Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103018651/gg1174sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103018651/gg1174Isup2.hkl |
CCDC reference: 224648
The title salt was obtained using the procedure described by Lorenc (2001) and was recrystallized from solution in a mixture of acetone and propan-2-ol (Ratio?).
The space group P42bc was assigned from the systematic absences observed in the diffraction pattern: hkl - no systematic absences, 0kl k = 2n+1 (h0l h = 2n+1), hhl l = 2n+1, 00 l l = 2n+1, and h00 h = 2n+1 (0k0 k = 2n+1). Among 352 space group extinctions only a few reflections could be considered as observed (7 reflections of type 0kl and 3 reflections of type hhl), with intensities in the range 4–7σ(I). The systematic absences are identical for space groups P42bc and P42/mbc. Nevertheless, all tests [mean ABS(E2-1) of SHELXS97 (Sheldrick, 1997), as well as ABS(E) distribution and the N(z) test of Nonius maXus] clearly indicated that the intensity distribution is acentric. Examination of the structure with PLATON (Spek, 2003) detected no obvious extra crystallographic symmetry. The absolute structure was established by the anomalous dispersion effect of the Br atoms in diffraction measurements on the crystal (3569 Bijvoet pairs) and is described by a Flack parameter of −0.006 (8) (Flack, 1983; Flack & Bernardinelli, 1999, 2000). More than half of the total number of H-atom positions were observed in the Fourier difference map. Nevertheless, in the refinement procedure all H atoms were included from geometrical constraints in a riding model (C—H 0.93–0.97 Å) and were refined with isotropic displacement factors, with Uiso(H) = 1.2Ueq(C). Please check that added text is OK.
Data collection: COLLECT (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: SHELXL97.
C16H28BrN | Dx = 1.240 Mg m−3 |
Mr = 314.31 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P42bc | Cell parameters from 7799 reflections |
a = 22.4411 (4) Å | θ = 1.0–27.5° |
c = 13.3749 (2) Å | µ = 2.43 mm−1 |
V = 6735.6 (2) Å3 | T = 293 K |
Z = 16 | Prism, colourless |
F(000) = 2656 | 0.25 × 0.20 × 0.20 mm |
Nonius KappaCCD area-detector diffractometer | 7591 independent reflections |
Radiation source: fine-focus sealed tube | 5740 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.031 |
ϕ and ω scans to fill Ewald sphere | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | h = −29→29 |
Tmin = 0.582, Tmax = 0.642 | k = −20→20 |
14346 measured reflections | l = −17→15 |
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | Calculated w = 1/[σ2(Fo2) + (0.0221P)2 + 1.9763P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
7591 reflections | Δρmax = 0.25 e Å−3 |
325 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.006 (8) |
C16H28BrN | Z = 16 |
Mr = 314.31 | Mo Kα radiation |
Tetragonal, P42bc | µ = 2.43 mm−1 |
a = 22.4411 (4) Å | T = 293 K |
c = 13.3749 (2) Å | 0.25 × 0.20 × 0.20 mm |
V = 6735.6 (2) Å3 |
Nonius KappaCCD area-detector diffractometer | 7591 independent reflections |
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 5740 reflections with I > 2σ(I) |
Tmin = 0.582, Tmax = 0.642 | Rint = 0.031 |
14346 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | Δρmax = 0.25 e Å−3 |
S = 1.05 | Δρmin = −0.29 e Å−3 |
7591 reflections | Absolute structure: Flack (1983) |
325 parameters | Absolute structure parameter: −0.006 (8) |
