catena-Poly[1,10-phenanthroline-1,10-diium [[dichlorido­bismuthate(III)]-di-μ-chlorido]]

The asymmetric unit of the title compound, {(C₁₂H₁₀N₂)[BiCl₄]}_n, comprises one 1,10-phenanthrolinium dication and one Bi atom with two terminal and two bridging chloride anions. The Bi atoms adopt a distorted octa­hedral configuration and are each bridged to two other Bi atoms by four chloride ligands to generate a one-dimensional polymer chain running along a. C—H...Cl hydrogen bonds link the phenanthrolinium dications to these chloro­bismuthate chains.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.015 Å
• Disorder in main residue
• R factor = 0.037
• wR factor = 0.105
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.42
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Bi1
PLAT301_ALERT_3_C Main Residue  Disorder .........................      17.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         15
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12    ..  CL2     ..       3.10 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12'   ..  CL2     ..       2.90 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         13

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL022_ALERT_1_A There is a mismatched ~ on line 107
              The asymmetric unit of the title compound, (C~12~H~10~N~2~)[BiCl~4],
              If you require a ~ then it should be escaped
              with a \, i.e. \~
              Otherwise there must be a matching closing ~, e.g. C~2~H~4~

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

The coordination chemistry of bismuth(III) is not widely investigated, although a number of adducts formed by nitrogen-containing ligands with bismuth(III) salts have been reported (Summers et al., 1994). More recently however, bismuth(III) coordination chemistry has gained more prominence, particularly in the light of the role of bismuth compounds in ²¹²Bi isotope therapy in cancer research (Sun et al., 1997) and the use of bismuth complexes in the treatment of peptic ulcers (Sun et al., 1997; Baxter, 1992). In a continuation of our studies of metal complexes with nitrogen ligands and salts of protonated nitrogen ligands with metal containing anions, we report here the synthesis and structure of the title compound, (phenH₂²⁺)₂(Bi₂Cl₈^4-).

The asymmetric unit of the title compound, C₁₂H₁₀BiCl₄N₂, comprises one 1,10-phenanthrolinium dication and one half of an octachlorodibismuthate tetraanion which lies about an inversion centre and forms the tetranion via Bi1—Cl1—Bi1ⁱ and Bi1—Cl1ⁱ—Bi1ⁱ bridges [i = - x + 1, - y + 1, - z + 1] to build the complex (phenH₂²⁺)₂(Bi₂Cl₈^4-). A view of the formula unit made up of two cations and anion is shown in Fig. 1. The dications are disordered with the two disorder components related in a head to tail fashion Fig 3.

The dimeric [Bi₂Cl₈]^4- tetraanions are made up from two octahedra sharing a common edge. The coordination geometry about Bi is distorted octahedral with Cl—Bi—Cl angles varying from 82.85 (7) - 94.43 (7)° for cis and 71.16 (8) -175.56 (6)° for trans arrangements. The Bi—Cl bond distances also vary with the role they play in the structure. The terminal Bi—Cl3 [2.508 (2) Å] and Bi—Cl4 [2.560 (2) Å] bonds are significantly shorter than those involving Cl bridges which range from 2.699 (2) to 2.985 (2) Å.

In the crystal tetraanions are further linked by Bi1—Cl2ⁱⁱ—Bi1 bridges [ii = - x + 2, - y + 1, - z + 1] to generate a one-dimensional polymer chain running along c axis. Cations and anions are linked by C—H···Cl hydrogen bonds (Fig. 2).

Related literature

For a general background to bismuth coordination chemistry see Summers et al. (1994), and for applications in medicine see Sun et al. (1997) and Baxter (1992). For related structures, see: Bowmaker et al. (1998); Benetollo et al. (1998); Blažič & Lazarini (1985).

S2. Experimental

Bismuth trichloride (0.5 mmol) was dissolved in 20 ml of dicholoromethane, and 0.5 mmol of 1,10-phenanthroline were added under stirring at room temperature. Pale yellow crystals precipitated after a few days and were filtered, washed with acetone and dried under vacuum. Yield 81%. m.p.: 421 K. Analysis calculated for C₁₂H₁₀BiCl₄N₂ : C 27.04, H 1.89, N 5.26%. Found: C 27.32, H 1.73, N 5.45%.

