Tetra­kis(2-amino-6-methyl­pyridinium) hexa­chloridobismuthate(III) chloride monohydrate

Yang, Z.; Chen, G.; Xu, W.; Fan, Z.

doi:10.1107/S1600536809025446

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m887

doi:10.1107/S1600536809025446

Open

access

Tetrakis(2-amino-6-methylpyridinium) hexachloridobismuthate(III) chloride monohydrate

Zhen Yang,^a Gang Chen,^a Wei Xu ^a and Zheng Fan ^b ^*

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^bCollege of Biological & Environmental Engineering, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: fzt713@163.com

(Received 23 June 2009; accepted 1 July 2009; online 8 July 2009)

The asymmetric unit of the title compound, (C₆H₉N₂)₄[BiCl₆]Cl·H₂O, contains four protonated 2-amino-6-methylpyridine (HAMP) cations and two-halves of two [BiCl₆]³⁻ anions, together with one water molecule and one chloride anion. The Bi^III atoms are hexacoordinated by Cl atoms, forming distorted octahedral geometries. In the crystal structure, intramolecular O—H⋯Cl and N—H⋯Cl, and intermolecular O—H⋯Cl and N—H⋯O interactions link the molecules into a three-dimensional network.

Related literature

For related structures, see: Albrecht et al. (2003 ); Feng et al. (2007 ); Inuzuka & Fujimoto (1986 , 1990 ); Ishikawa et al. (2002 ); Jin et al. (2000 , 2001 , 2005 ); Luque et al. (1997 ); Nahringbauer & Kvick (1977 ); Ren et al. (2002 ); Rivas et al. (2003 ); Salwa et al. (2008 ); Xu et al. (2006 ).

Experimental

Crystal data

(C₆H₉N₂)₄[BiCl₆]Cl·H₂O
M_r = 911.75
Triclinic, $[P \overline 1]$
a = 10.3345 (7) Å
b = 10.7605 (7) Å
c = 17.2673 (11) Å
α = 100.3370 (10)°
β = 103.7370 (10)°
γ = 99.2280 (10)°
V = 1793.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 5.47 mm⁻¹
T = 273 K
0.42 × 0.31 × 0.25 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.153, T_max = 0.185 (expected range = 0.211–0.255)
9489 measured reflections
6240 independent reflections
5171 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.070
S = 1.07
6240 reflections
373 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1WB⋯Cl7	0.825	2.28	3.051 (3)	157
N2—H2B⋯Cl5	0.86	2.65	3.432 (3)	151
N4—H4B⋯Cl2	0.86	2.48	3.307 (3)	163
N5—H5⋯Cl7	0.86	2.21	3.059 (3)	168
N7—H7⋯Cl4	0.86	2.38	3.204 (3)	161
N8—H8B⋯Cl1	0.86	2.51	3.343 (3)	164
O1—H1WA⋯Cl3ⁱ	0.828	2.49	3.290 (3)	163
N1—H1⋯O1ⁱⁱ	0.86	1.91	2.774 (3)	177
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025446/hk2720sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025446/hk2720Isup2.hkl

checkCIF report

Comment top

During the past decade, a series of 2-amino-substituted pyridine compounds have been investigated in which the 2-aminopyridines act as ligands or protonated cations (Ren et al., 2002; Rivas et al., 2003; Luque et al., 1997; Albrecht et al., 2003). Among them, the tautomerism phenomenon of 2-aminopyridine derivatives has been proved by x-ray diffraction, such as 2-amino-6-methylpyridinium chloride (Jin et al., 2000) and 2-amino-6-methylpyridinium neoabietate (Jin et al., 2005). All the above studies provide important references to further research into 2-amino pyridines. We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains four protonated 2-amino-6-methyl-pyridine (HAMP) cations and two-halves of crystallographically independent [BiCl₆]^3- anions, together with one water molecule and one chloride anion. The bismuth atoms are hexa-coordinated by chloride atoms, forming distorted-octahedral geometries. Intramolecular O-H···Cl and N-H···Cl interactions (Table 1) link the cations, anions and water molecule.

