Crystal structure of catena-poly[[potassium-tri-μ-di­methyl­acetamide-κ6O:O] iodide]

Comanescu, C.-C.; Oliver, A.G.

doi:10.1107/S1600536814020005

research communications

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages 196-198

doi:10.1107/S1600536814020005

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Crystal structure of catena-poly[[potassium-tri-μ-dimethylacetamide-κ⁶O:O] iodide]

Cezar-Catalin Comanescu ^a ^* and Allen G. Oliver ^a

^aDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA
^*Correspondence e-mail: ccomanes@nd.edu

Edited by M. Zeller, Youngstown State University, USA (Received 30 August 2014; accepted 4 September 2014; online 13 September 2014)

The structure of catena-poly[[potassium-tri-μ-dimethylacetamide-κ⁶O:O] iodide], {[K(C₄H₉NO)₃]I}_n, at 120 K has trigonal (P-3) symmetry. The structure adopts a linear chain motif parallel to the crystallographic c axis. Two crystallographically independent K⁺ cations are present in the asymmetric unit located on threefold rotoinversion axes at [0, 0, 0] and [0, 0, 1/2] and are bridged by the O atoms of the acetamide moiety. This is an example of a rare μ₂-bridging mode for dimethylacetamide O atoms. The iodide counter-ion resides on a threefold rotation axis in the channel formed by the [K(C₄H₉NO)]⁺ chains.

Keywords: crystal structure; one-dimensional coordination polymer; symmetry; dimethylacetamide; potassium salt.

CCDC reference: 1022963

1. Chemical context

Coordination of dimethylacetamide (DMA) to metal centers has been observed previously in a number of metal complexes, but μ₂-coordination of the O atom has only been reported in two crystallographically confirmed structures. Tikhonova et al. (2001 ) crystallized a bis(μ₃-N,N-dimethylacetamide)tris(μ₂-perfluoro-o-phenylene)trimercury(II) complex and found Hg—O(DMA) bond lengths in the range 2.776 (2)–2.989 (2) Å. Dias et al. (1995 ) synthesized bis{(μ₂-dimethylacetamido-O,O){μ₂-hydrogen tris[3,5-bis(trifluoromethyl)pyrazolyl]borate}potassium}, in which the O atom is μ₂-bridging between two K⁺ cations and the K—O bond length is 2.703 (2) Å. In the KI·3DMA structure reported here, the K—O bond lengths are in the range 2.763 (2)–2.774 (3) Å, slightly longer than in the closely related potassium complex synthesized by Dias et al. (1995).

2. Structural commentary

The cation of title compound consists of two crystallographically independent potassium cations. Each K⁺ cation is octahedrally coordinated by six O atoms from the DMA moieties, with each oxygen adopting a μ₂-bridging mode (Fig. 1 and Table 1). The C=O distance is comparable with that in free dimethylacetamide (see Database survey). The iodide anion is independent of the one-dimensional chain and does not form any covalent contacts to the cation.

Table 1
Selected geometric parameters (Å, °)

K1—O1	2.7438 (16)	O1—C2	1.254 (3)
K1—K2	3.6728 (4)	O1—K2	2.7627 (16)

O1ⁱ—K1—O1	180.0	O1ⁱⁱⁱ—K1—O1	80.70 (5)
O1ⁱⁱ—K1—O1	99.30 (5)
Symmetry codes: (i) -x, -y, -z; (ii) y, -x+y, -z; (iii) -y, x-y, z.

Figure 1
The atom-labeling scheme for KI·3DMA, with displacement ellipsoids depicted at the 50% probability level. [Symmetry codes: (i) −x, −y, −z; (ii) y, −x + y, −z; (iii) −y, x − y, z; (iv) x − y, x, −z; (v) −x + y, −x, z; (vi) x, y, z − 1.]

