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The low-temperature crystal structures of tetramethylammonium perchlorate, [(CH_{3})_{4}N](ClO_{4}), are analysed. At 210 K, a collection of 376 unique reflections on a single crystal gave R = 0.0567 for space group P4/nmm, with a_{1} ={}8.2376 (14), c_{1} = 5.8256 (12) Å and Z = 2, where the ClO_{4} groups are disordered over four orientations. Below T_{c} = 170 K, these groups order in four sublattices, each ion gradually choosing one unique orientation. At 150 K, the crystal is microtwinned. 1389 unique reflections were refined in the orthorhombic space group P2_{1}2_{1}2, with a_{3} = 11.714 (3), b_{3} = 11.784 (3), c_{3} = 5.8265 (9) Å, Z = 4 and R = 0.087. At 30 K, Rietveld refinement gave the same structure as is found at 150 K, with a clear difference between a_{3} and b_{3} [a_{3} = 11.566 (2), b_{3} = 11.806 (2) and c_{3} = 5.729 (1) Å]. The structural models and the phase transition are explained on the basis of electrostatic octopole-octopole interactions among the ClO_{4} groups within layers perpendicular to the c axis. The order parameters of the low-temperature phase are discussed in relation to the structural results.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103019013/bs0018sup1.cif
Contains datablocks I, II, global, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IIsup3.hkl
Contains datablock II

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IIIsup4.rtv
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IVsup5.hkl
Contains datablock IV

CCDC references: 223324; 223325; 223326; 223327

Computing details top

Data collection: Siemens XSCANS for (I), (II); Rigaku IUSA 2.8 for (III), (IV). Cell refinement: FULLPROF for (I), (II); FULLPROF (Rodriguez-Carvajal et al. 1987) for (III), (IV). Data reduction: Siemens XSCANS for (I), (II); FULLPROF for (III), (IV). Program(s) used to solve structure: none for (III), (IV). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I), (II); FULLPROF for (III), (IV).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
(I) Tetramethylammonium perchlorate top
Crystal data top
C4H12N·ClO4Dx = 1.434 Mg m3
Mr = 173.60Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212Cell parameters from 55 reflections
a = 11.714 (3) Åθ = 1.7–30.1°
b = 11.784 (3) ŵ = 0.44 mm1
c = 5.8265 (9) ÅT = 150 K
V = 804.3 (3) Å3Prismatic, colourless
Z = 40.3 × 0.2 × 0.2 mm
F(000) = 368
Data collection top
Siemens P4
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 30.1°, θmin = 1.7°
Graphite monochromatorh = 116
ω–2θ scansk = 116
1729 measured reflectionsl = 84
1389 independent reflections3 standard reflections every 60 min
1210 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.087H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.248 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.88(Δ/σ)max = 0.049
1389 reflectionsΔρmax = 1.27 e Å3
99 parametersΔρmin = 1.39 e Å3
10 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.1 (5)
Crystal data top
C4H12N·ClO4V = 804.3 (3) Å3
Mr = 173.60Z = 4
Orthorhombic, P21212Mo Kα radiation
a = 11.714 (3) ŵ = 0.44 mm1
b = 11.784 (3) ÅT = 150 K
c = 5.8265 (9) Å0.3 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.027
1729 measured reflections3 standard reflections every 60 min
1389 independent reflections intensity decay: none
1210 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.087H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.248Δρmax = 1.27 e Å3
S = 1.88Δρmin = 1.39 e Å3
1389 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
99 parametersAbsolute structure parameter: 0.1 (5)
10 restraints
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.

