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The crystal structure of the title complex, (C8H10N)2(C5H6N)[BiI6], contains discrete [BiI6]3- anions, and (HNC5H5)+ and (CH3COCH2NC5H5)+ cations separated by normal van der Waals contacts. The [BiI6]3- anion has the Bi atom on an inversion centre. The (HNC5H5)+ cation also lies about an inversion centre and is disordered. The (CH3COCH2NC5H5)+ cation lies in a general position.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100005230/qb0197sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005230/qb0197Isup2.hkl
Contains datablock I

CCDC reference: 145630

Comment top

In our systematic investigation of the hybrid Mo(W) main-group metal clusters, we have synthesized successfully the hybrid cluster [Mo3(BiI3)S4(OAc)(dtp)3(py)] (Lu, 1997) from the reaction of the trimolybdenum cluster [Mo33-S)(µ-S)3(µ-OAc)(dtp)3(py)] with BiI3 [dtp = S2P(OC2H5)2- and OAc = CH3COO-]. When we changed the reaction conditions and used [Mo3S4(dtp)4(H2O)], BiI3, NaOAc.3H2O and KS2CN(CH2CH2OH)2 as the starting materials to perform the reaction in the presence of acetone and pyridine, an unexpected complex, [(BiI6)(CH3COCH2NC5H5)2(HNC5H5)], was obtained. Although there are some reports about relevant complexes such as Ag3BiI6 (Dzeranova, 1985) and Cs3BiI6 (Dzeranova, 1984), their crystal structures have not been reported.

In the structure of the title complex, the Bi center exhibits a octahedral geometry with approximate Oh symmetry. A Bi—I distance of ca 3.08 Å is comparable with that in BiI3 (3.10 Å; Wells, 1975), which has an octahedral layer structure. Obviously, the formation of [BiI6]3- should be through the reaction of BiI3 with I-. To meet the need of the electrovalent balance of the molecule, [CH3COCH2NC5H5] must be a cation. The 1H NMR spectrum in DMSO-d6 of this complex shows the signals of CH2, CH3 at δ 5.66 and 2.28 p.p.m., respectively for [CH3COCH2NC5H5]+ and reveals two types of pyridine groups in a 1:2 ratio for (HNC5H5)+ and (CH3COCH2NC5H5)+, respectively. It seems that this novel cation [CH3COCH2NC5H5]+ resulted from the stepwise reaction of acetone, halogen(I2) and pyridine. But the reaction details are not yet known.

Experimental top

[Mo3S4(dtp)4(H2O)] (0.1 g), KS2CN(CH2CH2OH)2 (0.1 g), Na(OAc).3H2O) (0.03 g) and 0.1 ml pyridine were dissolved in 10 ml dichloromethane, then stirred for 10 min. BiI3 (0.1 g) in 8 ml acetone was added in the resulting solution. The mixture was stirred for 1 h and filtered, then evaporated in air. After two weeks, red crystals were obtained. The metal elements of the complex were proved to be Bi by ICP-AES analysis.

Refinement top

The three crystallographically independent positions (C9, C10 and C11) in a centrosymmetric six-membered ring of the (HNC5H5)+ cation exist a statistical distribution of C and N with an occupancy of 1.028 of a C atom (i.e. 5/6 C + 1/6 N). All calculations were performed using SHELXTL5 (Sheldrick, 1995) program package. The distance between the deepest hole and I3 atom is 0.92 Å, so this hole can be referred to as the ghost of the I3 atom.