0 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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.0000 | 0.0000 | 1.14210 (3) | 0.05987 (13) | |
Br2 | 0.5000 | 0.0000 | 0.6520 | 0.05580 (12) | |
Br3 | 0.761147 (13) | −0.187038 (13) | 1.00905 (5) | 0.05642 (9) | |
N1 | 1.12528 (10) | −0.06281 (10) | 1.39785 (19) | 0.0438 (5) | |
C1 | 1.07834 (14) | −0.10733 (14) | 1.4324 (3) | 0.0527 (8) | |
H11 | 1.0974 | −0.1458 | 1.4405 | 0.063* | |
H12 | 1.0640 | −0.0950 | 1.4976 | 0.063* | |
C11 | 1.02495 (15) | −0.11501 (17) | 1.3637 (3) | 0.0662 (9) | |
H111 | 1.0064 | −0.0767 | 1.3515 | 0.079* | |
H112 | 1.0377 | −0.1314 | 1.3001 | 0.079* | |
C12 | 0.98094 (17) | −0.15665 (18) | 1.4130 (4) | 0.0888 (14) | |
H121 | 0.9470 | −0.1619 | 1.3701 | 0.107* | |
H122 | 0.9682 | −0.1400 | 1.4756 | 0.107* | |
H123 | 0.9996 | −0.1945 | 1.4246 | 0.107* | |
C2 | 1.17915 (14) | −0.06774 (15) | 1.4663 (2) | 0.0483 (8) | |
H21 | 1.1979 | −0.1061 | 1.4549 | 0.058* | |
H22 | 1.2076 | −0.0372 | 1.4473 | 0.058* | |
C21 | 1.16685 (18) | −0.06171 (19) | 1.5764 (3) | 0.0634 (10) | |
H211 | 1.1409 | −0.0937 | 1.5984 | 0.076* | |
H212 | 1.1470 | −0.0241 | 1.5896 | 0.076* | |
C22 | 1.2253 (2) | −0.0643 (2) | 1.6330 (3) | 0.0945 (14) | |
H221 | 1.2177 | −0.0607 | 1.7034 | 0.113* | |
H222 | 1.2505 | −0.0322 | 1.6116 | 0.113* | |
H223 | 1.2446 | −0.1016 | 1.6198 | 0.113* | |
C3 | 1.14531 (14) | −0.07467 (13) | 1.2911 (2) | 0.0496 (7) | |
H31 | 1.1776 | −0.0476 | 1.2753 | 0.060* | |
H32 | 1.1125 | −0.0654 | 1.2465 | 0.060* | |
C31 | 1.1660 (2) | −0.13793 (17) | 1.2694 (3) | 0.0722 (11) | |
H311 | 1.1941 | −0.1505 | 1.3203 | 0.087* | |
H312 | 1.1322 | −0.1648 | 1.2713 | 0.087* | |
C32 | 1.1950 (2) | −0.14114 (19) | 1.1688 (3) | 0.0837 (12) | |
H321 | 1.2078 | −0.1813 | 1.1562 | 0.100* | |
H322 | 1.2289 | −0.1150 | 1.1673 | 0.100* | |
H323 | 1.1670 | −0.1292 | 1.1184 | 0.100* | |
C4 | 1.09752 (12) | −0.00034 (13) | 1.4018 (2) | 0.0467 (6) | |
H41 | 1.0646 | 0.0011 | 1.3548 | 0.056* | |
H42 | 1.0811 | 0.0058 | 1.4681 | 0.056* | |
C41 | 1.13932 (13) | 0.05047 (12) | 1.3787 (2) | 0.0439 (7) | |
C42 | 1.14464 (14) | 0.07202 (14) | 1.2815 (2) | 0.0516 (8) | |
H421 | 1.1236 | 0.0538 | 1.2300 | 0.062* | |
C43 | 1.18101 (17) | 0.12035 (16) | 1.2606 (3) | 0.0670 (10) | |
H431 | 1.1846 | 0.1340 | 1.1953 | 0.080* | |
C44 | 1.21179 (17) | 0.14816 (15) | 1.3360 (3) | 0.0668 (10) | |
H441 | 1.2367 | 0.1801 | 1.3215 | 0.080* | |
C45 | 1.20582 (18) | 0.12877 (16) | 1.4326 (3) | 0.0721 (10) | |
H451 | 1.2260 | 0.1481 | 1.4839 | 0.086* | |
C46 | 1.16983 (17) | 0.08044 (15) | 1.4536 (3) | 0.0628 (9) | |
H461 | 1.1660 | 0.0677 | 1.5195 | 0.075* | |
N2 | 0.62845 (10) | −0.04681 (10) | 0.90576 (17) | 0.0390 (5) | |
C5 | 0.59141 (13) | −0.09908 (13) | 0.9408 (2) | 0.0443 (7) | |
H51 | 0.5765 | −0.0902 | 1.0072 | 0.053* | |
H52 | 0.6172 | −0.1336 | 0.9464 | 0.053* | |
C51 | 0.53898 (14) | −0.11549 (14) | 0.8748 (2) | 0.0560 (8) | |
H511 | 0.5127 | −0.0815 | 0.8676 | 0.067* | |
H512 | 0.5531 | −0.1267 | 0.8089 | 0.067* | |
C52 | 0.50548 (16) | −0.16680 (15) | 0.9212 (3) | 0.0695 (10) | |
H521 | 0.4722 | −0.1772 | 0.8795 | 0.083* | |
H522 | 0.4913 | −0.1554 | 0.9861 | 0.083* | |
H523 | 0.5316 | −0.2005 | 0.9274 | 0.083* | |
C6 | 0.68219 (13) | −0.04064 (15) | 0.97385 (19) | 0.0449 (7) | |
H61 | 0.7087 | −0.0739 | 0.9611 | 0.054* | |
H62 | 0.7033 | −0.0046 | 0.9555 | 0.054* | |
C61 | 0.66964 (16) | −0.03840 (16) | 1.0846 (2) | 0.0549 (8) | |
H611 | 0.6595 | −0.0779 | 1.1087 | 0.066* | |
