Tetraisohexylammonium bromide [systematic name: tetrakis(4-methylpentyl)azanium bromide], C24H52N+·Br-, is a powerful structure II clathrate hydrate crystal-growth inhibitor. The crystal structure, in the space group P3221, contains one ammonium cation and one bromide anion in the asymmetric unit, both on general positions. At 100 K, the ammonium cation exhibits one ordered isohexyl chain and three disordered isohexyl chains. At 250 K, all four isohexyl chains are disordered. In an effort to reduce the disorder in the alkyl chains, the crystal was thermally cycled, but the disorder remained, indicating that it is dynamic in nature.
Supporting information
CCDC references: 879437; 879438; 879439
Isohexyl bromide (3.96 g, 24 mmol), powdered K2CO3 (3.31 g, 24 mmol) and
isohexylamine hydrochloride (1.00 g, 7.27 mmol) were refluxed in
isobutyronitrile (20 ml) for 5 d. The solution was filtered and the solvent
removed to leave an off-white solid (52% yield). Crystals were grown from an
ethyl acetate–diethyl ether mixture (Solvent ratio?) cooled to 243 K
over a period of 24 h. NMR data were recorded on a Varian 300 MHz instrument.
1H NMR (CDCl3, δ, p.p.m.): 0.92 (doublet, 6H), 1.31 (quartet, 2H), 1.66
(multiplet, 1H), 1.67 (multiplet, 2H), 3.39 (multiplet, 2H). 13C NMR
(CDCl3, δ, p.p.m.): 20.14, 22.27, 27.44, 35.16, 59.45.
Analysis of the Flack x (Flack, 1983; Flack & Bernardinelli,
2000) and
Hooft y parameters (Hooft et al., 2008) within
CRYSTALS
(Betteridge et al. 2003; Thompson & Watkin, 2009,
2011) indicated that
the crystal had spontaneously resolved and was enantiopure in space group
P3221. The disorder was modelled by splitting atoms with prolate
anisotropic displacement parameters (ADPs) into two components; the naming
convention used involved appending a 1 or 0 to the index number, such that C26
became C260 and C261 etc. To ensure a sensible geometry for the
disordered model, the bond distances and angles along the isohexyl chains were
restrained to be the same, with s.u. values of 0.01 Å and 0.1 °,
respectively, and the ADPs of the disordered atoms were restrained to be
similar, with an s.u. value of 0.01 Å2. The H atoms were generally visible
in difference maps, but were positioned geometrically then initially refined
with soft restraints, after which the positions were refined with riding
constraints (Cooper et al., 2010).
For all compounds, data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
(I_100KQ) tetrakis(4-methylpentyl)azanium bromide
top
Crystal data top
C24H52N+·Br− | Dx = 1.039 Mg m−3 |
Mr = 434.59 | Cu Kα radiation, λ = 1.54184 Å |