The extended structure forms a chain of K⁺ cations, bridged by μ₂-O-dimethylacetamide moieties. The two independent K⁺ cations are located at [0, 0, 0] and [0, 0, ½] (Wyckoff positions a and b, respectively) and the iodine is located at [ $[2\over3]$ , $[1\over3]$ , z] (Wyckoff position d). In the primary structure, each K⁺ cation adopts a slightly distorted octahedral coordination sphere (key bond lengths and angles are given in Table 1).

3. Supramolecular features

The μ₂-O-dimethylacetamide bridging the two K⁺ cations forms a linear [K(DMA)₃]⁺ chain parallel to the c axis. The application of the $[\overline{3}]$ symmetry results in an aesthetically pleasing `snowflake' configuration when viewed along the c axis (Fig. 2). The iodide counter-ion resides in the channels formed by the [K(DMA)₃]⁺ chains. With regards to the extended structure, there are very weak C—H⋯I interactions within the lattice (Table 2). These serve to locate the iodine in a pocket within the structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯I1^iv	0.98	3.20	4.178 (3)	177
C3—H3A⋯I1^iv	0.98	3.20	4.178 (3)	174
C4—H4C⋯I1	0.98	3.00	3.967 (3)	170
Symmetry code: (iv) x, y, z-1.

Figure 2
(A) Packing diagram viewed along the b axis. (B) View along the c axis. Legend: black = carbon, dark blue = nitrogen, light blue = potassium, magenta = iodine, and red = oxygen. H atoms have been omitted for clarity.

4. Database survey

A search in the Cambridge Structure Database (CSD, Version 5.35, November 2013 plus three updates; Allen, 2002 ) for structures in which K⁺ is triple bridged in a μ₂-fashion by three O atoms returns 17 results, but only 3 of them are relevant to the structure reported herein. Gonzalez-Rodriguez et al. (2009 ) have shown a complex guanosine-derived nucleoside to crystallize as an acetone solvate monohydrate in which the six bridging K⁺ cations are each coordinated to eight O atoms from eight guanosine ligands, and the two terminal K⁺ cations are coordinated to eight O atoms from four guanosine ligands and either four acetone molecules or four water molecules. Cunningham et al. (2000 ) crystallized catena-[tetrakis[N,N′-bis(3-methoxysalicylidene)propane-1,3-diaminoato]iodidonickel(II)potassium], where K⁺ is bridged by four μ₂-O, one μ₂-N, and one μ₂-I. In fact, both of these structures contain four μ₂-O atoms bridging K⁺ cations. No close K⋯K contacts were observed: the K⋯K distances are in the range 3.451 (2)–3.567 (2) Å. Most closely related is the structure of catena-[tris(μ₂-dimethylformamide-O,O)potassium iodide], reported by Batsanov & Struchkov (1994 ), with a K⋯K distance of 3.4170 (10) Å and a K—O distance of 2.6570 (13) Å. In the KI·3DMA structure reported herein, the K1⋯K2 distance is 3.6728 (4) Å, which is longer by approximately 0.106 Å. In the Gonzalez-Rodriguez and Cunningham structures, iodine is found to form bonds to the K⁺ cations, while it is located in a channel within the Batsanov structure and not covalently bound. In the title compound, the iodine is not covalently bonded to the cation chain.

A search in the Cambridge Structure Database for free acetamide returned 180 results, featuring C=O bond lengths between 1.123 Å (Patra & Goldberg, 2013 ) and 1.67 Å (Gole et al., 2011 ), with a mean of 1.259 Å (std. dev. 0.059), which is very close to the C=O bond length reported herein [1.254 (3) Å]