H612 | 0.6362 | −0.0122 | 1.0975 | 0.066* | |
C62 | 0.72470 (18) | −0.0156 (2) | 1.1387 (3) | 0.0851 (13) | |
H621 | 0.7170 | −0.0140 | 1.2093 | 0.102* | |
H622 | 0.7344 | 0.0236 | 1.1149 | 0.102* | |
H623 | 0.7575 | −0.0420 | 1.1262 | 0.102* | |
C7 | 0.65076 (13) | −0.05582 (13) | 0.7990 (2) | 0.0433 (6) | |
H71 | 0.6172 | −0.0512 | 0.7539 | 0.052* | |
H72 | 0.6790 | −0.0243 | 0.7838 | 0.052* | |
C71 | 0.68038 (17) | −0.11522 (16) | 0.7768 (2) | 0.0603 (9) | |
H711 | 0.7111 | −0.1232 | 0.8260 | 0.072* | |
H712 | 0.6511 | −0.1470 | 0.7801 | 0.072* | |
C72 | 0.70748 (17) | −0.11280 (17) | 0.6737 (2) | 0.0674 (10) | |
H721 | 0.7266 | −0.1501 | 0.6592 | 0.081* | |
H722 | 0.7363 | −0.0813 | 0.6709 | 0.081* | |
H723 | 0.6767 | −0.1055 | 0.6252 | 0.081* | |
C8 | 0.58974 (12) | 0.00949 (11) | 0.9083 (2) | 0.0429 (6) | |
H81 | 0.5588 | 0.0056 | 0.8582 | 0.052* | |
H82 | 0.5704 | 0.0117 | 0.9731 | 0.052* | |
C81 | 0.62231 (12) | 0.06690 (12) | 0.8905 (2) | 0.0458 (7) | |
C82 | 0.62927 (16) | 0.08891 (14) | 0.7944 (3) | 0.0579 (8) | |
H821 | 0.6137 | 0.0679 | 0.7404 | 0.070* | |
C83 | 0.6593 (2) | 0.14216 (17) | 0.7782 (4) | 0.0829 (14) | |
H831 | 0.6641 | 0.1566 | 0.7135 | 0.099* | |
C84 | 0.68177 (19) | 0.17332 (18) | 0.8575 (4) | 0.0871 (13) | |
H841 | 0.7029 | 0.2083 | 0.8463 | 0.105* | |
C85 | 0.6734 (2) | 0.15356 (17) | 0.9525 (4) | 0.0884 (14) | |
H851 | 0.6877 | 0.1758 | 1.0061 | 0.106* | |
C86 | 0.64384 (17) | 0.10061 (15) | 0.9701 (3) | 0.0687 (10) | |
H861 | 0.6383 | 0.0874 | 1.0353 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0755 (3) | 0.0572 (3) | 0.0469 (3) | −0.0120 (3) | 0.000 | 0.000 |
Br2 | 0.0761 (3) | 0.0487 (3) | 0.0426 (3) | 0.0045 (2) | 0.000 | 0.000 |
Br3 | 0.05087 (16) | 0.05375 (17) | 0.06462 (16) | −0.00048 (13) | 0.0020 (2) | −0.0071 (2) |
N1 | 0.0414 (13) | 0.0394 (13) | 0.0505 (13) | 0.0076 (10) | 0.0072 (11) | 0.0106 (11) |
C1 | 0.0461 (18) | 0.0436 (17) | 0.0685 (19) | 0.0008 (14) | 0.0075 (15) | 0.0161 (15) |
C11 | 0.051 (2) | 0.060 (2) | 0.087 (2) | −0.0070 (17) | −0.0059 (18) | 0.0207 (19) |
C12 | 0.060 (2) | 0.070 (3) | 0.136 (4) | −0.0137 (19) | −0.012 (2) | 0.035 (3) |
C2 | 0.0384 (17) | 0.0470 (19) | 0.0594 (17) | 0.0070 (14) | −0.0007 (13) | 0.0087 (14) |
C21 | 0.062 (2) | 0.071 (3) | 0.0572 (19) | 0.009 (2) | 0.0028 (17) | 0.0169 (18) |
C22 | 0.077 (3) | 0.136 (4) | 0.070 (2) | −0.007 (3) | −0.019 (2) | 0.005 (3) |
C3 | 0.0518 (19) | 0.0469 (18) | 0.0502 (16) | 0.0047 (15) | 0.0066 (14) | 0.0031 (14) |
C31 | 0.090 (3) | 0.053 (2) | 0.074 (2) | 0.013 (2) | 0.016 (2) | 0.0028 (17) |
C32 | 0.101 (3) | 0.070 (3) | 0.080 (3) | −0.001 (2) | 0.024 (2) | −0.017 (2) |
C4 | 0.0436 (15) | 0.0428 (15) | 0.0537 (15) | 0.0081 (14) | 0.0069 (14) | 0.0048 (14) |
C41 | 0.0421 (16) | 0.0371 (16) | 0.0526 (17) | 0.0087 (12) | 0.0019 (13) | 0.0040 (13) |
C42 | 0.056 (2) | 0.0481 (19) | 0.0510 (16) | 0.0002 (16) | −0.0027 (15) | 0.0084 (14) |
C43 | 0.070 (3) | 0.055 (2) | 0.076 (2) | 0.005 (2) | 0.0073 (18) | 0.0167 (17) |
C44 | 0.056 (2) | 0.0414 (19) | 0.103 (3) | −0.0002 (16) | −0.001 (2) | 0.0074 (19) |
C45 | 0.076 (3) | 0.050 (2) | 0.091 (3) | −0.0030 (19) | −0.022 (2) | −0.0029 (19) |
C46 | 0.084 (3) | 0.051 (2) | 0.0529 (18) | 0.0077 (18) | −0.0094 (17) | 0.0012 (16) |
N2 | 0.0382 (13) | 0.0399 (13) | 0.0390 (11) | 0.0022 (10) | 0.0022 (10) | 0.0020 (10) |
C5 | 0.0438 (17) | 0.0425 (16) | 0.0466 (14) | −0.0030 (13) | 0.0006 (12) | 0.0070 (12) |
