(18-Crown-6)potassium(I) di­phenyl­stibate(−1)

Red crystals of the title salt, [K(C₁₂H₂₄O₆)][Sb(C₆H₅)₂], were obtained by the reaction of SbPh₃, KSnBi and 18-crown-6 in liquid ammonia. The asymmetric unit contains one half of a [K(18-crown-6)]⁺ cation and one half of an SbPh₂⁻ anion, with the central element lying on a twofold axis and a centre of inversion, respectively. In the crystal structure, the sequestered potassium cations show weak inter­actions with the π-electrons of the phenyl groups of the SbPh₂⁻ anion [shortest K⋯C distances = 3.190 (2) and 3.441 (2) Å], leading to one-dimensional strands along the crystallographic c axis. These strands are aligned in a pseudo-hexa­gonal packing perpendicular to the ab plane.

Related literature

For literature focusing on mechanisms of crystallization and inter­molecular inter­actions or di­phenyl­stibide as a nucleophile, see: Desiraju (2007); Ugrinov & Sevov (2003). For a related compound, see Effendy et al. (1997).

Experimental

Crystal data

• [K(C₁₂H₂₄O₆)][Sb(C₆H₅)₂]

• M_r = 579.36

• Monoclinic, I 2/a

• a = 15.6933 (9) Å

• b = 9.2655 (3) Å

• c = 19.1321 (10) Å

• β = 112.654 (6)°

• V = 2567.3 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 1.27 mm⁻¹

• T = 123 K

• 0.47 × 0.27 × 0.15 mm

Data collection

• Agilent SuperNova (Single source at offset, Eos) diffractometer

• Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)] T_min = 0.726, T_max = 0.863

• 4194 measured reflections

• 2592 independent reflections

• 2297 reflections with I > 2σ(I)

• R_int = 0.019

Refinement

• R[F² > 2σ(F²)] = 0.023

• wR(F²) = 0.053

• S = 1.08

• 2592 reflections

• 147 parameters

• H-atom parameters constrained

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Sb1—C1	2.154 (2)
K1—O2	2.7823 (14)
K1—O3	2.8106 (16)
K1—O1	2.7738 (15)

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2011).

Supporting information

S1. Comment

The crystal structure of [K(18-crown-6)]SbPh₂ was obtained during the investigations of oxidation processes of SnBi-polyanions in liquid ammonia. The asymmetric unit contains one half of a [K(18-crown-6)]⁺-cation together with one half of a SbPh₂^- anion. Figure 1 shows these two molecular ions. K—O bond lengths within the complex range from 2.7738 (15) Å to 2.8106 (15) Å. The Sb—C bond lengths of SbPh₂^--anion of 2.154 (2) Å and the previously reported values for SbPh₃ of 2.1392 (77) Å - 2.1539 (68) Å (Effendy et al., 1997) are in good agreement. The two phenyl groups of SbPh₂^- exhibit a torsion angle of 28.53 (15)° between C2—C1—Sb1—C1ⁱⁱ and C1—Sb1—C1ⁱⁱ—C2ⁱⁱ. Short K—C distances suggest π-interactions between the alkali metal cation and the phenyl rings. Two carbon atoms of each phenyl ligand are connected to the cation with a hapticity of two and distances of 3.190 (2) Å and 3.441 (2) Å. Due to symmetry, the SbPh₂^--anion acts as a linker molecule between two [K(18-crown-6)]⁺ complexes that leads to the formation of one dimensional strands along the c-axis (Figure 2). The strands are arranged in a hexagonal packing and no further interactions can be found between neighbouring strands (Figure 3).

Related literature

For literature focusing on mechanisms of crystallization and intermolecular interactions or diphenylstibide as nucleophile: Desiraju (2007); Ugrinov & Sevov (2003). For a related compound, see Effendy et al. (1997).

S2. Experimental

KSnBi was prepared from the elements in a high temperature synthesis at 723 K in a sealed tube. 88 mg (0.25 mmol) SbPh₃, 203 mg (0.27 mmol) KSnBi and 66 mg (0.25 mmol) 18-crown-6 were dissolved in dried liquid ammonia in a baked-out reaction vessel. Liquid ammonia was dried over potassium metal and condensed using a standard Schlenk line. The mixture was stored at 237 K for crystallization. Crystals appeared as red blocks in a brownish red solution after 4 weeks.