5. Synthesis and crystallization

A carbon–carbon Heck coupling reaction catalyzed by a Pd^II diphosphane precatalyst was performed using conditions established previously by Brase & de Meijere (1998 ). In a typical synthesis, 1-iodo-4-nitrobenzene (IC₆H₄NO₂; 102.1 mg, 0.41 mmol) was mixed with 2 equivalents of n-butyl acrylate [CH₂=CHCOO(CH₂)₃CH₃; 105.6 mg, 0.82 mmol] in the presence of K₂CO₃ (63.6 mg, 0.46 mmol) and n-Bu₄NBr (13 mg, 0.041 mmol) in dimethylacetamide (DMA) over a period of 4 h at 413 K. The title compound formed and was recrystallized from the filtered reaction mixture at room temperature. The target Pd^II complex of the reaction has been reported (Comanescu & Iluc, 2014 ).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were included in a riding model and allowed to rotate to minimize electron-density contribution. C—H distances were set at 0.98 Å, with U_iso(H) = 1.5U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[K(C₄H₉NO)₃]I
M_r	427.37
Crystal system, space group	Trigonal, P $[\overline{3}]$
Temperature (K)	120
a, c (Å)	11.9776 (8), 7.3455 (7)
V (Å³)	912.62 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.99
Crystal size (mm)	0.20 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.615, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	11940, 1248, 1194
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.059, 1.07
No. of reflections	1248
No. of parameters	65
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97, SHELXL2013 and XP in SHELXTL (Sheldrick, 2013 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1022963

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814020005/zl2601sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020005/zl2601Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814020005/zl2601Isup3.cml

checkCIF report

Chemical context top

Coordination of dimethylacetamide to metal centers has been observed previously in a number of metal complexes, but µ₂-coordination of the O atom has only been reported in two crystallographically confirmed structures. Tikhonova et al. (2001) crystallized a bis(µ₃-N,N-dimethylacetamide)tris(µ₂-perfluoro-o-phenylene)trimercury(II) complex and found Hg—O(DMA) bond distances in the range 2.776 (2)–2.989 (2) Å. Dias et al. (1995) synthesized bis{(µ₂-dimethylacetamido-O,O){µ₂-hydrogen tris[3,5-bis(trifluoromethyl)pyrazolyl]borate}potassium), in which the O atom is µ₂-bridging between two K atoms and the K—O bond distance is 2.703 (2) Å. In the KI.DMA structure reported here, the K—O bond distances are in the range 2.763 (2)–2.774 (3) Å, slightly longer than in the closely-related potassium complex synthesized by Dias et al. (1995).

Structural commentary top

The cation of title compound, (I) or KI.DMA, consists of two crystallographically independent potassium centers. Each K atom is octahedrally coordinated by six O atoms from the O═C(CH₃)-N(CH₃)₂ dimethylacetamide (DMA) moieties, with each oxygen adopting a µ₂-bridging mode (Fig. 1 and Table 1). The C═O distance is comparable with that in free dimethylacetamide. The iodine is independent of the one-dimensional chain and does not form any covalent contacts to the cation.

The extended structure forms a one-dimensional chain of K bridged by µ₂-O-dimethylacetamide moieties. The two independent K centers are located at [0, 0, 0] and [0, 0, 0.5] (Wyckoff positions a and b, respectively) and the iodine is located at [0.6667, 0.3333, z] (Wyckoff position d). In the primary structure, each K ion adopts a slightly distorted octahedral geometry (key bond distances and angles are given in Table 1).

Supramolecular features top

The µ₂-O-dimethylacetamide bridging the two K centers forms a linear one-dimensional K–DMA chain parallel to the c axis. The application of the 3 symmetry results in an aesthetically pleasing `snowflake' configuration when viewed along the c axis (Fig. 2). The iodide counter-ion resides in the channels formed by the (K–DMA) chains. With regards to the extended structure, there are very weak C—H···I interactions within the lattice (Table 2). These serve to locate the iodine in a pocket within the structure.

