Salts of two pentahalo(N-donor)­bismuthate(III) anions: [BiX₅L]²⁻ (X = Cl, Br; L = pyridine, 4-picoline)

Two pentahalo(N-donor)­bismuthate(III) salts, bis­[hydrogen bis(4-picoline)(1+)] penta­bromo(4-picoline-N)bismuthate(III), (C₁₂H₁₅N₂)₂[BiBr₅(C₆H₇N)], (I), and bis­(pyridinium) penta­chloro­(pyridine-N)­bismuthate(III), (C₅H₆N)₂[BiCl₅(C₅H₅N)], (II), are described which show modest deviations from octahedral geometry at bismuth. In (I), the cations comprise two 4-picoline mol­ecules sharing a proton and in (II), pyridinium cations are present. The anion in (I) has twofold and that in (II) has mirror crystallographic symmetry. Both structures show a layered packing formed by the anions with the cations between the layers. Ring–ring interactions seem important in (I), whilst in (II), N/­C—H...Cl—Bi hydrogen bonding is abundant.

S1. Comment

The crystal structure of [(4-pic)₂H]₂[BiBr₅(4-pic)], (I) (4-pic = 4-picoline), contains the pentabromo(4-pic)bismuthate(III) dianion lying at a twofold axis of symmetry [along Br1—Bi1—N1—C4]. The cations are hydrogen-bonded containing two molecules of 4-picoline sharing a proton (Fig. 1). In the compound [(pyH)]₂[BiCl₅(py)], (II) (py = pyridine) (Fig. 2), the cations are simple pyridinium ions. In the anion of (I) the Br1—Bi1—N1 angle is exactly 180° and the symmetry-independent trans bond angles are 169.74 (2)° [Br3Bi1Br3ⁱ] and 173.59 (2)° [Br2Bi1Br2ⁱ]. The cis-angles range from 84.871 (12)° to 95.129 (12)°. Notably, the Bi—Br bond distance trans to the 4-picoline is shorter [Bi1—Br1 = 2.772 (2) Å] than the others [Bi1—Br2 = 2.869 (3) Å and Bi1—Br3 = 2.850 (2) Å] presumably due to the lower trans-influence of the N-donor ligand. \sch

In the anion of (II) which has mirror symmetry, the Bi—Cl bond distances range from 2.6950 (12)–2.728 (2) Å, but in this case the bond trans to the pyridine ligand is the longest of the Bi-halide bonds. The Bi—N distances in both anions [2.618 (5) Å in (I) and 2.536 (5) Å in (II)] are significantly shorter than the two Bi—N distances in cis-[BiI₄(py)₂]^- [2.703 (2) and 2.751 (3) Å] (Carmalt et al., 1996) in which there are no discernible differences in Bi—I distances.

Two other salts containing the [BiCl₅(py)]^2- anion have been structurally characterized as N',N'-diethylthiocarbamoyl-pyridinium (Raston et al., 1981), (III), and N-(N',N'-diethylcarbamoyl)pyridine, (IV), (Bharadwaj et al., 1994) salts. In both cases the anion lies over a twofold axis. The symmetry independent Bi—Cl bond distances in (III) are 2.638 (2) Å (trans to N) and 2.699 (2) and 2.691 (3) Å (trans to Cl). Similarly for (IV) the bond lengths are 2.626 (2) Å (trans to N) and 2.694 (2) Å (trans to Cl, for two bonds). Thus, the Bi—Cl distance in (III) and (IV) trans to the N is shorter than those trans to Cl, the opposite of that in (II). That it is difficult to assess the relative trans-influences for nitrogen and chlorine in these complexes is probably due to the relative soft intra-molecular parameters. These are prone to distortion by so-called packing effects such as hydrogen bonding.

