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The low-temperature crystal structures of tetramethylammonium perchlorate, [(CH
)
N](ClO
), are analysed. At 210 K, a collection of 376 unique reflections on a single crystal gave
for space group
, with
8.2376 (14),
(12) Å and
, where the ClO
groups are disordered over four orientations. Below
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
, with
(3),
11.784 (3),
(9) Å,
and
. At 30 K, Rietveld refinement gave the same structure as is found at 150 K, with a clear difference between
and
[
(2),
(2) and
(1) Å]. The structural models and the phase transition are explained on the basis of electrostatic octopole-octopole interactions among the ClO
groups within layers perpendicular to the
axis. The order parameters of the low-temperature phase are discussed in relation to the structural results.
Supporting information
CCDC references: 223324; 223325; 223326; 223327
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).
(I) Tetramethylammonium perchlorate
top
Crystal data top
C4H12N·ClO4 | Dx = 1.434 Mg m−3 |
Mr = 173.60 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 55 reflections |
a = 11.714 (3) Å | θ = 1.7–30.1° |
b = 11.784 (3) Å | µ = 0.44 mm−1 |
c = 5.8265 (9) Å | T = 150 K |
V = 804.3 (3) Å3 | Prismatic, colourless |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
F(000) = 368 | |
Data collection top
Siemens P4 diffractometer | Rint = 0.027 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 1.7° |
Graphite monochromator | h = −1→16 |
ω–2θ scans | k = −1→16 |
1729 measured reflections | l = −8→4 |
1389 independent reflections | 3 standard reflections every 60 min |
1210 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.087 | H 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 reflections | Δρmax = 1.27 e Å−3 |
99 parameters | Δρmin = −1.39 e Å−3 |
10 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (5) |
Crystal data top
C4H12N·ClO4 | V = 804.3 (3) Å3 |
Mr = 173.60 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 11.714 (3) Å | µ = 0.44 mm−1 |
b = 11.784 (3) Å | T = 150 K |
c = 5.8265 (9) Å | 0.3 × 0.2 × 0.2 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.027 |
1729 measured reflections | 3 standard reflections every 60 min |
1389 independent reflections | intensity decay: none |
1210 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.248 | Δρmax = 1.27 e Å−3 |
S = 1.88 | Δρmin = −1.39 e Å−3 |
1389 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
99 parameters | Absolute 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 | x | y | z | Uiso*/Ueq | |
Cl | 0.24025 (11) | 0.2557 (2) | 0.07090 (15) | 0.0274 (5) | |
O1 | 0.2506 (3) | 0.2516 (5) | −0.1730 (4) | 0.0365 (10) | |
O2 | 0.1234 (3) | 0.2409 (6) | 0.1334 (7) | 0.0574 (19) | |
O3 | 0.3070 (7) | 0.1673 (8) | 0.1702 (8) | 0.144 (6) | |
O4 | 0.2795 (7) | 0.3629 (6) | 0.1522 (12) | 0.099 (4) | |
N1 | 0.0000 | 0.0000 | 0.4969 (17) | 0.027 (2) | |
C2 | 0.0833 (5) | −0.0646 (8) | 0.3554 (16) | 0.0285 (18) | |
