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Most halogenoacetates of alkali salts readily undergo a thermally induced polymerization reaction to poly-(hydroxyacetic acid) in the solid state. The lithium salts represent a remarkable exception. The crystal structures of lithium chloroacetate, lithium bromoacetate and lithium iodoacetate were determined ab initio from synchrotron powder diffraction data. The three compounds are isostructural and differ considerably from the structures of sodium chloroacetate and silver chloroacetate, two compounds that undergo polymerization. Most likely, the strong polarizing effect of the small lithium cation is responsible for the unfavorable crystal structure in which each lithium cation is coordinated to four O atoms from four different halogenoacetate molecules. Lithium chloroacetate: a = 9.3882 (9), b = 4.8452 (4), c = 9.0119 (7) Å, β = 94.330 (5)°; lithium bromoacetate: a = 9.7165 (11), b = 4.8610 (6), c = 9.0228 (11) Å, β = 93.946 (5)°; lithium iodoacetate: a = 10.1812 (10), b = 4.8922 (8), c = 9.0468 (10) Å, β = 93.251 (5)°, all crystallizing in space group P21/c with Z = 4.

Supporting information

cif

Crystallographic Information File (CIF)
Contains datablocks global, cl, br, i

rtv

Rietveld powder data file (CIF format)
Contains datablock br

rtv

Rietveld powder data file (CIF format)
Contains datablock cl

rtv

Rietveld powder data file (CIF format)
Contains datablock i

CCDC references: 134773; 134774; 134775

Computing details top

For all compounds, cell refinement: FULLPROF; program(s) used to refine structure: FULLPROF.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
(cl) chloroacetic acid, lithium salt top
Crystal data top
C2H2ClLiO2Z = 4
Mr = 100.43Melting point: 483.7 K
Monoclinic, P21/cSynchrotron radiation, λ = 1.2841 Å
a = 9.3882 (9) ÅT = 298 K
b = 4.8452 (4) ÅParticle morphology: platelets
c = 9.0119 (7) Åcolorless
β = 94.330 (5)°cylinder, ? × ? × ? mm
V = 408.76 (6) Å3
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
Scan method: step
Germanium monochromator2θmin = 6°, 2θmax = 60°, 2θstep = 0.01°
Refinement top
Rp = 3.25Profile function: Pseudo-Voigt
Rwp = 4.21
Rexp = 1.88Background function: Fixed background
χ2 = 5.018Preferred orientation correction: March's function
5938 data points
Crystal data top
C2H2ClLiO2β = 94.330 (5)°
Mr = 100.43V = 408.76 (6) Å3
Monoclinic, P21/cZ = 4
a = 9.3882 (9) ÅSynchrotron radiation, λ = 1.2841 Å
b = 4.8452 (4) ÅT = 298 K
c = 9.0119 (7) Åcylinder, ? × ? × ? mm
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
2θmin = 6°, 2θmax = 60°, 2θstep = 0.01°
Scan method: step
Refinement top
Rp = 3.25χ2 = 5.018
Rwp = 4.215938 data points
Rexp = 1.88
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl(1)0.3600 (7)0.139 (1)0.1519 (7)0.108
O(1)0.112 (1)0.316 (2)0.962 (1)0.005
O(2)0.098 (2)0.051 (3)0.826 (1)0.005
C(1)0.148 (2)0.089 (3)0.933 (2)0.005
C(2)0.279 (2)0.093 (3)0.008 (2)0.005
Li(1)0.007 (4)0.583 (7)0.856 (4)0.005
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl(1)0.026 (1)0.097 (2)0.021 (1)0.022 (1)0.008 (1)0.014 (1)
Geometric parameters (Å, º) top
Cl(1)—C(2)1.84Li(1)—O(1)1.91
C(1)—C(2)i1.62Li(1)—O(1)ii2.03
C(1)—O(1)1.19Li(1)—O(2)iii1.91
C(1)—O(2)1.24Li(1)—O(2)iv2.06
C(1)i—C(2)i—C(1)102.7O(1)—Li(1)—O(1)ii93.5
O(1)—C(1)—O(2)125.5O(2)iii—Li(1)—O(2)iv111.7
C(2)i—C(1)—O(1)129.6O(1)—Li(1)—O(2)iii113.9
C(2)i—C(1)—O(2)104.7O(1)—Li(1)—O(2)iv112.3
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.
(br) bromoacetic acid, lithium salt top
Crystal data top
C2H2BrLiO2Z = 4
