Poly[[tetra-μ-cyanido-κ8 C:N-dodeca-cyanido-κ12 C-tris­(N,N-di­methyl­formamide-κO)tris­(methanol-κO)tris­(3,4,7,8-tetra­methyl-1,10-phenanthroline-κ2 N,N′)trimanganese(II)ditungstate(V)] dihydrate]

Fei-Lin Yang; Dan Yang

doi:10.1107/S1600536814007235

. 2014 Apr 5;70(Pt 5):m170–m171. doi: 10.1107/S1600536814007235

Poly[[tetra-μ-cyanido-κ⁸ C:N-dodeca-cyanido-κ¹² C-tris(N,N-dimethylformamide-κO)tris(methanol-κO)tris(3,4,7,8-tetramethyl-1,10-phenanthroline-κ² N,N′)trimanganese(II)ditungstate(V)] dihydrate]

Fei-Lin Yang ^a,^*, Dan Yang ^a

PMCID: PMC4011295 PMID: 24860305

Abstract

The asymmetric unit of the title compound, {[Mn₃{W(CN)₈}₂(C₁₆H₁₆N₂)₃(C₃H₇NO)₃(CH₃OH)₃]·2H₂O}_n, consists of three [Mn(N,N-dimethylformamide)(methanol)(3,4,7,8-tetramethyl-1,10-phenanthroline)]²⁺ cations, two [W(CN)₈]³⁻ anions and two water molecules. Each water molecule is disordered over three sets of sites, with a refined occupancy ratio of 0.310 (9):0.275 (9):0.415 (9) for one molecule and 0.335 (9):0.288 (9):0.377 (9) for the other molecule. The Mn^II atoms exhibit a distorted octahedral geometry, while the W^V atoms adopt a distorted square-antiprismatic geometry. The Mn^II and W^V atoms are linked alternatively through cyanide groups, forming a tetranuclear 12-atom rhombic metallacycle. Adjacent metallacycles are further connected by μ₂-bridging cyanide anions, generating a 3,2-chain structure running parallel to [101]. Interchain π–π interactions are observed [centroid–centroid distances = 3.763 (3) and 3.620 (2) Å].

Related literature

For general background to octacyanidometalate-based compounds, see: Nowicka et al. (2012 ▶); Sieklucka et al. (2011 ▶). For related structures, see: Li et al. (2002 ▶, 2003 ▶); Withers et al. (2007 ▶). For the synthesis of octacyanidotungstate(V), see: Bok et al. (1975 ▶).

Experimental

Crystal data

[Mn₃W₂(CN)₁₆(C₁₆H₁₆N₂)₃(C₃H₇NO)₃(CH₄O)₃]·2H₂O
M _r = 2009.20
Triclinic,
a = 15.5038 (17) Å
b = 16.4958 (18) Å
c = 21.4067 (13) Å
α = 70.008 (2)°
β = 82.663 (3)°
γ = 66.129 (2)°
V = 4704.4 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.89 mm⁻¹
T = 291 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.50, T _max = 0.60
35664 measured reflections
17934 independent reflections
14773 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.117
S = 1.05
17934 reflections
1078 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.38 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814007235/rz5113sup1.cif

e-70-0m170-sup1.cif^{(1.1MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007235/rz5113Isup2.hkl

e-70-0m170-Isup2.hkl^{(981.5KB, hkl)}

CCDC reference: 994877

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

1. Comment

Recently, increasing attention has been put into the design and syntheses of functional materials, among which octacyanometalates [M(CN)₈]ⁿ^- (M = Mo, W; n = 3, 4) with flexible coordination modes and low symmetries have been widely studied (Nowicka et al., 2012; Sieklucka et al., 2011). For such systems, chelated ligands are usually employed to control on metal centers for CN-bridging, hence generating low-dimensional architectures rather than extended networks. As a part of a detailed study of cyano-bridged assemblies, we used [W(CN)₈]^3- as precursor to react with Mn²⁺ ions and the chelated ligand 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), and a new bimetallic compound with 3,2 chain structure was obtained.

The asymmetric unit of the title compound (Fig. 1) consists of three [Mn(3,4,7,8-tetramethyl-1,10-phenanthroline)(methanol)(N,N-dimethylformamide)]²⁺ cations, two [W(CN)₈]^3- anions, and two disordered water molecules of crystallization. The Mn atoms exhibit a distorted octahedral geometry, where the coordination sites are occupied by two nitrogen atoms of one tmphen ligand, two bridging cyanide groups and two oxygen atoms of a DMF and a CH₃OH molecule. The eight-coordinated W centres adopt a distorted square antiprismatic geometry, where three cyanide groups bridge to adjacent three Mn atoms and the others are terminal. As a result, the W1 and Mn1 atoms are connected alternatively by cyanide groups to form a tetranuclear 12-atom rhombic metallacycle, Mn1₂W1₂(CN)₄, with the W1 and Mn1 centres located at the vertexes and the cyanide groups forming the sides. Similarly, another rhombic cycle, Mn3₂W2₂(CN)₄, is also formed by the connection of W2 and Mn3 atoms through cyanide anions. The Mn2 atoms further link alternatively adjacent circles through –CN–Mn2—NC– linkages, generating a 3,2-chain structure parallel to [1 0 1]. Adjacent chains are linked by π-π interactions involving the phenanthroline rings systems, with centroid-to-centroid distances of 3.763 (3) and 3.620 (2) Å. The structural feature observed in the title compound has been also found in other octacyanometalate-based materials (Li et al., 2002; Li et al., 2003; Withers et al., 2007).

2. Experimental

The title compound was prepared at room temperature by slow diffusion of a CH₃OH/DMF solution (1:1 v/v) containing [HN(n-C₄H₉)₃[W(CN)₈] (0.05 mmol) (Bok et al., 1975) and MnCl₂·4H₂O (0.15 mmol) into a methanol solution of tmphen (0.1 mmol). After about two weeks, brown block crystals were obtained on slow evaporation of the solvent.