S3. Refinement

All H atoms were placed geometrically (C—H = 0.93 Å, N—H = 0.88 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier). Atoms N1, N2, C4, C7, C11 and C12 of the 1,10-phenanthrolinium cations are disordered over two positions with occupancies that were fixed at at 0.58 (1) and 0.42 (1) for all five atoms in the final stages of the refinement. Atoms C1—C3, C5, C7 and C8—C10 were common to both disorder components, while the atom pairs C4, N1'; C7 N2'; N1, C4' and N2, C7' shared identical coordinates.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I) with 30% probability displacement ellipsoids and the atom-numbering scheme. Unlabeled atoms are related to the corresponding labeled atoms by the symmetry code -x + 1,-y + 1,-z + 1 with Cl2 related to Cl2A by the symmetry code -x + 2,-y + 1,-z + 1.
	Fig. 2. The crystal packing of (I) viewed down the c axis. Polymeric chains of chloride bridged octachlorodibismuthate tetraanions are linked to the cations by intermolecular C—H···Cl hydrogen bonds drawn as dashed lines.
	Fig. 3. A representation of the disorder in the phenathrolinium cations of (I). Atoms of the minor component are linked by double dashed lines and atoms sharing common coordinates are displayed as filled spheres.

catena-Poly[1,10-phenanthroline-1,10-diium [[dichloridobismuth(III)]-di-µ-chlorido]]

Crystal data

(C12H10N2)[BiCl4]	Z = 2
Mr = 533.00	F(000) = 494
Triclinic, P1	Dx = 2.200 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2569 (14) Å	Cell parameters from 2619 reflections
b = 10.1924 (19) Å	θ = 2.2–26.6°
c = 12.139 (2) Å	µ = 11.61 mm^−1
α = 77.944 (3)°	T = 298 K
β = 75.044 (2)°	Block, yellow
γ = 69.313 (2)°	0.22 × 0.21 × 0.20 mm
V = 804.6 (3) Å^3

Data collection

CCD area detector diffractometer	2804 independent reflections
Radiation source: fine-focus sealed tube	2469 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.088, Tmax = 0.098	k = −11→12
4232 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0769P)^2 + 0.0334P] where P = (Fo^2 + 2Fc^2)/3
2804 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 3.70 e Å^−3
13 restraints	Δρmin = −1.53 e Å^−3