Computing details top

Bis(acetonylpyridine) pyridinium hexaiodo-bismuth(III) top
Crystal data top
2(C8H10NO)(C5H6N)[BiI6]F(000) = 1180
Mr = 1322.83Dx = 2.572 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
a = 10.675 (2) ÅCell parameters from 20 reflections
b = 11.083 (2) Åθ = 8.0–12.9°
c = 15.195 (3) ŵ = 10.61 mm1
β = 108.19 (3)°T = 293 K
V = 1707.9 (6) Å3Prism, red
Z = 20.13 × 0.13 × 0.10 mm
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.000
ω–2θ scansθmax = 26.0°
Absorption correction: ψ scan
(North et al., 1968)
h = 013
Tmin = 0.261, Tmax = 0.346k = 013
3358 measured reflectionsl = 1817
3358 independent reflections3 standard reflections every 300 reflections
2264 reflections with I > 2σ(I) intensity decay: 3.4%
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.036 w = 1/[σ2(Fo2)]
wR(F2) = 0.091(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.94 e Å3
3358 reflectionsΔρmin = 1.00 e Å3
151 parameters
Crystal data top
2(C8H10NO)(C5H6N)[BiI6]V = 1707.9 (6) Å3
Mr = 1322.83Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.675 (2) ŵ = 10.61 mm1
b = 11.083 (2) ÅT = 293 K
c = 15.195 (3) Å0.13 × 0.13 × 0.10 mm
β = 108.19 (3)°
Data collection top
Rigaku AFC-5R
diffractometer
2264 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.261, Tmax = 0.3463 standard reflections every 300 reflections
3358 measured reflections intensity decay: 3.4%
3358 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036151 parameters
wR(F2) = 0.091H-atom parameters constrained
S = 1.04Δρmax = 0.94 e Å3
3358 reflectionsΔρmin = 1.00 e Å3
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Bi10.00000.50000.50000.03403 (14)
I10.23013 (7)0.33688 (7)0.49107 (5)0.0536 (2)
I20.03048 (7)0.58537 (7)0.30169 (5)0.0525 (2)
I30.20046 (7)0.29770 (7)0.41669 (5)0.0535 (2)
O10.0967 (9)0.0206 (11)0.3559 (9)0.112 (4)
N10.0040 (8)0.1306 (9)0.2136 (6)0.046 (2)
C10.1107 (14)0.0746 (15)0.3737 (11)0.091 (5)
H1A0.05950.12220.42520.137*
H1B0.16930.12630.32860.137*
H1C0.16110.01620.39490.137*
C20.0206 (13)0.0112 (11)0.3308 (10)0.064 (3)
C30.0904 (10)0.0669 (12)0.2486 (8)0.058 (3)
H3A0.14670.01680.19980.069*
H3B0.14570.12500.26670.069*
C40.0433 (11)0.2407 (12)0.2415 (8)0.059 (3)
H4A0.00560.28070.28080.071*
C50.1383 (14)0.2976 (13)0.2141 (9)0.070 (4)
H5A0.16630.37500.23460.083*
C60.1911 (14)0.2378 (13)0.1557 (9)0.070 (4)
H6A0.25470.27530.13500.084*
C70.1523 (13)0.1258 (15)0.1280 (10)0.074 (4)
H7A0.19020.08510.08920.089*
C80.0564 (11)0.0702 (12)0.1568 (8)0.060 (3)
H8A0.02850.00750.13720.072*
C90.511 (4)0.084 (2)0.4428 (11)0.120 (8)
H9A0.51810.14030.39950.144*
C100.616 (2)0.030 (3)0.495 (2)0.134 (10)
H10A0.69850.05520.49480.161*
C110.604 (3)0.059 (2)0.550 (2)0.135 (10)