C51 | 0.0515 (19) | 0.0473 (18) | 0.069 (2) | −0.0083 (15) | −0.0063 (16) | 0.0055 (16) |
C52 | 0.056 (2) | 0.060 (2) | 0.092 (3) | −0.0136 (18) | −0.0074 (19) | 0.0167 (19) |
C6 | 0.0380 (16) | 0.0458 (17) | 0.0509 (17) | 0.0015 (14) | −0.0017 (12) | 0.0014 (13) |
C61 | 0.055 (2) | 0.061 (2) | 0.0490 (17) | −0.0035 (17) | −0.0061 (15) | 0.0019 (16) |
C62 | 0.072 (3) | 0.123 (4) | 0.060 (2) | −0.019 (2) | −0.017 (2) | −0.005 (2) |
C7 | 0.0454 (17) | 0.0438 (17) | 0.0405 (14) | 0.0027 (13) | 0.0055 (12) | 0.0030 (12) |
C71 | 0.070 (2) | 0.056 (2) | 0.0552 (17) | 0.0167 (17) | 0.0041 (16) | −0.0007 (15) |
C72 | 0.066 (2) | 0.076 (3) | 0.0594 (19) | 0.0124 (19) | 0.0063 (17) | −0.0143 (17) |
C8 | 0.0400 (15) | 0.0388 (16) | 0.0501 (15) | 0.0070 (12) | 0.0047 (13) | 0.0014 (12) |
C81 | 0.0387 (16) | 0.0390 (15) | 0.0597 (18) | 0.0042 (12) | 0.0029 (14) | −0.0039 (14) |
C82 | 0.068 (2) | 0.0410 (18) | 0.065 (2) | 0.0017 (16) | 0.0114 (17) | 0.0038 (15) |
C83 | 0.095 (3) | 0.046 (2) | 0.108 (3) | 0.005 (2) | 0.033 (3) | 0.013 (2) |
C84 | 0.063 (3) | 0.042 (2) | 0.156 (4) | −0.0071 (18) | 0.006 (3) | 0.006 (3) |
C85 | 0.092 (3) | 0.049 (2) | 0.124 (4) | −0.002 (2) | −0.043 (3) | −0.007 (2) |
C86 | 0.083 (3) | 0.047 (2) | 0.076 (2) | 0.0017 (19) | −0.0170 (18) | −0.0097 (16) |
N1—C1 | 1.523 (4) | N2—C5 | 1.512 (3) |
N1—C2 | 1.521 (4) | N2—C6 | 1.518 (3) |
N1—C3 | 1.521 (4) | N2—C7 | 1.527 (3) |
N1—C4 | 1.535 (4) | N2—C8 | 1.534 (3) |
C1—C11 | 1.519 (5) | C5—C51 | 1.517 (4) |
C1—H11 | 0.9700 | C5—H51 | 0.9700 |
C1—H12 | 0.9700 | C5—H52 | 0.9700 |
C11—C12 | 1.511 (5) | C51—C52 | 1.508 (4) |
C11—H111 | 0.9700 | C51—H511 | 0.9700 |
C11—H112 | 0.9700 | C51—H512 | 0.9700 |
C12—H121 | 0.9600 | C52—H521 | 0.9600 |
C12—H122 | 0.9600 | C52—H522 | 0.9600 |
C12—H123 | 0.9600 | C52—H523 | 0.9600 |
C2—C21 | 1.504 (4) | C6—C61 | 1.509 (4) |
C2—H21 | 0.9700 | C6—H61 | 0.9700 |
C2—H22 | 0.9700 | C6—H62 | 0.9700 |
C21—C22 | 1.515 (5) | C61—C62 | 1.521 (5) |
C21—H211 | 0.9700 | C61—H611 | 0.9700 |
C21—H212 | 0.9700 | C61—H612 | 0.9700 |
C22—H221 | 0.9600 | C62—H621 | 0.9600 |
C22—H222 | 0.9600 | C62—H622 | 0.9600 |
C22—H223 | 0.9600 | C62—H623 | 0.9600 |
C3—C31 | 1.522 (5) | C7—C71 | 1.519 (4) |
C3—H31 | 0.9700 | C7—H71 | 0.9700 |
C3—H32 | 0.9700 | C7—H72 | 0.9700 |
C31—C32 | 1.496 (5) | C71—C72 | 1.509 (4) |
C31—H311 | 0.9700 | C71—H711 | 0.9700 |
C31—H312 | 0.9700 | C71—H712 | 0.9700 |
C32—H321 | 0.9600 | C72—H721 | 0.9600 |
C32—H322 | 0.9600 | C72—H722 | 0.9600 |
C32—H323 | 0.9600 | C72—H723 | 0.9600 |
C4—C41 | 1.509 (4) | C8—C81 | 1.500 (4) |
C4—H41 | 0.9700 | C8—H81 | 0.9700 |
C4—H42 | 0.9700 | C8—H82 | 0.9700 |
C41—C46 | 1.388 (4) | C81—C82 | 1.386 (4) |
C41—C42 | 1.393 (4) | C81—C86 | 1.392 (4) |
C42—C43 | 1.386 (5) | C82—C83 | 1.389 (5) |
C42—H421 | 0.9300 | C82—H821 | 0.9300 |
C43—C44 | 1.372 (5) | C83—C84 | 1.367 (6) |
C43—H431 | 0.9300 | C83—H831 | 0.9300 |
C44—C45 | 1.370 (5) | C84—C85 | 1.359 (6) |
C44—H441 | 0.9300 | C84—H841 | 0.9300 |
C45—C46 | 1.381 (5) | C85—C86 | 1.381 (5) |
C45—H451 | 0.9300 | C85—H851 | 0.9300 |
C46—H461 | 0.9300 | C86—H861 | 0.9300 |
C1—N1—C2 | 108.6 (2) | C5—N2—C6 | 108.8 (2) |
C1—N1—C3 | 112.0 (2) | C5—N2—C7 | 111.6 (2) |
C2—N1—C3 | 108.5 (2) | C6—N2—C7 | 108.2 (2) |
C1—N1—C4 | 107.9 (2) | C5—N2—C8 | 108.7 (2) |
C2—N1—C4 | 111.6 (2) | C6—N2—C8 | 111.2 (2) |
C3—N1—C4 | 108.2 (2) | C7—N2—C8 | 108.4 (2) |
N1—C1—C11 | 115.9 (2) | N2—C5—C51 | 115.7 (2) |