Mr = 144.88Melting point: 478.5 K
Monoclinic, P21/cSynchrotron radiation, λ = 1.2841 Å
a = 9.7165 (11) ÅT = 298 K
b = 4.8610 (6) ÅParticle morphology: platelets
c = 9.0228 (11) Åcolorless
β = 93.946 (5)°cylinder, ? × ? × ? mm
V = 425.15 (9) Å3
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
Scan method: step
Germanium monochromator2θmin = 6°, 2θmax = 61°, 2θstep = 0.01°
Refinement top
Rp = 4.76Profile function: Pseudo-Voigt
Rwp = 6.18
Rexp = 2.76Background function: Fixed background
χ2 = 5.018Preferred orientation correction: March's function
6701 data points
Crystal data top
C2H2BrLiO2β = 93.946 (5)°
Mr = 144.88V = 425.15 (9) Å3
Monoclinic, P21/cZ = 4
a = 9.7165 (11) ÅSynchrotron radiation, λ = 1.2841 Å
b = 4.8610 (6) ÅT = 298 K
c = 9.0228 (11) Åcylinder, ? × ? × ? mm
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
2θmin = 6°, 2θmax = 61°, 2θstep = 0.01°
Scan method: step
Refinement top
Rp = 4.76χ2 = 5.018
Rwp = 6.186701 data points
Rexp = 2.76
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br(1)0.3679 (3)0.1644 (7)0.1544 (5)0.058
O(1)0.102 (1)0.305 (4)0.969 (2)0.004
O(2)0.089 (2)0.067 (3)0.824 (2)0.004
C(1)0.140 (3)0.070 (5)0.921 (3)0.004
C(2)0.269 (2)0.083 (5)0.010 (3)0.004
Li(1)0.000 (5)0.60 (1)0.858 (6)0.004
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br(1)0.009 (1)0.051 (1)0.016 (1)0.009 (1)0.009 (1)0.009 (1)
Geometric parameters (Å, º) top
Br(1)—C(2)1.97Li(1)—O(1)1.99
C(1)—C(2)i1.62Li(1)—O(1)ii1.97
C(1)—O(1)1.29Li(1)—O(2)iii1.99
C(1)—O(2)1.18Li(1)—O(2)iv1.85
Br(1)i—C(2)i—C(1)111.9O(1)—Li(1)—O(1)ii91.4
O(1)—C(1)—O(2)129.7O(2)iii—Li(1)—O(2)iv114.1
C(2)i—C(1)—O(1)117.8O(1)—Li(1)—O(2)iii119.6
C(2)i—C(1)—O(2)112.3O(1)—Li(1)—O(2)iv106.5
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.
(i) iodoacetic acid, lithium salt top
Crystal data top
C2H2ILiO(2)Z = 4
Mr = 191.88Melting point: 530.2 K
Monoclinic, P21/cSynchrotron radiation, λ = 1.2006 Å
a = 10.1812 (10) ÅT = 298 K
b = 4.8922 (8) ÅParticle morphology: platelets
c = 9.0468 (10) Åcolorless
β = 93.251 (5)°cylinder, ? × ? × ? mm
V = 449.89 (10) Å3
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
Scan method: step
Germanium monochromator2θmin = 6°, 2θmax = 50°, 2θstep = 0.01°
Refinement top
Rp = 5.64Profile function: Pseudo-Voigt
Rwp = 7.40
Rexp = 3.65Background function: Fixed background
χ2 = 4.121Preferred orientation correction: March's function
4401 data points
Crystal data top
C2H2ILiO(2)β = 93.251 (5)°
Mr = 191.88V = 449.89 (10) Å3
Monoclinic, P21/cZ = 4
a = 10.1812 (10) ÅSynchrotron radiation, λ = 1.2006 Å
b = 4.8922 (8) ÅT = 298 K
c = 9.0468 (10) Åcylinder, ? × ? × ? mm
Data collection top
HASYLAB (Hamburg, Germany), Beamline B2
diffractometer
2θmin = 6°, 2θmax = 50°, 2θstep = 0.01°
Scan method: step
Refinement top
Rp = 5.64χ2 = 4.121
Rwp = 7.404401 data points
Rexp = 3.65
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I(1)0.3739 (4)0.181 (2)0.1504 (8)0.120
O(1)0.106 (5)0.32 (1)0.953 (7)0.038
O(2)0.078 (3)0.07 (1)0.831 (6)0.038
C(1)0.127 (8)0.07 (2)0.94 (1)0.038
C(2)0.249 (5)0.09 (1)0.039 (9)0.038
Li(1)0.01 (1)0.51 (4)0.81 (2)0.038
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I(1)0.006 (1)0.28 (1)0.004 (1)0.012 (4)0.009 (1)0.013 (6)
Geometric parameters (Å, º) top
I(1)—C(2)2.07Li(1)—O(1)1.78
C(1)—C(2)i1.68Li(1)—O(1)ii2.63
C(1)—O(1)1.21Li(1)—O(2)iii1.63
C(1)—O(2)1.33Li(1)—O(2)iv2.14
I(1)i—C(2)i—C(1)110.2O(1)—Li(1)—O(1)ii82.0
O(1)—C(1)—O(2)121.7O(2)iii—Li(1)—O(2)iv116.9
C(2)i—C(1)—O(1)125.0O(1)—Li(1)—O(2)iii133.9
C(2)i—C(1)—O(2)111.1O(1)—Li(1)—O(2)iv107.8
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.