Database survey top

A search in the Cambridge Structure Database (CSD, Version 5.35, November 2013 plus three updates; Allen, 2002) for structures in which K is triple bridged in a µ₂-fashion by three O atoms returns 17 results, but only 3 of them are relevant to the structure reported herein. Gonzalez-Rodriguez et al. (2009) have shown a complex guanosine-derived nucleoside to crystallize as an acetone solvate monohydrate in which the six bridging K atoms are each coordinated to eight O atoms from eight guanosine ligands, and the two terminal K atoms are coordinated to eight O atoms from four guanosine ligands and either four acetone molecules or four water molecules. Cunningham et al. (2000) crystallized catena-[tetrakis[N,N''-bis(3-methoxysalicylidene)propane-1,3-diaminoato]iodidonickel(II)potassium], where K⁺ is bridged by four µ₂-O, one µ₂-N, and one µ₂-I. In fact, both of these structures contain four µ₂-O atoms bridging potassium atoms. No close K···K contacts were observed: the K···K distances are in the range 3.451 (2)–3.567 (2) Å. Most closely related is the structure of catena-[tris(µ₂-dimethylformamide-O,O)potassium iodide], reported by Batsanov & Struchkov (1994), with a K···K distance of 3.4170 (10) Å and a K—O distance of 2.6570 (13) Å. In the KI.DMA structure reported herein, the K1···K2 distance is 3.6728 (4) Å, which is longer by approximately 0.106 Å. In the Gonzalez-Rodriguez and Cunningham structures, iodine is found to form bonds to the K centers, while it is located in a channel within the Batsanov structure and not covalently bound. In KI.DMA reported here, the iodine is not covalently bonded to the cation chain.

A search in the CSD for free acetamide returned 180 results, featuring C=O bond lengths between 1.123 Å (Patra & Goldberg, 2013) and 1.67 Å (Gole et al., 2011), with a mean of 1.259 Å (std. dev. 0.059), which is very close to the C=O bond length reported herein [1.254 (3) Å].

Synthesis and crystallization top

A carbon–carbon Heck coupling reaction catalyzed by a Pd^II diphosphane precatalyst was performed using conditions established previously by Brase & de Meijere (1998). In a typical synthesis, 1-iodo-4-nitrobenzene (IC₆H₄NO₂; 102.1 mg, 0.41 mmol) was mixed with 2 equivalents of n-butyl acrylate [CH₂═CHCOO(CH₂)₃CH₃; 105.6 mg, 0.82 mmol] in the presence of K₂CO₃ (63.6 mg, 0.46 mmol) and n-Bu₄NBr (13 mg, 0.041 mmol) in dimethylacetamide (DMA) over a period of 4 h at 413 K. The title compound formed and was recrystallized from the filtered reaction mixture at room temperature. The target Pd^II complex of the reaction has been reported (Comanescu & Iluc, 2014).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were included in a riding model and allowed to rotate to minimize electron-density contribution. C—-H distances were set at 0.98 Å, with U_iso(H) = 1.5U_eq(C).

Related literature top

For related compounds:

Batsanov & Struchkov, 1994; Cunningham et al., 2000; Dias et al., 1995; Gonzalez-Rodriguez et al., 2009; Tikhonova et al., 2001.

For synthesis:

Brase & de Meijere, 1998; Comanescu & Iluc, 2014.

Computing details top

Data collection: APEXII (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The atom-labeling scheme for KI·DMA, with displacement ellipsoids depicted at the 50% probability level. [Symmetry codes: (i) -x, -y, -z; (ii) y, -x+y, -z; (iii) -y, x-y, z; (iv) x-y, x, -z; (v) -x+y, -x, z; (vi) x, y, z-1.]
	Fig. 2. (a) Packing diagram viewed along the b axis. (b) View along the c axis. Legend: black = carbon, dark blue = nitrogen, light blue = potassium, magenta = iodine, and red = oxygen. H atoms have been omitted for clarity.

catena-Poly[[potassium-tri-µ-dimethylacetamide-κ⁶O:O] iodide] top

Crystal data top

[K(C₄H₉NO)₃]I	D_x = 1.555 Mg m⁻³
M_r = 427.37	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 7529 reflections
a = 11.9776 (8) Å	θ = 2.7–26.3°
c = 7.3455 (7) Å	µ = 1.99 mm⁻¹
V = 912.62 (15) Å³	T = 120 K
Z = 2	Block, colorless
F(000) = 432	0.20 × 0.09 × 0.06 mm