Trigonal, P3221 | Cell parameters from 47154 reflections |
Hall symbol: P 32 2" | θ = 3–76° |
a = 15.12762 (13) Å | µ = 2.04 mm−1 |
c = 21.0223 (2) Å | T = 100 K |
V = 4166.31 (6) Å3 | Plate, colourless |
Z = 6 | 0.15 × 0.14 × 0.07 mm |
F(000) = 1428 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5591 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 76.4°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | h = −18→18 |
Tmin = 0.57, Tmax = 0.87 | k = −19→19 |
89102 measured reflections | l = −26→26 |
5781 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.041 | Method = Modified Sheldrick
w = 1/[σ2(F2) + (0.07P)2 + 1.86P], where P = [max(Fo2,0) + 2Fc2]/3 |
wR(F2) = 0.114 | (Δ/σ)max = 0.002 |
S = 1.02 | Δρmax = 0.46 e Å−3 |
5781 reflections | Δρmin = −0.60 e Å−3 |
347 parameters | Absolute structure: Flack (1983), with 2550 Friedel pairs |
648 restraints | Absolute structure parameter: −0.02 (2) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C24H52N+·Br− | Z = 6 |
Mr = 434.59 | Cu Kα radiation |
Trigonal, P3221 | µ = 2.04 mm−1 |
a = 15.12762 (13) Å | T = 100 K |
c = 21.0223 (2) Å | 0.15 × 0.14 × 0.07 mm |
V = 4166.31 (6) Å3 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5781 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 5591 reflections with I > 2σ(I) |
Tmin = 0.57, Tmax = 0.87 | Rint = 0.033 |
89102 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.114 | Δρmax = 0.46 e Å−3 |
S = 1.02 | Δρmin = −0.60 e Å−3 |
5781 reflections | Absolute structure: Flack (1983), with 2550 Friedel pairs |
347 parameters | Absolute structure parameter: −0.02 (2) |
648 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.84883 (2) | 0.52844 (3) | 0.717967 (14) | 0.0586 | |
N1 | 0.58314 (17) | 0.42813 (17) | 0.59778 (10) | 0.0477 | |
C11 | 0.6075 (2) | 0.5377 (2) | 0.58712 (13) | 0.0444 | |
C12 | 0.7107 (3) | 0.6197 (3) | 0.61083 (15) | 0.0522 | |
C13 | 0.7231 (3) | 0.7247 (3) | 0.60029 (16) | 0.0575 | |
C14 | 0.8319 (3) | 0.8127 (3) | 0.6049 (2) | 0.0693 | |
C15 | 0.8375 (4) | 0.9134 (3) | 0.5887 (2) | 0.0865 | |
C16 | 0.8813 (4) | 0.8186 (4) | 0.6674 (2) | 0.0882 | |
C21 | 0.48075 (19) | 0.36059 (19) | 0.56525 (13) | 0.0497 | |
C22 | 0.4396 (2) | 0.2465 (2) | 0.57012 (17) | 0.0639 | |
C230 | 0.3396 (6) | 0.1876 (3) | 0.5320 (3) | 0.0850 | 0.264 (6) |
C240 | 0.2447 (6) | 0.1109 (7) | 0.5701 (6) | 0.1048 | 0.264 (6) |
C250 | 0.1505 (9) | 0.0523 (12) | 0.5286 (9) | 0.0956 | 0.264 (6) |
C260 | 0.2639 (9) | 0.0385 (8) | 0.6111 (6) | 0.0736 | 0.264 (6) |
C231 | 0.3306 (3) | 0.1886 (3) | 0.5481 (2) | 0.0636 | 0.736 (6) |
C241 | 0.2840 (3) | 0.0730 (3) | 0.54182 (17) | 0.0807 | 0.736 (6) |