C11—C1—H11 | 108.3 | N2—C5—H51 | 108.3 |
N1—C1—H11 | 108.3 | C51—C5—H51 | 108.3 |
C11—C1—H12 | 108.3 | N2—C5—H52 | 108.3 |
N1—C1—H12 | 108.3 | C51—C5—H52 | 108.3 |
H11—C1—H12 | 107.4 | H51—C5—H52 | 107.4 |
C12—C11—C1 | 108.8 (3) | C52—C51—C5 | 109.4 (3) |
C12—C11—H111 | 109.9 | C52—C51—H511 | 109.8 |
C1—C11—H111 | 109.9 | C5—C51—H511 | 109.8 |
C12—C11—H112 | 109.9 | C52—C51—H512 | 109.8 |
C1—C11—H112 | 109.9 | C5—C51—H512 | 109.8 |
H111—C11—H112 | 108.3 | H511—C51—H512 | 108.2 |
C11—C12—H121 | 109.5 | C51—C52—H521 | 109.5 |
C11—C12—H122 | 109.5 | C51—C52—H522 | 109.5 |
H121—C12—H122 | 109.5 | H521—C52—H522 | 109.5 |
C11—C12—H123 | 109.5 | C51—C52—H523 | 109.5 |
H121—C12—H123 | 109.5 | H521—C52—H523 | 109.5 |
H122—C12—H123 | 109.5 | H522—C52—H523 | 109.5 |
C21—C2—N1 | 115.9 (3) | C61—C6—N2 | 116.4 (3) |
C21—C2—H21 | 108.3 | C61—C6—H61 | 108.2 |
N1—C2—H21 | 108.3 | N2—C6—H61 | 108.2 |
C21—C2—H22 | 108.3 | C61—C6—H62 | 108.2 |
N1—C2—H22 | 108.3 | N2—C6—H62 | 108.2 |
H21—C2—H22 | 107.4 | H61—C6—H62 | 107.4 |
C2—C21—C22 | 109.0 (3) | C6—C61—C62 | 109.1 (3) |
C2—C21—H211 | 109.9 | C6—C61—H611 | 109.9 |
C22—C21—H211 | 109.9 | C62—C61—H611 | 109.9 |
C2—C21—H212 | 109.9 | C6—C61—H612 | 109.9 |
C22—C21—H212 | 109.9 | C62—C61—H612 | 109.9 |
H211—C21—H212 | 108.3 | H611—C61—H612 | 108.3 |
C21—C22—H221 | 109.5 | C61—C62—H621 | 109.5 |
C21—C22—H222 | 109.5 | C61—C62—H622 | 109.5 |
H221—C22—H222 | 109.5 | H621—C62—H622 | 109.5 |
C21—C22—H223 | 109.5 | C61—C62—H623 | 109.5 |
H221—C22—H223 | 109.5 | H621—C62—H623 | 109.5 |
H222—C22—H223 | 109.5 | H622—C62—H623 | 109.5 |
C31—C3—N1 | 115.7 (2) | C71—C7—N2 | 116.2 (2) |
N1—C3—H31 | 108.4 | C71—C7—H71 | 108.2 |
C31—C3—H31 | 108.4 | N2—C7—H71 | 108.2 |
N1—C3—H32 | 108.4 | C71—C7—H72 | 108.2 |
C31—C3—H32 | 108.4 | N2—C7—H72 | 108.2 |
H31—C3—H32 | 107.4 | H71—C7—H72 | 107.4 |
C32—C31—C3 | 110.5 (3) | C72—C71—C7 | 108.9 (3) |
C32—C31—H311 | 109.6 | C72—C71—H711 | 109.9 |
C3—C31—H311 | 109.6 | C7—C71—H711 | 109.9 |
C32—C31—H312 | 109.6 | C72—C71—H712 | 109.9 |
C3—C31—H312 | 109.6 | C7—C71—H712 | 109.9 |
H311—C31—H312 | 108.1 | H711—C71—H712 | 108.3 |
C31—C32—H321 | 109.5 | C71—C72—H721 | 109.5 |
C31—C32—H322 | 109.5 | C71—C72—H722 | 109.5 |
H321—C32—H322 | 109.5 | H721—C72—H722 | 109.5 |
C31—C32—H323 | 109.5 | C71—C72—H723 | 109.5 |
H321—C32—H323 | 109.5 | H721—C72—H723 | 109.5 |
H322—C32—H323 | 109.5 | H722—C72—H723 | 109.5 |
C41—C4—N1 | 115.5 (2) | C81—C8—N2 | 115.3 (2) |
C41—C4—H41 | 108.4 | C81—C8—H81 | 108.4 |
N1—C4—H41 | 108.4 | N2—C8—H81 | 108.4 |
C41—C4—H42 | 108.4 | C81—C8—H82 | 108.4 |
N1—C4—H42 | 108.4 | N2—C8—H82 | 108.4 |
H41—C4—H42 | 107.5 | H81—C8—H82 | 107.5 |
C42—C41—C46 | 117.6 (3) | C82—C81—C86 | 118.5 (3) |
C46—C41—C4 | 121.7 (3) | C82—C81—C8 | 120.6 (3) |
C42—C41—C4 | 120.5 (3) | C86—C81—C8 | 120.9 (3) |
C43—C42—C41 | 120.7 (3) | C81—C82—C83 | 120.4 (4) |
C43—C42—H421 | 119.7 | C81—C82—H821 | 119.8 |
C41—C42—H421 | 119.7 | C83—C82—H821 | 119.8 |
C44—C43—C42 | 120.3 (3) | C84—C83—C82 | 119.9 (4) |
C44—C43—H431 | 119.8 | C84—C83—H831 | 120.1 |
C42—C43—H431 | 119.8 | C82—C83—H831 | 120.1 |
C45—C44—C43 | 119.9 (3) | C85—C84—C83 | 120.5 (4) |
C45—C44—H441 | 120.0 | C85—C84—H841 | 119.7 |
C43—C44—H441 | 120.0 | C83—C84—H841 | 119.7 |
C44—C45—C46 | 119.9 (3) | C84—C85—C86 | 120.4 (4) |
C44—C45—H451 | 120.0 | C84—C85—H851 | 119.8 |
C46—C45—H451 | 120.0 | C86—C85—H851 | 119.8 |
C45—C46—C41 | 121.4 (3) | C85—C86—C81 | 120.3 (4) |