The average value of Bi—Cl bond distance [2.7061 Å] observed in the [BiCl₆]^3- anion is shorter than the corresponding average values of [2.7130 Å] (Salwa et al., 2008) and [2.7150 Å] (Xu et al., 2006). In the cation, the N4—C11 bond [1.334 (5) Å] is shorter than the N3—C11 [1.341 (5) Å] and N3—C7 [1.358 (5) Å] bonds, and the C10—C11 [1.384 (6) Å] and C8—C9 [1.402 (6) Å] bonds are significantly longer than C9—C10 [1.362 (7) Å] and C7—C8 [1.342 (6) Å] bonds, in which they are similar to those in the HAMP cation (C₆H₉N₂)₂[Sb₂Cl₆O] (Feng et al., 2007). In contrast, in the solid state structure of 2-amino-6-methyl-pyridine (AMP), the N—C bond out of the ring is clearly longer than that in the ring (Nahringbauer et al., 1977). The geometric features of HAMP cation [N7/N8/C19/C24] resemble those observed in other 2-aminopyridine structures (Jin et al., 2001) that are believed to be involved in amine-imine tautomerism (Inuzuka et al., 1986; Inuzuka et al., 1990; Ishikawa et al., 2002). Similar features are also observed in other HAMP cations.

In the crystal structure (Fig. 2), intramolecular O-H···Cl and N-H···Cl and intermolecular O-H···Cl and N-H···O interactions (Table 1) link the molecules into a three-dimensional network.

Related literature top

For related structures, see: Albrecht et al. (2003); Feng et al. (2007); Inuzuka & Fujimoto (1986, 1990); Ishikawa et al. (2002); Jin et al. (2000, 2001, 2005); Luque et al. (1997); Nahringbauer et al. (1977); Ren et al. (2002); Rivas et al. (2003); Salwa et al. (2008); Xu et al. (2006).

Experimental top

For the preparation of the title compound, AMP, aqueous HCl and BiCl₃ in a molar ratio of 4:4:1 were mixed and dissolved in water (20 ml). The mixture was stirred and heated until a clear solution was resulted. Crystals suitable for X-ray analysis were obtained by gradual evaporation of excess water over a period of one week at 300 K. Analysis: C 31.65; H 4.13; N 12.32. calc. for Bi₁C₂₄H₃₄N₈O₁Cl₇: C 31.61; H 4.17; N 12.29 IR Spectrum (KBr, cm^-1): 3411(s), 3295 (s), 3195 (m), 3090 (m), 1656 (versus), 1630 (w), 1565 (w), 1474 (w), 1392 (m), 1309 (m), 1174 (w), 1042 (w), 997 (w), 793 (m), 715 (w), 612 (w), 564 (w), 421 (m).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A packing diagram viewed down along the a axis. Hydrogen bonds are shown as dashed lines.

Tetrakis(2-amino-6-methylpyridinium) hexachloridobismuthate(III) chloride monohydrate top

Crystal data top

(C₆H₉N₂)₄[BiCl₆]Cl·H₂O	Z = 2
M_r = 911.75	F(000) = 896.0
Triclinic, P1	D_x = 1.689 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3345 (7) Å	Cell parameters from 3117 reflections
b = 10.7605 (7) Å	θ = 2.2–25.1°
c = 17.2673 (11) Å	µ = 5.47 mm⁻¹
α = 100.337 (1)°	T = 273 K
β = 103.737 (1)°	Block, colorless
γ = 99.228 (1)°	0.42 × 0.31 × 0.25 mm
V = 1793.1 (2) Å³

Data collection top

Bruker SMART APEX area-detector diffractometer	6240 independent reflections
Radiation source: fine-focus sealed tube	5171 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→12
T_min = 0.153, T_max = 0.185	k = −9→12
9489 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0359P)² + 0.5382P] where P = (F_o² + 2F_c²)/3
6240 reflections	(Δ/σ)_max < 0.001
373 parameters	Δρ_max = 0.55 e Å⁻³
3 restraints	Δρ_min = −1.13 e Å⁻³

Crystal data top

(C₆H₉N₂)₄[BiCl₆]Cl·H₂O	γ = 99.228 (1)°
M_r = 911.75	V = 1793.1 (2) Å³
Triclinic, P1	Z = 2
a = 10.3345 (7) Å	Mo Kα radiation
b = 10.7605 (7) Å	µ = 5.47 mm⁻¹
c = 17.2673 (11) Å	T = 273 K
α = 100.337 (1)°	0.42 × 0.31 × 0.25 mm
β = 103.737 (1)°