C251 | 0.1716 (5) | 0.0189 (4) | 0.5282 (4) | 0.1155 | 0.736 (6) |
C261 | 0.3419 (5) | 0.0424 (4) | 0.4931 (3) | 0.0985 | 0.736 (6) |
C31 | 0.6669 (2) | 0.4119 (2) | 0.57056 (12) | 0.0533 | |
C32 | 0.6922 (2) | 0.4401 (3) | 0.50165 (12) | 0.0573 | |
C33 | 0.7771 (2) | 0.4205 (3) | 0.48023 (14) | 0.0715 | |
C340 | 0.7887 (7) | 0.4140 (9) | 0.4087 (3) | 0.0943 | 0.236 (13) |
C350 | 0.8913 (13) | 0.426 (2) | 0.3900 (4) | 0.1020 | 0.236 (13) |
C360 | 0.7658 (17) | 0.4868 (16) | 0.3711 (5) | 0.0947 | 0.236 (13) |
C341 | 0.8034 (3) | 0.4362 (4) | 0.41078 (19) | 0.0879 | 0.764 (13) |
C351 | 0.8835 (5) | 0.4080 (6) | 0.3922 (2) | 0.0975 | 0.764 (13) |
C361 | 0.8320 (7) | 0.5399 (6) | 0.3885 (3) | 0.1073 | 0.764 (13) |
C41 | 0.57975 (19) | 0.4075 (3) | 0.66861 (12) | 0.0573 | |
C421 | 0.4945 (5) | 0.3997 (6) | 0.70202 (18) | 0.0495 | 0.464 (7) |
C431 | 0.4851 (4) | 0.3510 (4) | 0.7667 (2) | 0.0517 | 0.464 (7) |
C441 | 0.4190 (3) | 0.3635 (3) | 0.81380 (17) | 0.0487 | 0.464 (7) |
C451 | 0.4203 (5) | 0.3202 (7) | 0.8782 (3) | 0.0669 | 0.464 (7) |
C461 | 0.3112 (5) | 0.3226 (6) | 0.7903 (3) | 0.0543 | 0.464 (7) |
C420 | 0.5194 (5) | 0.4486 (6) | 0.71066 (19) | 0.0594 | 0.536 (7) |
C430 | 0.5004 (4) | 0.4036 (5) | 0.7773 (2) | 0.0784 | 0.536 (7) |
C440 | 0.4079 (4) | 0.2974 (5) | 0.7851 (2) | 0.0850 | 0.536 (7) |
C450 | 0.3975 (6) | 0.2552 (8) | 0.8526 (4) | 0.1024 | 0.536 (7) |
C460 | 0.3091 (5) | 0.2911 (7) | 0.7631 (4) | 0.0871 | 0.536 (7) |
H111 | 0.5541 | 0.5469 | 0.6065 | 0.0670* | |
H112 | 0.6025 | 0.5459 | 0.5423 | 0.0656* | |
H121 | 0.7155 | 0.6065 | 0.6566 | 0.0791* | |
H122 | 0.7645 | 0.6133 | 0.5887 | 0.0793* | |
H131 | 0.6871 | 0.7353 | 0.6356 | 0.0859* | |
H132 | 0.6903 | 0.7264 | 0.5619 | 0.0854* | |
H141 | 0.8719 | 0.8002 | 0.5737 | 0.1021* | |
H151 | 0.9082 | 0.9703 | 0.5916 | 0.1558* | |
H152 | 0.7966 | 0.9245 | 0.6208 | 0.1561* | |
H153 | 0.8094 | 0.9098 | 0.5469 | 0.1558* | |
H161 | 0.9493 | 0.8785 | 0.6665 | 0.1585* | |
H162 | 0.8408 | 0.8256 | 0.7002 | 0.1589* | |
H163 | 0.8858 | 0.7573 | 0.6735 | 0.1584* | |
H211 | 0.4332 | 0.3766 | 0.5854 | 0.0742* | |
H212 | 0.4871 | 0.3802 | 0.5205 | 0.0733* | |
H221 | 0.4271 | 0.2264 | 0.6149 | 0.0902* | 0.264 (6) |
H222 | 0.4888 | 0.2297 | 0.5534 | 0.0899* | 0.264 (6) |
H2301 | 0.3235 | 0.2361 | 0.5140 | 0.1172* | 0.264 (6) |
H2302 | 0.3495 | 0.1494 | 0.4985 | 0.1172* | 0.264 (6) |
H2401 | 0.2326 | 0.1523 | 0.6020 | 0.1391* | 0.264 (6) |
H2501 | 0.1105 | −0.0178 | 0.5430 | 0.1700* | 0.264 (6) |
H2502 | 0.1107 | 0.0856 | 0.5335 | 0.1701* | 0.264 (6) |
H2503 | 0.1691 | 0.0540 | 0.4842 | 0.1700* | 0.264 (6) |
