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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
CCDC reference: 145630
[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.
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.
Bis(acetonylpyridine) pyridinium hexaiodo-bismuth(III)
top
Crystal data top
2(C8H10NO)(C5H6N)[BiI6] | F(000) = 1180 |
Mr = 1322.83 | Dx = 2.572 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 10.675 (2) Å | Cell parameters from 20 reflections |
b = 11.083 (2) Å | θ = 8.0–12.9° |
c = 15.195 (3) Å | µ = 10.61 mm−1 |
β = 108.19 (3)° | T = 293 K |
V = 1707.9 (6) Å3 | Prism, red |
Z = 2 | 0.13 × 0.13 × 0.10 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.000 |
ω–2θ scans | θmax = 26.0° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→13 |
Tmin = 0.261, Tmax = 0.346 | k = 0→13 |
3358 measured reflections | l = −18→17 |
3358 independent reflections | 3 standard reflections every 300 reflections |
2264 reflections with I > 2σ(I) | intensity decay: 3.4% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2)] |
wR(F2) = 0.091 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.94 e Å−3 |
3358 reflections | Δρmin = −1.00 e Å−3 |
151 parameters | |
Crystal data top
2(C8H10NO)(C5H6N)[BiI6] | V = 1707.9 (6) Å3 |
Mr = 1322.83 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.675 (2) Å | µ = 10.61 mm−1 |
b = 11.083 (2) Å | T = 293 K |
c = 15.195 (3) Å | 0.13 × 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 = 0.346 | 3 standard reflections every 300 reflections |
3358 measured reflections | intensity decay: 3.4% |
3358 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 151 parameters |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.94 e Å−3 |
3358 reflections | Δρmin = −1.00 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Bi1 | 0.0000 | 0.5000 | 0.5000 | 0.03403 (14) | |
I1 | 0.23013 (7) | 0.33688 (7) | 0.49107 (5) | 0.0536 (2) | |
I2 | −0.03048 (7) | 0.58537 (7) | 0.30169 (5) | 0.0525 (2) | |
I3 | −0.20046 (7) | 0.29770 (7) | 0.41669 (5) | 0.0535 (2) | |
O1 | 0.0967 (9) | −0.0206 (11) | 0.3559 (9) | 0.112 (4) | |
N1 | 0.0040 (8) | 0.1306 (9) | 0.2136 (6) | 0.046 (2) | |
C1 | −0.1107 (14) | −0.0746 (15) | 0.3737 (11) | 0.091 (5) | |
H1A | −0.0595 | −0.1222 | 0.4252 | 0.137* | |
H1B | −0.1693 | −0.1263 | 0.3286 | 0.137* | |
H1C | −0.1611 | −0.0162 | 0.3949 | 0.137* | |
C2 | −0.0206 (13) | −0.0112 (11) | 0.3308 (10) | 0.064 (3) | |
C3 | −0.0904 (10) | 0.0669 (12) | 0.2486 (8) | 0.058 (3) | |
H3A | −0.1467 | 0.0168 | 0.1998 | 0.069* | |
H3B | −0.1457 | 0.1250 | 0.2667 | 0.069* | |
C4 | 0.0433 (11) | 0.2407 (12) | 0.2415 (8) | 0.059 (3) | |
H4A | 0.0056 | 0.2807 | 0.2808 | 0.071* | |
C5 | 0.1383 (14) | 0.2976 (13) | 0.2141 (9) | 0.070 (4) | |
H5A | 0.1663 | 0.3750 | 0.2346 | 0.083* | |
C6 | 0.1911 (14) | 0.2378 (13) | 0.1557 (9) | 0.070 (4) | |
H6A | 0.2547 | 0.2753 | 0.1350 | 0.084* | |
C7 | 0.1523 (13) | 0.1258 (15) | 0.1280 (10) | 0.074 (4) | |
H7A | 0.1902 | 0.0851 | 0.0892 | 0.089* | |
C8 | 0.0564 (11) | 0.0702 (12) | 0.1568 (8) | 0.060 (3) | |
H8A | 0.0285 | −0.0075 | 0.1372 | 0.072* | |
C9 | 0.511 (4) | 0.084 (2) | 0.4428 (11) | 0.120 (8) | |
H9A | 0.5181 | 0.1403 | 0.3995 | 0.144* | |
C10 | 0.616 (2) | 0.030 (3) | 0.495 (2) | 0.134 (10) | |
H10A | 0.6985 | 0.0552 | 0.4948 | 0.161* | |
C11 | 0.604 (3) | −0.059 (2) | 0.550 (2) | 0.135 (10) | |
H11A | 0.6781 | −0.1031 | 0.5820 | 0.162* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Bi1 | 0.0342 (3) | 0.0336 (3) | 0.0346 (3) | −0.0010 (2) | 0.0112 (2) | −0.0013 (2) |
