trans-Di­chloro(1,5,9,13-tetra­methyl-1,5,9,13-tetr­aza­cyclo­hexa­decane-[kappa]⁴N)ruthenium(III) triiodide

In the title complex, [RuCl₂(C₁₆H₃₆N₄)]I₃, the overall symmetry of the centrosymmetric cation is approximately C_2h and the I anions are slightly asymmetric. The I...I distance is 4.313 (1) Å. The cations and the linear anions are arranged in alternate layers and thus form the intercalating structure.

S1. Comment

Crystal engineering has become an area of great interest over recent years (Roboson et al., 1992; Desiraju, 1989; Zuo et al., 1998). Different cation networks have been developed through ligand design and the use of different transition metal ions such as Zn²⁺, Cd²⁺, Cu⁺ and Ag⁺ (Xiong et al., 1999 and references therein). However, the only examples of anionic and nonzeolitic supramolecular architectures are iodine-rich compounds (Blake et al., 1996, 1998). The synthesis and structural characterization of polyiodides continue to be an active area of investigation. Metal thioether macrocyclic complexes have been used as templating agents in the preparation of polymeric one-dimensional chain structures or infinite two or three-dimensional networks, in which the polyiodide arrays form unusual supramolecular inorganic matrices. High-valent oxo complexes of ruthenium are of interest because of their potential usefulness as oxidative catalysts (Mak et al., 1985). Several trichloro ruthenium complexes of macrocyclic amines have been studied by Che et al. (1986). Owing to their strong σ donor properties, the tetradentate macrocyclic tertiary amines, such as 16-TMC (1,5,9,13-tetramethyl-1,5,9,13-tetrazacyclohexadecane) are introduced being capable of stabilizing high valent metal-oxo complexes. In this paper, we choose the cation, [Ru(16-TMC)Cl₂]+, (I), as a template to synthesize extended polyiodide arrays. \sch

The asymmetric unit contains a half molecule and the overall symmetry of the centrosymmetric cation is approximately C₂h. The Ru—N bond lengths, Ru1—N1 = 2.266 (4) and Ru1—N2 = 2.267 (3) Å, are slightly longer than that in [Ru(16-TMC)O₂]²⁺ [2.17–2.22 (2) Å] (Mak et al., 1985). The anions are slightly asymmetric I₃⁻ ions with bond distances I1—I2 = 2.883 (1) and I2—I3 = 2.949 (1) Å, which is different from the symmetric I₃⁻ in [Ag([18]aneS₆)I₃] (Blake et al., 1995). The Ru—N and Ru—Cl distances are slightly longer than the values reported in the literature (Allen et al., 1989). The 16-membered ring leaving the Ru and Cl atoms is essentially planar and the C4 and C8 atoms are in axial orientation. The six-membered rings adopt twist-boat conformation.

The I···I (x − 1/2, y, −z + 1/2) distance is 4.313 (1) Å. The cations and the linear anions are arranged as alternate layers and thus forming the intercalating structure along the b direction.

S2. Experimental

A solution of diiodine (76.2 mg, 0.30 mmol) in acetonitrile (5 ml) was added to the solution of [Ru(16-TMC)Cl₂]Cl (98.3 mg, 0.20 mmol) in acetontrile (10 ml). After slow evaporation of the solvent, dark-red crystals were formed and washed with acetontrile [yield 125.6 mg (75.0%)].

S3. Refinement

All the hydrogen atoms were fixed at calculated distances.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Trans-dichloro (1, 5, 9, 13-tetramethyl-1, 5, 9, 13-tetrazacyclohexadecane) Ruthenium(III)triiodide

Crystal data

[RuCl2(C16H36N4)]I3	F(000) = 1588
Mr = 837.16	Dx = 2.212 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 6317 reflections
a = 7.7198 (1) Å	θ = 1.6–28.4°
b = 20.4639 (3) Å	µ = 4.53 mm^−1
c = 15.9112 (2) Å	T = 293 K
V = 2513.61 (6) Å^3	Needle, red
Z = 4	0.18 × 0.16 × 0.14 mm