H2601 | 0.2442 | 0.0397 | 0.6539 | 0.1409* | 0.264 (6) |
H2602 | 0.3341 | 0.0567 | 0.6100 | 0.1408* | 0.264 (6) |
H2603 | 0.2235 | −0.0284 | 0.5949 | 0.1410* | 0.264 (6) |
H223 | 0.4450 | 0.2288 | 0.6147 | 0.0902* | 0.736 (6) |
H224 | 0.4789 | 0.2269 | 0.5451 | 0.0894* | 0.736 (6) |
H2311 | 0.2908 | 0.2058 | 0.5748 | 0.0886* | 0.736 (6) |
H2312 | 0.3292 | 0.2110 | 0.5063 | 0.0890* | 0.736 (6) |
H2411 | 0.2894 | 0.0466 | 0.5839 | 0.1099* | 0.736 (6) |
H2511 | 0.1484 | −0.0525 | 0.5188 | 0.1930* | 0.736 (6) |
H2512 | 0.1358 | 0.0216 | 0.5668 | 0.1931* | 0.736 (6) |
H2513 | 0.1587 | 0.0506 | 0.4917 | 0.1930* | 0.736 (6) |
H2611 | 0.3160 | −0.0310 | 0.4948 | 0.1651* | 0.736 (6) |
H2612 | 0.4138 | 0.0777 | 0.5012 | 0.1653* | 0.736 (6) |
H2613 | 0.3318 | 0.0599 | 0.4501 | 0.1652* | 0.736 (6) |
H311 | 0.7272 | 0.4518 | 0.5969 | 0.0777* | |
H312 | 0.6435 | 0.3396 | 0.5764 | 0.0780* | |
H321 | 0.7161 | 0.5122 | 0.4965 | 0.0830* | |
H322 | 0.6317 | 0.4014 | 0.4752 | 0.0832* | |
H331 | 0.8421 | 0.4735 | 0.4978 | 0.1010* | 0.236 (13) |
H332 | 0.7621 | 0.3543 | 0.4976 | 0.1011* | 0.236 (13) |
H3401 | 0.7368 | 0.3446 | 0.3942 | 0.1250* | 0.236 (13) |
H3501 | 0.8779 | 0.3662 | 0.3585 | 0.1659* | 0.236 (13) |
H3502 | 0.9316 | 0.4979 | 0.3671 | 0.1659* | 0.236 (13) |
H3503 | 0.9286 | 0.4240 | 0.4317 | 0.1660* | 0.236 (13) |
H3601 | 0.8367 | 0.5380 | 0.3419 | 0.1620* | 0.236 (13) |
H3602 | 0.7507 | 0.5305 | 0.4085 | 0.1620* | 0.236 (13) |
H3603 | 0.6968 | 0.4374 | 0.3406 | 0.1620* | 0.236 (13) |
H333 | 0.8416 | 0.4686 | 0.5051 | 0.1010* | 0.764 (13) |
H334 | 0.7589 | 0.3505 | 0.4906 | 0.1016* | 0.764 (13) |
H3411 | 0.7368 | 0.3895 | 0.3864 | 0.1232* | 0.764 (13) |
H3511 | 0.8967 | 0.4189 | 0.3471 | 0.1669* | 0.764 (13) |
H3512 | 0.9474 | 0.4479 | 0.4142 | 0.1670* | 0.764 (13) |
H3513 | 0.8594 | 0.3368 | 0.4000 | 0.1667* | 0.764 (13) |
H3611 | 0.8671 | 0.5525 | 0.3477 | 0.1837* | 0.764 (13) |
H3612 | 0.8750 | 0.5894 | 0.4195 | 0.1838* | 0.764 (13) |
H3613 | 0.7699 | 0.5430 | 0.3816 | 0.1842* | 0.764 (13) |
H411 | 0.6436 | 0.4593 | 0.6873 | 0.0839* | 0.464 (7) |
H412 | 0.5745 | 0.3409 | 0.6735 | 0.0838* | 0.464 (7) |
H4211 | 0.5067 | 0.4678 | 0.7091 | 0.0752* | 0.464 (7) |
H4212 | 0.4318 | 0.3623 | 0.6767 | 0.0760* | 0.464 (7) |
H4311 | 0.5536 | 0.3828 | 0.7854 | 0.0761* | 0.464 (7) |
H4312 | 0.4604 | 0.2791 | 0.7599 | 0.0761* | 0.464 (7) |
H4411 | 0.4463 | 0.4358 | 0.8197 | 0.0746* | 0.464 (7) |
H4511 | 0.3669 | 0.3192 | 0.9045 | 0.1207* | 0.464 (7) |
H4512 | 0.4861 | 0.3629 | 0.8977 | 0.1210* | 0.464 (7) |
H4513 | 0.4086 | 0.2521 | 0.8742 | 0.1211* | 0.464 (7) |
H4611 | 0.2702 | 0.3295 | 0.8230 | 0.1047* | 0.464 (7) |