H4 | 0.1197 | −0.0134 | 0.2451 | 0.031 (5)* | |
H5 | 0.0435 | −0.1252 | 0.2726 | 0.031 (5)* | |
H6 | 0.1417 | −0.0979 | 0.4554 | 0.031 (5)* | |
C3 | 0.0646 (6) | 0.0834 (8) | 0.6448 (17) | 0.0300 (18) | |
H7 | 0.0106 | 0.1352 | 0.7191 | 0.031 (5)* | |
H8 | 0.1175 | 0.1271 | 0.5489 | 0.031 (5)* | |
H9 | 0.1078 | 0.0421 | 0.7622 | 0.031 (5)* | |
N2 | 0.0000 | 0.5000 | 0.4873 (11) | 0.023 (2) | |
C1 | 0.0740 (7) | 0.5699 (10) | 0.3321 (15) | 0.040 (2) | |
H1 | 0.0259 | 0.6194 | 0.2377 | 0.031 (5)* | |
H2 | 0.1185 | 0.5196 | 0.2324 | 0.031 (5)* | |
H3 | 0.1259 | 0.6163 | 0.4247 | 0.031 (5)* | |
C4 | 0.0719 (7) | 0.4254 (9) | 0.6384 (17) | 0.0378 (17) | |
H10 | 0.1244 | 0.3809 | 0.5433 | 0.031 (5)* | |
H11 | 0.0224 | 0.3739 | 0.7254 | 0.031 (5)* | |
H12 | 0.1157 | 0.4726 | 0.7452 | 0.031 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0154 (6) | 0.0478 (12) | 0.0189 (5) | 0.0093 (7) | 0.0001 (4) | 0.0023 (8) |
O1 | 0.030 (2) | 0.057 (4) | 0.0222 (16) | 0.004 (4) | 0.0035 (16) | 0.001 (3) |
O2 | 0.036 (2) | 0.083 (5) | 0.053 (3) | −0.036 (3) | 0.019 (2) | −0.005 (5) |
O3 | 0.188 (12) | 0.186 (13) | 0.058 (5) | 0.149 (10) | −0.040 (7) | −0.006 (8) |
O4 | 0.085 (5) | 0.144 (10) | 0.069 (6) | −0.065 (6) | 0.051 (5) | −0.076 (7) |
N1 | 0.010 (4) | 0.049 (7) | 0.022 (5) | −0.002 (4) | 0.000 | 0.000 |
C2 | 0.012 (2) | 0.052 (5) | 0.021 (3) | 0.000 (3) | 0.003 (3) | −0.004 (4) |
C3 | 0.018 (3) | 0.045 (5) | 0.026 (3) | 0.000 (3) | −0.013 (3) | 0.002 (4) |
N2 | 0.004 (3) | 0.051 (7) | 0.015 (4) | 0.000 (2) | 0.000 | 0.000 |
C1 | 0.023 (3) | 0.066 (6) | 0.031 (4) | −0.007 (3) | 0.005 (3) | 0.016 (5) |
C4 | 0.020 (3) | 0.061 (6) | 0.032 (3) | 0.008 (3) | −0.003 (4) | 0.014 (5) |
Geometric parameters (Å, º) top
Cl—O1 | 1.427 (2) | C3—H8 | 0.9800 |
Cl—O4 | 1.425 (2) | C3—H9 | 0.9800 |
Cl—O3 | 1.425 (2) | N2—C4ii | 1.503 (9) |
Cl—O2 | 1.427 (2) | N2—C4 | 1.503 (9) |
N1—C2i | 1.488 (9) | N2—C1ii | 1.499 (8) |
N1—C2 | 1.488 (10) | N2—C1 | 1.499 (8) |
N1—C3 | 1.511 (10) | C1—H1 | 0.9800 |
N1—C3i | 1.511 (10) | C1—H2 | 0.9800 |
C2—H4 | 0.9800 | C1—H3 | 0.9800 |
C2—H5 | 0.9800 | C4—H10 | 0.9800 |
C2—H6 | 0.9800 | C4—H11 | 0.9800 |
C3—H7 | 0.9800 | C4—H12 | 0.9800 |
| | | |
O1—Cl—O4 | 109.48 (9) | N1—C3—H9 | 109.5 |
O1—Cl—O3 | 109.49 (9) | H7—C3—H9 | 109.5 |
O4—Cl—O3 | 109.61 (9) | H8—C3—H9 | 109.5 |
O1—Cl—O2 | 109.35 (8) | C4ii—N2—C4 | 108.3 (8) |
O4—Cl—O2 | 109.40 (8) | C4ii—N2—C1ii | 110.6 (6) |
O3—Cl—O2 | 109.50 (9) | C4—N2—C1ii | 110.9 (7) |
C2i—N1—C2 | 112.7 (10) | C4ii—N2—C1 | 110.9 (7) |
C2i—N1—C3 | 108.2 (5) | C4—N2—C1 | 110.6 (6) |
C2—N1—C3 | 108.7 (5) | C1ii—N2—C1 | 105.8 (8) |
C2i—N1—C3i | 108.7 (5) | N2—C1—H1 | 109.5 |
C2—N1—C3i | 108.2 (5) | N2—C1—H2 | 109.5 |
C3—N1—C3i | 110.5 (10) | H1—C1—H2 | 109.5 |
N1—C2—H4 | 109.5 | N2—C1—H3 | 109.5 |
N1—C2—H5 | 109.5 | H1—C1—H3 | 109.5 |
H4—C2—H5 | 109.5 | H2—C1—H3 | 109.5 |
N1—C2—H6 | 109.5 | N2—C4—H10 | 109.5 |
H4—C2—H6 | 109.5 | N2—C4—H11 | 109.5 |
H5—C2—H6 | 109.5 | H10—C4—H11 | 109.5 |
