research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 196-198

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

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.

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[Tikhonova, I. A., Dolgushin, F. M., Tugashov, K. I., Furin, G. G., Petrovskii, P. V. & Shur, V. B. (2001). Russ. Chem. Bull. Int. Ed. 50, 1673-1678.]) 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[Dias, R. H. V., Huai, L., Jin, W. & Bott, S. G. (1995). Inorg. Chem. 34, 1973-1974.]) 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[Dias, R. H. V., Huai, L., Jin, W. & Bott, S. G. (1995). Inorg. Chem. 34, 1973-1974.]).

[Scheme 1]

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[link] and Table 1[link]). The C=O distance is comparable with that in free di­methyl­acetamide (see Database survey[link]). 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]
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[link]).

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[link]). 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[link]). 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 DA D—H⋯A
C1—H1A⋯I1iv 0.98 3.20 4.178 (3) 177
C3—H3A⋯I1iv 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]
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[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) 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[Gonzalez-Rodriguez, D., van Dongen, J. L. J., Lutz, M., Spek, A. L., Schenning, A. P. H. J. & Meijer, E. W. (2009). Nat. Chem. 1, 151-155.]) 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[Cunningham, D., McArdle, P., Mitchell, M., Chonchubhair, N. N., O'Gara, M., Franceschi, F. & Floriani, C. (2000). Inorg. Chem. 39, 1639-1649.]) 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[Batsanov, A. S. & Struchkov, Y. T. (1994). Koord. Khim. 20, 354-356.]), 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[Patra, R. & Goldberg, I. (2013). Acta Cryst. C69, 344-347.]) and 1.67 Å (Gole et al., 2011[Gole, B., Bar, A. K. & Mukherjee, P. S. (2011). Chem. Commun. 47, 12137-12139.]), 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 PdII diphosphane precatalyst was performed using conditions established previously by Brase & de Meijere (1998[Brase, S. & de Meijere, A. (1998). Metal-catalyzed Cross-coupling Reactions, pp. 99-166. New York: Wiley-VCH.]). 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 PdII complex of the reaction has been reported (Comanescu & Iluc, 2014[Comanescu, C.-C. & Iluc, V. (2014). Inorg. Chem. 53, 8517-8528.]).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. 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 Uiso(H) = 1.5Ueq(C).