Data collection top

Bruker SMART APEX area-detector diffractometer	6240 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	5171 reflections with I > 2σ(I)
T_min = 0.153, T_max = 0.185	R_int = 0.016
9489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	3 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	Δρ_max = 0.55 e Å⁻³
6240 reflections	Δρ_min = −1.13 e Å⁻³
373 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Bi1	0.5000	0.5000	0.5000	0.03208 (7)
Bi2	0.5000	0.5000	0.0000	0.03407 (7)
Cl1	0.76385 (11)	0.55587 (11)	0.49688 (6)	0.0503 (3)
Cl2	0.46967 (13)	0.73844 (10)	0.48394 (7)	0.0537 (3)
Cl3	0.42723 (11)	0.42048 (10)	0.33422 (6)	0.0489 (3)
Cl4	0.56519 (12)	0.32481 (10)	0.08902 (7)	0.0573 (3)
Cl5	0.33494 (12)	0.56458 (11)	0.09478 (7)	0.0547 (3)
Cl6	0.70316 (12)	0.68084 (10)	0.10950 (7)	0.0599 (3)
Cl7	0.88297 (16)	0.15531 (15)	0.23702 (9)	0.0826 (4)
O1	1.1851 (4)	0.1659 (3)	0.3096 (2)	0.0857 (11)
H1WB	1.1129	0.1812	0.2849	0.103*
H1WA	1.2497	0.2292	0.3265	0.103*
N1	0.1776 (4)	0.0607 (4)	0.1493 (3)	0.0592 (11)
H1	0.1767	0.0927	0.1985	0.071*
N2	0.2421 (5)	0.2693 (4)	0.1378 (3)	0.0810 (13)
H2A	0.2425	0.2963	0.1878	0.097*
H2B	0.2629	0.3238	0.1095	0.097*
N3	0.5100 (4)	0.8575 (3)	0.20673 (19)	0.0474 (9)
H3A	0.5145	0.7911	0.1722	0.057*
N4	0.4851 (5)	0.7216 (4)	0.2933 (2)	0.0781 (14)
H4A	0.4900	0.6588	0.2563	0.094*
H4B	0.4747	0.7079	0.3392	0.094*
N5	0.8447 (4)	0.0458 (4)	0.3837 (3)	0.0502 (9)
H5	0.8607	0.0669	0.3407	0.060*
N6	0.8249 (5)	0.2543 (4)	0.4248 (3)	0.0840 (14)
H6D	0.8403	0.2684	0.3800	0.101*
H6E	0.8112	0.3155	0.4593	0.101*
N7	0.8615 (3)	0.4698 (3)	0.2053 (2)	0.0421 (8)
H7	0.7861	0.4446	0.1672	0.050*
N8	0.7323 (4)	0.4673 (4)	0.2964 (2)	0.0664 (11)
H8A	0.6604	0.4426	0.2556	0.080*
H8B	0.7251	0.4784	0.3456	0.080*
C1	0.2094 (5)	0.1432 (6)	0.1040 (3)	0.0618 (13)
C2	0.2063 (7)	0.0900 (8)	0.0237 (4)	0.094 (2)
H2	0.2286	0.1435	−0.0100	0.112*
C3	0.1711 (9)	−0.0385 (10)	−0.0048 (5)	0.124 (3)
H3	0.1641	−0.0735	−0.0593	0.149*
C4	0.1446 (9)	−0.1207 (8)	0.0466 (6)	0.130 (3)
H4	0.1259	−0.2099	0.0274	0.156*
C5	0.1466 (6)	−0.0699 (6)	0.1232 (4)	0.0808 (17)
C6	0.1129 (8)	−0.1460 (6)	0.1820 (5)	0.126 (3)
H6A	0.1219	−0.0885	0.2333	0.189*
H6B	0.1741	−0.2038	0.1902	0.189*
H6C	0.0209	−0.1951	0.1606	0.189*
C7	0.4938 (5)	0.8408 (4)	0.2794 (2)	0.0474 (10)
C8	0.4871 (5)	0.9476 (5)	0.3355 (3)	0.0513 (11)
H8	0.4766	0.9398	0.3866	0.062*
C9	0.4962 (5)	1.0642 (5)	0.3144 (3)	0.0547 (12)
H9	0.4914	1.1366	0.3513	0.066*
C10	0.5125 (5)	1.0763 (4)	0.2382 (3)	0.0510 (11)
H10	0.5185	1.1565	0.2247	0.061*
C11	0.5198 (5)	0.9730 (4)	0.1841 (3)	0.0452 (10)
C12	0.5398 (6)	0.9723 (5)	0.1016 (3)	0.0676 (14)
H12A	0.5410	0.8862	0.0753	0.101*
H12B	0.6248	1.0290	0.1069	0.101*
H12C	0.4665	1.0014	0.0692	0.101*
C13	0.8223 (5)	0.1368 (5)	0.4407 (3)	0.0536 (12)
C14	0.7972 (6)	0.1029 (6)	0.5099 (3)	0.0726 (16)
H14	0.7820	0.1638	0.5504	0.087*
C15	0.7949 (6)	−0.0189 (8)	0.5181 (4)	0.086 (2)
H15	0.7779	−0.0417	0.5647	0.103*
C16	0.8170 (6)	−0.1111 (6)	0.4591 (5)	0.084 (2)
H16	0.8141	−0.1954	0.4655	0.101*
C17	0.8431 (5)	−0.0771 (5)	0.3914 (4)	0.0673 (15)
C18	0.8685 (7)	−0.1648 (6)	0.3227 (4)	0.110 (3)
H18A	0.8842	−0.1179	0.2823	0.166*
H18B	0.7906	−0.2347	0.2984	0.166*
H18C	0.9471	−0.1988	0.3427	0.166*
C19	0.8552 (4)	0.4883 (4)	0.2832 (2)	0.0434 (10)