The geometry about the Bi centre in (II) is close to regular octahedral, with cis-angles 90±3°. The trans angle deviating most from 180° is Cl1Bi1Cl1ⁱ [174.21 (5)°]. Slightly larger distortions are found in the anions of (III) and (IV) with cis-angles deviating up to 6° and trans-angles 10° away from ideal geometries.

In (I) Br1 is involved in two weak hydrogen bonds with the [(4-pic)₂H]⁺ cations in a bifurcated mode [Br1···H9 = 2.98 Å, Br1···H8 = 3.00 Å, C8—H8···Br1 = 127.2°, C9—H9···Br1 = 128.7°]. The cations contain a short hydrogen bond [N3—H3 0.92, H3···N2 = 1.76, N···N = 2.667 (6) Å and N3—H3···N2 = 167°], conistent with the formulation of the cations as [(4-pic)₂H]⁺ rather than as separate [(4-pic)]⁺ cations and 4-pic solvent molecules.

The crystal structure of (I) is shown in Fig. 3. The packing can be best described as layers in an ABBA arrangement along the crystallographic c direction, with two [(4-pic)₂H]⁺ cations encased by A layers of the anion. The driving force behind this packing arrangement appears to be ring-ring interactions affording a close-packed structure. As shown in Fig. 3 there are ring-ring interactions between the 4-pic ligand of the anion and a cation with a 3.31 Å separation. The inter-plane separation between the cations is 3.63 Å. In the b direction the separation between the cation rings is 4.19 Å.

The crystal structure of (II) is made up of chains of anions running approximately parallel to the crystallographic b axis that are hydrogen-bonded to cations which occupy the space between adjacent layers (Fig. 4). There are two different orientations of chains, tilted at an angle of 65.9° to each other (Bi1 Cl1 Cl1' Cl2 Cl4 plane), one of which is shown in detail in Fig. 4. There is a plethora of Bi—Cl···H—C/N hydrogen bonds [H···Cl distances = 2.633–2.865 Å] (see Table 2 for hydrogen-bond details) whilst ring-ring interactions that were important in the structure of (I) are absent. Anions in chains are held together by CH···Cl hydrogen bonds related by a centre of symmetry. The anion hydrogen bonds

to a cation (Cl1···H7) and Cl4 which is perpendicular to the anion chains hydrogen bonds to two separate cations. A tetrameric motif is formed between two chlorines in separate chains and the NH protons of two separate cations. The pyridinium cation is inclined at an angle of 45.3° to the pyridine ligand.

S2. Experimental

Compound (I): The reaction of 4-picoline (0.030 cm³, 0.300 mmol) and Bi(1,2-S₂-4-MeC₆H₃)Br (0.300 mmol) in tetrahydrofuran (15 cm³) afforded an orange precipitate and an orange mother liquor. Yellow crystals of (I) were obtained by cooling of the orange mother liquor.

Compound (II): A solution of BiCl₃ in pyridine (1.5 cm³) was layered with more pyridine (1.5 cm³) and then hexane (10 cm³) and colourless block-like crystals of (I) were grown over several days at room temprature. [pyH]₂ [BiCl₅(py)] requires C 28.80, N 6.70, H 2.75, Cl 28.4%, obtained C 25.30, N 5.55, H 2.35, Cl 22.50%.

S3. Refinement

Hydrogen atoms were constrained to idealized geometries and assigned isotropic displacement parameters 1.2 times U_iso value of their attached carbon for aromatic H atoms and 1.5 U_iso for methyl H atoms, with the exception of H3 in (I) which was located in the electron density difference map and the coordinates refined. In (I) the methyl H atoms on C4 are disordered over the twofold axis.

Computing details

For both compounds, data collection: SMART (Siemens, 1995a); cell refinement: SAINT (Siemens, 1995a). Data reduction: SAINT (Siemens, 1995a) for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXTL (Siemens, 1995b). Program(s) used to refine structure: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II). Molecular graphics: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II). Software used to prepare material for publication: SHELXTL (Siemens, 1995b) for (I); SHELXTL for (II).