N1—C3—H7 | 109.5 | N2—C4—H12 | 109.5 |
N1—C3—H8 | 109.5 | H10—C4—H12 | 109.5 |
H7—C3—H8 | 109.5 | H11—C4—H12 | 109.5 |
Symmetry codes: (i) −x, −y, z; (ii) −x, −y+1, z. |
(II) tetramethylammonium perchlorate
top
Crystal data top
C4H12N·ClO4 | Dx = 1.458 Mg m−3 |
Mr = 173.60 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/nmm | Cell parameters from 45 reflections |
a = 8.2376 (14) Å | θ = 3.5–30.4° |
c = 5.8256 (12) Å | µ = 0.45 mm−1 |
V = 395.31 (13) Å3 | T = 210 K |
Z = 2 | Prismatic, colourless |
F(000) = 184 | 0.3 × 0.2 × 0.2 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.046 |
Radiation source: fine-focus sealed tube | θmax = 30.5°, θmin = 3.5° |
Graphite monochromator | h = −1→11 |
ω–2θ scan | k = −1→11 |
1534 measured reflections | l = −8→8 |
376 independent reflections | 3 standard reflections every 60 min |
331 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H 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 parameters | Δρmax = 0.73 e Å−3 |
6 restraints | Δρmin = −0.66 e Å−3 |
Crystal data top
C4H12N·ClO4 | Z = 2 |
Mr = 173.60 | Mo Kα radiation |
Tetragonal, P4/nmm | µ = 0.45 mm−1 |
a = 8.2376 (14) Å | T = 210 K |
c = 5.8256 (12) Å | 0.3 × 0.2 × 0.2 mm |
V = 395.31 (13) Å3 | |
Data collection top
Siemens P4 diffractometer | Rint = 0.046 |
1534 measured reflections | 3 standard reflections every 60 min |
376 independent reflections | intensity decay: none |
331 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 6 restraints |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.25 | Δρmax = 0.73 e Å−3 |
376 reflections | Δρmin = −0.66 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
N | 0.7500 | 0.2500 | 0.5000 | 0.0253 (7) | |
C | 0.2500 | 0.6030 (3) | 0.3538 (4) | 0.0409 (6) | |
H1 | 0.2500 | 0.5030 | 0.4520 | 0.050 (10)* | |
H2 | 0.3490 | 0.6020 | 0.2560 | 0.053 (6)* | |
Cl | 0.2307 (8) | 0.2500 | −0.0742 (2) | 0.0252 (10) | 0.25 |
O1 | 0.2500 | 0.2500 | 0.1644 (6) | 0.0532 (11) | |
O2 | 0.1453 (11) | 0.3892 (5) | −0.1398 (7) | 0.069 (3) | 0.25 |
O3 | 0.3832 (12) | 0.2500 | −0.1790 (11) | 0.143 (10) | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N | 0.0236 (10) | 0.0236 (10) | 0.0286 (14) | 0.000 | 0.000 | 0.000 |
C | 0.0461 (15) | 0.0348 (13) | 0.0419 (13) | 0.000 | 0.000 | −0.0123 (10) |
Cl | 0.012 (5) | 0.034 (6) | 0.0297 (5) | 0.000 | 0.0008 (7) | 0.000 |
O1 | 0.0613 (18) | 0.0613 (18) | 0.0370 (19) | 0.000 | 0.000 | 0.000 |
O2 | 0.085 (8) | 0.036 (4) | 0.088 (4) | 0.012 (4) | −0.050 (5) | 0.003 (4) |
O3 | 0.105 (13) | 0.17 (2) | 0.151 (13) | 0.000 | 0.105 (11) | 0.000 |
Geometric parameters (Å, º) top
N—Ci | 1.481 (2) | C—Nii | 1.481 (2) |
N—Cii | 1.481 (2) | Cl—O1 | 1.399 (3) |
N—Ciii | 1.481 (2) | Cl—O2 | 1.398 (3) |
N—Civ | 1.481 (2) | Cl—O3 | 1.397 (3) |
| | | |
Ci—N—Cii | 109.31 (11) | O3—Cl—O2v | 109.44 (11) |
Ci—N—Ciii | 109.8 (2) | O3—Cl—O2 | 109.44 (11) |
Cii—N—Ciii | 109.31 (11) | O2v—Cl—O2 | 110.2 (4) |
Ci—N—Civ | 109.31 (11) | O3—Cl—O1 | 109.38 (11) |
Cii—N—Civ | 109.8 (2) | O2v—Cl—O1 | 109.19 (10) |