S3. Refinement

All H-atoms could be located in the difference map but were positioned with idealized geometry, with Uiso(H) set to 1.2Ueq of the parent atom. Furthermore there were no irregularities such as dislocation.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2011).

Figures

	Fig. 1. Molecular unit of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) 1.5 - x, 1.5 - y, 1.5 - z, (ii) 1.5 - x, y, 2 - z
	Fig. 2. View of the crystal structure showing the one-dimensional strands along the c-axis.
	Fig. 3. : Projection of the crystal structure showing the pseudo-hexagonal arrangement of the strands perpendicular to the ab-plane.

(1,4,7,10,13,16-Hexaoxacyclooctadecane)potassium diphenylstibide

Crystal data

[K(C12H24O6)][Sb(C6H5)2]	F(000) = 1184
Mr = 579.36	Dx = 1.499 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 15.6933 (9) Å	Cell parameters from 1900 reflections
b = 9.2655 (3) Å	θ = 3.4–28.0°
c = 19.1321 (10) Å	µ = 1.27 mm^−1
β = 112.654 (6)°	T = 123 K
V = 2567.3 (2) Å^3	Block, clear reddish red
Z = 4	0.47 × 0.27 × 0.15 mm

Data collection

Agilent SuperNova (Single source at offset, Eos) diffractometer	2297 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
phi and ω scans	θmax = 26.4°, θmin = 3.1°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	h = −18→19
Tmin = 0.726, Tmax = 0.863	k = −11→10
4194 measured reflections	l = −15→23
2592 independent reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.019P)^2 + 0.7904P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2592 reflections	Δρmax = 0.39 e Å^−3
147 parameters	Δρmin = −0.56 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Sb1	0.7500	1.08580 (2)	1.0000	0.02163 (8)
K1	0.7500	0.7500	0.7500	0.02190 (15)
O2	0.62864 (10)	0.83061 (17)	0.60590 (8)	0.0237 (3)
O3	0.74551 (10)	1.03820 (17)	0.70288 (8)	0.0241 (4)
O1	0.60734 (10)	0.56706 (17)	0.66609 (8)	0.0225 (3)
C1	0.67008 (14)	0.9316 (2)	0.91614 (11)	0.0191 (5)
C10	0.54293 (15)	0.7554 (3)	0.57688 (12)	0.0278 (5)
H10A	0.5106	0.7774	0.5236	0.033*
H10B	0.5045	0.7855	0.6036	0.033*
C4	0.56109 (15)	0.7424 (3)	0.79930 (12)	0.0279 (5)
H4	0.5263	0.6798	0.7609	0.033*
C11	0.61898 (16)	0.9803 (3)	0.58922 (12)	0.0292 (5)