The tetrahedral shape of the ClO4 group is maintaned, the Cl—O distance is fixed.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.24025 (11)0.2557 (2)0.07090 (15)0.0274 (5)
O10.2506 (3)0.2516 (5)0.1730 (4)0.0365 (10)
O20.1234 (3)0.2409 (6)0.1334 (7)0.0574 (19)
O30.3070 (7)0.1673 (8)0.1702 (8)0.144 (6)
O40.2795 (7)0.3629 (6)0.1522 (12)0.099 (4)
N10.00000.00000.4969 (17)0.027 (2)
C20.0833 (5)0.0646 (8)0.3554 (16)0.0285 (18)
H40.11970.01340.24510.031 (5)*
H50.04350.12520.27260.031 (5)*
H60.14170.09790.45540.031 (5)*
C30.0646 (6)0.0834 (8)0.6448 (17)0.0300 (18)
H70.01060.13520.71910.031 (5)*
H80.11750.12710.54890.031 (5)*
H90.10780.04210.76220.031 (5)*
N20.00000.50000.4873 (11)0.023 (2)
C10.0740 (7)0.5699 (10)0.3321 (15)0.040 (2)
H10.02590.61940.23770.031 (5)*
H20.11850.51960.23240.031 (5)*
H30.12590.61630.42470.031 (5)*
C40.0719 (7)0.4254 (9)0.6384 (17)0.0378 (17)
H100.12440.38090.54330.031 (5)*
H110.02240.37390.72540.031 (5)*
H120.11570.47260.74520.031 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0154 (6)0.0478 (12)0.0189 (5)0.0093 (7)0.0001 (4)0.0023 (8)
O10.030 (2)0.057 (4)0.0222 (16)0.004 (4)0.0035 (16)0.001 (3)
O20.036 (2)0.083 (5)0.053 (3)0.036 (3)0.019 (2)0.005 (5)
O30.188 (12)0.186 (13)0.058 (5)0.149 (10)0.040 (7)0.006 (8)
O40.085 (5)0.144 (10)0.069 (6)0.065 (6)0.051 (5)0.076 (7)
N10.010 (4)0.049 (7)0.022 (5)0.002 (4)0.0000.000
C20.012 (2)0.052 (5)0.021 (3)0.000 (3)0.003 (3)0.004 (4)
C30.018 (3)0.045 (5)0.026 (3)0.000 (3)0.013 (3)0.002 (4)
N20.004 (3)0.051 (7)0.015 (4)0.000 (2)0.0000.000
C10.023 (3)0.066 (6)0.031 (4)0.007 (3)0.005 (3)0.016 (5)
C40.020 (3)0.061 (6)0.032 (3)0.008 (3)0.003 (4)0.014 (5)
Geometric parameters (Å, º) top
Cl—O11.427 (2)C3—H80.9800
Cl—O41.425 (2)C3—H90.9800
Cl—O31.425 (2)N2—C4ii1.503 (9)
Cl—O21.427 (2)N2—C41.503 (9)
N1—C2i1.488 (9)N2—C1ii1.499 (8)
N1—C21.488 (10)N2—C11.499 (8)
N1—C31.511 (10)C1—H10.9800
N1—C3i1.511 (10)C1—H20.9800
C2—H40.9800C1—H30.9800
C2—H50.9800C4—H100.9800
C2—H60.9800C4—H110.9800
C3—H70.9800C4—H120.9800
O1—Cl—O4109.48 (9)N1—C3—H9109.5
O1—Cl—O3109.49 (9)H7—C3—H9109.5
O4—Cl—O3109.61 (9)H8—C3—H9109.5
O1—Cl—O2109.35 (8)C4ii—N2—C4108.3 (8)
O4—Cl—O2109.40 (8)C4ii—N2—C1ii110.6 (6)
O3—Cl—O2109.50 (9)C4—N2—C1ii110.9 (7)
C2i—N1—C2112.7 (10)C4ii—N2—C1110.9 (7)
C2i—N1—C3108.2 (5)C4—N2—C1110.6 (6)
C2—N1—C3108.7 (5)C1ii—N2—C1105.8 (8)
C2i—N1—C3i108.7 (5)N2—C1—H1109.5
C2—N1—C3i108.2 (5)N2—C1—H2109.5
C3—N1—C3i110.5 (10)H1—C1—H2109.5
N1—C2—H4109.5N2—C1—H3109.5
N1—C2—H5109.5H1—C1—H3109.5
H4—C2—H5109.5H2—C1—H3109.5
N1—C2—H6109.5N2—C4—H10109.5
H4—C2—H6109.5N2—C4—H11109.5
H5—C2—H6109.5H10—C4—H11109.5
N1—C3—H7109.5N2—C4—H12109.5
N1—C3—H8109.5H10—C4—H12109.5
H7—C3—H8109.5H11—C4—H12109.5
Symmetry codes: (i) x, y, z; (ii) x, y+1, z.
(II) tetramethylammonium perchlorate top
Crystal data top
C4H12N·ClO4Dx = 1.458 Mg m3
Mr = 173.60Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/nmmCell parameters from 45 reflections
a = 8.2376 (14) Åθ = 3.5–30.4°
c = 5.8256 (12) ŵ = 0.45 mm1
V = 395.31 (13) Å3T = 210 K
Z = 2Prismatic, colourless
F(000) = 1840.3 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.046
Radiation source: fine-focus sealed tubeθmax = 30.5°, θmin = 3.5°
Graphite monochromatorh = 111
ω–2θ scank = 111
1534 measured reflectionsl = 88
376 independent reflections3 standard reflections every 60 min
331 reflections with I > 2σ(I) intensity decay: none
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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.25 w = 1/[σ2(Fo2) + (0.043P)2 + 0.1615P]
where P = (Fo2 + 2Fc2)/3
376 reflections(Δ/σ)max < 0.001
36 parametersΔρmax = 0.73 e Å3
6 restraintsΔρmin = 0.66 e Å3
Crystal data top
C4H12N·ClO4Z = 2
Mr = 173.60Mo Kα radiation
Tetragonal, P4/nmmµ = 0.45 mm1
a = 8.2376 (14) ÅT = 210 K
c = 5.8256 (12) Å0.3 × 0.2 × 0.2 mm
V = 395.31 (13) Å3
Data collection top
Siemens P4
diffractometer
Rint = 0.046
1534 measured reflections3 standard reflections every 60 min
376 independent reflections intensity decay: none
331 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0576 restraints
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.25Δρmax = 0.73 e Å3
376 reflectionsΔρmin = 0.66 e Å3
36 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.