I1 | 0.0488 (4) | 0.0534 (5) | 0.0580 (4) | 0.0128 (3) | 0.0159 (3) | −0.0005 (3) |
I2 | 0.0478 (4) | 0.0680 (5) | 0.0416 (4) | 0.0019 (3) | 0.0137 (3) | 0.0096 (3) |
I3 | 0.0585 (4) | 0.0461 (4) | 0.0569 (4) | −0.0186 (3) | 0.0194 (3) | −0.0107 (3) |
O1 | 0.048 (6) | 0.111 (9) | 0.155 (11) | 0.009 (5) | 0.000 (6) | 0.065 (8) |
N1 | 0.039 (5) | 0.060 (6) | 0.042 (4) | 0.007 (4) | 0.015 (4) | 0.003 (4) |
C1 | 0.088 (11) | 0.097 (13) | 0.093 (11) | 0.000 (9) | 0.033 (9) | 0.036 (10) |
C2 | 0.066 (8) | 0.050 (8) | 0.079 (9) | −0.014 (6) | 0.029 (7) | −0.002 (6) |
C3 | 0.033 (6) | 0.085 (10) | 0.052 (6) | 0.010 (5) | 0.008 (5) | 0.003 (6) |
C4 | 0.062 (7) | 0.061 (8) | 0.056 (7) | 0.015 (6) | 0.020 (6) | −0.009 (6) |
C5 | 0.085 (10) | 0.063 (9) | 0.066 (8) | −0.008 (7) | 0.031 (7) | −0.010 (7) |
C6 | 0.078 (9) | 0.062 (9) | 0.078 (9) | 0.009 (7) | 0.034 (7) | 0.012 (7) |
C7 | 0.065 (8) | 0.091 (12) | 0.073 (8) | 0.019 (8) | 0.032 (7) | −0.004 (8) |
C8 | 0.053 (7) | 0.067 (9) | 0.063 (7) | −0.002 (6) | 0.023 (6) | −0.019 (6) |
C9 | 0.19 (2) | 0.115 (17) | 0.055 (9) | −0.073 (18) | 0.036 (12) | −0.001 (9) |
C10 | 0.073 (13) | 0.17 (3) | 0.19 (3) | −0.046 (15) | 0.083 (17) | −0.09 (2) |
C11 | 0.093 (16) | 0.073 (13) | 0.18 (2) | 0.038 (10) | −0.039 (14) | −0.048 (14) |
Geometric parameters (Å, º) top
Bi1—I2 | 3.0772 (9) | C1—C2 | 1.50 (2) |
Bi1—I2i | 3.0772 (9) | C2—C3 | 1.51 (2) |
Bi1—I3 | 3.0850 (9) | C4—C5 | 1.37 (2) |
Bi1—I3i | 3.0850 (9) | C5—C6 | 1.36 (2) |
Bi1—I1 | 3.0871 (8) | C6—C7 | 1.33 (2) |
Bi1—I1i | 3.0871 (8) | C7—C8 | 1.38 (2) |
O1—C2 | 1.194 (15) | C9—C11ii | 1.30 (2) |
N1—C4 | 1.32 (2) | C9—C10 | 1.30 (2) |
N1—C8 | 1.345 (14) | C10—C11 | 1.31 (2) |
N1—C3 | 1.459 (14) | C11—C9ii | 1.30 (2) |
| | | |
I2—Bi1—I2i | 180.0 | C4—N1—C8 | 120.8 (10) |
I2—Bi1—I3 | 88.50 (3) | C4—N1—C3 | 121.2 (10) |
I2i—Bi1—I3 | 91.50 (3) | C8—N1—C3 | 117.8 (10) |
I2—Bi1—I3i | 91.50 (3) | O1—C2—C1 | 124.9 (13) |
I2i—Bi1—I3i | 88.50 (3) | O1—C2—C3 | 120.8 (12) |
I3—Bi1—I3i | 180.0 | C1—C2—C3 | 114.3 (11) |
I2—Bi1—I1 | 88.82 (3) | N1—C3—C2 | 111.1 (9) |
I2i—Bi1—I1 | 91.18 (3) | N1—C4—C5 | 121.4 (11) |
I3—Bi1—I1 | 90.91 (3) | C6—C5—C4 | 118.2 (13) |
I3i—Bi1—I1 | 89.09 (3) | C7—C6—C5 | 120.5 (14) |
I2—Bi1—I1i | 91.18 (3) | C6—C7—C8 | 120.3 (13) |
I2i—Bi1—I1i | 88.82 (3) | N1—C8—C7 | 118.7 (12) |
I3—Bi1—I1i | 89.09 (3) | C11ii—C9—C10 | 120.2 (16) |
I3i—Bi1—I1i | 90.91 (3) | C9—C10—C11 | 120.0 (17) |
I1—Bi1—I1i | 180.0 | C9ii—C11—C10 | 119.4 (16) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data |
Chemical formula | 2(C8H10NO)(C5H6N)[BiI6] |
Mr | 1322.83 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.675 (2), 11.083 (2), 15.195 (3) |
β (°) | 108.19 (3) |
V (Å3) | 1707.9 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 10.61 |
Crystal size (mm) | 0.13 × 0.13 × 0.10 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.261, 0.346 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3358, 3358, 2264 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.091, 1.04 |
No. of reflections | 3358 |
No. of parameters | 151 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.94, −1.00 |
Selected geometric parameters (Å, º) topBi1—I2 | 3.0772 (9) | Bi1—I1 | 3.0871 (8) |
Bi1—I3 | 3.0850 (9) | | |
| | | |
I2—Bi1—I3 | 88.50 (3) | I3—Bi1—I1 | 90.91 (3) |
I2—Bi1—I1 | 88.82 (3) | | |
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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 [Mo3(µ3-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.