C20	0.9768 (5)	0.5280 (4)	0.3444 (3)	0.0513 (11)
H20	0.9765	0.5424	0.3991	0.062*
C21	1.0970 (5)	0.5458 (5)	0.3242 (3)	0.0513 (11)
H21	1.1790	0.5707	0.3653	0.062*
C22	1.0979 (5)	0.5268 (4)	0.2419 (3)	0.0482 (11)
H22	1.1800	0.5408	0.2282	0.058*
C23	0.9793 (4)	0.4882 (4)	0.1830 (3)	0.0428 (10)
C24	0.9655 (5)	0.4629 (6)	0.0929 (3)	0.0738 (15)
H24A	0.8707	0.4364	0.0633	0.111*
H24B	1.0121	0.3957	0.0783	0.111*
H24C	1.0048	0.5403	0.0793	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.03694 (12)	0.03611 (12)	0.02651 (11)	0.00931 (9)	0.01195 (8)	0.00979 (8)
Bi2	0.03917 (13)	0.03067 (12)	0.02879 (11)	0.00442 (9)	0.00502 (9)	0.00606 (8)
Cl1	0.0429 (6)	0.0620 (7)	0.0507 (6)	0.0078 (5)	0.0165 (5)	0.0224 (5)
Cl2	0.0791 (8)	0.0442 (6)	0.0486 (6)	0.0211 (5)	0.0280 (6)	0.0170 (5)
Cl3	0.0524 (6)	0.0586 (7)	0.0340 (5)	0.0077 (5)	0.0125 (5)	0.0090 (4)
Cl4	0.0568 (7)	0.0446 (6)	0.0610 (7)	0.0003 (5)	−0.0039 (5)	0.0237 (5)
Cl5	0.0553 (7)	0.0571 (7)	0.0534 (6)	0.0082 (5)	0.0265 (5)	0.0047 (5)
Cl6	0.0538 (7)	0.0436 (6)	0.0631 (7)	0.0017 (5)	−0.0073 (5)	0.0026 (5)
Cl7	0.0804 (10)	0.0984 (11)	0.0720 (9)	0.0159 (8)	0.0196 (8)	0.0314 (8)
O1	0.075 (3)	0.089 (3)	0.078 (2)	−0.007 (2)	0.016 (2)	0.009 (2)
N1	0.054 (2)	0.054 (3)	0.070 (3)	0.0043 (19)	0.021 (2)	0.014 (2)
N2	0.101 (4)	0.066 (3)	0.091 (3)	0.015 (3)	0.046 (3)	0.033 (3)
N3	0.077 (3)	0.0354 (19)	0.0299 (17)	0.0145 (18)	0.0157 (17)	0.0055 (14)
N4	0.133 (4)	0.054 (3)	0.047 (2)	0.009 (3)	0.024 (2)	0.022 (2)
N5	0.050 (2)	0.041 (2)	0.058 (2)	0.0123 (17)	0.0093 (19)	0.0108 (18)
N6	0.113 (4)	0.050 (3)	0.098 (4)	0.029 (3)	0.040 (3)	0.015 (2)
N7	0.0369 (19)	0.053 (2)	0.0365 (18)	0.0087 (16)	0.0089 (15)	0.0119 (16)
N8	0.052 (2)	0.096 (3)	0.058 (2)	0.011 (2)	0.027 (2)	0.021 (2)
C1	0.047 (3)	0.073 (4)	0.071 (3)	0.008 (2)	0.025 (3)	0.021 (3)
C2	0.082 (5)	0.130 (7)	0.071 (4)	0.004 (4)	0.037 (4)	0.023 (4)
C3	0.112 (6)	0.144 (8)	0.083 (5)	−0.019 (6)	0.043 (5)	−0.037 (5)
C4	0.146 (8)	0.089 (6)	0.125 (7)	−0.025 (5)	0.059 (6)	−0.035 (5)
C5	0.072 (4)	0.059 (4)	0.101 (5)	−0.003 (3)	0.021 (3)	0.013 (3)
C6	0.143 (7)	0.078 (5)	0.148 (7)	−0.016 (4)	0.036 (6)	0.046 (5)
C7	0.056 (3)	0.047 (3)	0.039 (2)	0.006 (2)	0.013 (2)	0.0141 (19)
C8	0.056 (3)	0.067 (3)	0.031 (2)	0.013 (2)	0.015 (2)	0.007 (2)
C9	0.057 (3)	0.051 (3)	0.052 (3)	0.020 (2)	0.015 (2)	−0.004 (2)
C10	0.065 (3)	0.040 (3)	0.048 (3)	0.015 (2)	0.013 (2)	0.008 (2)
C11	0.052 (3)	0.041 (2)	0.045 (2)	0.012 (2)	0.014 (2)	0.014 (2)
C12	0.106 (4)	0.063 (3)	0.047 (3)	0.025 (3)	0.035 (3)	0.023 (2)
C13	0.048 (3)	0.048 (3)	0.059 (3)	0.011 (2)	0.008 (2)	0.006 (2)
C14	0.058 (3)	0.099 (5)	0.059 (3)	0.018 (3)	0.014 (3)	0.015 (3)
C15	0.060 (4)	0.117 (6)	0.086 (5)	0.010 (4)	0.013 (3)	0.056 (4)
C16	0.062 (4)	0.055 (4)	0.132 (6)	0.007 (3)	0.006 (4)	0.047 (4)
C17	0.055 (3)	0.043 (3)	0.097 (4)	0.008 (2)	0.009 (3)	0.016 (3)
C18	0.131 (6)	0.067 (4)	0.119 (5)	0.042 (4)	0.024 (5)	−0.020 (4)
C19	0.046 (2)	0.046 (2)	0.044 (2)	0.0137 (19)	0.017 (2)	0.0166 (19)
C20	0.056 (3)	0.062 (3)	0.035 (2)	0.012 (2)	0.008 (2)	0.015 (2)
C21	0.042 (3)	0.062 (3)	0.047 (3)	0.011 (2)	0.003 (2)	0.019 (2)
C22	0.039 (2)	0.062 (3)	0.047 (3)	0.014 (2)	0.014 (2)	0.016 (2)
C23	0.041 (2)	0.051 (3)	0.042 (2)	0.0134 (19)	0.0153 (19)	0.0137 (19)
C24	0.064 (3)	0.112 (5)	0.040 (3)	0.009 (3)	0.017 (2)	0.009 (3)