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
xyzUiso*/UeqOcc. (<1)
N0.75000.25000.50000.0253 (7)
C0.25000.6030 (3)0.3538 (4)0.0409 (6)
H10.25000.50300.45200.050 (10)*
H20.34900.60200.25600.053 (6)*
Cl0.2307 (8)0.25000.0742 (2)0.0252 (10)0.25
O10.25000.25000.1644 (6)0.0532 (11)
O20.1453 (11)0.3892 (5)0.1398 (7)0.069 (3)0.25
O30.3832 (12)0.25000.1790 (11)0.143 (10)0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N0.0236 (10)0.0236 (10)0.0286 (14)0.0000.0000.000
C0.0461 (15)0.0348 (13)0.0419 (13)0.0000.0000.0123 (10)
Cl0.012 (5)0.034 (6)0.0297 (5)0.0000.0008 (7)0.000
O10.0613 (18)0.0613 (18)0.0370 (19)0.0000.0000.000
O20.085 (8)0.036 (4)0.088 (4)0.012 (4)0.050 (5)0.003 (4)
O30.105 (13)0.17 (2)0.151 (13)0.0000.105 (11)0.000
Geometric parameters (Å, º) top
N—Ci1.481 (2)C—Nii1.481 (2)
N—Cii1.481 (2)Cl—O11.399 (3)
N—Ciii1.481 (2)Cl—O21.398 (3)
N—Civ1.481 (2)Cl—O31.397 (3)
Ci—N—Cii109.31 (11)O3—Cl—O2v109.44 (11)
Ci—N—Ciii109.8 (2)O3—Cl—O2109.44 (11)
Cii—N—Ciii109.31 (11)O2v—Cl—O2110.2 (4)
Ci—N—Civ109.31 (11)O3—Cl—O1109.38 (11)
Cii—N—Civ109.8 (2)O2v—Cl—O1109.19 (10)
Ciii—N—Civ109.31 (11)O2—Cl—O1109.19 (10)
Symmetry codes: (i) y, x+1/2, z; (ii) x+1, y+1, z+1; (iii) y+3/2, x, z; (iv) x+1/2, y1/2, z+1; (v) x, y+1/2, z.
(III) tetramethylammonium perchlorate top
Crystal data top
(CH3)4NClO4F(000) = 368
Mr = 173.60Dx = 1.474 (4) Mg m3
Orthorhombic, P21212Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å
a = 11.566 (2) ÅT = 30 K
b = 11.806 (2) ÅParticle morphology: irregular
c = 5.7292 (11) Åwhite
V = 782.3 (3) Å3flat sheet, 20 × 10 mm
Z = 4Specimen preparation: Prepared at 293 K
Data collection top
Dmax Rigaku
diffractometer
Data collection mode: reflection
Radiation source: X-ray, rotating anode tubeScan method: step
Graphite monochromator2θmin = 5°, 2θmax = 60°, 2θstep = 0.03°
Specimen mounting: ground from single crystals
Refinement top
Refinement on InetProfile function: pseudo-Voigt
Least-squares matrix: full with fixed elements per cycle34 parameters
Rp = 0.139H-atom parameters not refined
Rwp = 0.189Weighting scheme based on measured s.u.'s
Rexp = 0.127(Δ/σ)max = 0.02
χ2 = 2.220Background function: polynomyal up to 5th order
1834 data pointsPreferred orientation correction: none
Excluded region(s): none
Crystal data top
(CH3)4NClO4V = 782.3 (3) Å3
Mr = 173.60Z = 4
Orthorhombic, P21212Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å
a = 11.566 (2) ÅT = 30 K
b = 11.806 (2) Åflat sheet, 20 × 10 mm
c = 5.7292 (11) Å
Data collection top
Dmax Rigaku
diffractometer
Scan method: step
Specimen mounting: ground from single crystals2θmin = 5°, 2θmax = 60°, 2θstep = 0.03°
Data collection mode: reflection
Refinement top
Rp = 0.1391834 data points
Rwp = 0.18934 parameters
Rexp = 0.127H-atom parameters not refined
χ2 = 2.220
Special details top