Data collection top

Bruker APEX diffractometer	1248 independent reflections
Radiation source: fine-focus sealed tube	1194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.33 pixels mm^-1	θ_max = 26.3°, θ_min = 2.0°
combination of ω and ϕ–scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −14→14
T_min = 0.615, T_max = 0.745	l = −9→9
11940 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0227P)² + 1.7319P] where P = (F_o² + 2F_c²)/3
1248 reflections	(Δ/σ)_max = 0.001
65 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[K(C₄H₉NO)₃]I	Z = 2
M_r = 427.37	Mo Kα radiation
Trigonal, P3	µ = 1.99 mm⁻¹
a = 11.9776 (8) Å	T = 120 K
c = 7.3455 (7) Å	0.20 × 0.09 × 0.06 mm
V = 912.62 (15) Å³

Data collection top

Bruker APEX diffractometer	1248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	1194 reflections with I > 2σ(I)
T_min = 0.615, T_max = 0.745	R_int = 0.026
11940 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.07	Δρ_max = 1.14 e Å⁻³
1248 reflections	Δρ_min = −0.43 e Å⁻³
65 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.6667	0.3333	0.83886 (4)	0.02490 (11)
K1	0.0000	0.0000	0.0000	0.0172 (2)
O1	0.18933 (16)	0.14411 (16)	0.2481 (2)	0.0229 (4)
N1	0.3896 (2)	0.2882 (2)	0.3421 (3)	0.0262 (5)
C1	0.3288 (3)	0.3114 (3)	0.0349 (3)	0.0281 (5)
H1A	0.4093	0.3202	−0.0125	0.042*
H1B	0.3388	0.3971	0.0517	0.042*
H1C	0.2588	0.2620	−0.0516	0.042*
K2	0.0000	0.0000	0.5000	0.0227 (3)
C2	0.2970 (2)	0.2414 (2)	0.2163 (3)	0.0249 (5)
C3	0.5155 (3)	0.4036 (3)	0.3094 (4)	0.0320 (6)
H3A	0.5574	0.3884	0.2054	0.048*
H3B	0.5697	0.4223	0.4178	0.048*
H3C	0.5033	0.4770	0.2830	0.048*
C4	0.3621 (3)	0.2247 (3)	0.5200 (4)	0.0315 (6)
H4A	0.3164	0.1310	0.5031	0.047*
H4B	0.3083	0.2488	0.5913	0.047*
H4C	0.4432	0.2516	0.5848	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02578 (13)	0.02578 (13)	0.02315 (16)	0.01289 (6)	0.000	0.000
K1	0.0195 (4)	0.0195 (4)	0.0126 (5)	0.00975 (18)	0.000	0.000
O1	0.0183 (8)	0.0237 (9)	0.0202 (8)	0.0057 (7)	−0.0003 (6)	−0.0034 (7)
N1	0.0242 (11)	0.0271 (11)	0.0237 (10)	0.0100 (9)	0.0003 (8)	−0.0003 (8)
C1	0.0284 (13)	0.0352 (14)	0.0196 (12)	0.0152 (11)	0.0012 (10)	0.0047 (10)
K2	0.0278 (4)	0.0278 (4)	0.0123 (5)	0.0139 (2)	0.000	0.000
C2	0.0291 (13)	0.0286 (13)	0.0223 (12)	0.0185 (11)	0.0013 (10)	−0.0037 (10)
C3	0.0212 (12)	0.0280 (13)	0.0336 (14)	0.0025 (11)	0.0023 (10)	−0.0045 (11)
C4	0.0325 (14)	0.0321 (14)	0.0218 (12)	0.0100 (12)	−0.0043 (11)	0.0038 (10)