H4612 | 0.2833 | 0.2519 | 0.7791 | 0.1044* | 0.464 (7) |
H4613 | 0.3126 | 0.3607 | 0.7526 | 0.1047* | 0.464 (7) |
H413 | 0.6505 | 0.4405 | 0.6828 | 0.0835* | 0.536 (7) |
H414 | 0.5499 | 0.3343 | 0.6755 | 0.0837* | 0.536 (7) |
H4201 | 0.5616 | 0.5215 | 0.7134 | 0.0850* | 0.536 (7) |
H4202 | 0.4550 | 0.4327 | 0.6905 | 0.0847* | 0.536 (7) |
H4301 | 0.4887 | 0.4484 | 0.8042 | 0.1051* | 0.536 (7) |
H4302 | 0.5615 | 0.4037 | 0.7925 | 0.1050* | 0.536 (7) |
H4401 | 0.4201 | 0.2533 | 0.7555 | 0.1143* | 0.536 (7) |
H4501 | 0.3688 | 0.1828 | 0.8517 | 0.1669* | 0.536 (7) |
H4502 | 0.3531 | 0.2706 | 0.8780 | 0.1667* | 0.536 (7) |
H4503 | 0.4632 | 0.2861 | 0.8734 | 0.1669* | 0.536 (7) |
H4601 | 0.2609 | 0.2214 | 0.7554 | 0.1480* | 0.536 (7) |
H4602 | 0.2833 | 0.3172 | 0.7953 | 0.1482* | 0.536 (7) |
H4603 | 0.3200 | 0.3283 | 0.7242 | 0.1479* | 0.536 (7) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.04245 (16) | 0.0880 (3) | 0.05031 (16) | 0.03637 (16) | −0.00008 (12) | 0.01638 (14) |
N1 | 0.0437 (11) | 0.0563 (13) | 0.0508 (12) | 0.0309 (10) | −0.0004 (9) | 0.0086 (10) |
C11 | 0.0480 (14) | 0.0549 (16) | 0.0416 (13) | 0.0342 (13) | −0.0053 (11) | −0.0013 (11) |
C12 | 0.0562 (17) | 0.0582 (17) | 0.0512 (15) | 0.0353 (15) | −0.0122 (13) | −0.0032 (13) |
C13 | 0.0645 (19) | 0.0551 (17) | 0.0604 (18) | 0.0355 (16) | −0.0192 (15) | −0.0097 (14) |
C14 | 0.074 (2) | 0.061 (2) | 0.070 (2) | 0.0315 (18) | −0.0162 (18) | −0.0011 (17) |
C15 | 0.103 (3) | 0.060 (2) | 0.088 (3) | 0.035 (2) | −0.035 (3) | −0.005 (2) |
C16 | 0.082 (3) | 0.069 (2) | 0.100 (3) | 0.027 (2) | −0.040 (3) | −0.003 (2) |
C21 | 0.0456 (13) | 0.0552 (14) | 0.0524 (13) | 0.0282 (11) | −0.0018 (11) | 0.0048 (11) |
C22 | 0.0683 (19) | 0.0548 (16) | 0.0653 (17) | 0.0283 (15) | −0.0103 (16) | 0.0086 (13) |
C230 | 0.086 (5) | 0.070 (5) | 0.072 (6) | 0.019 (5) | −0.025 (4) | 0.022 (5) |
C240 | 0.102 (6) | 0.077 (5) | 0.090 (6) | 0.010 (5) | −0.024 (5) | 0.024 (5) |
C250 | 0.100 (8) | 0.068 (7) | 0.093 (8) | 0.022 (6) | −0.025 (7) | 0.015 (7) |
C260 | 0.087 (7) | 0.045 (5) | 0.064 (6) | 0.013 (5) | −0.021 (5) | 0.010 (5) |
C231 | 0.069 (3) | 0.056 (2) | 0.042 (2) | 0.013 (2) | −0.0024 (19) | 0.0069 (17) |
C241 | 0.097 (3) | 0.046 (2) | 0.061 (2) | 0.007 (2) | −0.015 (2) | 0.0059 (19) |
C251 | 0.102 (4) | 0.079 (4) | 0.097 (4) | −0.006 (4) | 0.012 (4) | −0.004 (4) |
C261 | 0.114 (5) | 0.064 (3) | 0.103 (4) | 0.033 (3) | −0.009 (3) | −0.001 (3) |
C31 | 0.0462 (13) | 0.0504 (14) | 0.0720 (16) | 0.0306 (12) | 0.0042 (12) | 0.0067 (13) |
C32 | 0.0490 (14) | 0.0583 (16) | 0.0680 (16) | 0.0294 (13) | 0.0030 (12) | −0.0089 (14) |