H11A0.67810.10310.58200.162*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.0342 (3)0.0336 (3)0.0346 (3)0.0010 (2)0.0112 (2)0.0013 (2)
I10.0488 (4)0.0534 (5)0.0580 (4)0.0128 (3)0.0159 (3)0.0005 (3)
I20.0478 (4)0.0680 (5)0.0416 (4)0.0019 (3)0.0137 (3)0.0096 (3)
I30.0585 (4)0.0461 (4)0.0569 (4)0.0186 (3)0.0194 (3)0.0107 (3)
O10.048 (6)0.111 (9)0.155 (11)0.009 (5)0.000 (6)0.065 (8)
N10.039 (5)0.060 (6)0.042 (4)0.007 (4)0.015 (4)0.003 (4)
C10.088 (11)0.097 (13)0.093 (11)0.000 (9)0.033 (9)0.036 (10)
C20.066 (8)0.050 (8)0.079 (9)0.014 (6)0.029 (7)0.002 (6)
C30.033 (6)0.085 (10)0.052 (6)0.010 (5)0.008 (5)0.003 (6)
C40.062 (7)0.061 (8)0.056 (7)0.015 (6)0.020 (6)0.009 (6)
C50.085 (10)0.063 (9)0.066 (8)0.008 (7)0.031 (7)0.010 (7)
C60.078 (9)0.062 (9)0.078 (9)0.009 (7)0.034 (7)0.012 (7)
C70.065 (8)0.091 (12)0.073 (8)0.019 (8)0.032 (7)0.004 (8)
C80.053 (7)0.067 (9)0.063 (7)0.002 (6)0.023 (6)0.019 (6)
C90.19 (2)0.115 (17)0.055 (9)0.073 (18)0.036 (12)0.001 (9)
C100.073 (13)0.17 (3)0.19 (3)0.046 (15)0.083 (17)0.09 (2)
C110.093 (16)0.073 (13)0.18 (2)0.038 (10)0.039 (14)0.048 (14)
Geometric parameters (Å, º) top
Bi1—I23.0772 (9)C1—C21.50 (2)
Bi1—I2i3.0772 (9)C2—C31.51 (2)
Bi1—I33.0850 (9)C4—C51.37 (2)
Bi1—I3i3.0850 (9)C5—C61.36 (2)
Bi1—I13.0871 (8)C6—C71.33 (2)
Bi1—I1i3.0871 (8)C7—C81.38 (2)
O1—C21.194 (15)C9—C11ii1.30 (2)
N1—C41.32 (2)C9—C101.30 (2)
N1—C81.345 (14)C10—C111.31 (2)
N1—C31.459 (14)C11—C9ii1.30 (2)
I2—Bi1—I2i180.0C4—N1—C8120.8 (10)
I2—Bi1—I388.50 (3)C4—N1—C3121.2 (10)
I2i—Bi1—I391.50 (3)C8—N1—C3117.8 (10)
I2—Bi1—I3i91.50 (3)O1—C2—C1124.9 (13)
I2i—Bi1—I3i88.50 (3)O1—C2—C3120.8 (12)
I3—Bi1—I3i180.0C1—C2—C3114.3 (11)
I2—Bi1—I188.82 (3)N1—C3—C2111.1 (9)
I2i—Bi1—I191.18 (3)N1—C4—C5121.4 (11)
I3—Bi1—I190.91 (3)C6—C5—C4118.2 (13)
I3i—Bi1—I189.09 (3)C7—C6—C5120.5 (14)
I2—Bi1—I1i91.18 (3)C6—C7—C8120.3 (13)
I2i—Bi1—I1i88.82 (3)N1—C8—C7118.7 (12)
I3—Bi1—I1i89.09 (3)C11ii—C9—C10120.2 (16)
I3i—Bi1—I1i90.91 (3)C9—C10—C11120.0 (17)
I1—Bi1—I1i180.0C9ii—C11—C10119.4 (16)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula2(C8H10NO)(C5H6N)[BiI6]
Mr1322.83
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)10.675 (2), 11.083 (2), 15.195 (3)
β (°) 108.19 (3)
V3)1707.9 (6)
Z2
Radiation typeMo Kα
µ (mm1)10.61
Crystal size (mm)0.13 × 0.13 × 0.10
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.261, 0.346
No. of measured, independent and
observed [I > 2σ(I)] reflections
3358, 3358, 2264
Rint0.000
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.091, 1.04
No. of reflections3358
No. of parameters151
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.94, 1.00

Selected geometric parameters (Å, º) top
Bi1—I23.0772 (9)Bi1—I13.0871 (8)
Bi1—I33.0850 (9)
I2—Bi1—I388.50 (3)I3—Bi1—I190.91 (3)
I2—Bi1—I188.82 (3)
 

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