C45—C46—H461 | 119.3 | C85—C86—H861 | 119.9 |
C41—C46—H461 | 119.3 | C81—C86—H861 | 119.9 |
C2—N1—C1—C11 | −171.5 (3) | C6—N2—C5—C51 | −174.2 (2) |
C3—N1—C1—C11 | −51.7 (4) | C7—N2—C5—C51 | −54.9 (3) |
C4—N1—C1—C11 | 67.3 (4) | C8—N2—C5—C51 | 64.6 (3) |
N1—C1—C11—C12 | −175.5 (3) | N2—C5—C51—C52 | −178.2 (3) |
C1—N1—C2—C21 | −53.7 (4) | C5—N2—C6—C61 | −51.9 (4) |
C3—N1—C2—C21 | −175.7 (3) | C7—N2—C6—C61 | −173.2 (3) |
C4—N1—C2—C21 | 65.1 (4) | C8—N2—C6—C61 | 67.8 (3) |
N1—C2—C21—C22 | −176.9 (3) | N2—C6—C61—C62 | −164.7 (3) |
C1—N1—C3—C31 | −52.9 (4) | C5—N2—C7—C71 | −49.4 (3) |
C2—N1—C3—C31 | 67.0 (4) | C6—N2—C7—C71 | 70.2 (3) |
C4—N1—C3—C31 | −171.7 (3) | C8—N2—C7—C71 | −169.1 (3) |
N1—C3—C31—C32 | −169.4 (3) | N2—C7—C71—C72 | −171.7 (3) |
C3—N1—C4—C41 | −63.8 (3) | C5—N2—C8—C81 | 171.2 (2) |
C2—N1—C4—C41 | 55.5 (3) | C6—N2—C8—C81 | 51.5 (3) |
C1—N1—C4—C41 | 174.8 (3) | C7—N2—C8—C81 | −67.4 (3) |
N1—C4—C41—C46 | −93.1 (4) | N2—C8—C81—C82 | 89.4 (3) |
N1—C4—C41—C42 | 92.3 (3) | N2—C8—C81—C86 | −93.6 (3) |
C46—C41—C42—C43 | 2.4 (5) | C86—C81—C82—C83 | 2.7 (5) |
C4—C41—C42—C43 | 177.2 (3) | C8—C81—C82—C83 | 179.8 (3) |
C41—C42—C43—C44 | −0.8 (5) | C81—C82—C83—C84 | −0.5 (6) |
C42—C43—C44—C45 | −1.1 (6) | C82—C83—C84—C85 | −2.0 (7) |
C43—C44—C45—C46 | 1.4 (6) | C83—C84—C85—C86 | 2.2 (7) |
C44—C45—C46—C41 | 0.2 (6) | C84—C85—C86—C81 | 0.1 (6) |
C42—C41—C46—C45 | −2.1 (5) | C82—C81—C86—C85 | −2.5 (5) |
C4—C41—C46—C45 | −176.8 (3) | C8—C81—C86—C85 | −179.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H12···Br1i | 0.97 | 3.22 | 4.094 (3) | 151 |
C4—H42···Br1i | 0.97 | 2.96 | 3.888 (3) | 161 |
C4—H41···Br1 | 0.97 | 3.19 | 4.106 (3) | 157 |
C8—H81···Br2 | 0.97 | 3.06 | 3.982 (3) | 159 |
C8—H82···Br2ii | 0.97 | 2.88 | 3.837 (3) | 169 |
C61—H612···Br2ii | 0.97 | 3.15 | 4.006 (4) | 148 |
C7—H71···Br2 | 0.97 | 3.18 | 4.108 (3) | 161 |
C82—H821···Br2 | 0.93 | 3.20 | 4.003 (4) | 146 |
C6—H61···Br3 | 0.97 | 2.87 | 3.762 (3) | 153 |
C71—H711···Br3 | 0.97 | 3.05 | 3.941 (3) | 153 |
C1—H11···Br3i | 0.97 | 3.04 | 3.964 (3) | 160 |
C43—H431···Br3iii | 0.93 | 3.02 | 3.905 (4) | 160 |
C2—H21···Br3i | 0.97 | 3.08 | 3.886 (3) | 142 |
C31—H311···Br3i | 0.97 | 3.21 | 3.953 (4) | 134 |
C45—H451···Br3iv | 0.93 | 3.22 | 3.956 (4) | 138 |
C12—H121···Cg1iii | 0.96 | 3.07 | 3.791 (15) | 133 |
C52—H521···Cg2v | 0.96 | 3.06 | 3.735 (15) | 128 |
Symmetry codes: (i) −y+1, x−1, z+1/2; (ii) y+1/2, x−1/2, z+1/2; (iii) −x+2, −y, z; (iv) y+3/2, x−1/2, z+1/2; (v) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H28BrN |
Mr | 314.31 |
Crystal system, space group | Tetragonal, P42bc |
Temperature (K) | 293 |
a, c (Å) | 22.4411 (4), 13.3749 (2) |
V (Å3) | 6735.6 (2) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 2.43 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.582, 0.642 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14346, 7591, 5740 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.076, 1.05 |
No. of reflections | 7591 |
No. of parameters | 325 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.29 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.006 (8) |
Computer programs: COLLECT (Nonius, 1997), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994) and SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1999), SHELXL97.
N1—C1 | 1.523 (4) | N2—C5 | 1.512 (3) |
N1—C2 | 1.521 (4) | N2—C6 | 1.518 (3) |
N1—C3 | 1.521 (4) | N2—C7 | 1.527 (3) |
N1—C4 | 1.535 (4) | N2—C8 | 1.534 (3) |