Ciii—N—Civ | 109.31 (11) | O2—Cl—O1 | 109.19 (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, y−1/2, −z+1; (v) x, −y+1/2, z. |
(III) tetramethylammonium perchlorate
top
Crystal data top
(CH3)4NClO4 | F(000) = 368 |
Mr = 173.60 | Dx = 1.474 (4) Mg m−3 |
Orthorhombic, P21212 | Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å |
a = 11.566 (2) Å | T = 30 K |
b = 11.806 (2) Å | Particle morphology: irregular |
c = 5.7292 (11) Å | white |
V = 782.3 (3) Å3 | flat sheet, 20 × 10 mm |
Z = 4 | Specimen preparation: Prepared at 293 K |
Data collection top
Dmax Rigaku diffractometer | Data collection mode: reflection |
Radiation source: X-ray, rotating anode tube | Scan method: step |
Graphite monochromator | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Specimen mounting: ground from single crystals | |
Refinement top
Refinement on Inet | Profile function: pseudo-Voigt |
Least-squares matrix: full with fixed elements per cycle | 34 parameters |
Rp = 0.139 | H-atom parameters not refined |
Rwp = 0.189 | Weighting scheme based on measured s.u.'s |
Rexp = 0.127 | (Δ/σ)max = 0.02 |
χ2 = 2.220 | Background function: polynomyal up to 5th order |
1834 data points | Preferred orientation correction: none |
Excluded region(s): none | |
Crystal data top
(CH3)4NClO4 | V = 782.3 (3) Å3 |
Mr = 173.60 | Z = 4 |
Orthorhombic, P21212 | Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å |
a = 11.566 (2) Å | T = 30 K |
b = 11.806 (2) Å | flat sheet, 20 × 10 mm |
c = 5.7292 (11) Å | |
Data collection top
Dmax Rigaku diffractometer | Scan method: step |
Specimen mounting: ground from single crystals | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Data collection mode: reflection | |
Refinement top
Rp = 0.139 | 1834 data points |
Rwp = 0.189 | 34 parameters |
Rexp = 0.127 | H-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 | x | y | z | Uiso*/Ueq | |
Cl | 0.2353 (4) | 0.2471 (16) | 0.0680 (7) | 0.027 (3)* | |
O1 | 0.2497 | 0.2464 | −0.1847 | 0.026 (4)* | |
O2 | 0.1127 | 0.2403 | 0.1249 | 0.026 (4)* | |
O3 | 0.2955 | 0.1503 | 0.1686 | 0.026 (4)* | |
O4 | 0.2832 | 0.3515 | 0.1632 | 0.026 (4)* | |
N1 | 0 | 0 | 0.482 (14) | 0* | |
N2 | 0 | 0.5 | 0.484 (14) | 0* | |
C1 | 0.0828 | 0.5663 | 0.3347 | 0* | |
C2 | 0.0809 | −0.0620 | 0.3220 | 0* | |
C3 | 0.06380 | 0.0800 | 0.6404 | 0* | |
C4 | −0.0828 | 0.4338 | 0.3347 | 0* | |
H1 | 0.1356 | 0.6085 | 0.4352 | 0* | |
H2 | 0.1256 | 0.5112 | 0.2337 | 0* | |
H3 | 0.0362 | 0.6183 | 0.2337 | 0* | |
H4 | −0.0927 | −0.1455 | 0.4339 | 0* | |
H5 | 0.0046 | −0.1235 | 0.2324 | 0* | |
H6 | −0.1152 | −0.0502 | 0.2324 | 0* | |
H7 | 0.1078 | 0.1351 | 0.5307 | 0* | |
H8 | 0.1200 | 0.0381 | 0.7322 | 0* | |
H9 | 0.0087 | 0.1232 | 0.7322 | 0* | |
H10 | 0.1108 | 0.3672 | 0.4352 | 0* | |
H11 | 0.1208 | 0.4645 | 0.2337 | 0* | |
H12 | 0.0114 | 0.3770 | 0.2337 | 0* | |
Geometric parameters (Å, º) top
N1—C2 | 1.5018 (2) | Cl—O1 | 1.4572 (1) |
N1—C3 | 1.5018 (2) | Cl—O2 | 1.4572 (1) |
N2—C1 | 1.5018 (2) | Cl—O3 | 1.4572 (1) |
