Rhodamine 6G hexa­chlorido­stannate(IV) acetonitrile disolvate

Ramaiyer Venkatraman; Lungile Sitole; Frank R Fronczek

doi:10.1107/S1600536807066287

. 2007 Dec 18;64(Pt 1):m199. doi: 10.1107/S1600536807066287

Rhodamine 6G hexachloridostannate(IV) acetonitrile disolvate

Ramaiyer Venkatraman ^a, Lungile Sitole ^a, Frank R Fronczek ^b,^*

PMCID: PMC2915129 PMID: 21200545

Abstract

In the title compound, bis({6-ethylamino-10-[2-(methoxycarbonyl)phenyl]-2,7-dimethylxanthen-3-ylidene}ethanaminium) hexachloridotin(IV) acetonitrile disolvate, (C₂₇H₂₉N₂O₃)₂[SnCl₆]·2C₂H₃N, the octahedral SnCl₆ ²⁻ anion lies on an inversion center. The xanthene ring system is essentially planar, with an average deviation of 0.020 Å, and the substituent benzene ring forms a dihedral angle of 85.89 (2)° with it. The Sn—Cl distances are in the range 2.4237 (3)–2.4454 (3) Å. There are N—H⋯Cl hydrogen bonds between SnCl₆ ²⁻ ions and rhodamine 6G cations as well as π–π stacking interactions between rhodamine 6G cations (interplanar distance of 3.827 Å).

Related literature

For related literature, see: Bhagavthy et al. (1993 ▶); Fun et al. (1997 ▶); Herz (1974 ▶); Johnson & McGrane (1993 ▶); Liu et al. (1998 ▶); Nguyen & Meyer (1992 ▶); Wang et al. (1997 ▶). For the structure of the analogous ethyl ester as the chloride salt hydrate, see: Adhikesavalu et al. (2001 ▶).

Experimental

Crystal data

(C₂₇H₂₉N₂O₃)₂[SnCl₆]·2C₂H₃N
M _r = 1272.54
Triclinic,
a = 9.7871 (10) Å
b = 11.7827 (11) Å
c = 13.2893 (12) Å
α = 80.583 (4)°
β = 77.309 (4)°
γ = 82.467 (4)°
V = 1467.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 90.0 (5) K
0.28 × 0.27 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer with Oxford Cryostream
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.815, T _max = 0.832
54250 measured reflections
14412 independent reflections
12969 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.073
S = 1.03
14412 reflections
362 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066287/pv2056sup1.cif

e-64-0m199-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066287/pv2056Isup2.hkl

e-64-0m199-Isup2.hkl^{(704.4KB, 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
N1—H1N⋯Cl2	0.81 (2)	2.61 (2)	3.3644 (10)	156 (2)
N2—H2N⋯Cl1ⁱ	0.86 (2)	2.75 (2)	3.5603 (10)	159 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

RV acknowledges support for supplies by the grant JSU RISE program (NIH grant No. 1RO25GM067122). The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

The excellent photo-physical properties of rhodamines are well known (Herz, 1974; Johnson & McGrane, 1993; Nguyen & Meyer, 1992), and recently metal complexes of rhodamine 6 G have been reported by several authors (Bhagavthy et al., 1993; Fun et al., 1997; Wang et al., 1997; Liu et al., 1998). The aggregative properties of cationic species of the dye were observed to be dependent on the anionic environment created by the metal ions. We have synthesized a rhodamine 6 G derivative, 9-[2-methoxycarbonyl)phenyl]-3,6-bis(ethylamino)-2,7-dimethylxanthylium hexachlorotin(IV) diacetonitrile solvate, (I), the structure of which is presented in this paper.

The structure of (I) consists of discrete SnCl₆^2- anions lying on inversion centers, rhodamine 6 G cations and acetonitrile solvent molecules (Fig. 1). The xanthene ring of the cation is planar within an average deviation of 0.020 Å (maximum deviation is 0.045 (1) Å for C4), and the phenyl ring forms a dihedral angle of 85.89 (2)° with it. The C—N distances N1—C24 and N2—C26 are normal for this type of single bond, whereas C3—N1 and C11—N2 are much shorter, showing partial double-bond character; details are in the Table. A similar trend is observed in the other rhodamine 6 G cations (Wang et al., 1997; Liu et al., 1998).

Both hydrogen bonding between cations and anions and π-π stacking interactions between rhodamine 6 G cations exist. Parallel rhodamine ions related by the inversion center have an interplanar distance of 3.827 Å (Fig. 2), and are slipped such that their O1—C13 bonds exactly overlap.

Experimental

Diphenyl tin dichloride (0.344 g, 1 mmol) was dissolved in 20 ml me thanol, and then 20 ml of methanol solution of rhodamine 6 G (0.479 g, 1 mmol) was added. The bright red solution was refluxed for 1 hr, whereafter red brown solid were obtained on cooling. Suitable size crystals were obtained by the recrystallization at room temperature from acetonitrile (yield ca 85%).