Figures

	Fig. 1. Hydrogen bonding in (I) showing the image of the disordered methyl group in the picoline ligand. Ellipsoids are drawn at the 50% level.
	Fig. 2. Molecular structure of (II) with ellipsoids at the 50% level.
	Fig. 3. Crystal structure of (I) along the b axis.
	Fig. 4. Crystal structure of (II) viewed along the b axis. Symmetry codes: (i) 1 - x, 1 - y, 2 - z, (ii) x, y, 1 - z, (iii) x, 3/2 - y, 1 - z.

(I)

Crystal data

(C12H15N2)2[BiBr5(C6H7N)]	F(000) = 2040
Mr = 1076.18	Dx = 1.948 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.789 (13) Å	Cell parameters from 272 reflections
b = 13.140 (8) Å	θ = 5–25°
c = 19.064 (16) Å	µ = 10.28 mm^−1
β = 97.94 (3)°	T = 173 K
V = 3669 (5) Å^3	Block, yellow
Z = 4	0.25 × 0.25 × 0.20 mm

Data collection

Siemens SMART Area Detector diffractometer	4188 independent reflections
Radiation source: fine-focus sealed tube	3306 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 1? pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ω rotation with narrow frame scans	h = −19→18
Absorption correction: multi-scan SADABS: sheldrick (1997) ?	k = 0→17
Tmin = 0.097, Tmax = 0.100	l = 0→24
4188 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms: see text
wR(F^2) = 0.055	Calculated w = 1/[σ^2(Fo^2) + (0.0238P)^2] where P = [Max(Fo^2,0) + 2Fc^2]/3
S = 0.92	(Δ/σ)max = 0.001
4188 reflections	Δρmax = 1.22 e Å^−3
191 parameters	Δρmin = −0.89 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000125 (18)