Geometric parameters (Å, º) top

Bi1—Cl1ⁱ	2.7121 (11)	C3—C4	1.401 (12)
Bi1—Cl1	2.7121 (11)	C3—H3	0.9300
Bi1—Cl2	2.6888 (10)	C4—C5	1.331 (10)
Bi1—Cl2ⁱ	2.6888 (10)	C4—H4	0.9300
Bi1—Cl3ⁱ	2.7175 (10)	C5—C6	1.484 (9)
Bi1—Cl3	2.7175 (10)	C6—H6A	0.9600
Bi2—Cl4	2.7066 (10)	C6—H6B	0.9600
Bi2—Cl5	2.7146 (10)	C6—H6C	0.9600
Bi2—Cl5ⁱⁱ	2.7146 (10)	C7—C8	1.386 (6)
Bi2—Cl6ⁱⁱ	2.6932 (10)	C8—C9	1.364 (7)
Bi2—Cl6	2.6932 (11)	C8—H8	0.9300
Bi2—Cl4ⁱⁱ	2.7066 (10)	C9—C10	1.390 (7)
O1—H1WA	0.8278	C9—H9	0.9300
O1—H1WB	0.8249	C10—C11	1.342 (6)
N1—C1	1.336 (6)	C10—H10	0.9300
N1—C5	1.357 (7)	C11—C12	1.487 (6)
N1—H1	0.8600	C12—H12A	0.9600
N2—C1	1.331 (6)	C12—H12B	0.9600
N2—H2A	0.8600	C12—H12C	0.9600
N2—H2B	0.8600	C13—C14	1.379 (8)
N3—C7	1.344 (5)	C14—C15	1.340 (9)
N3—C11	1.363 (5)	C14—H14	0.9300
N3—H3A	0.8600	C15—C16	1.376 (10)
N4—C7	1.340 (5)	C15—H15	0.9300
N4—H4A	0.8600	C16—C17	1.358 (9)
N4—H4B	0.8600	C16—H16	0.9300
N5—C13	1.348 (6)	C17—C18	1.481 (8)
N5—C17	1.350 (6)	C18—H18A	0.9600
N5—H5	0.8600	C18—H18B	0.9600
N6—C13	1.338 (6)	C18—H18C	0.9600
N6—H6D	0.8600	C19—C20	1.384 (6)
N6—H6E	0.8600	C20—C21	1.362 (7)
N7—C19	1.341 (5)	C20—H20	0.9300
N7—C23	1.358 (5)	C21—C22	1.402 (6)
N7—H7	0.8600	C21—H21	0.9300
N8—C19	1.334 (5)	C22—C23	1.342 (6)
N8—H8A	0.8600	C22—H22	0.9300
N8—H8B	0.8600	C23—C24	1.498 (6)
C1—C2	1.392 (8)	C24—H24A	0.9600
C2—C3	1.340 (11)	C24—H24B	0.9600
C2—H2	0.9300	C24—H24C	0.9600

