Redetermination of catena-poly[[sodium(I)-tri-μ-dimethyl­formamide-κ6O:O] iodide] at 140 K

Chessa, S.; Wright, J.A.

doi:10.1107/S1600536807007052

metal-organic compounds

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Volume 63| Part 3| March 2007| Pages m787-m789

https://doi.org/10.1107/S1600536807007052

Redetermination of catena-poly[[sodium(I)-tri-μ-dimethylformamide-κ⁶O:O] iodide] at 140 K

Simona Chessa ^a and Joseph A. Wright ^a ^*

^aSchool of Chemical Sciences and Pharmacy, University of East Anglia, Norwich NR4 7TJ, England
^*Correspondence e-mail: joseph.wright@uea.ac.uk

(Received 22 January 2007; accepted 11 February 2007; online 21 February 2007)

The structure of the title compound, {[Na(C₃H₇NO)₃]I}_n, has been redetermined at 140 (2) K. The Na⁺ cations lie on sites of 32 point symmetry and are linked into one-dimensional chains via bridging DMF molecules lying on mirror planes. The coordination geometry of Na⁺ is intermediate between octahedral and trigonal prismatic. The I⁻ anions lie on sites of $[\overline{6}]$ point symmetry between the chains.

Comment

The structure of the title compound, (I), has been determined previously at room temperature (Gobillon et al., 1962 ; Batsanov & Struchkov, 1994 ). In the first case, all atoms were refined using only isotropic displacement parameters. The second determination gave unsatisfactory R values (R = 0.140). Compound (I) has been obtained as a by-product of a Heck reaction involving an aryl iodide in DMF, using Na₂CO₃ as base. We have taken this opportunity to redetermine the structure of (I) at 140 (2) K, leading to significantly improved precision.

The Na⁺ cation in (I) is coordinated by six DMF molecules lying on mirror planes (Fig. 1). The bond distances (Table 1) and coplanar nature of O1, C1 and N1 suggests a degree of double-bond character between C1 and N1 in addition to that between C1 and O1. This suggests the presence of a partial positive charge on N1 and a partial negative charge on O1, as suggested by Gobillon et al. (1962), which may lead to enhanced electrostatic interaction between the DMF molecules and the Na⁺ cation.

The geometry at Na1 is intermediate between octahedral and trigonal prismatic; when viewed along the c axis (Fig. 2), the angle between O atoms in successive layers is 29.0°. The bridging DMF molecules generate one-dimensional chains along c. The positions of the DMF molecules alternate along the c axis, leading to an ABAB pattern of DMF sites.

Gobillon et al. (1962) have described the structure of (I) as containing C—H⋯I hydrogen bonds, involving C1 and C3. The C⋯I distances determined in the current study [C1⋯I1 = 4.261 (3) and C3⋯I1 4.349 (4) Å] are outside the normal range for such an interaction, based on the van der Waals radii of the elements involved (Pauling, 1960 ). The interaction of the cationic polymer with the anions is, therefore, best described as largely electrostatic.

Figure 1
Part of the polymeric structure of (I)

, viewed approximately perpendicular to the c axis, showing displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted. [Symmetry codes: (i) −x + y, −x, $[{1\over 2}]$ − z; (ii) y, x, − $[{1\over 2}]$ + z; (iii) −y, x − y, z; (iv) y, x, $[{1\over 2}]$ + z; (v) −x, −x + y, − $[{1\over 2}]$ + z; (vi) −x, −x + y, $[{1\over 2}]$ + z; (vii) x − y, −y, −z; (viii) x − y, −y, 1 − z.]

Figure 2
Perspective view of (I)

along the c axis. H atoms have been omitted.

Experimental

Crystals of (I) were obtained by crystallization from a hexane–chloroform (1:1) mixture of the solid residues from a Heck reaction. A mixture of 1-butyl-3-methylimidazolium hexafluorophosphate (0.188 ml, 1.0 mmol), Pd(OAc)₂ (112 mg, 0.50 mmol) and triphenylphosphane (256 mg, 1.0 mmol) was suspended in dry tetrahydrofuran (15 ml) and stirred overnight under nitrogen. The resulting brown suspension was evaporated in vacuo and washed with CH₂Cl₂. The dried residue was then used as a catalyst for a Mizoroki–Heck reaction, according to the following typical procedure. Iodobenzene (1.0 mmol), sodium acetate (1.5 mmol), and tert-butyl acrylate (1.4 mmol) were placed in a Schlenk tube under N₂, and the reagents were suspended in dimethylformamide (DMF, 3 ml), before injection of the catalyst (0.05 mmol) in DMF (3 ml). The reaction mixture was stirred for 8 h at 353 K, before cooling and extraction of the organic components with several portions of hexane. Extraction of the residue with chloroform followed by layering with hexane yielded crystals of (I).