Geometric parameters (Å, º) top

K1—O1ⁱ	2.7437 (16)	C1—H1B	0.9800
K1—O1ⁱⁱ	2.7437 (16)	C1—H1C	0.9800
K1—O1ⁱⁱⁱ	2.7437 (16)	K2—O1^vii	2.7627 (16)
K1—O1^iv	2.7437 (16)	K2—O1^v	2.7627 (16)
K1—O1^v	2.7437 (16)	K2—O1^viii	2.7627 (16)
K1—O1	2.7438 (16)	K2—O1ⁱⁱⁱ	2.7627 (16)
K1—K2^vi	3.6728 (4)	K2—O1^ix	2.7627 (17)
K1—K2	3.6728 (4)	K2—K1^x	3.6728 (4)
O1—C2	1.254 (3)	C3—H3A	0.9800
O1—K2	2.7627 (16)	C3—H3B	0.9800
N1—C2	1.333 (3)	C3—H3C	0.9800
N1—C4	1.465 (3)	C4—H4A	0.9800
N1—C3	1.468 (3)	C4—H4B	0.9800
C1—C2	1.517 (3)	C4—H4C	0.9800
C1—H1A	0.9800

O1ⁱ—K1—O1ⁱⁱ	80.70 (5)	O1^v—K2—O1^viii	99.97 (5)
O1ⁱ—K1—O1ⁱⁱⁱ	99.30 (5)	O1^vii—K2—O1ⁱⁱⁱ	99.97 (5)
O1ⁱⁱ—K1—O1ⁱⁱⁱ	180.00 (7)	O1^v—K2—O1ⁱⁱⁱ	80.03 (5)
O1ⁱ—K1—O1^iv	80.70 (5)	O1^viii—K2—O1ⁱⁱⁱ	180.0
O1ⁱⁱ—K1—O1^iv	80.70 (5)	O1^vii—K2—O1^ix	80.03 (5)
O1ⁱⁱⁱ—K1—O1^iv	99.30 (5)	O1^v—K2—O1^ix	99.97 (5)
O1ⁱ—K1—O1^v	99.30 (5)	O1^viii—K2—O1^ix	80.03 (5)
O1ⁱⁱ—K1—O1^v	99.30 (5)	O1ⁱⁱⁱ—K2—O1^ix	99.97 (5)
O1ⁱⁱⁱ—K1—O1^v	80.70 (5)	O1^vii—K2—O1	99.97 (5)
O1^iv—K1—O1^v	180.00 (7)	O1^v—K2—O1	80.03 (5)
O1ⁱ—K1—O1	180.0	O1^viii—K2—O1	99.96 (5)
O1ⁱⁱ—K1—O1	99.30 (5)	O1ⁱⁱⁱ—K2—O1	80.04 (5)
O1ⁱⁱⁱ—K1—O1	80.70 (5)	O1^ix—K2—O1	180.0
O1^iv—K1—O1	99.30 (5)	O1^vii—K2—K1	132.06 (3)
O1^v—K1—O1	80.70 (5)	O1^v—K2—K1	47.94 (3)
O1ⁱ—K1—K2^vi	48.39 (3)	O1^viii—K2—K1	132.06 (3)
O1ⁱⁱ—K1—K2^vi	48.39 (3)	O1ⁱⁱⁱ—K2—K1	47.94 (3)
O1ⁱⁱⁱ—K1—K2^vi	131.61 (3)	O1^ix—K2—K1	132.06 (3)
O1^iv—K1—K2^vi	48.39 (3)	O1—K2—K1	47.94 (3)
O1^v—K1—K2^vi	131.61 (3)	O1^vii—K2—K1^x	47.94 (3)
O1—K1—K2^vi	131.61 (3)	O1^v—K2—K1^x	132.06 (3)
O1ⁱ—K1—K2	131.61 (3)	O1^viii—K2—K1^x	47.94 (3)
O1ⁱⁱ—K1—K2	131.61 (3)	O1ⁱⁱⁱ—K2—K1^x	132.06 (3)
O1ⁱⁱⁱ—K1—K2	48.39 (3)	O1^ix—K2—K1^x	47.94 (3)
O1^iv—K1—K2	131.61 (3)	O1—K2—K1^x	132.06 (3)
O1^v—K1—K2	48.39 (3)	K1—K2—K1^x	180.0
O1—K1—K2	48.39 (3)	O1—C2—N1	121.0 (2)
K2^vi—K1—K2	180.0	O1—C2—C1	122.3 (2)
C2—O1—K1	127.11 (15)	N1—C2—C1	116.8 (2)
C2—O1—K2	147.87 (15)	N1—C3—H3A	109.5
K1—O1—K2	83.67 (5)	N1—C3—H3B	109.5
C2—N1—C4	118.5 (2)	H3A—C3—H3B	109.5
C2—N1—C3	121.9 (2)	N1—C3—H3C	109.5
C4—N1—C3	119.6 (2)	H3A—C3—H3C	109.5
C2—C1—H1A	109.5	H3B—C3—H3C	109.5
C2—C1—H1B	109.5	N1—C4—H4A	109.5
H1A—C1—H1B	109.5	N1—C4—H4B	109.5
C2—C1—H1C	109.5	H4A—C4—H4B	109.5
H1A—C1—H1C	109.5	N1—C4—H4C	109.5
H1B—C1—H1C	109.5	H4A—C4—H4C	109.5
O1^vii—K2—O1^v	180.0	H4B—C4—H4C	109.5
O1^vii—K2—O1^viii	80.03 (5)