N2—C4 | 1.5018 (2) | Cl—O4 | 1.4572 (1) |
| | | |
O1—Cl—O2 | 109.47 | O2—Cl—O3 | 109.47 |
O1—Cl—O3 | 109.47 | O2—Cl—O4 | 109.47 |
O1—Cl—O4 | 109.47 | O3—Cl—O4 | 109.47 |
(IV) tetramethylammonium perchlorate
top
Crystal data top
(CH3)4NClO4 | F(000) = 368 |
Mr = 173.60 | Dx = 1.453 (4) Mg m−3 |
Orthorhombic, P21212 | Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å |
a = 11.639 (3) Å | T = 100 K |
b = 11.798 (3) Å | Particle morphology: irregular |
c = 5.7790 (13) Å | white |
V = 793.6 (3) Å3 | flat sheet, 20 × 10 mm |
Z = 4 | Specimen preparation: Prepared at 293 K |
Data collection top
Dmax Rigaku diffractometer | Data collection mode: reflection |
Radiation source: X-ray, rotating anode tube | Scan method: step |
Graphite monochromator | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Specimen mounting: ground from single crystals | |
Refinement top
Refinement on Inet | Profile function: pseudo-Voigt |
Least-squares matrix: full with fixed elements per cycle | 34 parameters |
Rp = 0.130 | H-atom parameters not refined |
Rwp = 0.179 | Weighting scheme based on measured s.u.'s |
Rexp = 0.128 | (Δ/σ)max = 0.02 |
χ2 = 1.960 | Background function: polynomyal up to 5th order |
1834 data points | Preferred orientation correction: none |
Excluded region(s): none | |
Crystal data top
(CH3)4NClO4 | V = 793.6 (3) Å3 |
Mr = 173.60 | Z = 4 |
Orthorhombic, P21212 | Cu Kα1, Cu Kα2 radiation, λ = 1.540562, 1.544390 Å |
a = 11.639 (3) Å | T = 100 K |
b = 11.798 (3) Å | flat sheet, 20 × 10 mm |
c = 5.7790 (13) Å | |
Data collection top
Dmax Rigaku diffractometer | Scan method: step |
Specimen mounting: ground from single crystals | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Data collection mode: reflection | |
Refinement top
Rp = 0.130 | 1834 data points |
Rwp = 0.179 | 34 parameters |
Rexp = 0.128 | H-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 | x | y | z | Uiso*/Ueq | |
Cl | 0.236 (5) | 0.2527 (18) | 0.0672 (7) | 0.036 (4)* | |
O1 | 0.25055 | 0.2520 | −0.1835 | 0.040 (4)* | |
O2 | 0.1141 | 0.2447 | 0.1234 | 0.040 (4)* | |
O3 | 0.2969 | 0.1563 | 0.1672 | 0.0406 (4)* | |
O4 | 0.2827 | 0.3577 | 0.1617 | 0.040 (4)* | |
N1 | 0 | 0 | 0.486 (15) | 0.000* | |
N2 | 0.5 | 0 | 0.496 (9) | 0.000* | |
C1 | 0.0812 | 0.5672 | 0.3422 | 0.000* | |
C2 | 0.0808 | −0.0616 | 0.3251 | 0.000* | |
C3 | 0.0624 | 0.0797 | 0.6478 | 0.000* | |
C4 | −0.0812 | 0.4328 | 0.3422 | 0.000* | |
H1 | 0.1333 | 0.6103 | 0.4452 | 0* | |
H2 | 0.1246 | 0.5128 | 0.2454 | 0* | |
H3 | 0.0345 | 0.6189 | 0.2454 | 0* | |
H4 | −0.0913 | −0.1455 | 0.4384 | 0* | |
H5 | 0.0052 | −0.1235 | 0.2385 | 0* | |
H6 | −0.1142 | −0.0509 | 0.2385 | 0* | |
H7 | 0.1064 | 0.1358 | 0.5343 | 0* | |
H8 | 0.1190 | 0.0387 | 0.7341 | 0* | |
H9 | 0.0080 | 0.1234 | 0.7341 | 0* | |
H10 | 0.1118 | 0.3685 | 0.4452 | 0* | |
H11 | 0.1300 | 0.4660 | 0.2454 | 0* | |
H12 | 0.0114 | 0.3770 | 0.2454 | 0* | |
Geometric parameters (Å, º) top
N1—C2 | 1.5105 (2) | Cl—O1 | 1.4586 (1) |
N1—C3 | 1.5105 (2) | Cl—O2 | 1.4586 (1) |
