Chloridobis(1,10-phenanthroline)zinc(II) tetra­chlorido(1,10-phenan­throline)bis­muthate(III) monohydrate

Chunlei Song; Wenxiang Chai; Li Song; Yunyun Yang; Jian Lin

doi:10.1107/S1600536810052682

. 2010 Dec 24;67(Pt 1):m109–m110. doi: 10.1107/S1600536810052682

Chloridobis(1,10-phenanthroline)zinc(II) tetrachlorido(1,10-phenanthroline)bismuthate(III) monohydrate

Chunlei Song ^a, Wenxiang Chai ^a,^*, Li Song ^b, Yunyun Yang ^a, Jian Lin ^a

PMCID: PMC3050139 PMID: 21522522

Abstract

In the crystal structure of the title monohydrate salt, [ZnCl(C₁₂H₈N₂)₂][BiCl₄(C₁₂H₈N₂)]·H₂O, the ionic components are linked into three-dimensional supramolecular channels by five pairs of C—H⋯Cl hydrogen bonds and π–π stacking interactions with an interplanar distance of 3.643 (2) Å. The solvent water molecules are lodged in the channels.

Related literature

For related bismuth compounds, see: James et al. (2000 ▶); Jarraya et al. (1995 ▶); Bowmaker et al. (1998 ▶). For a related [Zn(phen)₂Cl]⁺ coordinated cation structure, see: Yu & Zhang (2006 ▶). For supramolecular systems containing halometallate groups as their main component, see: Mitzi & Brock (2001 ▶); Zhu et al. (2003 ▶); Papavassiliou et al. (1995 ▶); Pohl et al. (1994 ▶); Carmalt et al. (1995 ▶). For π–π interactions, see: Chandrasekhar et al. (2006 ▶). For hydrogen bonds, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

[ZnCl(C₁₂H₈N₂)₂][BiCl₄(C₁₂H₈N₂)]·H₂O
M _r = 1010.25
Triclinic,
a = 9.748 (2) Å
b = 13.694 (4) Å
c = 14.249 (4) Å
α = 86.848 (7)°
β = 74.660 (5)°
γ = 80.692 (7)°
V = 1810.0 (8) Å³
Z = 2
Mo Kα radiation
μ = 5.93 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.200, T _max = 0.269
13923 measured reflections
8140 independent reflections
7571 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.061
S = 1.03
8140 reflections
451 parameters
H-atom parameters constrained
Δρ_max = 1.76 e Å⁻³
Δρ_min = −1.03 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052682/bg2383sup1.cif

e-67-0m109-sup1.cif^{(31.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052682/bg2383Isup2.hkl

e-67-0m109-Isup2.hkl^{(398.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cl3ⁱ	0.93	2.82	3.588 (4)	141
C6—H6⋯Cl4ⁱⁱ	0.93	2.82	3.637 (4)	147
C10—H10⋯Cl5ⁱⁱⁱ	0.93	2.80	3.707 (4)	164
C15—H15⋯Cl1^iv	0.93	2.69	3.579 (4)	160
C25—H25⋯Cl2^v	0.93	2.80	3.506 (4)	134

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We are grateful for financial support from the National Natural Science Foundation of China (project 20803070) and the Natural Science Foundation of Zhejiang Province (project Y4100610).

supplementary crystallographic information

Comment

Supramolecular compounds are attractting much interest due to their importance for the study of biological systems and their potential applications in material research, as sensors, gas storage and catalysis, or as optoelectronic and magnetic devices. Recently, many supramolecular systems containing halometallate groups as their main component have been reported (Mitzi et al., 2001; Zhu et al., 2003; Papavassiliou et al., 1995; Pohl et al., 1994; Carmalt et al., 1995). Here, we present one of those supramolecular compounds [Zn(phen)₂Cl][Bi(phen)Cl₄].H₂O (I), composed of an halometallate main anionic group ( [Bi(phen)Cl₄]^-, phen = C₁₂H₈N₂ = 1,10-phenanthroline), a coordinated cation containing a transition-metal, ( [Zn(phen)₂Cl]⁺ ) and a solvent H₂O.

In compound (I), the Bi atom is located in a distorted octahedral enviroment of four chlorine atoms and two nitrogen atoms from the phen ligand. In this BiN₂Cl₄ octahedron, the Bi1—N1 = 2.505 (3) Å, Bi1—N2 = 2.474 (3) Å, Bi1—Cl1 = 2.7272 (10) Å, Bi1—Cl2 = 2.6708 (10) Å, Bi1—Cl3 = 2.7841 (12) Å, Bi1—Cl4 = 2.5853 (11) Å. All bond lengths are within commonly accepted values in the literature (James et al., 2000; Jarraya et al., 1995). The crystal structure of the [Bi(phen)I₄]^- salt has already been determined (Bowmaker et al., 1998), and the Bi atom therein is coordinated in a similar distorted octahedron by two N atoms and four I atoms.

The axial and equatorial I—Bi—I bond angles therein are 165.81 (3) and 111.59 (5)° as compared to Cl3—Bi1—Cl4 = 169.50 (4) and Cl1—Bi1—Cl2 = 117.18 (4)° , respectively. The large deviations of these bond angles from those in the perfect octahedron are probably derived from the inert electron pair effect of the Bi atom. A [Zn(phen)₂Cl]⁺ cation balances charge in the salt. This coordinated cation has been reported elsewhere (Yu et al., 2006), with the Zn atom also located in a distorted trigonal-bipyramidal coordination.

In the crystal structure of I, hydrogen bonds and offset face-to face aromatic π-π stacking interactions lead to the formation of a three-dimensional supramolecular channel, and the solvent water molecules are located within. Firstly, the [Bi(phen)Cl₄]^- anion and [Zn(phen)₂Cl]⁺ cations connect to each other by hydrogen bonding interactions (details listed in Table 1), and the result is the building up a supramolecular sheet. The hydrogen bonding data are in the normal range (Desiraju et al., 1999). Adjacent sheets are joined together by way of π-π stacking interactions between two phen ligands to form a three-dimensional framework (Chandrasekhar et al., 2006). The phen skeletons are arranged in a parallel fashion; ring 1 (N5/C25—C29) [symmetry code: (x, y, z)] of one cation stacks with ring 2 (C28—C33) [symmetry code: (1 - x, -y, 1 - z)] of a neighbouring cation with an interplanar distance of 3.643 (2) Å. As a result, through these π-π stacking interactions, the supramolecular sheets stack one by one to present a firm three-dimensional supramolecular channel, where the water molecules are located. Even if the water hydrogens could not be determined in the difference Fourier, the geometry around O1 strongly suggests H-bonding interactions between O1 and the neighbouring Cl atoms (O1···Cl3 : 3.3723 (7) Å ; O1···Cl5: 3.3776 (6) Å ).

Experimental

The title compound (I) was synthesized by hydrothermal reaction of ZnCl₂ (136 mg, 1 mmol), Bi(NO₃)₃.5H₂O (250 mg, 0.52 mmol), oxalic acid (380 mg, 3 mmol) and 1,10-phenanthroline monohydrate (400 mg, 2 mmol) in 5 mL water. The mixture was heated to 393 K at the rate of 20 K/h, and kept at this temperature for 2 days and then cooled to room temperature at the rate of 2 K/h. The yellow crystals of (I) were obtained in a yield of 18% (73 mg). Anal. Calc. for C₃₆H₂₆BiCl₅N₆OZn (%): C, 42.80; H, 2.59; N, 8.32; O, 1.58. Found: C, 42.96; H, 2.77; N, 8.23;O, 1.74. Crystals of (I) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.