Cl2—Bi1—Cl2ⁱ	180.0	C5—C6—H6A	109.5
Cl2—Bi1—Cl1ⁱ	88.75 (3)	C5—C6—H6B	109.5
Cl2ⁱ—Bi1—Cl1ⁱ	91.25 (3)	H6A—C6—H6B	109.5
Cl2—Bi1—Cl1	91.25 (3)	C5—C6—H6C	109.5
Cl2ⁱ—Bi1—Cl1	88.75 (3)	H6A—C6—H6C	109.5
Cl1ⁱ—Bi1—Cl1	180.0	H6B—C6—H6C	109.5
Cl2—Bi1—Cl3ⁱ	90.89 (3)	N4—C7—N3	117.9 (4)
Cl2ⁱ—Bi1—Cl3ⁱ	89.11 (3)	N4—C7—C8	123.9 (4)
Cl1ⁱ—Bi1—Cl3ⁱ	88.60 (3)	N3—C7—C8	118.2 (4)
Cl1—Bi1—Cl3ⁱ	91.40 (3)	C9—C8—C7	118.7 (4)
Cl2—Bi1—Cl3	89.11 (3)	C9—C8—H8	120.6
Cl2ⁱ—Bi1—Cl3	90.89 (3)	C7—C8—H8	120.6
Cl1ⁱ—Bi1—Cl3	91.40 (3)	C8—C9—C10	120.8 (4)
Cl1—Bi1—Cl3	88.60 (3)	C8—C9—H9	119.6
Cl3ⁱ—Bi1—Cl3	180.0	C10—C9—H9	119.6
Cl6ⁱⁱ—Bi2—Cl6	180.00 (5)	C11—C10—C9	120.5 (4)
Cl6ⁱⁱ—Bi2—Cl4ⁱⁱ	89.13 (3)	C11—C10—H10	119.8
Cl6—Bi2—Cl4ⁱⁱ	90.87 (3)	C9—C10—H10	119.8
Cl6ⁱⁱ—Bi2—Cl4	90.87 (3)	C10—C11—N3	117.5 (4)
Cl6—Bi2—Cl4	89.13 (3)	C10—C11—C12	126.2 (4)
Cl4ⁱⁱ—Bi2—Cl4	180.00 (3)	N3—C11—C12	116.3 (4)
Cl6ⁱⁱ—Bi2—Cl5	92.40 (4)	C11—C12—H12A	109.5
Cl6—Bi2—Cl5	87.60 (4)	C11—C12—H12B	109.5
Cl4ⁱⁱ—Bi2—Cl5	91.47 (4)	H12A—C12—H12B	109.5
Cl4—Bi2—Cl5	88.53 (4)	C11—C12—H12C	109.5
Cl6ⁱⁱ—Bi2—Cl5ⁱⁱ	87.60 (4)	H12A—C12—H12C	109.5
Cl6—Bi2—Cl5ⁱⁱ	92.40 (4)	H12B—C12—H12C	109.5
Cl4ⁱⁱ—Bi2—Cl5ⁱⁱ	88.53 (4)	N6—C13—N5	116.6 (5)
Cl4—Bi2—Cl5ⁱⁱ	91.47 (4)	N6—C13—C14	125.0 (5)
Cl5—Bi2—Cl5ⁱⁱ	180.00 (3)	N5—C13—C14	118.5 (5)
H1WB—O1—H1WA	114.5	C15—C14—C13	119.2 (6)
C1—N1—C5	124.6 (5)	C15—C14—H14	120.4
C1—N1—H1	117.7	C13—C14—H14	120.4
C5—N1—H1	117.7	C14—C15—C16	121.6 (6)
C1—N2—H2A	120.0	C14—C15—H15	119.2
C1—N2—H2B	120.0	C16—C15—H15	119.2
H2A—N2—H2B	120.0	C17—C16—C15	119.0 (6)
C7—N3—C11	124.3 (4)	C17—C16—H16	120.5
C7—N3—H3A	117.9	C15—C16—H16	120.5
C11—N3—H3A	117.9	N5—C17—C16	118.8 (6)
C7—N4—H4A	120.0	N5—C17—C18	115.7 (6)
C7—N4—H4B	120.0	C16—C17—C18	125.4 (6)
H4A—N4—H4B	120.0	C17—C18—H18A	109.5
C13—N5—C17	122.8 (5)	C17—C18—H18B	109.5
C13—N5—H5	118.6	H18A—C18—H18B	109.5
C17—N5—H5	118.6	C17—C18—H18C	109.5
C13—N6—H6D	120.0	H18A—C18—H18C	109.5
C13—N6—H6E	120.0	H18B—C18—H18C	109.5
H6D—N6—H6E	120.0	N8—C19—N7	117.9 (4)
C19—N7—C23	124.2 (4)	N8—C19—C20	124.4 (4)
C19—N7—H7	117.9	N7—C19—C20	117.7 (4)
C23—N7—H7	117.9	C21—C20—C19	119.7 (4)
C19—N8—H8A	120.0	C21—C20—H20	120.1
C19—N8—H8B	120.0	C19—C20—H20	120.1
H8A—N8—H8B	120.0	C20—C21—C22	120.3 (4)
N2—C1—N1	118.7 (5)	C20—C21—H21	119.8
N2—C1—C2	124.3 (6)	C22—C21—H21	119.8
N1—C1—C2	117.0 (6)	C23—C22—C21	119.5 (4)
C3—C2—C1	119.8 (7)	C23—C22—H22	120.3
C3—C2—H2	120.1	C21—C22—H22	120.3
C1—C2—H2	120.1	C22—C23—N7	118.6 (4)
C2—C3—C4	120.8 (7)	C22—C23—C24	125.0 (4)
C2—C3—H3	119.6	N7—C23—C24	116.3 (4)
C4—C3—H3	119.6	C23—C24—H24A	109.5
C5—C4—C3	119.4 (7)	C23—C24—H24B	109.5
C5—C4—H4	120.3	H24A—C24—H24B	109.5
C3—C4—H4	120.3	C23—C24—H24C	109.5
C4—C5—N1	118.3 (7)	H24A—C24—H24C	109.5
C4—C5—C6	124.6 (7)	H24B—C24—H24C	109.5
N1—C5—C6	117.0 (6)