Special details

Experimental. Unit-cell dimensions were determined from reflections taken from three sets of 30 frames (at 0.3° steps in ω) at 10 s. A full hemisphere of reciprocal space was scanned by 0.3° ω steps at ϕ = 0, 90 and 180° at 20 s per frame with the area detector held at 2θ = -27°. The crystal-to-detector distance was 4.974 cm. Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analysing the duplicate reflections. No decay was observed for either data set.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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	Occ. (<1)
Bi1	0.0000	0.886315 (18)	0.2500	0.02002 (7)
Br1	0.0000	0.67534 (5)	0.2500	0.03098 (16)
Br2	0.19559 (3)	0.89852 (4)	0.27138 (2)	0.03611 (13)
Br3	−0.00383 (3)	0.90570 (4)	0.39845 (2)	0.03186 (12)
N1	0.0000	1.0856 (4)	0.2500	0.0263 (12)
C1	0.0718 (3)	1.1389 (3)	0.2352 (2)	0.0306 (11)
H1	0.1227	1.1037	0.2244	0.037*
C2	0.0740 (4)	1.2428 (4)	0.2351 (2)	0.0408 (12)
H2	0.1258	1.2767	0.2248	0.049*
C3	0.0000	1.2971 (5)	0.2500	0.0439 (19)
C4	0.0000	1.4121 (6)	0.2500	0.078 (3)
H4A	0.0607	1.4365	0.2476	0.116*	0.50
H4B	−0.0203	1.4365	0.2927	0.116*	0.50
H4C	−0.0404	1.4365	0.2097	0.116*	0.50
N3	−0.0818 (3)	0.7179 (3)	0.55482 (19)	0.0363 (9)
H3	−0.0357	0.6925	0.5380	0.044*
C11	−0.1500 (3)	0.6581 (4)	0.5679 (2)	0.0406 (12)
H11	−0.1471	0.5888	0.5585	0.049*
C12	−0.2234 (3)	0.6952 (4)	0.5943 (2)	0.0380 (12)
H12	−0.2702	0.6515	0.6027	0.046*
C13	−0.2294 (3)	0.7976 (4)	0.6089 (2)	0.0313 (11)
C14	−0.1579 (3)	0.8591 (4)	0.5944 (2)	0.0318 (11)
H14	−0.1595	0.9288	0.6026	0.038*
C15	−0.0850 (3)	0.8168 (4)	0.5679 (2)	0.0327 (11)
H15	−0.0369	0.8583	0.5589	0.039*
C16	−0.3093 (3)	0.8419 (5)	0.6386 (3)	0.0499 (14)
H16A	−0.3645	0.8098	0.6168	0.075*
H16B	−0.3126	0.9137	0.6293	0.075*
H16C	−0.3022	0.8306	0.6888	0.075*
N2	0.0691 (3)	0.6475 (3)	0.5093 (2)	0.0417 (10)
C5	0.1462 (3)	0.6291 (4)	0.5538 (2)	0.0439 (13)
H5	0.1435	0.6272	0.6022	0.053*
C6	0.2290 (3)	0.6130 (4)	0.5302 (2)	0.0377 (11)
H6	0.2809	0.6007	0.5625	0.045*
