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In the title complex, [RuCl2(C16H36N4)]I3, the overall symmetry of the centrosymmetric cation is approximately C2h and the I^-_3 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007460/sk1397sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007460/sk1397Isup2.hkl
Contains datablock I

CCDC reference: 150315

Comment top

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.

Experimental top

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%)].

Refinement top

All the hydrogen atoms were fixed at calculated distances.

Computing details top

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 top
[Figure 1] 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 top
Crystal data top
[RuCl2(C16H36N4)]I3F(000) = 1588
Mr = 837.16Dx = 2.212 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 6317 reflections
a = 7.7198 (1) Åθ = 1.6–28.4°
b = 20.4639 (3) ŵ = 4.53 mm1
c = 15.9112 (2) ÅT = 293 K
V = 2513.61 (6) Å3Needle, red
Z = 40.18 × 0.16 × 0.14 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3199 independent reflections
Radiation source: fine-focus sealed tube2682 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 1.6°
ω scansh = 1010
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1996)
k = 2727
Tmin = 0.462, Tmax = 0.530l = 1121
18757 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0275P)2 + 6.6027P]
where P = (Fo2 + 2Fc2)/3
3199 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 1.29 e Å3
0 restraintsΔρmin = 1.96 e Å3
Crystal data top
[RuCl2(C16H36N4)]I3V = 2513.61 (6) Å3
Mr = 837.16Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.7198 (1) ŵ = 4.53 mm1
b = 20.4639 (3) ÅT = 293 K
c = 15.9112 (2) Å0.18 × 0.16 × 0.14 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3199 independent reflections
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1996)
2682 reflections with I > 2σ(I)
Tmin = 0.462, Tmax = 0.530Rint = 0.052
18757 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.16Δρmax = 1.29 e Å3
3199 reflectionsΔρmin = 1.96 e Å3
124 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. 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 (Å2) top
xyzUiso*/Ueq
Ru10.00000.50000.00000.01963 (10)
Cl10.24338 (13)0.51679 (6)0.08482 (7)0.0393 (3)
I10.12920 (11)0.25000.31048 (4)0.0846 (2)
I20.07460 (5)0.25000.48974 (3)0.03676 (12)
I30.00071 (9)0.25000.67157 (3)0.06406 (18)
N10.1098 (5)0.40085 (17)0.0343 (2)0.0334 (8)
N20.1359 (4)0.54223 (17)0.1140 (2)0.0295 (7)
C10.2812 (7)0.4078 (3)0.0775 (4)0.0500 (13)
H1A0.35480.43550.04330.060*
H1B0.33530.36510.08010.060*
C20.2754 (8)0.4359 (3)0.1657 (3)0.0517 (13)
H2A0.24760.40060.20410.062*
H2B0.39080.45110.17970.062*
C30.1501 (7)0.4913 (2)0.1821 (3)0.0435 (11)
H3A0.03600.47280.19140.052*
H3B0.18460.51300.23370.052*
C40.3144 (6)0.5684 (2)0.0972 (3)0.0432 (11)
H4A0.36260.58530.14840.065*
H4B0.30780.60280.05630.065*
H4C0.38680.53390.07630.065*
C50.0356 (7)0.5958 (3)0.1559 (3)0.0468 (12)
H5A0.10100.61090.20420.056*
H5B0.07250.57770.17660.056*
C60.0056 (8)0.6543 (2)0.1006 (4)0.0522 (13)
H6A0.03520.69130.13590.063*
H6B0.09630.66590.06820.063*
C70.1547 (7)0.6403 (3)0.0411 (4)0.0515 (13)
H7A0.24570.61850.07230.062*
H7B0.20110.68170.02140.062*
C80.0052 (8)0.3595 (3)0.0882 (4)0.0567 (14)
H8A0.05100.31860.09960.085*
H8B0.11250.35160.05940.085*
H8C0.02790.38170.14010.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.01643 (19)0.02450 (19)0.01795 (18)0.00081 (14)0.00222 (15)0.00071 (15)
Cl10.0249 (5)0.0606 (7)0.0324 (5)0.0066 (5)0.0096 (4)0.0008 (5)
I10.1060 (6)0.1040 (5)0.0439 (3)0.0000.0040 (3)0.000