Table 3
Experimental details

Crystal data
Chemical formula [K(C4H9NO)3]I
Mr 427.37
Crystal system, space group Trigonal, P[\overline{3}]
Temperature (K) 120
a, c (Å) 11.9776 (8), 7.3455 (7)
V3) 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[Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.615, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections 11940, 1248, 1194
Rint 0.026
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 1.14, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL2013 and XP in SHELXTL (Sheldrick, 2013[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 OC(CH3)-N(CH3)2 di­methyl­acetamide (DMA) moieties, with each oxygen adopting a µ2-bridging mode (Fig. 1 and Table 1). The CO 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 PdII 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 [CH2CHCOO(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 PdII 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 Uiso(H) = 1.5Ueq(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
[Figure 1] 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.]
[Figure 2] 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]IDx = 1.555 Mg m3
Mr = 427.37Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3Cell parameters from 7529 reflections
a = 11.9776 (8) Åθ = 2.7–26.3°
c = 7.3455 (7) ŵ = 1.99 mm1
V = 912.62 (15) Å3T = 120 K
Z = 2Block, colorless
F(000) = 4320.20 × 0.09 × 0.06 mm
Data collection top
Bruker APEX
diffractometer
1248 independent reflections
Radiation source: fine-focus sealed tube1194 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.33 pixels mm-1θmax = 26.3°, θmin = 2.0°
combination of ω and ϕ–scansh = 1414
Absorption correction: multi-scan
(SADABS; Bruker, 2012)
k = 1414
Tmin = 0.615, Tmax = 0.745l = 99
11940 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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0227P)2 + 1.7319P]
where P = (Fo2 + 2Fc2)/3
1248 reflections(Δ/σ)max = 0.001
65 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
[K(C4H9NO)3]IZ = 2
Mr = 427.37Mo Kα radiation
Trigonal, P3µ = 1.99 mm1
a = 11.9776 (8) ÅT = 120 K
c = 7.3455 (7) Å0.20 × 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)
Tmin = 0.615, Tmax = 0.745Rint = 0.026
11940 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.059H-atom parameters constrained
S = 1.07Δρmax = 1.14 e Å3
1248 reflectionsΔρmin = 0.43 e Å3
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
xyzUiso*/Ueq
I10.66670.33330.83886 (4)0.02490 (11)
K10.00000.00000.00000.0172 (2)
O10.18933 (16)0.14411 (16)0.2481 (2)0.0229 (4)
N10.3896 (2)0.2882 (2)0.3421 (3)0.0262 (5)
C10.3288 (3)0.3114 (3)0.0349 (3)0.0281 (5)
H1A0.40930.32020.01250.042*
H1B0.33880.39710.05170.042*
H1C0.25880.26200.05160.042*
K20.00000.00000.50000.0227 (3)
C20.2970 (2)0.2414 (2)0.2163 (3)0.0249 (5)
C30.5155 (3)0.4036 (3)0.3094 (4)0.0320 (6)
H3A0.55740.38840.20540.048*
H3B0.56970.42230.41780.048*
H3C0.50330.47700.28300.048*
C40.3621 (3)0.2247 (3)0.5200 (4)0.0315 (6)
H4A0.31640.13100.50310.047*
H4B0.30830.24880.59130.047*
H4C0.44320.25160.58480.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02578 (13)0.02578 (13)0.02315 (16)0.01289 (6)0.0000.000
K10.0195 (4)0.0195 (4)0.0126 (5)0.00975 (18)0.0000.000
O10.0183 (8)0.0237 (9)0.0202 (8)0.0057 (7)0.0003 (6)0.0034 (7)
N10.0242 (11)0.0271 (11)0.0237 (10)0.0100 (9)0.0003 (8)0.0003 (8)
C10.0284 (13)0.0352 (14)0.0196 (12)0.0152 (11)0.0012 (10)0.0047 (10)
K20.0278 (4)0.0278 (4)0.0123 (5)0.0139 (2)0.0000.000
C20.0291 (13)0.0286 (13)0.0223 (12)0.0185 (11)0.0013 (10)0.0037 (10)
C30.0212 (12)0.0280 (13)0.0336 (14)0.0025 (11)0.0023 (10)0.0045 (11)