C7	0.2351 (3)	0.6151 (4)	0.4586 (2)	0.0360 (11)
C8	0.1559 (3)	0.6335 (4)	0.4134 (2)	0.0374 (12)
H8	0.1569	0.6345	0.3647	0.045*
C9	0.0753 (3)	0.6503 (4)	0.4398 (2)	0.0427 (13)
H9	0.0229	0.6641	0.4082	0.051*
C10	0.3238 (3)	0.5982 (4)	0.4308 (3)	0.0536 (16)
H10A	0.3629	0.5566	0.4635	0.080*	0.50
H10B	0.3528	0.6626	0.4255	0.080*	0.50
H10C	0.3126	0.5647	0.3857	0.080*	0.50
H10D	0.3226	0.6327	0.3863	0.080*	0.50
H10E	0.3327	0.5267	0.4243	0.080*	0.50
H10F	0.3729	0.6246	0.4640	0.080*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01787 (11)	0.02141 (13)	0.02074 (11)	0.000	0.00256 (8)	0.000
Br1	0.0375 (4)	0.0245 (4)	0.0305 (3)	0.000	0.0033 (3)	0.000
Br2	0.0219 (2)	0.0476 (3)	0.0383 (2)	0.0035 (2)	0.00222 (18)	−0.0066 (2)
Br3	0.0332 (2)	0.0388 (3)	0.0244 (2)	0.0009 (2)	0.00640 (18)	−0.00104 (19)
N1	0.033 (3)	0.023 (3)	0.023 (3)	0.000	0.004 (2)	0.000
C1	0.031 (2)	0.032 (3)	0.029 (2)	−0.002 (2)	0.0065 (19)	0.001 (2)
C2	0.053 (3)	0.032 (3)	0.034 (3)	−0.014 (3)	−0.005 (2)	0.007 (2)
C3	0.066 (5)	0.018 (4)	0.043 (4)	0.000	−0.007 (4)	0.000
C4	0.118 (8)	0.031 (5)	0.078 (6)	0.000	−0.006 (6)	0.000
N3	0.031 (2)	0.046 (3)	0.033 (2)	0.006 (2)	0.0071 (17)	−0.001 (2)
C11	0.051 (3)	0.031 (3)	0.040 (3)	0.000 (3)	0.008 (2)	−0.005 (2)
C12	0.038 (3)	0.044 (3)	0.033 (3)	−0.016 (2)	0.005 (2)	0.001 (2)
C13	0.028 (2)	0.044 (3)	0.022 (2)	0.000 (2)	0.0021 (18)	0.000 (2)
C14	0.029 (2)	0.033 (3)	0.032 (2)	−0.006 (2)	0.0023 (19)	−0.002 (2)
C15	0.029 (2)	0.040 (3)	0.030 (2)	−0.004 (2)	0.0047 (19)	0.007 (2)
C16	0.031 (3)	0.067 (4)	0.054 (3)	0.001 (3)	0.013 (2)	−0.003 (3)
N2	0.039 (2)	0.046 (3)	0.041 (2)	0.013 (2)	0.0079 (19)	0.001 (2)
C5	0.052 (3)	0.053 (4)	0.026 (2)	0.016 (3)	0.003 (2)	0.006 (2)
C6	0.036 (3)	0.041 (3)	0.034 (2)	0.009 (2)	−0.005 (2)	0.002 (2)
C7	0.031 (2)	0.033 (3)	0.043 (3)	0.003 (2)	0.003 (2)	−0.006 (2)
C8	0.035 (3)	0.049 (4)	0.029 (2)	0.006 (3)	0.005 (2)	0.003 (2)
C9	0.037 (3)	0.052 (4)	0.036 (3)	0.006 (3)	−0.004 (2)	0.007 (2)
C10	0.031 (3)	0.076 (5)	0.055 (3)	0.010 (3)	0.011 (2)	−0.003 (3)