Geometry. Shape of the molecules fixed

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.2353 (4)0.2471 (16)0.0680 (7)0.027 (3)*
O10.24970.24640.18470.026 (4)*
O20.11270.24030.12490.026 (4)*
O30.29550.15030.16860.026 (4)*
O40.28320.35150.16320.026 (4)*
N1000.482 (14)0*
N200.50.484 (14)0*
C10.08280.56630.33470*
C20.08090.06200.32200*
C30.063800.08000.64040*
C40.08280.43380.33470*
H10.13560.60850.43520*
H20.12560.51120.23370*
H30.03620.61830.23370*
H40.09270.14550.43390*
H50.00460.12350.23240*
H60.11520.05020.23240*
H70.10780.13510.53070*
H80.12000.03810.73220*
H90.00870.12320.73220*
H100.11080.36720.43520*
H110.12080.46450.23370*
H120.01140.37700.23370*
Geometric parameters (Å, º) top
N1—C21.5018 (2)Cl—O11.4572 (1)
N1—C31.5018 (2)Cl—O21.4572 (1)
N2—C11.5018 (2)Cl—O31.4572 (1)
N2—C41.5018 (2)Cl—O41.4572 (1)
O1—Cl—O2109.47O2—Cl—O3109.47
O1—Cl—O3109.47O2—Cl—O4109.47
O1—Cl—O4109.47O3—Cl—O4109.47
(IV) tetramethylammonium perchlorate top
Crystal data top
(CH3)4NClO4F(000) = 368
Mr = 173.60Dx = 1.453 (4) Mg m3
Orthorhombic, P21212Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å
a = 11.639 (3) ÅT = 100 K
b = 11.798 (3) ÅParticle morphology: irregular
c = 5.7790 (13) Åwhite
V = 793.6 (3) Å3flat sheet, 20 × 10 mm
Z = 4Specimen preparation: Prepared at 293 K
Data collection top
Dmax Rigaku
diffractometer
Data collection mode: reflection
Radiation source: X-ray, rotating anode tubeScan method: step
Graphite monochromator2θmin = 5°, 2θmax = 60°, 2θstep = 0.03°
Specimen mounting: ground from single crystals
Refinement top
Refinement on InetProfile function: pseudo-Voigt
Least-squares matrix: full with fixed elements per cycle34 parameters
Rp = 0.130H-atom parameters not refined
Rwp = 0.179Weighting scheme based on measured s.u.'s
Rexp = 0.128(Δ/σ)max = 0.02
χ2 = 1.960Background function: polynomyal up to 5th order
1834 data pointsPreferred orientation correction: none
Excluded region(s): none
Crystal data top
(CH3)4NClO4V = 793.6 (3) Å3
Mr = 173.60Z = 4
Orthorhombic, P21212Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å
a = 11.639 (3) ÅT = 100 K
b = 11.798 (3) Åflat sheet, 20 × 10 mm
c = 5.7790 (13) Å
Data collection top
Dmax Rigaku
diffractometer
Scan method: step
Specimen mounting: ground from single crystals2θmin = 5°, 2θmax = 60°, 2θstep = 0.03°
Data collection mode: reflection
Refinement top
Rp = 0.1301834 data points
Rwp = 0.17934 parameters
Rexp = 0.128H-atom parameters not refined
χ2 = 1.960
Special details top