C40.0325 (14)0.0321 (14)0.0218 (12)0.0100 (12)0.0043 (11)0.0038 (10)
Geometric parameters (Å, º) top
K1—O1i2.7437 (16)C1—H1B0.9800
K1—O1ii2.7437 (16)C1—H1C0.9800
K1—O1iii2.7437 (16)K2—O1vii2.7627 (16)
K1—O1iv2.7437 (16)K2—O1v2.7627 (16)
K1—O1v2.7437 (16)K2—O1viii2.7627 (16)
K1—O12.7438 (16)K2—O1iii2.7627 (16)
K1—K2vi3.6728 (4)K2—O1ix2.7627 (17)
K1—K23.6728 (4)K2—K1x3.6728 (4)
O1—C21.254 (3)C3—H3A0.9800
O1—K22.7627 (16)C3—H3B0.9800
N1—C21.333 (3)C3—H3C0.9800
N1—C41.465 (3)C4—H4A0.9800
N1—C31.468 (3)C4—H4B0.9800
C1—C21.517 (3)C4—H4C0.9800
C1—H1A0.9800
O1i—K1—O1ii80.70 (5)O1v—K2—O1viii99.97 (5)
O1i—K1—O1iii99.30 (5)O1vii—K2—O1iii99.97 (5)
O1ii—K1—O1iii180.00 (7)O1v—K2—O1iii80.03 (5)
O1i—K1—O1iv80.70 (5)O1viii—K2—O1iii180.0
O1ii—K1—O1iv80.70 (5)O1vii—K2—O1ix80.03 (5)
O1iii—K1—O1iv99.30 (5)O1v—K2—O1ix99.97 (5)
O1i—K1—O1v99.30 (5)O1viii—K2—O1ix80.03 (5)
O1ii—K1—O1v99.30 (5)O1iii—K2—O1ix99.97 (5)
O1iii—K1—O1v80.70 (5)O1vii—K2—O199.97 (5)
O1iv—K1—O1v180.00 (7)O1v—K2—O180.03 (5)
O1i—K1—O1180.0O1viii—K2—O199.96 (5)
O1ii—K1—O199.30 (5)O1iii—K2—O180.04 (5)
O1iii—K1—O180.70 (5)O1ix—K2—O1180.0
O1iv—K1—O199.30 (5)O1vii—K2—K1132.06 (3)
O1v—K1—O180.70 (5)O1v—K2—K147.94 (3)
O1i—K1—K2vi48.39 (3)O1viii—K2—K1132.06 (3)
O1ii—K1—K2vi48.39 (3)O1iii—K2—K147.94 (3)
O1iii—K1—K2vi131.61 (3)O1ix—K2—K1132.06 (3)
O1iv—K1—K2vi48.39 (3)O1—K2—K147.94 (3)
O1v—K1—K2vi131.61 (3)O1vii—K2—K1x47.94 (3)
O1—K1—K2vi131.61 (3)O1v—K2—K1x132.06 (3)
O1i—K1—K2131.61 (3)O1viii—K2—K1x47.94 (3)
O1ii—K1—K2131.61 (3)O1iii—K2—K1x132.06 (3)
O1iii—K1—K248.39 (3)O1ix—K2—K1x47.94 (3)
O1iv—K1—K2131.61 (3)O1—K2—K1x132.06 (3)
O1v—K1—K248.39 (3)K1—K2—K1x180.0
O1—K1—K248.39 (3)O1—C2—N1121.0 (2)
K2vi—K1—K2180.0O1—C2—C1122.3 (2)
C2—O1—K1127.11 (15)N1—C2—C1116.8 (2)
C2—O1—K2147.87 (15)N1—C3—H3A109.5
K1—O1—K283.67 (5)N1—C3—H3B109.5
C2—N1—C4118.5 (2)H3A—C3—H3B109.5
C2—N1—C3121.9 (2)N1—C3—H3C109.5
C4—N1—C3119.6 (2)H3A—C3—H3C109.5
C2—C1—H1A109.5H3B—C3—H3C109.5
C2—C1—H1B109.5N1—C4—H4A109.5
H1A—C1—H1B109.5N1—C4—H4B109.5
C2—C1—H1C109.5H4A—C4—H4B109.5
H1A—C1—H1C109.5N1—C4—H4C109.5
H1B—C1—H1C109.5H4A—C4—H4C109.5
O1vii—K2—O1v180.0H4B—C4—H4C109.5
O1vii—K2—O1viii80.03 (5)
K1—O1—C2—N1167.19 (17)C4—N1—C2—O11.0 (4)
K2—O1—C2—N132.0 (4)C3—N1—C2—O1178.7 (2)
K1—O1—C2—C112.8 (3)C4—N1—C2—C1179.0 (2)
K2—O1—C2—C1148.1 (2)C3—N1—C2—C11.4 (4)
Symmetry codes: (i) x, y, z; (ii) y, x+y, z; (iii) y, xy, z; (iv) xy, x, z; (v) x+y, x, z; (vi) x, y, z1; (vii) xy, 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···AD—HH···AD···AD—H···A
C1—H1A···I1vi0.983.204.178 (3)177
C3—H3A···I1vi0.983.204.178 (3)174
C4—H4C···I10.983.003.967 (3)170
Symmetry code: (vi) x, y, z1.
Selected geometric parameters (Å, º) top
K1—O12.7438 (16)O1—C21.254 (3)
K1—K23.6728 (4)O1—K22.7627 (16)
O1i—K1—O1180.0O1iii—K1—O180.70 (5)
O1ii—K1—O199.30 (5)
Symmetry codes: (i) x, y, z; (ii) y, x+y, z; (iii) y, xy, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···I1iv0.983.204.178 (3)176.9
C3—H3A···I1iv0.983.204.178 (3)173.5
C4—H4C···I10.983.003.967 (3)170.4
Symmetry code: (iv) x, y, z1.

Experimental details

Crystal data
Chemical formula[K(C4H9NO)3]I
Mr427.37
Crystal system, space groupTrigonal, P3
Temperature (K)120
a, c (Å)11.9776 (8), 7.3455 (7)
V3)912.62 (15)
Z2
Radiation typeMo Kα
µ (mm1)1.99
Crystal size (mm)0.20 × 0.09 × 0.06
Data collection
DiffractometerBruker APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2012)
Tmin, Tmax0.615, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections
11940, 1248, 1194
Rint0.026
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.059, 1.07
No. of reflections1248
No. of parameters65
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

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