Data collection

Siemens SMART CCD area detector diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2682 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 1.6°
ω scans	h = −10→10
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996)	k = −27→27
Tmin = 0.462, Tmax = 0.530	l = −11→21
18757 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0275P)^2 + 6.6027P] where P = (Fo^2 + 2Fc^2)/3
3199 reflections	(Δ/σ)max = 0.001
124 parameters	Δρmax = 1.29 e Å^−3
0 restraints	Δρmin = −1.96 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. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ru1	0.0000	0.5000	0.0000	0.01963 (10)
Cl1	0.24338 (13)	0.51679 (6)	−0.08482 (7)	0.0393 (3)
I1	0.12920 (11)	0.2500	0.31048 (4)	0.0846 (2)
I2	0.07460 (5)	0.2500	0.48974 (3)	0.03676 (12)
I3	0.00071 (9)	0.2500	0.67157 (3)	0.06406 (18)
N1	0.1098 (5)	0.40085 (17)	0.0343 (2)	0.0334 (8)
N2	0.1359 (4)	0.54223 (17)	0.1140 (2)	0.0295 (7)
C1	0.2812 (7)	0.4078 (3)	0.0775 (4)	0.0500 (13)
H1A	0.3548	0.4355	0.0433	0.060*
H1B	0.3353	0.3651	0.0801	0.060*
C2	0.2754 (8)	0.4359 (3)	0.1657 (3)	0.0517 (13)
H2A	0.2476	0.4006	0.2041	0.062*
H2B	0.3908	0.4511	0.1797	0.062*
C3	0.1501 (7)	0.4913 (2)	0.1821 (3)	0.0435 (11)
H3A	0.0360	0.4728	0.1914	0.052*
H3B	0.1846	0.5130	0.2337	0.052*
C4	0.3144 (6)	0.5684 (2)	0.0972 (3)	0.0432 (11)
H4A	0.3626	0.5853	0.1484	0.065*
H4B	0.3078	0.6028	0.0563	0.065*
H4C	0.3868	0.5339	0.0763	0.065*
C5	0.0356 (7)	0.5958 (3)	0.1559 (3)	0.0468 (12)
H5A	0.1010	0.6109	0.2042	0.056*
H5B	−0.0725	0.5777	0.1766	0.056*
C6	−0.0056 (8)	0.6543 (2)	0.1006 (4)	0.0522 (13)
H6A	−0.0352	0.6913	0.1359	0.063*
H6B	0.0963	0.6659	0.0682	0.063*
C7	−0.1547 (7)	0.6403 (3)	0.0411 (4)	0.0515 (13)
H7A	−0.2457	0.6185	0.0723	0.062*
H7B	−0.2011	0.6817	0.0214	0.062*
C8	−0.0052 (8)	0.3595 (3)	0.0882 (4)	0.0567 (14)
H8A	0.0510	0.3186	0.0996	0.085*
H8B	−0.1125	0.3516	0.0594	0.085*
H8C	−0.0279	0.3817	0.1401	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.01643 (19)	0.02450 (19)	0.01795 (18)	−0.00081 (14)	0.00222 (15)	−0.00071 (15)
Cl1	0.0249 (5)	0.0606 (7)	0.0324 (5)	−0.0066 (5)	0.0096 (4)	−0.0008 (5)
I1	0.1060 (6)	0.1040 (5)	0.0439 (3)	0.000	−0.0040 (3)	0.000
I2	0.0293 (2)	0.0335 (2)	0.0475 (2)	0.000	−0.00335 (18)	0.000
I3	0.0944 (5)	0.0556 (3)	0.0422 (3)	0.000	0.0056 (3)	0.000
N1	0.0319 (18)	0.0292 (17)	0.0392 (19)	0.0020 (14)	−0.0039 (15)	−0.0012 (15)
N2	0.0290 (17)	0.0345 (17)	0.0250 (16)	−0.0050 (14)	−0.0029 (13)	−0.0029 (14)
C1	0.045 (3)	0.046 (3)	0.060 (3)	0.011 (2)	−0.016 (2)	0.003 (2)
C2	0.058 (3)	0.050 (3)	0.047 (3)	0.001 (3)	−0.024 (2)	0.011 (2)
C3	0.048 (3)	0.055 (3)	0.027 (2)	−0.009 (2)	−0.0086 (19)	0.007 (2)
C4	0.035 (2)	0.049 (3)	0.046 (3)	−0.012 (2)	−0.006 (2)	−0.004 (2)
C5	0.049 (3)	0.054 (3)	0.037 (2)	0.002 (2)	0.000 (2)	−0.019 (2)
C6	0.065 (3)	0.037 (2)	0.054 (3)	0.008 (2)	−0.008 (3)	−0.021 (2)
C7	0.054 (3)	0.041 (3)	0.059 (3)	0.014 (2)	−0.004 (3)	−0.012 (2)
C8	0.068 (4)	0.038 (3)	0.064 (4)	−0.010 (3)	−0.004 (3)	0.016 (2)

Geometric parameters (Å, º)