Crystal data

[Na(C₃H₇NO)₃]I
M_r = 369.18
Hexagonal, $[P \overline 62c ]$
a = 11.8038 (14) Å
c = 6.3881 (7) Å
V = 770.81 (15) Å³
Z = 2
Mo Kα radiation
μ = 2.11 mm⁻¹
T = 140 (2) K
0.25 × 0.04 × 0.01 mm

Data collection

Oxford Diffraction Xcalibur3 CCD diffractometer
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). ABSPACK, CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.621, T_max = 0.979
10001 measured reflections
657 independent reflections
607 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.032
S = 1.01
657 reflections
37 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ), 281 Friedel pairs
Flack parameter: 0.00 (3)

Table 1
Selected geometric parameters (Å, °)

C1—O1	1.238 (3)
C1—N1	1.316 (4)
C2—N1	1.460 (5)
C3—N1	1.457 (4)
Na1—O1	2.3954 (15)

O1—Na1—O1ⁱ	80.40 (5)
O1—Na1—O1ⁱⁱ	87.62 (7)
Symmetry codes: (i) $[-x+y, -x, -z+{\script{1\over 2}}]$ ; (ii) $[y, x, z-{\script{1\over 2}}]$ .

H atoms were included in calculated positions and refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for H1, and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methyl groups. The methyl groups were allowed to rotate about their local threefold axes.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). ABSPACK, CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). ABSPACK, CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003 ), WinGX (Farrugia, 1999 ) and enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807007052/bi2152sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007052/bi2152Isup2.hkl

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

catena-poly[[sodium(I)-tri-µ-dimethylformamide-κ⁶O:O] iodide] top

Crystal data top

[Na(C₃H₇NO)₃]I	D_x = 1.591 Mg m⁻³
M_r = 369.18	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P62c	Cell parameters from 4526 reflections
Hall symbol: P -6c -2c	θ = 3.8–27.5°
a = 11.8038 (14) Å	µ = 2.11 mm⁻¹
c = 6.3881 (7) Å	T = 140 K
V = 770.81 (15) Å³	Needle, colourless
Z = 2	0.25 × 0.04 × 0.01 mm
F(000) = 368

Data collection top

Oxford Diffraction Xcalibur3 CCD diffractometer	657 independent reflections
Radiation source: Enhance (Mo) X-ray Source	607 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Thin–slice φ and ω scans	θ_max = 27.6°, θ_min = 3.8°
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006)	h = −15→15
T_min = 0.621, T_max = 0.979	k = −15→15
10001 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.032	w = 1/[σ²(F_o²) + (0.0162P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
657 reflections	Δρ_max = 0.41 e Å⁻³
37 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 281 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (3)

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2666 (3)	0.2349 (3)	0.2500	0.0182 (6)
H1	0.3494	0.2396	0.2500	0.022*
C2	0.1453 (3)	0.3513 (4)	0.2500	0.0249 (9)
H2A	0.0717	0.2648	0.2152	0.037*	0.50
H2B	0.1515	0.4151	0.1458	0.037*	0.50
H2C	0.1315	0.3775	0.3890	0.037*	0.50
C3	0.3875 (3)	0.4718 (3)	0.2500	0.0261 (8)
H3A	0.3957	0.5170	0.3826	0.039*	0.50
H3B	0.3864	0.5254	0.1337	0.039*	0.50
H3C	0.4620	0.4575	0.2336	0.039*	0.50
I1	0.6667	0.3333	0.2500	0.02405 (9)
N1	0.2663 (3)	0.3463 (3)	0.2500	0.0197 (6)
Na1	0.0000	0.0000	0.0000	0.0191 (3)
O1	0.1683 (2)	0.12459 (19)	0.2500	0.0206 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0183 (16)	0.0198 (16)	0.0173 (15)	0.0100 (14)	0.000	0.000
C2	0.021 (2)	0.0151 (17)	0.0412 (19)	0.0106 (15)	0.000	0.000
C3	0.0259 (18)	0.0160 (16)	0.0264 (18)	0.0029 (15)	0.000	0.000
I1	0.02509 (11)	0.02509 (11)	0.02196 (14)	0.01255 (6)	0.000	0.000
N1	0.0200 (16)	0.0160 (15)	0.0238 (14)	0.0095 (14)	0.000	0.000
Na1	0.0177 (5)	0.0177 (5)	0.0219 (8)	0.0088 (2)	0.000	0.000
O1	0.0156 (11)	0.0141 (10)	0.0298 (12)	0.0057 (9)	0.000	0.000