K1—O1—C2—N1	−167.19 (17)	C4—N1—C2—O1	−1.0 (4)
K2—O1—C2—N1	32.0 (4)	C3—N1—C2—O1	−178.7 (2)
K1—O1—C2—C1	12.8 (3)	C4—N1—C2—C1	179.0 (2)
K2—O1—C2—C1	−148.1 (2)	C3—N1—C2—C1	1.4 (4)

Symmetry codes: (i) −x, −y, −z; (ii) y, −x+y, −z; (iii) −y, x−y, z; (iv) x−y, x, −z; (v) −x+y, −x, z; (vi) x, y, z−1; (vii) x−y, x, −z+1; (viii) y, −x+y, −z+1; (ix) −x, −y, −z+1; (x) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···I1^vi	0.98	3.20	4.178 (3)	177
C3—H3A···I1^vi	0.98	3.20	4.178 (3)	174
C4—H4C···I1	0.98	3.00	3.967 (3)	170

Symmetry code: (vi) x, y, z−1.

Selected geometric parameters (Å, º) top

K1—O1	2.7438 (16)	O1—C2	1.254 (3)
K1—K2	3.6728 (4)	O1—K2	2.7627 (16)

O1ⁱ—K1—O1	180.0	O1ⁱⁱⁱ—K1—O1	80.70 (5)
O1ⁱⁱ—K1—O1	99.30 (5)

Symmetry codes: (i) −x, −y, −z; (ii) y, −x+y, −z; (iii) −y, x−y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···I1^iv	0.98	3.20	4.178 (3)	176.9
C3—H3A···I1^iv	0.98	3.20	4.178 (3)	173.5
C4—H4C···I1	0.98	3.00	3.967 (3)	170.4

Symmetry code: (iv) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[K(C₄H₉NO)₃]I
M_r	427.37
Crystal system, space group	Trigonal, P3
Temperature (K)	120
a, c (Å)	11.9776 (8), 7.3455 (7)
V (Å³)	912.62 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.99
Crystal size (mm)	0.20 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.615, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	11940, 1248, 1194
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.059, 1.07
No. of reflections	1248
No. of parameters	65
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.43

Computer programs: APEXII (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

CCC thanks Professor Vlad Iluc for insightful discussions.

References

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Volume 70| Part 10| October 2014| Pages 196-198

doi:10.1107/S1600536814020005

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