C1—C11 | 1.519 (5) | C5—C51 | 1.517 (4) |
C11—C12 | 1.511 (5) | C51—C52 | 1.508 (4) |
C2—C21 | 1.504 (4) | C6—C61 | 1.509 (4) |
C21—C22 | 1.515 (5) | C61—C62 | 1.521 (5) |
C3—C31 | 1.522 (5) | C7—C71 | 1.519 (4) |
C31—C32 | 1.496 (5) | C71—C72 | 1.509 (4) |
C1—N1—C2 | 108.6 (2) | C5—N2—C6 | 108.8 (2) |
C1—N1—C3 | 112.0 (2) | C5—N2—C7 | 111.6 (2) |
C2—N1—C3 | 108.5 (2) | C6—N2—C7 | 108.2 (2) |
C1—N1—C4 | 107.9 (2) | C5—N2—C8 | 108.7 (2) |
C2—N1—C4 | 111.6 (2) | C6—N2—C8 | 111.2 (2) |
C3—N1—C4 | 108.2 (2) | C7—N2—C8 | 108.4 (2) |
N1—C1—C11 | 115.9 (2) | N2—C5—C51 | 115.7 (2) |
C12—C11—C1 | 108.8 (3) | C52—C51—C5 | 109.4 (3) |
C21—C2—N1 | 115.9 (3) | C61—C6—N2 | 116.4 (3) |
C2—C21—C22 | 109.0 (3) | C6—C61—C62 | 109.1 (3) |
C31—C3—N1 | 115.7 (2) | C71—C7—N2 | 116.2 (2) |
C32—C31—C3 | 110.5 (3) | C72—C71—C7 | 108.9 (3) |
C41—C4—N1 | 115.5 (2) | C81—C8—N2 | 115.3 (2) |
C42—C41—C46 | 117.6 (3) | C82—C81—C86 | 118.5 (3) |
C2—N1—C1—C11 | −171.5 (3) | C6—N2—C5—C51 | −174.2 (2) |
C3—N1—C1—C11 | −51.7 (4) | C7—N2—C5—C51 | −54.9 (3) |
C4—N1—C1—C11 | 67.3 (4) | C8—N2—C5—C51 | 64.6 (3) |
N1—C1—C11—C12 | −175.5 (3) | N2—C5—C51—C52 | −178.2 (3) |
C1—N1—C2—C21 | −53.7 (4) | C5—N2—C6—C61 | −51.9 (4) |
C3—N1—C2—C21 | −175.7 (3) | C7—N2—C6—C61 | −173.2 (3) |
C4—N1—C2—C21 | 65.1 (4) | C8—N2—C6—C61 | 67.8 (3) |
N1—C2—C21—C22 | −176.9 (3) | N2—C6—C61—C62 | −164.7 (3) |
C1—N1—C3—C31 | −52.9 (4) | C5—N2—C7—C71 | −49.4 (3) |
C2—N1—C3—C31 | 67.0 (4) | C6—N2—C7—C71 | 70.2 (3) |
C4—N1—C3—C31 | −171.7 (3) | C8—N2—C7—C71 | −169.1 (3) |
N1—C3—C31—C32 | −169.4 (3) | N2—C7—C71—C72 | −171.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H42···Br1i | 0.97 | 2.96 | 3.888 (3) | 161 |
C4—H41···Br1 | 0.97 | 3.19 | 4.106 (3) | 157 |
C8—H81···Br2 | 0.97 | 3.06 | 3.982 (3) | 159 |
C8—H82···Br2ii | 0.97 | 2.88 | 3.837 (3) | 169 |
C61—H612···Br2ii | 0.97 | 3.15 | 4.006 (4) | 148 |
C7—H71···Br2 | 0.97 | 3.18 | 4.108 (3) | 161 |
C82—H821···Br2 | 0.93 | 3.20 | 4.003 (4) | 146 |
C6—H61···Br3 | 0.97 | 2.87 | 3.762 (3) | 153 |
C71—H711···Br3 | 0.97 | 3.05 | 3.941 (3) | 153 |
C1—H11···Br3i | 0.97 | 3.04 | 3.964 (3) | 160 |
C43—H431···Br3iii | 0.93 | 3.02 | 3.905 (4) | 160 |
C2—H21···Br3i | 0.97 | 3.08 | 3.886 (3) | 142 |
C31—H311···Br3i | 0.97 | 3.21 | 3.953 (4) | 134 |
C12—H121···Cg1iii | 0.96 | 3.07 | 3.791 (15) | 133 |
C52—H521···Cg2iv | 0.96 | 3.06 | 3.735 (15) | 128 |
Symmetry codes: (i) −y+1, x−1, z+1/2; (ii) y+1/2, x−1/2, z+1/2; (iii) −x+2, −y, z; (iv) −x+1, −y, z. |
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Quaternary alkyl ammonium cations are the subject of wide interest because they are able to change the nature of the surface of clay minerals, such as montmorillonite or bentonite, from hydrophilic to hydrophobic. The surface of the resultant organoclays can adsorb organic pollutants which have low solubility in water (Lee et al., 1989; Lo et al., 1997; Polubesova et al., 1997). Recently, the cation of the title compound was investigated for its sorption properties on montmorillonite (Lorenc, 2001) and was found to have a significantly lower ability than benzyltrimethylammonium used as a reference cation.
The crystal structure analysis of selected quaternary alkyl ammonium salts was undertaken to find the relationship between the length and conformation of the alkyl chains and the packing properties of the ammonium cations. The other important question we wished to address was how a possible mutual arrangement of the cations could influence their sorption behaviour, either on a montmorillonite or on a bentonite. Here, the tetragonal polar structure of crystals of benzyltripropylammonium bromide, (I), is reported. \sch