H11A	0.5781	1.0236	0.6106	0.035*
H11B	0.5924	0.9947	0.5348	0.035*
C3	0.59436 (14)	0.6990 (3)	0.87465 (12)	0.0249 (5)
H3	0.5813	0.6068	0.8870	0.030*
C7	0.66870 (16)	0.3883 (3)	0.76152 (13)	0.0286 (5)
H7A	0.6253	0.4205	0.7831	0.034*
H7B	0.6779	0.2853	0.7701	0.034*
C2	0.64697 (14)	0.7928 (3)	0.93162 (12)	0.0215 (5)
H2	0.6675	0.7622	0.9817	0.026*
C5	0.58069 (15)	0.8799 (3)	0.78264 (12)	0.0283 (6)
H5	0.5577	0.9111	0.7326	0.034*
C9	0.56103 (15)	0.5973 (3)	0.58705 (12)	0.0256 (5)
H9A	0.5032	0.5446	0.5668	0.031*
H9B	0.5991	0.5670	0.5600	0.031*
C8	0.63067 (16)	0.4186 (3)	0.67829 (13)	0.0267 (5)
H8A	0.6763	0.3946	0.6574	0.032*
H8B	0.5762	0.3600	0.6530	0.032*
C12	0.71193 (16)	1.0495 (3)	0.62224 (12)	0.0276 (5)
H12A	0.7541	1.0016	0.6037	0.033*
H12B	0.7075	1.1502	0.6074	0.033*
C6	0.63440 (15)	0.9725 (3)	0.83964 (12)	0.0248 (5)
H6	0.6471	1.0645	0.8267	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sb1	0.02653 (12)	0.01591 (12)	0.02407 (12)	0.000	0.01153 (9)	0.000
K1	0.0173 (3)	0.0167 (3)	0.0253 (3)	−0.0019 (3)	0.0011 (3)	0.0031 (3)
O2	0.0198 (8)	0.0233 (9)	0.0239 (8)	0.0032 (7)	0.0040 (6)	0.0018 (7)
O3	0.0268 (8)	0.0216 (9)	0.0252 (8)	−0.0006 (7)	0.0114 (7)	0.0043 (7)
O1	0.0253 (8)	0.0221 (9)	0.0194 (7)	−0.0013 (7)	0.0078 (6)	−0.0053 (6)
C1	0.0175 (10)	0.0202 (12)	0.0218 (10)	0.0044 (9)	0.0098 (9)	−0.0001 (9)
C10	0.0185 (11)	0.0411 (16)	0.0187 (11)	0.0017 (11)	0.0016 (9)	−0.0024 (11)
C4	0.0201 (11)	0.0368 (15)	0.0276 (12)	0.0002 (11)	0.0102 (9)	−0.0106 (11)
C11	0.0305 (13)	0.0315 (14)	0.0248 (12)	0.0122 (12)	0.0098 (10)	0.0096 (11)
C3	0.0192 (11)	0.0213 (12)	0.0367 (13)	−0.0001 (10)	0.0134 (10)	−0.0017 (10)
C7	0.0311 (13)	0.0200 (13)	0.0400 (14)	−0.0053 (11)	0.0195 (11)	0.0003 (11)
C2	0.0200 (11)	0.0240 (12)	0.0213 (11)	0.0019 (10)	0.0088 (9)	0.0032 (9)
C5	0.0230 (12)	0.0424 (16)	0.0192 (11)	0.0038 (12)	0.0080 (9)	0.0020 (11)
C9	0.0221 (11)	0.0327 (14)	0.0200 (11)	−0.0061 (11)	0.0058 (9)	−0.0080 (10)
C8	0.0308 (12)	0.0194 (12)	0.0338 (12)	−0.0096 (11)	0.0167 (10)	−0.0076 (10)
C12	0.0356 (13)	0.0236 (13)	0.0286 (12)	0.0084 (11)	0.0178 (10)	0.0090 (10)
C6	0.0245 (12)	0.0264 (13)	0.0251 (11)	0.0020 (11)	0.0114 (9)	0.0041 (10)