Geometric parameters (Å, º)

Bi1—N1	2.618 (5)	C13—C16	1.496 (6)
Bi1—Br1	2.7723 (18)	C14—C15	1.370 (6)
Bi1—Br3^i	2.850 (2)	C14—H14	0.9300
Bi1—Br3	2.850 (2)	C15—H15	0.9300
Bi1—Br2	2.869 (3)	C16—H16A	0.9600
Bi1—Br2^i	2.869 (3)	C16—H16B	0.9600
N1—C1	1.335 (5)	C16—H16C	0.9600
N1—C1^i	1.335 (5)	N2—C9	1.341 (6)
C1—C2	1.366 (6)	N2—C5	1.345 (6)
C1—H1	0.9300	C5—C6	1.379 (6)
C2—C3	1.369 (6)	C5—H5	0.9300
C2—H2	0.9300	C6—C7	1.380 (6)
C3—C2^i	1.369 (6)	C6—H6	0.9300
C3—C4	1.511 (10)	C7—C8	1.376 (6)
C4—H4A	0.9600	C7—C10	1.497 (6)
C4—H4B	0.9600	C8—C9	1.375 (6)
C4—H4C	0.9600	C8—H8	0.9300
N3—C15	1.325 (6)	C9—H9	0.9300
N3—C11	1.330 (6)	C10—H10A	0.9600
N3—H3	0.8600	C10—H10B	0.9600
C11—C12	1.349 (6)	C10—H10C	0.9600
C11—H11	0.9300	C10—H10D	0.9600
C12—C13	1.380 (7)	C10—H10E	0.9600
C12—H12	0.9300	C10—H10F	0.9600
C13—C14	1.388 (6)
N1—Bi1—Br1	180.000 (1)	C13—C14—H14	120.1
N1—Bi1—Br3^i	84.871 (12)	N3—C15—C14	121.1 (4)
Br1—Bi1—Br3^i	95.129 (12)	N3—C15—H15	119.4
N1—Bi1—Br3	84.872 (11)	C14—C15—H15	119.4
Br1—Bi1—Br3	95.128 (11)	C13—C16—H16A	109.5
Br3^i—Bi1—Br3	169.74 (2)	C13—C16—H16B	109.5
N1—Bi1—Br2	86.797 (12)	H16A—C16—H16B	109.5
Br1—Bi1—Br2	93.203 (12)	C13—C16—H16C	109.5
Br3^i—Bi1—Br2	88.75 (3)	H16A—C16—H16C	109.5
Br3—Bi1—Br2	90.68 (3)	H16B—C16—H16C	109.5
N1—Bi1—Br2^i	86.797 (12)	C9—N2—C5	117.5 (4)
Br1—Bi1—Br2^i	93.203 (12)	N2—C5—C6	122.3 (4)
Br3^i—Bi1—Br2^i	90.68 (3)	N2—C5—H5	118.8
Br3—Bi1—Br2^i	88.75 (3)	C6—C5—H5	118.8
Br2—Bi1—Br2^i	173.59 (2)	C5—C6—C7	120.1 (4)
C1—N1—C1^i	116.7 (5)	C5—C6—H6	119.9
C1—N1—Bi1	121.6 (3)	C7—C6—H6	119.9
C1^i—N1—Bi1	121.7 (3)	C8—C7—C6	117.2 (4)
N1—C1—C2	123.0 (5)	C8—C7—C10	121.1 (4)
N1—C1—H1	118.5	C6—C7—C10	121.8 (4)
C2—C1—H1	118.5	C9—C8—C7	120.3 (4)
C1—C2—C3	120.1 (5)	C9—C8—H8	119.8
C1—C2—H2	119.9	C7—C8—H8	119.8
C3—C2—H2	119.9	N2—C9—C8	122.5 (4)
C2^i—C3—C2	117.1 (6)	N2—C9—H9	118.7
C2^i—C3—C4	121.4 (3)	C8—C9—H9	118.7
C2—C3—C4	121.4 (3)	C7—C10—H10A	109.5
C3—C4—H4A	109.5	C7—C10—H10B	109.5
C3—C4—H4B	109.5	H10A—C10—H10B	109.5
H4A—C4—H4B	109.5	C7—C10—H10C	109.5
C3—C4—H4C	109.5	H10A—C10—H10C	109.5
H4A—C4—H4C	109.5	H10B—C10—H10C	109.5
H4B—C4—H4C	109.5	C7—C10—H10D	109.5
C15—N3—C11	119.8 (4)	H10A—C10—H10D	141.1
C15—N3—H3	120.1	H10B—C10—H10D	56.3
C11—N3—H3	120.1	H10C—C10—H10D	56.3
N3—C11—C12	121.8 (5)	C7—C10—H10E	109.5
N3—C11—H11	119.1	H10A—C10—H10E	56.3
C12—C11—H11	119.1	H10B—C10—H10E	141.1
C11—C12—C13	120.4 (5)	H10C—C10—H10E	56.3
C11—C12—H12	119.8	H10D—C10—H10E	109.5
C13—C12—H12	119.8	C7—C10—H10F	109.5
C12—C13—C14	117.0 (4)	H10A—C10—H10F	56.3
C12—C13—C16	122.2 (4)	H10B—C10—H10F	56.3
C14—C13—C16	120.8 (5)	H10C—C10—H10F	141.1
C15—C14—C13	119.9 (5)	H10D—C10—H10F	109.5
C15—C14—H14	120.1	H10E—C10—H10F	109.5

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2	0.92	1.76	2.667 (6)	167

(II) pentachloropyridylbismuthate(III) pyridinium

Crystal data

(C5H6N)2[BiCl5(C5H5N)]	Dx = 2.015 Mg m^−3
Mr = 625.55	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 158 reflections
a = 18.699 (2) Å	θ = 5–25°
b = 14.889 (3) Å	µ = 9.20 mm^−1
c = 7.408 (3) Å	T = 173 K
V = 2062.4 (9) Å^3	Block, yellow
Z = 4	0.2 × 0.2 × 0.2 mm
F(000) = 1184

