6)C7—H70.9500
Cl1—Bi1i2.8915 (5)C8—C111.520 (3)
S1—C51.7188 (18)C8—H8A0.9800
S2—C121.7354 (18)C8—H8B0.9800
S3—C191.7326 (18)C8—H8C0.9800
N1—C51.369 (2)C9—C111.530 (3)
N1—C61.381 (2)C9—H9A0.9800
N1—C41.507 (2)C9—H9B0.9800
N2—C51.356 (2)C9—H9C0.9800
N2—C71.381 (2)C10—C111.536 (3)
N2—B11.554 (2)C10—H10A0.9800
N3—C121.366 (2)C10—H10B0.9800
N3—C131.385 (2)C10—H10C0.9800
N3—C111.517 (2)C13—C141.344 (3)
N4—C121.355 (2)C13—H130.9500
N4—C141.383 (2)C14—H140.9500
N4—B11.558 (2)C15—C181.525 (3)
N5—C191.364 (2)C15—H15A0.9800
N5—C201.385 (2)C15—H15B0.9800
N5—C181.510 (2)C15—H15C0.9800
N6—C191.352 (2)C16—C181.528 (3)
N6—C211.381 (2)C16—H16A0.9800
N6—B11.549 (2)C16—H16B0.9800
C1—C41.529 (3)C16—H16C0.9800
C1—H1A0.9800C17—C181.527 (3)
C1—H1B0.9800C17—H17A0.9800
C1—H1C0.9800C17—H17B0.9800
C2—C41.529 (3)C17—H17C0.9800
C2—H2A0.9800C20—C211.342 (3)
C2—H2B0.9800C20—H200.9500
C2—H2C0.9800C21—H210.9500
C3—C41.529 (3)B1—H11.0000
Cl2—Bi1—S377.787 (16)C11—C8—H8B109.5
Cl2—Bi1—S297.312 (17)H8A—C8—H8B109.5
S3—Bi1—S291.074 (15)C11—C8—H8C109.5
Cl2—Bi1—Cl1i87.108 (17)H8A—C8—H8C109.5
S3—Bi1—Cl1i160.787 (15)H8B—C8—H8C109.5
S2—Bi1—Cl1i79.020 (15)C11—C9—H9A109.5
Cl2—Bi1—S1164.283 (15)C11—C9—H9B109.5
S3—Bi1—S186.949 (15)H9A—C9—H9B109.5
S2—Bi1—S186.582 (15)C11—C9—H9C109.5
Cl1i—Bi1—S1108.598 (16)H9A—C9—H9C109.5
Cl2—Bi1—Cl186.939 (18)H9B—C9—H9C109.5
S3—Bi1—Cl1102.541 (15)C11—C10—H10A109.5
S2—Bi1—Cl1166.327 (14)C11—C10—H10B109.5
Cl1i—Bi1—Cl188.262 (15)H10A—C10—H10B109.5
S1—Bi1—Cl192.814 (16)C11—C10—H10C109.5
Bi1i—Cl1—Bi191.738 (15)H10A—C10—H10C109.5
C5—S1—Bi1103.01 (6)H10B—C10—H10C109.5
C12—S2—Bi1105.95 (6)N3—C11—C8108.35 (15)
C19—S3—Bi1106.11 (6)N3—C11—C9110.42 (14)
C5—N1—C6108.04 (15)C8—C11—C9112.19 (16)
C5—N1—C4127.44 (15)N3—C11—C10108.72 (15)
C6—N1—C4124.51 (14)C8—C11—C10109.60 (16)
C5—N2—C7108.25 (14)C9—C11—C10107.50 (15)
C5—N2—B1133.29 (15)N4—C12—N3108.17 (15)
C7—N2—B1118.34 (15)N4—C12—S2126.23 (13)
C12—N3—C13107.79 (14)N3—C12—S2125.59 (13)
C12—N3—C11128.24 (14)C14—C13—N3107.74 (16)
C13—N3—C11123.97 (14)C14—C13—H13126.1
C12—N4—C14107.80 (15)N3—C13—H13126.1
C12—N4—B1133.49 (15)C13—C14—N4108.45 (16)
