Bis(tetraphenylphosphonium) tetra­cyanido­nitridochromate(V) dihydrate

Magnus Schau-Magnussen; Jesper Bendix

doi:10.1107/S1600536811002108

. 2011 Jan 22;67(Pt 2):m227–m228. doi: 10.1107/S1600536811002108

Bis(tetraphenylphosphonium) tetracyanidonitridochromate(V) dihydrate

Magnus Schau-Magnussen ^a, Jesper Bendix ^a,^*

PMCID: PMC3051685 PMID: 21522886

Abstract

In the title compound, (C₂₄H₂₀P)₂[Cr(CN)₄(N)]·2H₂O, the complex anion exhibits a square-based pyramidal geometry around the central Cr^V atom, which is coordinated by a nitride ligand in the apical position and by four cyanide ligands in the equatorial plane. The chromium atom is located 0.4493 (13) Å out of the plane formed by the ligating C atoms of the cyanide ligands. The water molecules of crystallization form intermolecular O—H⋯N hydrogen bonds to the N atoms of two cyanide ligands of neighbouring complex anions, forming an infinite hydrogen-bonded chain parallel to [011] of water molecules and [Cr(N)(CN)₄]²⁻ anions. The terminal nitride ligands are not engaged in intermolecular interactions.

Related literature

For related structures of nitridocyanidometalates, see: Baldas et al. (1990 ▶); Bendix et al. (1998 ▶, 2000 ▶); Britten et al. (1993 ▶); Che et al. (1989 ▶); Purcell et al. (1991 ▶); van der Westhuizen et al. (1994 ▶). For general background to Cr^V nitrido complexes, see: Birk & Bendix (2003 ▶).

Experimental

Crystal data

(C₂₄H₂₀P)₂[Cr(CN)₄(N)]·2H₂O
M _r = 884.86
Triclinic,
a = 11.996 (5) Å
b = 12.387 (5) Å
c = 16.721 (4) Å
α = 98.34 (3)°
β = 110.01 (2)°
γ = 90.52 (4)°
V = 2305.3 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 122 K
0.12 × 0.09 × 0.06 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: integration (Gaussian; Coppens, 1970 ▶) T _min = 0.952, T _max = 0.980
72047 measured reflections
8118 independent reflections
6480 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.092
S = 1.10
8118 reflections
571 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002108/fj2383sup1.cif

e-67-0m227-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002108/fj2383Isup2.hkl

e-67-0m227-Isup2.hkl^{(396.9KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cr—N1	1.538 (2)
Cr—C2	2.066 (3)
Cr—C3	2.040 (3)
Cr—C4	2.068 (3)
Cr—C5	2.049 (3)

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N1—Cr—C2	99.23 (11)
N1—Cr—C3	105.79 (11)
N1—Cr—C4	99.95 (11)
N1—Cr—C5	105.70 (11)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N2	0.86 (2)	2.23 (2)	3.065 (3)	167 (4)
O1—H1B⋯N2ⁱ	0.85 (2)	2.18 (2)	3.035 (3)	177 (4)
O2—H2A⋯N4	0.81 (2)	2.16 (2)	2.973 (3)	178 (3)
O2—H2B⋯N4ⁱⁱ	0.82 (2)	2.22 (2)	3.039 (3)	173 (3)

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Symmetry codes: (i) Inline graphic ; (ii) .

Table 3. Comparative geometric parameters (Å) of cyanidonitridometalates of chromate(V) and manganate(V).

	[Cr(CN)₄(N)]^2−a	[Mn(CN)₄(N)]^2−b	[Cr(CN)₅(N)]^3−c	[Mn(CN)₅(N)]^3−c
M N	1.538 (2)	1.507 (2)	1.594 (9)	1.499 (8)
M—C_cis	2.040 (3)–2.068 (3)	1.974 (2)–1.995 (2)	2.039 (7)–2.08 (2)	1.985 (6)–2.001 (7)
M—C_trans			2.299 (12)	2.243 (7)
M—oop^d	0.449	0.436	0.255	0.222

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Notes: (a) this work; (b) Bendix et al. (1998 ▶); (c) Bendix et al. (2000 ▶); (d) oop = out-of-plane.

supplementary crystallographic information

Comment

Crystal structures of mononuclear nitridocyanidometalates have previously been reported for technetium (Baldas et al., 1990), rhenium (Britten et al., 1993; Purcell et al., 1991), osmium (Che et al., 1989; van der Westhuizen et al., 1994). We have previously reported the syntheses and crystal stuctures of six coordinated pentacyanidonitridometalates of chromate(V) and manganate(V) (Bendix et al., 2000) as well as the synthesis of the title compound and crystal structure of the isostructural manganese compound (Bendix et al., 1998). In all the cases the nitride ligand imposes a strong trans-influence on the auxiliary ligands evidenced by a significant elongation of the M—X_trans bond length and the displacement of the metal out of the plane spanned by cyanido-carbon atoms.

The molecular structure of the title compound is shown in Fig. 1. The Cr^V has a square based pyramidal coordination geometry frequently seen for Cr^V nitrido complexes (Birk & Bendix, 2003). The nitride occupy the apical position and the four cyanide ligands span the equatorial plane. The Cr atom is displaced 0.4493 (13) Å out of the plane spanned by the cyanido-carbon atoms. Selected geometric parameters are listed in Table 1. The water of crystallization form weak intermolecular hydrogen bonds (Table 2) to two nitrogen atoms of two cyanide ligands as depicted in Fig. 2. The complex anions and water molecules form an infinite chain. For comparison, Table 3 lists selected geometric parameters of the isostructural manganese compound and the six coordinated pentacyanidonitridometalates of chromate(V) and manganate(V).

Experimental

The title compound was prepared as previously reported (Bendix et al., 1998). A solution of [Cr(N)(CN)₄]^2- (0.10 g; 0.21 mmol) in water (6.5 ml) was allowed to slowly diffuse into a solution of [PPh₄]Cl (0.20 g; 0.53 mmol) in water (15 ml). The pale yellow crystals that precipitated were collected by filtration, washed with water, and air-dried. Yield: 0.16 g (86%).