The asymmetric part of the unit cell of (I) contains five distinct moieties: two symmetrically independent benzyltripropyloammonium (BTPA) cations, A and B, and three Br− anions. The bond lengths and angles of these symmetry-independent molecules are quite similar (Table 1) and the normal probability plot analysis (Abrahams & Keve, 1971; International Tables for X-ray Crystallography, 1974, Vol. IV, pp. 293–309) shows that the differences are of a statistical rather than systematic nature. The correlation coefficients between experimental and theoretical distributions are 0.9962 for bond lengths and 0.9903 for bond angles.
The conformation of the BTPA cations in the crystalline state is shown in Fig. 1. Each cation has a synclinal (gauche) conformation of two propyl chains against the benzyl moiety, defined by the C4(benzyl)-N1—C1—C11 and C4(benzyl)-N1—C2—C21 torsion angles for cation A, and C8(benzyl)-N2—C5—C51 and C8(benzyl)-N2—C6—C61 for cation B, with an anti-periplanar conformation for the third propyl substituent in each case (Table 1). All propyl chains have a zigzag-like conformation, with NX—CX—CX1—CX2 torsion angles close to −180°.
The packing in the structure of (I) is given in Fig. 2. The ammonium cations form a framework enclosing two types of molecular columns running along the [001] direction, one at Wyckoff positions 0,0,z (4 a 2..) and the second at 0,1/2,z (4 b 2..). The column at 0,0,z (of 42 symmetry) is built up of translationally repeated kerbs, each containing four BTPA cations of type A, arranged into two dimers rotated relative to each other by 90°. The cations included in these dimers are interconnected by C—H···π interactions (Fig. 3a). Such a kerb is stabilized by Coulombic interactions with the Br1− counterion (Fig. 3c). The second molecular column at 0,1/2,z is also of twofold symmetry but results from crossing two c glide planes. Here, the dimers are formed of type B cations symmetrically independent of the first type but stabilized according to a similar scheme (i.e. C—H···π interactions and Coulombic interactions with the Br2− cation; Fig. 3 b,d). Both columns are joined together into a tetragonal structure via interactions with the Br3− anions in the general position. The geometry of the short C—H···Br contacts and weak C—H..π hydrogen bonds is given in Table 2.
In conclusion, the three propyl-chain substituents of (I), with their specific conformations relative to the benzyl moiety, could sterically hinder the hypothetical direct interaction of N+ cations with the negatively charged surface of montmorillonite particles when adsorbed at the surface of grains or intercalated between silicate particles. Such steric hindrance could be the reason for the much worse sorption properties of BTPA cations on montmorillonite clay than those of the benzyltrimethylammonium cations used as reference (Lorenc, 2001). Additonally, the tendency of BTPA to form molecular columns, through hydrophobic interactions between the cations, hampers their intercalation between montmorillonite particles.
Table 2. Geometry of short C—H···Br contacts and weak C—H···π hydrogen bonds (Å, °). Cg1 is the centroid of the C41/C46 benzene ring and Cg2 the centroid of the C81/C86 ring.