Geometric parameters (Å, º)

Sb1—C1	2.154 (2)	C4—C5	1.376 (3)
K1—O2	2.7823 (14)	C11—H11A	0.9700
K1—O3	2.8106 (16)	C11—H11B	0.9700
K1—O1	2.7738 (15)	C11—C12	1.493 (3)
K1—C4	3.441 (2)	C3—H3	0.9300
K1—C5	3.190 (2)	C3—C2	1.390 (3)
O2—C10	1.424 (3)	C7—H7A	0.9700
O2—C11	1.418 (3)	C7—H7B	0.9700
O3—C7^i	1.426 (3)	C7—C8	1.496 (3)
O3—C12	1.429 (2)	C2—H2	0.9300
O1—C9	1.431 (2)	C5—H5	0.9300
O1—C8	1.419 (3)	C5—C6	1.389 (3)
C1—C2	1.399 (3)	C9—H9A	0.9700
C1—C6	1.403 (3)	C9—H9B	0.9700
C10—H10A	0.9700	C8—H8A	0.9700
C10—H10B	0.9700	C8—H8B	0.9700
C10—C9	1.490 (3)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C4—C3	1.390 (3)	C6—H6	0.9300
C1—Sb1—C1^ii	96.89 (12)	O2—C10—H10A	109.9
O2—K1—O2^i	180.00 (6)	O2—C10—H10B	109.9
O2^i—K1—O3^i	60.27 (4)	O2—C10—C9	109.03 (18)
O2^i—K1—O3	119.73 (4)	H10A—C10—H10B	108.3
O2—K1—O3^i	119.73 (4)	C9—C10—H10A	109.9
O2—K1—O3	60.27 (4)	C9—C10—H10B	109.9
O2—K1—C4	86.78 (5)	K1—C4—H4	95.9
O2—K1—C4^i	93.22 (5)	C3—C4—K1	105.73 (13)
O2^i—K1—C4	93.22 (5)	C3—C4—H4	120.7
O2^i—K1—C4^i	86.78 (5)	C5—C4—K1	67.95 (13)
O2—K1—C5	77.81 (5)	C5—C4—H4	120.7
O2—K1—C5^i	102.19 (5)	C5—C4—C3	118.7 (2)
O2^i—K1—C5^i	77.81 (5)	O2—C11—H11A	109.9
O2^i—K1—C5	102.19 (5)	O2—C11—H11B	109.9
O3—K1—O3^i	180.0	O2—C11—C12	108.82 (18)
O3—K1—C4^i	79.08 (5)	H11A—C11—H11B	108.3
O3^i—K1—C4^i	100.92 (5)	C12—C11—H11A	109.9
O3—K1—C4	100.92 (5)	C12—C11—H11B	109.9
O3^i—K1—C4	79.08 (5)	C4—C3—H3	119.8
O3—K1—C5^i	102.44 (6)	C2—C3—C4	120.3 (2)
O3^i—K1—C5^i	77.56 (6)	C2—C3—H3	119.8
O3^i—K1—C5	102.44 (6)	O3^i—C7—H7A	109.8
O3—K1—C5	77.56 (6)	O3^i—C7—H7B	109.8
O1—K1—O2	59.91 (4)	O3^i—C7—C8	109.56 (18)
O1—K1—O2^i	120.09 (5)	H7A—C7—H7B	108.2
O1^i—K1—O2^i	59.91 (5)	C8—C7—H7A	109.8
O1^i—K1—O2	120.09 (5)	C8—C7—H7B	109.8
O1^i—K1—O3	61.31 (4)	C1—C2—H2	118.9
O1—K1—O3^i	61.31 (4)	C3—C2—C1	122.2 (2)
O1^i—K1—O3^i	118.69 (4)	C3—C2—H2	118.9
O1—K1—O3	118.69 (4)	K1—C5—H5	86.5
O1^i—K1—O1	180.0	C4—C5—K1	88.49 (14)
O1^i—K1—C4	116.26 (5)	C4—C5—H5	119.6
O1—K1—C4^i	116.26 (5)	C4—C5—C6	120.8 (2)
O1—K1—C4	63.74 (5)	C6—C5—K1	95.02 (14)
O1^i—K1—C4^i	63.74 (5)	C6—C5—H5	119.6
O1—K1—C5	78.25 (5)	O1—C9—C10	108.91 (18)
O1^i—K1—C5^i	78.25 (5)	O1—C9—H9A	109.9
O1^i—K1—C5	101.75 (5)	O1—C9—H9B	109.9
O1—K1—C5^i	101.75 (5)	C10—C9—H9A	109.9
C4—K1—C4^i	180.00 (10)	C10—C9—H9B	109.9
C5—K1—C4	23.57 (6)	H9A—C9—H9B	108.3
C5^i—K1—C4^i	23.57 (6)	O1—C8—C7	109.22 (18)
C5—K1—C4^i	156.43 (6)	O1—C8—H8A	109.8
C5^i—K1—C4	156.43 (6)	O1—C8—H8B	109.8
C5^i—K1—C5	180.0	C7—C8—H8A	109.8
C10—O2—K1	115.99 (12)	C7—C8—H8B	109.8
C11—O2—K1	117.29 (12)	H8A—C8—H8B	108.3
C11—O2—C10	112.83 (17)	O3—C12—C11	108.62 (18)
C7^i—O3—K1	113.46 (12)	O3—C12—H12A	110.0
C7^i—O3—C12	111.61 (16)	O3—C12—H12B	110.0
C12—O3—K1	111.65 (13)	C11—C12—H12A	110.0
C9—O1—K1	117.40 (12)	C11—C12—H12B	110.0
C8—O1—K1	113.42 (12)	H12A—C12—H12B	108.3
C8—O1—C9	110.95 (17)	C1—C6—H6	119.0
C2—C1—Sb1	125.20 (15)	C5—C6—C1	122.0 (2)
C2—C1—C6	115.9 (2)	C5—C6—H6	119.0
C6—C1—Sb1	118.81 (17)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+3/2; (ii) −x+3/2, y, −z+2.