Data collection

Siemens SMART Area Detector diffractometer	2459 independent reflections
Radiation source: fine-focus sealed tube	1956 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω rotation with narrow frame scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; sheldrick, 1997) ?	h = −24→24
Tmin = 0.137, Tmax = 0.158	k = −18→19
12283 measured reflections	l = −9→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.052	Calculated w = 1/[σ^2(Fo^2) + (0.024P)^2] where P = Max{(Fo^2,0) + 2Fc^2)/3}
S = 1.05	(Δ/σ)max = 0.001
2459 reflections	Δρmax = 0.77 e Å^−3
119 parameters	Δρmin = −1.00 e Å^−3
0 restraints	Extinction correction: SHELXTL (Siemens, 1995b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00194 (10)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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	0.604453 (12)	−0.2500	1.16096 (3)	0.02241 (9)
Cl1	0.60006 (6)	−0.06922 (7)	1.1463 (2)	0.0352 (3)
Cl2	0.67932 (9)	−0.2500	0.8532 (2)	0.0351 (4)
Cl3	0.72604 (9)	−0.2500	1.3646 (2)	0.0316 (4)
Cl4	0.52284 (9)	−0.2500	1.4619 (3)	0.0381 (4)
N1	0.4894 (3)	−0.2500	0.9796 (8)	0.0270 (12)
C1	0.4574 (2)	−0.1732 (3)	0.9301 (7)	0.0303 (11)
H1	0.4791 (2)	−0.1180 (3)	0.9643 (7)	0.036*
C2	0.3949 (3)	−0.1699 (3)	0.8324 (7)	0.0365 (11)
H2	0.3743 (3)	−0.1139 (3)	0.7998 (7)	0.044*
N2	0.6555 (5)	−0.0780 (3)	1.5940 (8)	0.079 (2)
H9	0.6613 (5)	−0.1364 (3)	1.5826 (8)	0.095*
C3	0.3624 (3)	−0.2500	0.7821 (10)	0.035 (2)
H3	0.3191 (3)	−0.2500	0.7151 (10)	0.043*
C4	0.7107 (4)	−0.0247 (6)	1.5679 (10)	0.078 (3)
H4	0.7557 (4)	−0.0490 (6)	1.5340 (10)	0.094*
C5	0.7032 (4)	0.0623 (5)	1.5889 (10)	0.067 (2)
H5	0.7429 (4)	0.1015 (5)	1.5731 (10)	0.081*
C6	0.6390 (4)	0.0950 (4)	1.6329 (9)	0.060 (2)
H6	0.6331 (4)	0.1580 (4)	1.6476 (9)	0.073*
C7	0.5832 (3)	0.0409 (5)	1.6564 (9)	0.062 (2)
H7	0.5376 (3)	0.0648 (5)	1.6871 (9)	0.075*
C8	0.5921 (4)	−0.0469 (5)	1.6363 (8)	0.070 (2)
H8	0.5529 (4)	−0.0868 (5)	1.6524 (8)	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01880 (12)	0.01993 (13)	0.02848 (14)	0.000	0.00209 (13)	0.000
Cl1	0.0332 (6)	0.0223 (5)	0.0502 (8)	−0.0013 (5)	−0.0052 (7)	0.0006 (5)
Cl2	0.0316 (8)	0.0414 (9)	0.0324 (10)	0.000	0.0063 (9)	0.000
Cl3	0.0262 (8)	0.0327 (9)	0.0361 (10)	0.000	−0.0037 (8)	0.000
Cl4	0.0338 (9)	0.0361 (9)	0.0446 (11)	0.000	0.0159 (9)	0.000
N1	0.023 (3)	0.023 (3)	0.035 (3)	0.000	0.000 (3)	0.000
C1	0.030 (2)	0.026 (3)	0.034 (3)	0.000 (2)	0.000 (2)	−0.008 (2)
C2	0.032 (2)	0.029 (3)	0.048 (3)	0.003 (2)	−0.004 (3)	−0.003 (2)
N2	0.168 (7)	0.017 (3)	0.053 (4)	0.017 (4)	−0.035 (5)	−0.008 (2)
C3	0.021 (3)	0.043 (4)	0.043 (5)	0.000	−0.008 (3)	0.000
C4	0.061 (5)	0.109 (7)	0.065 (5)	0.050 (5)	−0.023 (4)	−0.028 (5)
C5	0.053 (4)	0.081 (5)	0.068 (5)	−0.029 (4)	−0.005 (4)	−0.011 (4)
C6	0.086 (5)	0.029 (3)	0.066 (5)	0.002 (3)	−0.022 (4)	−0.014 (3)
C7	0.038 (3)	0.093 (6)	0.056 (4)	0.013 (3)	0.002 (3)	−0.035 (4)
C8	0.098 (6)	0.074 (5)	0.040 (4)	−0.060 (5)	0.007 (4)	−0.003 (4)