Ru1—N1	2.266 (3)	N1—C7^i	1.506 (6)
Ru1—N1^i	2.266 (3)	N2—C5	1.499 (6)
Ru1—N2^i	2.266 (3)	N2—C4	1.503 (6)
Ru1—N2	2.266 (3)	N2—C3	1.508 (6)
Ru1—Cl1	2.339 (1)	C1—C2	1.517 (7)
Ru1—Cl1^i	2.3387 (10)	C2—C3	1.514 (7)
I1—I2	2.883 (1)	C5—C6	1.520 (8)
I2—I3	2.949 (1)	C6—C7	1.518 (8)
N1—C8	1.497 (6)	C7—N1^i	1.506 (6)
N1—C1	1.498 (6)
N1—Ru1—N1^i	180.0 (2)	C8—N1—C7^i	106.0 (4)
N1—Ru1—N2^i	91.4 (1)	C1—N1—C7^i	102.4 (4)
N1^i—Ru1—N2^i	88.61 (13)	C8—N1—Ru1	115.0 (3)
N1—Ru1—N2	88.6 (1)	C1—N1—Ru1	110.9 (3)
N1^i—Ru1—N2	91.39 (13)	C7^i—N1—Ru1	113.3 (3)
N2^i—Ru1—N2	180.00 (19)	C5—N2—C4	107.0 (4)
N1—Ru1—Cl1	88.3 (1)	C5—N2—C3	102.8 (3)
N1^i—Ru1—Cl1	91.7 (1)	C4—N2—C3	107.9 (4)
N2^i—Ru1—Cl1	88.1 (1)	C5—N2—Ru1	113.4 (3)
N2—Ru1—Cl1	91.94 (9)	C4—N2—Ru1	114.8 (3)
N1—Ru1—Cl1^i	91.73 (10)	C3—N2—Ru1	110.3 (3)
N1^i—Ru1—Cl1^i	88.27 (10)	N1—C1—C2	115.8 (4)
N2^i—Ru1—Cl1^i	91.94 (9)	C3—C2—C1	117.6 (4)
N2—Ru1—Cl1^i	88.06 (9)	N2—C3—C2	116.1 (4)
Cl1—Ru1—Cl1^i	180.0 (1)	N2—C5—C6	115.2 (4)
I1—I2—I3	177.25 (3)	C7—C6—C5	111.8 (5)
C8—N1—C1	108.3 (4)	N1^i—C7—C6	115.3 (4)
N1^i—Ru1—N1—C8	33 (60)	N2^i—Ru1—N2—C4	152 (100)
N2^i—Ru1—N1—C8	−87.3 (3)	Cl1—Ru1—N2—C4	3.6 (3)
N2—Ru1—N1—C8	92.7 (3)	Cl1^i—Ru1—N2—C4	−176.4 (3)
Cl1—Ru1—N1—C8	−175.4 (3)	N1—Ru1—N2—C3	−30.2 (3)
Cl1^i—Ru1—N1—C8	4.6 (3)	N1^i—Ru1—N2—C3	149.8 (3)
N1^i—Ru1—N1—C1	−90 (59)	N2^i—Ru1—N2—C3	29 (100)
N2^i—Ru1—N1—C1	149.4 (3)	Cl1—Ru1—N2—C3	−118.4 (3)
N2—Ru1—N1—C1	−30.6 (3)	Cl1^i—Ru1—N2—C3	61.6 (3)
Cl1—Ru1—N1—C1	61.4 (3)	C8—N1—C1—C2	−56.7 (6)
Cl1^i—Ru1—N1—C1	−118.6 (3)	C7^i—N1—C1—C2	−168.5 (4)
N1^i—Ru1—N1—C7^i	155 (60)	Ru1—N1—C1—C2	70.4 (5)
N2^i—Ru1—N1—C7^i	34.8 (3)	N1—C1—C2—C3	−39.6 (7)
N2—Ru1—N1—C7^i	−145.2 (3)	C5—N2—C3—C2	−168.3 (4)
Cl1—Ru1—N1—C7^i	−53.2 (3)	C4—N2—C3—C2	−55.5 (5)
Cl1^i—Ru1—N1—C7^i	126.8 (3)	Ru1—N2—C3—C2	70.5 (4)
N1—Ru1—N2—C5	−144.9 (3)	C1—C2—C3—N2	−40.5 (6)
N1^i—Ru1—N2—C5	35.1 (3)	C4—N2—C5—C6	68.6 (5)
N2^i—Ru1—N2—C5	−85 (100)	C3—N2—C5—C6	−177.9 (4)
Cl1—Ru1—N2—C5	126.9 (3)	Ru1—N2—C5—C6	−58.9 (5)
Cl1^i—Ru1—N2—C5	−53.1 (3)	N2—C5—C6—C7	77.4 (6)
N1—Ru1—N2—C4	91.8 (3)	C5—C6—C7—N1^i	−77.1 (6)
N1^i—Ru1—N2—C4	−88.2 (3)

Symmetry code: (i) −x, −y+1, −z.