Experimental details

(cl)(br)(i)
Crystal data
Chemical formulaC2H2ClLiO2C2H2BrLiO2C2H2ILiO(2)
Mr100.43144.88191.88
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)298298298
a, b, c (Å)9.3882 (9), 4.8452 (4), 9.0119 (7)9.7165 (11), 4.8610 (6), 9.0228 (11)10.1812 (10), 4.8922 (8), 9.0468 (10)
β (°) 94.330 (5) 93.946 (5) 93.251 (5)
V3)408.76 (6)425.15 (9)449.89 (10)
Z444
Radiation typeSynchrotron, λ = 1.2841 ÅSynchrotron, λ = 1.2841 ÅSynchrotron, λ = 1.2006 Å
Specimen shape, size (mm)Cylinder, ? × ? × ?Cylinder, ? × ? × ?Cylinder, ? × ? × ?
Data collection
Data collection methodHASYLAB (Hamburg, Germany), Beamline B2HASYLAB (Hamburg, Germany), Beamline B2HASYLAB (Hamburg, Germany), Beamline B2
Specimen mounting???
Data collection mode???
Scan methodStepStepStep
2θ values (°)2θmin = 6 2θmax = 60 2θstep = 0.012θmin = 6 2θmax = 61 2θstep = 0.012θmin = 6 2θmax = 50 2θstep = 0.01
Refinement
R factors and goodness of fitRp = 3.25, Rwp = 4.21, Rexp = 1.88, χ2 = 5.018Rp = 4.76, Rwp = 6.18, Rexp = 2.76, χ2 = 5.018Rp = 5.64, Rwp = 7.40, Rexp = 3.65, χ2 = 4.121
No. of data points593867014401
No. of parameters???
No. of restraints???

Computer programs: FULLPROF.

Selected geometric parameters (Å, º) for (cl) top
Cl(1)—C(2)1.84Li(1)—O(1)1.91
C(1)—C(2)i1.62Li(1)—O(1)ii2.03
C(1)—O(1)1.19Li(1)—O(2)iii1.91
C(1)—O(2)1.24Li(1)—O(2)iv2.06
C(1)i—C(2)i—C(1)102.7O(1)—Li(1)—O(1)ii93.5
O(1)—C(1)—O(2)125.5O(2)iii—Li(1)—O(2)iv111.7
C(2)i—C(1)—O(1)129.6O(1)—Li(1)—O(2)iii113.9
C(2)i—C(1)—O(2)104.7O(1)—Li(1)—O(2)iv112.3
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.
Selected geometric parameters (Å, º) for (br) top
Br(1)—C(2)1.97Li(1)—O(1)1.99
C(1)—C(2)i1.62Li(1)—O(1)ii1.97
C(1)—O(1)1.29Li(1)—O(2)iii1.99
C(1)—O(2)1.18Li(1)—O(2)iv1.85
Br(1)i—C(2)i—C(1)111.9O(1)—Li(1)—O(1)ii91.4
O(1)—C(1)—O(2)129.7O(2)iii—Li(1)—O(2)iv114.1
C(2)i—C(1)—O(1)117.8O(1)—Li(1)—O(2)iii119.6
C(2)i—C(1)—O(2)112.3O(1)—Li(1)—O(2)iv106.5
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.
Selected geometric parameters (Å, º) for (i) top
I(1)—C(2)2.07Li(1)—O(1)1.78
C(1)—C(2)i1.68Li(1)—O(1)ii2.63
C(1)—O(1)1.21Li(1)—O(2)iii1.63
C(1)—O(2)1.33Li(1)—O(2)iv2.14
I(1)i—C(2)i—C(1)110.2O(1)—Li(1)—O(1)ii82.0
O(1)—C(1)—O(2)121.7O(2)iii—Li(1)—O(2)iv116.9
C(2)i—C(1)—O(1)125.0O(1)—Li(1)—O(2)iii133.9
C(2)i—C(1)—O(2)111.1O(1)—Li(1)—O(2)iv107.8
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+2; (iii) x, y+1/2, z+3/2; (iv) x, y+1, z.
 

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