Geometric parameters (Å, º)

Bi1—N1	2.536 (5)	C4—C5	1.312 (9)
Bi1—Cl2	2.675 (2)	C5—C6	1.337 (9)
Bi1—Cl1^i	2.6950 (12)	C6—C7	1.330 (9)
Bi1—Cl1	2.6950 (12)	C7—C8	1.327 (10)
Bi1—Cl4	2.702 (2)	Cl1—H2^ii	2.796 (5)
Bi1—Cl3	2.728 (2)	Cl1—H7^iii	2.856 (6)
N1—C1	1.342 (5)	Cl2—H9^iv	2.644 (6)
N1—C1^i	1.342 (5)	Cl2—H9^v	2.644 (6)
C1—C2	1.375 (7)	Cl3—H9	2.633 (7)
C2—C3	1.389 (6)	Cl3—H9^i	2.633 (7)
N2—C8	1.311 (9)	Cl4—H8	2.865 (7)
N2—C4	1.317 (9)	Cl4—H8^i	2.865 (7)
C3—C2^i	1.389 (6)
N1—Bi1—Cl2	89.57 (13)	C8—N2—C4	122.1 (6)
N1—Bi1—Cl1^i	87.30 (3)	C2^i—C3—C2	118.2 (6)
Cl2—Bi1—Cl1^i	88.95 (3)	C5—C4—N2	119.7 (6)
N1—Bi1—Cl1	87.30 (3)	C4—C5—C6	118.9 (6)
Cl2—Bi1—Cl1	88.95 (3)	C7—C6—C5	121.1 (6)
Cl1^i—Bi1—Cl1	174.21 (5)	C8—C7—C6	119.0 (6)
N1—Bi1—Cl4	87.59 (13)	N2—C8—C7	119.2 (6)
Cl2—Bi1—Cl4	177.16 (5)	Bi1—Cl1—H2^ii	164.29 (11)
Cl1^i—Bi1—Cl4	90.91 (3)	Bi1—Cl1—H7^iii	91.9 (2)
Cl1—Bi1—Cl4	90.91 (3)	H2^ii—Cl1—H7^iii	94.0 (2)
N1—Bi1—Cl3	178.42 (13)	H9^iv—Cl2—H9^v	79.5 (2)
Cl2—Bi1—Cl3	92.01 (6)	H9^iv—Cl2—Bi1	125.4 (2)
Cl1^i—Bi1—Cl3	92.73 (3)	H9^v—Cl2—Bi1	125.4 (2)
Cl1—Bi1—Cl3	92.73 (3)	H9—Cl3—H9^i	79.9 (3)
Cl4—Bi1—Cl3	90.82 (6)	H9—Cl3—Bi1	87.5 (2)
C1—N1—C1^i	116.9 (5)	H9^i—Cl3—Bi1	87.5 (2)
C1—N1—Bi1	121.5 (3)	Bi1—Cl4—H8	107.19 (13)
C1^i—N1—Bi1	121.5 (3)	Bi1—Cl4—H8^i	107.19 (14)
N1—C1—C2	123.5 (4)	H8—Cl4—H8^i	116.0 (3)
C1—C2—C3	118.9 (5)

Symmetry codes: (i) x, −y−1/2, z; (ii) −x+1, −y, −z+2; (iii) −x+1, −y, −z+3; (iv) x, −y−1/2, z−1; (v) x, y, z−1.