C5—N1—C1—N2	−177.8 (5)	C17—N5—C13—N6	−179.1 (5)
C5—N1—C1—C2	1.9 (8)	C17—N5—C13—C14	0.3 (7)
N2—C1—C2—C3	−179.6 (7)	N6—C13—C14—C15	178.8 (5)
N1—C1—C2—C3	0.7 (10)	N5—C13—C14—C15	−0.5 (8)
C1—C2—C3—C4	−3.6 (13)	C13—C14—C15—C16	0.0 (9)
C2—C3—C4—C5	4.1 (14)	C14—C15—C16—C17	0.7 (10)
C3—C4—C5—N1	−1.6 (12)	C13—N5—C17—C16	0.4 (8)
C3—C4—C5—C6	176.5 (8)	C13—N5—C17—C18	179.4 (5)
C1—N1—C5—C4	−1.4 (10)	C15—C16—C17—N5	−0.9 (9)
C1—N1—C5—C6	−179.6 (6)	C15—C16—C17—C18	−179.8 (6)
C11—N3—C7—N4	179.8 (4)	C23—N7—C19—N8	179.6 (4)
C11—N3—C7—C8	−0.3 (7)	C23—N7—C19—C20	−0.4 (6)
N4—C7—C8—C9	−179.6 (5)	N8—C19—C20—C21	179.5 (4)
N3—C7—C8—C9	0.5 (7)	N7—C19—C20—C21	−0.4 (7)
C7—C8—C9—C10	−0.3 (7)	C19—C20—C21—C22	1.3 (7)
C8—C9—C10—C11	0.0 (7)	C20—C21—C22—C23	−1.4 (7)
C9—C10—C11—N3	0.2 (6)	C21—C22—C23—N7	0.5 (6)
C9—C10—C11—C12	−178.7 (5)	C21—C22—C23—C24	−179.3 (5)
C7—N3—C11—C10	0.0 (7)	C19—N7—C23—C22	0.4 (6)
C7—N3—C11—C12	179.0 (4)	C19—N7—C23—C24	−179.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1WB···Cl7	0.83	2.28	3.051 (3)	157
N2—H2B···Cl5	0.86	2.65	3.432 (3)	151
N4—H4B···Cl2	0.86	2.48	3.307 (3)	163
N5—H5···Cl7	0.86	2.21	3.059 (3)	168
N7—H7···Cl4	0.86	2.38	3.204 (3)	161
N8—H8B···Cl1	0.86	2.51	3.343 (3)	164
O1—H1WA···Cl3ⁱⁱⁱ	0.83	2.49	3.290 (3)	163
N1—H1···O1^iv	0.86	1.91	2.774 (3)	177