I20.0293 (2)0.0335 (2)0.0475 (2)0.0000.00335 (18)0.000
I30.0944 (5)0.0556 (3)0.0422 (3)0.0000.0056 (3)0.000
N10.0319 (18)0.0292 (17)0.0392 (19)0.0020 (14)0.0039 (15)0.0012 (15)
N20.0290 (17)0.0345 (17)0.0250 (16)0.0050 (14)0.0029 (13)0.0029 (14)
C10.045 (3)0.046 (3)0.060 (3)0.011 (2)0.016 (2)0.003 (2)
C20.058 (3)0.050 (3)0.047 (3)0.001 (3)0.024 (2)0.011 (2)
C30.048 (3)0.055 (3)0.027 (2)0.009 (2)0.0086 (19)0.007 (2)
C40.035 (2)0.049 (3)0.046 (3)0.012 (2)0.006 (2)0.004 (2)
C50.049 (3)0.054 (3)0.037 (2)0.002 (2)0.000 (2)0.019 (2)
C60.065 (3)0.037 (2)0.054 (3)0.008 (2)0.008 (3)0.021 (2)
C70.054 (3)0.041 (3)0.059 (3)0.014 (2)0.004 (3)0.012 (2)
C80.068 (4)0.038 (3)0.064 (4)0.010 (3)0.004 (3)0.016 (2)
Geometric parameters (Å, º) top
Ru1—N12.266 (3)N1—C7i1.506 (6)
Ru1—N1i2.266 (3)N2—C51.499 (6)
Ru1—N2i2.266 (3)N2—C41.503 (6)
Ru1—N22.266 (3)N2—C31.508 (6)
Ru1—Cl12.339 (1)C1—C21.517 (7)
Ru1—Cl1i2.3387 (10)C2—C31.514 (7)
I1—I22.883 (1)C5—C61.520 (8)
I2—I32.949 (1)C6—C71.518 (8)
N1—C81.497 (6)C7—N1i1.506 (6)
N1—C11.498 (6)
N1—Ru1—N1i180.0 (2)C8—N1—C7i106.0 (4)
N1—Ru1—N2i91.4 (1)C1—N1—C7i102.4 (4)
N1i—Ru1—N2i88.61 (13)C8—N1—Ru1115.0 (3)
N1—Ru1—N288.6 (1)C1—N1—Ru1110.9 (3)
N1i—Ru1—N291.39 (13)C7i—N1—Ru1113.3 (3)
N2i—Ru1—N2180.00 (19)C5—N2—C4107.0 (4)
N1—Ru1—Cl188.3 (1)C5—N2—C3102.8 (3)
N1i—Ru1—Cl191.7 (1)C4—N2—C3107.9 (4)
N2i—Ru1—Cl188.1 (1)C5—N2—Ru1113.4 (3)
N2—Ru1—Cl191.94 (9)C4—N2—Ru1114.8 (3)
N1—Ru1—Cl1i91.73 (10)C3—N2—Ru1110.3 (3)
N1i—Ru1—Cl1i88.27 (10)N1—C1—C2115.8 (4)
N2i—Ru1—Cl1i91.94 (9)C3—C2—C1117.6 (4)
N2—Ru1—Cl1i88.06 (9)N2—C3—C2116.1 (4)
Cl1—Ru1—Cl1i180.0 (1)N2—C5—C6115.2 (4)
I1—I2—I3177.25 (3)C7—C6—C5111.8 (5)
C8—N1—C1108.3 (4)N1i—C7—C6115.3 (4)
N1i—Ru1—N1—C833 (60)N2i—Ru1—N2—C4152 (100)
N2i—Ru1—N1—C887.3 (3)Cl1—Ru1—N2—C43.6 (3)
N2—Ru1—N1—C892.7 (3)Cl1i—Ru1—N2—C4176.4 (3)
Cl1—Ru1—N1—C8175.4 (3)N1—Ru1—N2—C330.2 (3)
Cl1i—Ru1—N1—C84.6 (3)N1i—Ru1—N2—C3149.8 (3)
N1i—Ru1—N1—C190 (59)N2i—Ru1—N2—C329 (100)
N2i—Ru1—N1—C1149.4 (3)Cl1—Ru1—N2—C3118.4 (3)
N2—Ru1—N1—C130.6 (3)Cl1i—Ru1—N2—C361.6 (3)
Cl1—Ru1—N1—C161.4 (3)C8—N1—C1—C256.7 (6)
Cl1i—Ru1—N1—C1118.6 (3)C7i—N1—C1—C2168.5 (4)
N1i—Ru1—N1—C7i155 (60)Ru1—N1—C1—C270.4 (5)
N2i—Ru1—N1—C7i34.8 (3)N1—C1—C2—C339.6 (7)
N2—Ru1—N1—C7i145.2 (3)C5—N2—C3—C2168.3 (4)
Cl1—Ru1—N1—C7i53.2 (3)C4—N2—C3—C255.5 (5)
Cl1i—Ru1—N1—C7i126.8 (3)Ru1—N2—C3—C270.5 (4)
N1—Ru1—N2—C5144.9 (3)C1—C2—C3—N240.5 (6)
N1i—Ru1—N2—C535.1 (3)C4—N2—C5—C668.6 (5)
N2i—Ru1—N2—C585 (100)C3—N2—C5—C6177.9 (4)
Cl1—Ru1—N2—C5126.9 (3)Ru1—N2—C5—C658.9 (5)
Cl1i—Ru1—N2—C553.1 (3)N2—C5—C6—C777.4 (6)
N1—Ru1—N2—C491.8 (3)C5—C6—C7—N1i77.1 (6)
N1i—Ru1—N2—C488.2 (3)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[RuCl2(C16H36N4)]I3
Mr837.16
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)293
a, b, c (Å)7.7198 (1), 20.4639 (3), 15.9112 (2)
V3)2513.61 (6)
Z4
Radiation typeMo Kα
µ (mm1)4.53
Crystal size (mm)0.18 × 0.16 × 0.14
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
SADABS (Sheldrick, 1996)
Tmin, Tmax0.462, 0.530
No. of measured, independent and
observed [I > 2σ(I)] reflections
18757, 3199, 2682
Rint0.052
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.087, 1.16
No. of reflections3199
No. of parameters124
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.29, 1.96

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Ru1—N12.266 (3)I1—I22.883 (1)
Ru1—N22.266 (3)I2—I32.949 (1)
Ru1—Cl12.339 (1)
N1—Ru1—N1i180.0 (2)N2i—Ru1—Cl188.1 (1)
N1—Ru1—N2i91.4 (1)N2—Ru1—Cl191.94 (9)
N1—Ru1—N288.6 (1)Cl1—Ru1—Cl1i180.0 (1)
N1i—Ru1—Cl191.7 (1)I1—I2—I3177.25 (3)
Symmetry code: (i) x, y+1, z.
 

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