C14—N4—B1118.60 (15)C13—C14—H14125.8
C19—N5—C20108.11 (15)N4—C14—H14125.8
C19—N5—C18127.96 (15)C18—C15—H15A109.5
C20—N5—C18123.93 (15)C18—C15—H15B109.5
C19—N6—C21107.90 (15)H15A—C15—H15B109.5
C19—N6—B1133.39 (15)C18—C15—H15C109.5
C21—N6—B1118.46 (15)H15A—C15—H15C109.5
C4—C1—H1A109.5H15B—C15—H15C109.5
C4—C1—H1B109.5C18—C16—H16A109.5
H1A—C1—H1B109.5C18—C16—H16B109.5
C4—C1—H1C109.5H16A—C16—H16B109.5
H1A—C1—H1C109.5C18—C16—H16C109.5
H1B—C1—H1C109.5H16A—C16—H16C109.5
C4—C2—H2A109.5H16B—C16—H16C109.5
C4—C2—H2B109.5C18—C17—H17A109.5
H2A—C2—H2B109.5C18—C17—H17B109.5
C4—C2—H2C109.5H17A—C17—H17B109.5
H2A—C2—H2C109.5C18—C17—H17C109.5
H2B—C2—H2C109.5H17A—C17—H17C109.5
C4—C3—H3A109.5H17B—C17—H17C109.5
C4—C3—H3B109.5N5—C18—C15109.08 (15)
H3A—C3—H3B109.5N5—C18—C16108.88 (16)
C4—C3—H3C109.5C15—C18—C16112.63 (18)
H3A—C3—H3C109.5N5—C18—C17108.47 (16)
H3B—C3—H3C109.5C15—C18—C17109.27 (18)
N1—C4—C1109.13 (15)C16—C18—C17108.43 (17)
N1—C4—C3108.54 (16)N6—C19—N5107.98 (15)
C1—C4—C3109.24 (17)N6—C19—S3125.53 (13)
N1—C4—C2109.24 (15)N5—C19—S3126.47 (14)
C1—C4—C2112.29 (18)C21—C20—N5107.37 (16)
C3—C4—C2108.33 (16)C21—C20—H20126.3
N2—C5—N1107.40 (15)N5—C20—H20126.3
N2—C5—S1126.30 (13)C20—C21—N6108.63 (16)
N1—C5—S1126.29 (14)C20—C21—H21125.7
C7—C6—N1107.97 (16)N6—C21—H21125.7
C7—C6—H6126.0N6—B1—N2111.95 (15)
N1—C6—H6126.0N6—B1—N4114.25 (15)
C6—C7—N2108.34 (16)N2—B1—N4112.26 (14)
C6—C7—H7125.8N6—B1—H1105.9
N2—C7—H7125.8N2—B1—H1105.9
C11—C8—H8A109.5N4—B1—H1105.9
C5—N1—C4—C161.3 (2)C11—N3—C13—C14178.21 (16)
C6—N1—C4—C1117.48 (19)N3—C13—C14—N40.5 (2)
C5—N1—C4—C3179.70 (17)C12—N4—C14—C130.9 (2)
C6—N1—C4—C31.5 (2)B1—N4—C14—C13175.76 (16)
C5—N1—C4—C261.8 (2)C19—N5—C18—C1563.0 (2)
C6—N1—C4—C2119.41 (19)C20—N5—C18—C15117.0 (2)
C7—N2—C5—N10.31 (19)C19—N5—C18—C1660.3 (2)
B1—N2—C5—N1176.07 (17)C20—N5—C18—C16119.7 (2)
C7—N2—C5—S1178.81 (13)C19—N5—C18—C17178.08 (18)
B1—N2—C5—S15.4 (3)C20—N5—C18—C171.9 (3)
C6—N1—C5—N20.53 (19)C21—N6—C19—N50.84 (19)
C4—N1—C5—N2179.50 (15)B1—N6—C19—N5174.81 (17)
C6—N1—C5—S1179.03 (14)C21—N6—C19—S3179.12 (14)
C4—N1—C5—S12.0 (3)B1—N6—C19—S36.9 (3)