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

Experimental details

Crystal data
Chemical formula	(C₆H₉N₂)₄[BiCl₆]Cl·H₂O
M_r	911.75
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	10.3345 (7), 10.7605 (7), 17.2673 (11)
α, β, γ (°)	100.337 (1), 103.737 (1), 99.228 (1)
V (Å³)	1793.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.47
Crystal size (mm)	0.42 × 0.31 × 0.25

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.153, 0.185
No. of measured, independent and observed [I > 2σ(I)] reflections	9489, 6240, 5171
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.070, 1.07
No. of reflections	6240
No. of parameters	373
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −1.13

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1WB···Cl7	0.825	2.28	3.051 (3)	157
N2—H2B···Cl5	0.86	2.65	3.432 (3)	151
N4—H4B···Cl2	0.86	2.48	3.307 (3)	163
N5—H5···Cl7	0.86	2.21	3.059 (3)	168
N7—H7···Cl4	0.86	2.38	3.204 (3)	161
N8—H8B···Cl1	0.86	2.51	3.343 (3)	164
O1—H1WA···Cl3ⁱ	0.828	2.49	3.290 (3)	163
N1—H1···O1ⁱⁱ	0.86	1.91	2.774 (3)	177

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

References

Albrecht, A. S., Landee, C. P. & Turnbull, M. M. (2003). J. Chem. Crystallogr. 33, 269–276. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Feng, W.-J., Wang, H.-B., Ma, X.-J., Li, H.-Y. & Jin, Z.-M. (2007). Acta Cryst. E63, m1786–m1787. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Inuzuka, K. & Fujimoto, A. (1986). Spectrochim. Acta Part A, 42, 929–937. CrossRef Web of Science Google Scholar
Inuzuka, K. & Fujimoto, A. (1990). Bull. Chem. Soc. Jpn, 63, 971–975. CrossRef CAS Web of Science Google Scholar
Ishikawa, H., Iwata, K. & Hamaguchi, H. (2002). J. Phys. Chem. A, 106, 2305–2312. Web of Science CrossRef CAS Google Scholar
Jin, Z. M., Pan, Y. J., Hu, M. L. & Shen, L. (2001). J. Chem. Crystallogr. 31, 191–195. Web of Science CSD CrossRef CAS Google Scholar
Jin, Z. M., Pan, Y. J., Liu, J. G. & Xu, D. J. (2000). J. Chem. Crystallogr. 30, 195–198. Web of Science CSD CrossRef CAS Google Scholar
Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43–m45. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Luque, A., Sertucha, J., Lezama, L., Rojo, T. & Roman, P. (1997). J. Chem. Soc. Dalton Trans. pp. 847–854. CSD CrossRef Web of Science Google Scholar
Nahringbauer, I. & Kvick, Å. (1977). Acta Cryst. B33, 2902–2905. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Ren, P., Su, N. B., Qin, J. G., Day, M. W. & Chen, C. T. (2002). Chin. J. Struct. Chem. 33, 38–41. Google Scholar
Rivas, J. C. M., Salvagni, E., Rosales, R. T. M. & Parsons, S. (2003). Dalton Trans. pp. 3339–3349. Web of Science CSD CrossRef Google Scholar
Salwa, N., Fatma, Z. & Hafed, E. F. (2008). J. Chem. Crystallogr. 38, 729–732. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, G., Fu, M. L., Cai, L. Z., Zhang, Z. J., Guo, G. C. & Huang, J. S. (2006). Chin. J. Struct. Chem. 25, 338–342. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m887

doi:10.1107/S1600536809025446

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Tetra­kis(2-amino-6-methyl­pyridinium) hexa­chloridobismuthate(III) chloride monohydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

Tetrakis(2-amino-6-methylpyridinium) hexachloridobismuthate(III) chloride monohydrate