Bis­(1-acetonyl­pyridinium) pyridinium hexa­iodobismuth(III)

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.

S1. Comment

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.

S2. Experimental

[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.

S3. Refinement

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

Bis(acetonylpyridine) pyridinium hexaiodo-bismuth(III)

Crystal data

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) Å^3	Prism, red
Z = 2	0.13 × 0.13 × 0.10 mm

Data collection

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

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2)]
wR(F^2) = 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

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Bi1—I2	3.0772 (9)	C1—C2	1.50 (2)
Bi1—I2^i	3.0772 (9)	C2—C3	1.51 (2)
Bi1—I3	3.0850 (9)	C4—C5	1.37 (2)
Bi1—I3^i	3.0850 (9)	C5—C6	1.36 (2)
Bi1—I1	3.0871 (8)	C6—C7	1.33 (2)
Bi1—I1^i	3.0871 (8)	C7—C8	1.38 (2)
O1—C2	1.194 (15)	C9—C11^ii	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—C9^ii	1.30 (2)
I2—Bi1—I2^i	180.0	C4—N1—C8	120.8 (10)
I2—Bi1—I3	88.50 (3)	C4—N1—C3	121.2 (10)
I2^i—Bi1—I3	91.50 (3)	C8—N1—C3	117.8 (10)
I2—Bi1—I3^i	91.50 (3)	O1—C2—C1	124.9 (13)
I2^i—Bi1—I3^i	88.50 (3)	O1—C2—C3	120.8 (12)
I3—Bi1—I3^i	180.0	C1—C2—C3	114.3 (11)
I2—Bi1—I1	88.82 (3)	N1—C3—C2	111.1 (9)
I2^i—Bi1—I1	91.18 (3)	N1—C4—C5	121.4 (11)
I3—Bi1—I1	90.91 (3)	C6—C5—C4	118.2 (13)
I3^i—Bi1—I1	89.09 (3)	C7—C6—C5	120.5 (14)
I2—Bi1—I1^i	91.18 (3)	C6—C7—C8	120.3 (13)
I2^i—Bi1—I1^i	88.82 (3)	N1—C8—C7	118.7 (12)
I3—Bi1—I1^i	89.09 (3)	C11^ii—C9—C10	120.2 (16)
I3^i—Bi1—I1^i	90.91 (3)	C9—C10—C11	120.0 (17)
I1—Bi1—I1^i	180.0	C9^ii—C11—C10	119.4 (16)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.