Bi1—S1—C5—N272.74 (15)C20—N5—C19—N61.25 (19)
Bi1—S1—C5—N1109.03 (15)C18—N5—C19—N6178.75 (16)
C5—N1—C6—C70.6 (2)C20—N5—C19—S3179.52 (14)
C4—N1—C6—C7179.56 (16)C18—N5—C19—S30.5 (3)
N1—C6—C7—N20.4 (2)Bi1—S3—C19—N675.54 (16)
C5—N2—C7—C60.0 (2)Bi1—S3—C19—N5106.49 (15)
B1—N2—C7—C6176.46 (16)C19—N5—C20—C211.2 (2)
C12—N3—C11—C870.0 (2)C18—N5—C20—C21178.81 (17)
C13—N3—C11—C8110.14 (19)N5—C20—C21—N60.7 (2)
C12—N3—C11—C953.2 (2)C19—N6—C21—C200.1 (2)
C13—N3—C11—C9126.62 (18)B1—N6—C21—C20175.12 (16)
C12—N3—C11—C10170.92 (16)C19—N6—B1—N299.4 (2)
C13—N3—C11—C108.9 (2)C21—N6—B1—N274.0 (2)
C14—N4—C12—N31.89 (19)C19—N6—B1—N429.6 (3)
B1—N4—C12—N3174.02 (17)C21—N6—B1—N4156.96 (16)
C14—N4—C12—S2177.92 (14)C5—N2—B1—N629.7 (3)
B1—N4—C12—S26.2 (3)C7—N2—B1—N6154.84 (15)
C13—N3—C12—N42.19 (19)C5—N2—B1—N4100.3 (2)
C11—N3—C12—N4177.66 (15)C7—N2—B1—N475.1 (2)
C13—N3—C12—S2177.62 (13)C12—N4—B1—N6104.3 (2)
C11—N3—C12—S22.5 (3)C14—N4—B1—N680.2 (2)
Bi1—S2—C12—N468.38 (16)C12—N4—B1—N224.6 (3)
Bi1—S2—C12—N3111.39 (14)C14—N4—B1—N2150.95 (16)
C12—N3—C13—C141.6 (2)
Symmetry code: (i) x+1, y+1, z+2.
Selected bond lengths (Å) and bond angles (°) in (I) and (II) top
(I)(II)
Bi1—S12.6463 (6)Bi1—S12.9128 (5)
Bi1—S22.8307 (5)Bi1—S22.7222 (5)
Bi1—S32.7242 (4)Bi1—S32.6931 (5)
Bi1—Cl12.6933 (5)Bi1—Cl12.9401 (6)
Bi1—Cl22.7499 (4)Bi1—Cl1i2.8915 (5)
Bi1—O12.8023 (14)Bi1—Cl22.5949 (5)
Bi1···Bi1i4.1858 (5)
S1—Bi1—Cl1100.115 (14)S1—Bi1—Cl192.814 (16)
S2—Bi1—Cl1160.302 (13)S2—Bi1—Cl1166.327 (14)
S3—Bi1—Cl176.546 (13)S3—Bi1—Cl1102.541 (15)
S1—Bi1—Cl274.926 (13)S1—Bi1—Cl1i108.598 (16)
S2—Bi1—Cl2103.836 (14)S2—Bi1—Cl1i79.020 (15)
S3—Bi1—Cl2160.381 (14)S3—Bi1—Cl1i160.787 (15)
S1—Bi1—S290.300 (14)S1—Bi1—Cl2164.283 (15)
S1—Bi1—S388.960 (13)S2—Bi1—Cl297.312 (17)
S2—Bi1—S387.065 (14)S3—Bi1—Cl277.787 (16)
Cl1—Bi1—Cl295.046 (14)S1—Bi1—S286.582 (15)
S1—Bi1—O1152.76 (4)S1—Bi1—S386.949 (15)
S2—Bi1—O174.07 (3)S2—Bi1—S391.074 (15)
S3—Bi1—O1111.80 (4)Cl1—Bi1—Cl286.939 (18)
Cl1—Bi1—O1101.73 (3)Cl1—Bi1—Cl1i88.262 (15)
Cl2—Bi1—O187.10 (4)Cl1i—Bi1—Cl287.108 (17)
Symmetry code: (i) -x+1, -y+1, -z+2.
 

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