Geometric parameters (Å, º) top

C1—O1	1.238 (3)	C3—H3A	0.980
C1—N1	1.316 (4)	C3—H3B	0.980
C1—H1	0.950	C3—H3C	0.980
C2—N1	1.460 (5)	Na1—O1	2.3954 (15)
C2—H2A	0.980	Na1—O1ⁱ	2.3954 (15)
C2—H2B	0.980	Na1—O1ⁱⁱ	2.3954 (15)
C2—H2C	0.980	Na1—Na1ⁱⁱⁱ	3.1941 (4)
C3—N1	1.457 (4)	O1—Na1ⁱⁱⁱ	2.3954 (15)

O1—C1—N1	125.5 (3)	O1—Na1—O1ⁱ	117.02 (8)
O1—C1—H1	117.2	O1ⁱⁱⁱ—Na1—O1ⁱ	87.62 (7)
N1—C1—H1	117.2	O1^v—Na1—O1ⁱ	80.40 (5)
N1—C2—H2A	109.5	O1^iv—Na1—O1ⁱⁱ	87.62 (7)
N1—C2—H2B	109.5	O1—Na1—O1ⁱⁱ	80.40 (5)
H2A—C2—H2B	109.5	O1ⁱⁱⁱ—Na1—O1ⁱⁱ	80.40 (5)
N1—C2—H2C	109.5	O1^v—Na1—O1ⁱⁱ	117.02 (8)
H2A—C2—H2C	109.5	O1ⁱ—Na1—O1ⁱⁱ	157.01 (9)
H2B—C2—H2C	109.5	O1^iv—Na1—Na1^vi	48.19 (3)
N1—C3—H3A	109.5	O1—Na1—Na1^vi	131.81 (3)
N1—C3—H3B	109.5	O1ⁱⁱⁱ—Na1—Na1^vi	131.81 (3)
H3A—C3—H3B	109.5	O1^v—Na1—Na1^vi	48.19 (3)
N1—C3—H3C	109.5	O1ⁱ—Na1—Na1^vi	48.19 (3)
H3A—C3—H3C	109.5	O1ⁱⁱ—Na1—Na1^vi	131.81 (3)
H3B—C3—H3C	109.5	O1^iv—Na1—Na1ⁱⁱⁱ	131.81 (3)
C1—N1—C3	121.6 (3)	O1—Na1—Na1ⁱⁱⁱ	48.19 (3)
C1—N1—C2	122.2 (3)	O1ⁱⁱⁱ—Na1—Na1ⁱⁱⁱ	48.19 (3)
C3—N1—C2	116.2 (3)	O1^v—Na1—Na1ⁱⁱⁱ	131.81 (3)
O1^iv—Na1—O1	157.01 (9)	O1ⁱ—Na1—Na1ⁱⁱⁱ	131.81 (3)
O1^iv—Na1—O1ⁱⁱⁱ	117.02 (8)	O1ⁱⁱ—Na1—Na1ⁱⁱⁱ	48.19 (3)
O1—Na1—O1ⁱⁱⁱ	80.40 (5)	Na1^vi—Na1—Na1ⁱⁱⁱ	180.0
O1^iv—Na1—O1^v	80.40 (5)	C1—O1—Na1	134.40 (8)
O1—Na1—O1^v	87.62 (7)	C1—O1—Na1ⁱⁱⁱ	134.40 (8)
O1ⁱⁱⁱ—Na1—O1^v	157.01 (9)	Na1—O1—Na1ⁱⁱⁱ	83.62 (6)
O1^iv—Na1—O1ⁱ	80.40 (5)

Symmetry codes: (i) x−y, −y, −z; (ii) −y, x−y, z; (iii) −x+y, −x, −z+1/2; (iv) −x, −x+y, z−1/2; (v) y, x, z−1/2; (vi) −x+y, −x, −z−1/2.

Acknowledgements

The authors thank the EPSRC for funding and Dr David Hughes for the provision of X-ray facilities.

References

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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m787-m789

https://doi.org/10.1107/S1600536807007052

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