Geometry. Shape of the molecules fixed

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.236 (5)0.2527 (18)0.0672 (7)0.036 (4)*
O10.250550.25200.18350.040 (4)*
O20.11410.24470.12340.040 (4)*
O30.29690.15630.16720.0406 (4)*
O40.28270.35770.16170.040 (4)*
N1000.486 (15)0.000*
N20.500.496 (9)0.000*
C10.08120.56720.34220.000*
C20.08080.06160.32510.000*
C30.06240.07970.64780.000*
C40.08120.43280.34220.000*
H10.13330.61030.44520*
H20.12460.51280.24540*
H30.03450.61890.24540*
H40.09130.14550.43840*
H50.00520.12350.23850*
H60.11420.05090.23850*
H70.10640.13580.53430*
H80.11900.03870.73410*
H90.00800.12340.73410*
H100.11180.36850.44520*
H110.13000.46600.24540*
H120.01140.37700.24540*
Geometric parameters (Å, º) top
N1—C21.5105 (2)Cl—O11.4586 (1)
N1—C31.5105 (2)Cl—O21.4586 (1)
N2—C11.5105 (2)Cl—O31.4586 (1)
N2—C41.5105 (2)Cl—O41.4586 (1)
O1—Cl—O2109.47O2—Cl—O3109.47
O1—Cl—O3109.47O2—Cl—O4109.47
O1—Cl—O4109.47O3—Cl—O4109.47

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC4H12N·ClO4C4H12N·ClO4(CH3)4NClO4(CH3)4NClO4
Mr173.60173.60173.60173.60
Crystal system, space groupOrthorhombic, P21212Tetragonal, P4/nmmOrthorhombic, P21212Orthorhombic, P21212
Temperature (K)15021030100
a, b, c (Å)11.714 (3), 11.784 (3), 5.8265 (9)8.2376 (14), 8.2376 (14), 5.8256 (12)11.566 (2), 11.806 (2), 5.7292 (11)11.639 (3), 11.798 (3), 5.7790 (13)
α, β, γ (°)90, 90, 9090, 90, 9090, 90, 9090, 90, 90
V3)804.3 (3)395.31 (13)782.3 (3)793.6 (3)
Z4244
Radiation typeMo KαMo KαCu Kα1, Cu Kα2, λ = 1.540562, 1.544390 ÅCu Kα1, Cu Kα2, λ = 1.540562, 1.544390 Å
µ (mm1)0.440.45
Specimen shape, size (mm)0.3 × 0.2 × 0.20.3 × 0.2 × 0.2Flat sheet, 20 × 10Flat sheet, 20 × 10
Data collection
DiffractometerSiemens P4
diffractometer
Siemens P4
diffractometer
Dmax Rigaku
diffractometer
Dmax Rigaku
diffractometer
Specimen mountingGround from single crystalsGround from single crystals
Data collection modeReflectionReflection
Data collection methodω–2θ scansω–2θ scanStepStep
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1729, 1389, 1210 1534, 376, 331
Rint0.0270.046
θ values (°)θmax = 30.1, θmin = 1.7θmax = 30.5, θmin = 3.52θmin = 5 2θmax = 60 2θstep = 0.032θmin = 5 2θmax = 60 2θstep = 0.03
(sin θ/λ)max1)0.7050.713
Refinement
R factors and goodness of fitR[F2 > 2σ(F2)] = 0.087, wR(F2) = 0.248, S = 1.88R[F2 > 2σ(F2)] = 0.057, wR(F2) = 0.136, S = 1.25Rp = 0.139, Rwp = 0.189, Rexp = 0.127, χ2 = 2.220Rp = 0.130, Rwp = 0.179, Rexp = 0.128, χ2 = 1.960
No. of reflections/data points138937618341834
No. of parameters99363434
No. of restraints106??
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH-atom parameters not refinedH-atom parameters not refined
Δρmax, Δρmin (e Å3)1.27, 1.390.73, 0.66
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881?
Absolute structure parameter0.1 (5)?

Computer programs: Siemens XSCANS, Rigaku IUSA 2.8, FULLPROF (Rodriguez-Carvajal et al. 1987), none, SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) for (I) top
Cl—O11.427 (2)N2—C41.503 (9)
N1—C21.488 (10)N2—C11.499 (8)
N1—C31.511 (10)
C2i—N1—C2112.7 (10)C4ii—N2—C4108.3 (8)
C2i—N1—C3108.2 (5)C4—N2—C1ii110.9 (7)
C2—N1—C3108.7 (5)C4—N2—C1110.6 (6)
C3—N1—C3i110.5 (10)
Symmetry codes: (i) x, y, z; (ii) x, y+1, z.
Selected geometric parameters (Å, º) for (II) top
N—Ci1.481 (2)Cl—O21.398 (3)
Cl—O11.399 (3)Cl—O31.397 (3)
Ci—N—Cii109.31 (11)Ci—N—Ciii109.8 (2)
Symmetry codes: (i) y, x+1/2, z; (ii) x+1, y+1, z+1; (iii) y+3/2, x, z.
Selected bond lengths (Å) for (III) top
N1—C21.5018 (2)Cl—O11.4572 (1)
Selected bond lengths (Å) for (IV) top
N1—C21.5105 (2)Cl—O11.4586 (1)
 

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