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 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	Occ. (<1)
Bi1	0.68159 (4)	0.57991 (3)	0.56389 (2)	0.03303 (15)
Cl1	0.3605 (3)	0.6925 (2)	0.4619 (2)	0.0430 (5)
Cl2	1.0241 (4)	0.4526 (3)	0.6542 (2)	0.0473 (5)
Cl3	0.6950 (4)	0.8238 (3)	0.5580 (2)	0.0544 (6)
Cl4	0.4662 (4)	0.5734 (3)	0.7672 (2)	0.0570 (7)
N1	0.3086 (11)	−0.0610 (8)	−0.0603 (7)	0.041 (2)	0.580 (11)
H1A	0.2899	−0.1385	−0.0233	0.049*	0.580 (11)
N2	0.1154 (12)	−0.0722 (9)	0.1714 (7)	0.0421 (19)	0.580 (11)
H2A	0.1572	−0.1471	0.1381	0.050*	0.580 (11)
C4	0.2683 (12)	0.1853 (9)	−0.0634 (7)	0.0399 (18)	0.580 (11)
C7	0.0775 (12)	0.1708 (9)	0.1679 (7)	0.0407 (19)	0.580 (11)
C4'	0.3086 (11)	−0.0610 (8)	−0.0603 (7)	0.041 (2)	0.420 (11)
C7'	0.1154 (12)	−0.0722 (9)	0.1714 (7)	0.0421 (19)	0.420 (11)
N1'	0.2683 (12)	0.1853 (9)	−0.0634 (7)	0.0399 (18)	0.420 (11)
H1'	0.2268	0.2581	−0.0276	0.048*	0.420 (11)
N2'	0.0775 (12)	0.1708 (9)	0.1679 (7)	0.0407 (19)	0.420 (11)
H2'	0.0972	0.2486	0.1325	0.049*	0.420 (11)
C1	0.4030 (14)	−0.0518 (10)	−0.1717 (8)	0.044 (2)
H1	0.4517	−0.1329	−0.2078	0.053*
C2	0.4303 (16)	0.0681 (11)	−0.2330 (9)	0.052 (3)
H2	0.4927	0.0715	−0.3103	0.063*
C3	0.3575 (16)	0.1941 (13)	−0.1730 (10)	0.060 (3)
H3	0.3743	0.2792	−0.2120	0.072*
C5	0.2425 (12)	0.0623 (9)	−0.0078 (7)	0.0339 (18)
C6	0.1431 (13)	0.0550 (9)	0.1109 (8)	0.0363 (19)
C8	−0.0172 (15)	0.1638 (12)	0.2782 (9)	0.054 (3)
H8	−0.0625	0.2437	0.3156	0.065*
C9	−0.0488 (18)	0.0387 (13)	0.3378 (10)	0.060 (3)
H9	−0.1176	0.0348	0.4139	0.072*
C10	0.0207 (14)	−0.0742 (11)	0.2841 (9)	0.049 (2)
H10	0.0045	−0.1588	0.3249	0.059*
C11	0.203 (3)	0.311 (2)	−0.0032 (15)	0.051 (4)	0.580 (11)
H11	0.2299	0.3932	−0.0413	0.061*	0.580 (11)
C12	0.107 (2)	0.3055 (17)	0.1029 (14)	0.044 (4)	0.580 (11)
H12	0.0569	0.3867	0.1389	0.053*	0.580 (11)
C11'	0.278 (3)	−0.195 (2)	0.011 (2)	0.043 (6)	0.420 (11)
H11'	0.3238	−0.2774	−0.0236	0.051*	0.420 (11)
C12'	0.189 (3)	−0.1999 (19)	0.1209 (18)	0.040 (5)	0.420 (11)
H12'	0.1748	−0.2839	0.1639	0.047*	0.420 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0318 (2)	0.0319 (2)	0.0345 (2)	−0.00910 (14)	−0.00571 (13)	−0.00526 (13)
Cl1	0.0442 (12)	0.0359 (11)	0.0463 (13)	−0.0084 (9)	−0.0142 (10)	−0.0009 (9)
Cl2	0.0451 (13)	0.0528 (14)	0.0400 (12)	−0.0084 (10)	−0.0132 (10)	−0.0042 (10)
Cl3	0.0726 (17)	0.0413 (13)	0.0529 (14)	−0.0248 (12)	−0.0050 (12)	−0.0112 (10)
Cl4	0.0592 (16)	0.0574 (15)	0.0435 (14)	−0.0164 (12)	0.0023 (11)	−0.0027 (11)
N1	0.043 (5)	0.044 (5)	0.040 (5)	−0.014 (4)	−0.013 (4)	−0.007 (4)
N2	0.035 (4)	0.043 (5)	0.049 (5)	−0.010 (4)	−0.015 (4)	−0.003 (4)
C4	0.041 (4)	0.040 (5)	0.036 (4)	−0.009 (4)	−0.009 (4)	−0.004 (3)
C7	0.038 (4)	0.042 (5)	0.039 (5)	−0.008 (4)	−0.009 (4)	−0.007 (4)
C4'	0.043 (5)	0.044 (5)	0.040 (5)	−0.014 (4)	−0.013 (4)	−0.007 (4)
C7'	0.035 (4)	0.043 (5)	0.049 (5)	−0.010 (4)	−0.015 (4)	−0.003 (4)
N1'	0.041 (4)	0.040 (5)	0.036 (4)	−0.009 (4)	−0.009 (4)	−0.004 (3)
N2'	0.038 (4)	0.042 (5)	0.039 (5)	−0.008 (4)	−0.009 (4)	−0.007 (4)
C1	0.046 (5)	0.045 (5)	0.046 (6)	−0.017 (4)	−0.010 (4)	−0.010 (4)
C2	0.049 (6)	0.060 (7)	0.046 (6)	−0.012 (5)	−0.003 (5)	−0.018 (5)
C3	0.055 (6)	0.067 (7)	0.056 (7)	−0.010 (5)	−0.022 (5)	−0.007 (5)
C5	0.028 (4)	0.036 (5)	0.038 (5)	−0.006 (3)	−0.010 (4)	−0.006 (4)
C6	0.041 (5)	0.036 (5)	0.037 (5)	−0.015 (4)	−0.014 (4)	0.000 (4)
C8	0.043 (5)	0.062 (7)	0.058 (7)	−0.011 (5)	−0.008 (5)	−0.026 (5)
C9	0.064 (7)	0.073 (8)	0.043 (6)	−0.025 (6)	−0.016 (5)	0.001 (5)
C10	0.038 (5)	0.047 (6)	0.053 (6)	−0.016 (4)	−0.008 (4)	0.017 (5)
C11	0.044 (9)	0.055 (11)	0.051 (10)	−0.021 (8)	0.003 (8)	−0.009 (8)
C12	0.043 (7)	0.042 (7)	0.045 (7)	−0.011 (6)	−0.009 (6)	−0.005 (6)
C11'	0.038 (12)	0.031 (11)	0.059 (14)	−0.018 (9)	0.000 (10)	−0.003 (10)
C12'	0.039 (8)	0.045 (9)	0.036 (8)	−0.015 (7)	−0.010 (7)	−0.003 (7)

