Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103019013/bs0018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IIsup3.hkl | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IIIsup4.rtv | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768103019013/bs0018IVsup5.hkl |
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).
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 |
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 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) |
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 |
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) |
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 |
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. |
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)* |
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) |
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. |
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 |
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 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 |
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 |
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) |
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 |
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. |
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 |
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 |
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. |
(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 |
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 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 |
(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 |
Dmax Rigaku diffractometer | Scan method: step |
Specimen mounting: ground from single crystals | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Data collection mode: reflection |
Rp = 0.139 | 1834 data points |
Rwp = 0.189 | 34 parameters |
Rexp = 0.127 | H-atom parameters not refined |
χ2 = 2.220 |
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* |
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 |
(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 |
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 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 |
(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 |
Dmax Rigaku diffractometer | Scan method: step |
Specimen mounting: ground from single crystals | 2θmin = 5°, 2θmax = 60°, 2θstep = 0.03° |
Data collection mode: reflection |
Rp = 0.130 | 1834 data points |
Rwp = 0.179 | 34 parameters |
Rexp = 0.128 | H-atom parameters not refined |
χ2 = 1.960 |
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* |
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) | ? | – | – |
Computer programs: Siemens XSCANS, Rigaku IUSA 2.8, FULLPROF (Rodriguez-Carvajal et al. 1987), none, SHELXL97 (Sheldrick, 1997).
Cl—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. |
N—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. |