N2—C1 | 1.5105 (2) | Cl—O3 | 1.4586 (1) |
N2—C4 | 1.5105 (2) | Cl—O4 | 1.4586 (1) |
| | | |
O1—Cl—O2 | 109.47 | O2—Cl—O3 | 109.47 |
O1—Cl—O3 | 109.47 | O2—Cl—O4 | 109.47 |
O1—Cl—O4 | 109.47 | O3—Cl—O4 | 109.47 |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C4H12N·ClO4 | C4H12N·ClO4 | (CH3)4NClO4 | (CH3)4NClO4 |
Mr | 173.60 | 173.60 | 173.60 | 173.60 |
Crystal system, space group | Orthorhombic, P21212 | Tetragonal, P4/nmm | Orthorhombic, P21212 | Orthorhombic, P21212 |
Temperature (K) | 150 | 210 | 30 | 100 |
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, 90 | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 804.3 (3) | 395.31 (13) | 782.3 (3) | 793.6 (3) |
Z | 4 | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Cu Kα1, Cu Kα2, λ = 1.540562, 1.544390 Å | Cu Kα1, Cu Kα2, λ = 1.540562, 1.544390 Å |
µ (mm−1) | 0.44 | 0.45 | – | – |
Specimen shape, size (mm) | 0.3 × 0.2 × 0.2 | 0.3 × 0.2 × 0.2 | Flat sheet, 20 × 10 | Flat sheet, 20 × 10 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer | Dmax Rigaku diffractometer | Dmax Rigaku diffractometer |
Specimen mounting | – | – | Ground from single crystals | Ground from single crystals |
Data collection mode | – | – | Reflection | Reflection |
Data collection method | ω–2θ scans | ω–2θ scan | Step | Step |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1729, 1389, 1210 | 1534, 376, 331 | – | – |
Rint | 0.027 | 0.046 | – | – |
θ values (°) | θmax = 30.1, θmin = 1.7 | θmax = 30.5, θmin = 3.5 | 2θmin = 5 2θmax = 60 2θstep = 0.03 | 2θmin = 5 2θmax = 60 2θstep = 0.03 |
(sin θ/λ)max (Å−1) | 0.705 | 0.713 | – | – |
|
Refinement |
R factors and goodness of fit | R[F2 > 2σ(F2)] = 0.087, wR(F2) = 0.248, S = 1.88 | R[F2 > 2σ(F2)] = 0.057, wR(F2) = 0.136, S = 1.25 | Rp = 0.139, Rwp = 0.189, Rexp = 0.127, χ2 = 2.220 | Rp = 0.130, Rwp = 0.179, Rexp = 0.128, χ2 = 1.960 |
No. of reflections/data points | 1389 | 376 | 1834 | 1834 |
No. of parameters | 99 | 36 | 34 | 34 |
No. of restraints | 10 | 6 | ? | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.27, −1.39 | 0.73, −0.66 | – | – |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | ? | – | – |
Absolute structure parameter | 0.1 (5) | ? | – | – |
Selected geometric parameters (Å, º) for (I) topCl—O1 | 1.427 (2) | N2—C4 | 1.503 (9) |
N1—C2 | 1.488 (10) | N2—C1 | 1.499 (8) |
N1—C3 | 1.511 (10) | | |
| | | |
C2i—N1—C2 | 112.7 (10) | C4ii—N2—C4 | 108.3 (8) |
C2i—N1—C3 | 108.2 (5) | C4—N2—C1ii | 110.9 (7) |
C2—N1—C3 | 108.7 (5) | C4—N2—C1 | 110.6 (6) |
C3—N1—C3i | 110.5 (10) | | |
Symmetry codes: (i) −x, −y, z; (ii) −x, −y+1, z. |
Selected geometric parameters (Å, º) for (II) topN—Ci | 1.481 (2) | Cl—O2 | 1.398 (3) |
Cl—O1 | 1.399 (3) | Cl—O3 | 1.397 (3) |
| | | |
Ci—N—Cii | 109.31 (11) | Ci—N—Ciii | 109.8 (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) topN1—C2 | 1.5018 (2) | Cl—O1 | 1.4572 (1) |
Selected bond lengths (Å) for (IV) topN1—C2 | 1.5105 (2) | Cl—O1 | 1.4586 (1) |
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