Geometric parameters (Å, º)

Bi1—Cl3	2.508 (2)	C7—C12	1.492 (18)
Bi1—Cl4	2.560 (2)	C1—C2	1.343 (14)
Bi1—Cl1	2.699 (2)	C1—H1	0.9300
Bi1—Cl2	2.756 (2)	C2—C3	1.474 (15)
Bi1—Cl2^i	2.937 (2)	C2—H2	0.9300
Bi1—Cl1^ii	2.985 (2)	C3—H3	0.9300
Cl1—Bi1^ii	2.985 (2)	C5—C6	1.435 (13)
Cl2—Bi1^i	2.937 (2)	C8—C9	1.393 (16)
N1—C1	1.349 (12)	C8—H8	0.9300
N1—C5	1.403 (11)	C9—C10	1.317 (16)
N1—H1A	0.8600	C9—H9	0.9300
N2—C10	1.363 (13)	C10—H10	0.9300
N2—C6	1.405 (12)	C11—C12	1.30 (2)
N2—H2A	0.8600	C11—H11	0.9300
C4—C3	1.321 (14)	C12—H12	0.9300
C4—C5	1.345 (12)	C11'—C12'	1.32 (3)
C4—C11	1.475 (19)	C11'—H11'	0.9300
C7—C8	1.338 (13)	C12'—H12'	0.9300
C7—C6	1.367 (12)
Cl3—Bi1—Cl4	94.42 (9)	N1—C1—H1	118.3
Cl3—Bi1—Cl1	89.50 (9)	C1—C2—C3	117.3 (10)
Cl4—Bi1—Cl1	93.70 (8)	C1—C2—H2	121.3
Cl3—Bi1—Cl2	92.93 (9)	C3—C2—H2	121.3
Cl4—Bi1—Cl2	89.82 (9)	C4—C3—C2	119.6 (11)
Cl1—Bi1—Cl2	175.56 (6)	C4—C3—H3	120.2
Cl3—Bi1—Cl2^i	90.29 (8)	C2—C3—H3	120.2
Cl4—Bi1—Cl2^i	170.84 (8)	C4—C5—N1	123.1 (8)
Cl1—Bi1—Cl2^i	94.19 (7)	C4—C5—C6	119.2 (7)
Cl2—Bi1—Cl2^i	82.09 (7)	N1—C5—C6	117.7 (8)
Cl3—Bi1—Cl1^ii	171.16 (8)	C7—C6—N2	118.8 (8)
Cl4—Bi1—Cl1^ii	90.50 (8)	C7—C6—C5	120.7 (8)
Cl1—Bi1—Cl1^ii	82.85 (7)	N2—C6—C5	120.5 (8)
Cl2—Bi1—Cl1^ii	94.43 (7)	C7—C8—C9	120.9 (10)
Cl2^i—Bi1—Cl1^ii	85.88 (7)	C7—C8—H8	119.6
Bi1—Cl1—Bi1^ii	97.15 (7)	C9—C8—H8	119.6
Bi1—Cl2—Bi1^i	97.91 (7)	C10—C9—C8	118.6 (10)
C1—N1—C5	116.6 (8)	C10—C9—H9	120.7
C1—N1—H1A	121.7	C8—C9—H9	120.7
C5—N1—H1A	121.7	C9—C10—N2	122.7 (9)
C10—N2—C6	118.4 (8)	C9—C10—H10	118.6
C10—N2—H2A	120.8	N2—C10—H10	118.6
C6—N2—H2A	120.8	C12—C11—C4	119.6 (15)
C3—C4—C5	119.9 (9)	C12—C11—H11	120.2
C3—C4—C11	119.0 (10)	C4—C11—H11	120.2
C5—C4—C11	121.1 (10)	C11—C12—C7	120.8 (15)
C8—C7—C6	120.5 (9)	C11—C12—H12	119.6
C8—C7—C12	121.1 (10)	C7—C12—H12	119.6
C6—C7—C12	118.4 (9)	C12'—C11'—H11'	118.9
C2—C1—N1	123.5 (9)	C11'—C12'—H12'	121.0
C2—C1—H1	118.3

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl2^ii	0.93	3.10	3.951 (17)	153
C12′—H12′···Cl2^iii	0.93	2.90	3.77 (2)	155

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