C33 | 0.067 (2) | 0.0470 (15) | 0.103 (2) | 0.0304 (14) | 0.0268 (18) | −0.0005 (16) |
C340 | 0.096 (6) | 0.061 (5) | 0.112 (5) | 0.028 (5) | 0.042 (6) | −0.001 (5) |
C350 | 0.096 (8) | 0.073 (8) | 0.117 (9) | 0.027 (7) | 0.043 (8) | −0.011 (8) |
C360 | 0.104 (8) | 0.060 (7) | 0.112 (8) | 0.034 (6) | 0.064 (7) | 0.007 (6) |
C341 | 0.074 (3) | 0.093 (3) | 0.101 (3) | 0.044 (3) | 0.020 (3) | −0.021 (3) |
C351 | 0.065 (3) | 0.092 (5) | 0.127 (5) | 0.033 (3) | 0.030 (3) | −0.027 (4) |
C361 | 0.110 (5) | 0.104 (4) | 0.109 (4) | 0.054 (4) | 0.030 (4) | −0.008 (4) |
C41 | 0.0435 (13) | 0.0795 (19) | 0.0525 (14) | 0.0333 (13) | −0.0020 (11) | 0.0166 (14) |
C421 | 0.045 (3) | 0.056 (3) | 0.044 (3) | 0.022 (3) | −0.007 (2) | 0.007 (3) |
C431 | 0.054 (3) | 0.058 (3) | 0.039 (3) | 0.025 (3) | −0.014 (2) | 0.003 (2) |
C441 | 0.059 (3) | 0.063 (3) | 0.032 (2) | 0.037 (2) | −0.006 (2) | 0.005 (2) |
C451 | 0.085 (4) | 0.079 (5) | 0.038 (3) | 0.042 (4) | −0.008 (3) | 0.013 (3) |
C461 | 0.056 (3) | 0.070 (4) | 0.035 (3) | 0.030 (3) | 0.008 (3) | 0.004 (3) |
C420 | 0.040 (3) | 0.103 (4) | 0.040 (2) | 0.040 (3) | −0.003 (2) | 0.004 (3) |
C430 | 0.070 (4) | 0.121 (5) | 0.041 (3) | 0.045 (4) | −0.006 (3) | 0.002 (3) |
C440 | 0.092 (4) | 0.115 (5) | 0.059 (3) | 0.060 (3) | 0.011 (3) | 0.019 (3) |
C450 | 0.108 (5) | 0.138 (7) | 0.074 (4) | 0.071 (5) | 0.008 (4) | 0.035 (5) |
C460 | 0.083 (4) | 0.112 (6) | 0.066 (4) | 0.048 (4) | 0.011 (4) | 0.022 (4) |
Geometric parameters (Å, º) top
N1—C11 | 1.524 (4) | C33—C340 | 1.523 (7) |
N1—C21 | 1.526 (3) | C33—H331 | 0.978 |
N1—C31 | 1.518 (3) | C33—H332 | 0.979 |
N1—C41 | 1.517 (3) | C33—C341 | 1.500 (5) |
C11—C12 | 1.513 (4) | C33—H333 | 1.022 |
C11—H111 | 0.975 | C33—H334 | 0.977 |
C11—H112 | 0.958 | C340—C350 | 1.520 (7) |
C12—C13 | 1.519 (4) | C340—C360 | 1.528 (7) |
C12—H121 | 0.993 | C340—H3401 | 0.993 |
C12—H122 | 0.983 | C350—H3501 | 1.060 |
C13—C14 | 1.517 (5) | C350—H3502 | 1.056 |
C13—H131 | 0.980 | C350—H3503 | 1.052 |
C13—H132 | 0.956 | C360—H3601 | 1.138 |
C14—C15 | 1.522 (6) | C360—H3602 | 1.122 |
C14—C16 | 1.493 (5) | C360—H3603 | 1.131 |
C14—H141 | 0.972 | C341—C351 | 1.524 (5) |
C15—H151 | 0.984 | C341—C361 | 1.479 (6) |
C15—H152 | 0.984 | C341—H3411 | 1.032 |
C15—H153 | 0.967 | C351—H3511 | 0.966 |
C16—H161 | 0.974 | C351—H3512 | 0.964 |
C16—H162 | 0.963 | C351—H3513 | 0.963 |
C16—H163 | 0.971 | C361—H3611 | 0.977 |
C21—C22 | 1.517 (3) | C361—H3612 | 0.960 |
C21—H211 | 0.963 | C361—H3613 | 0.974 |
C21—H212 | 0.977 | C41—C421 | 1.420 (5) |
C22—C230 | 1.542 (7) | C41—H411 | 0.972 |
C22—H221 | 0.979 | C41—H412 | 0.976 |
C22—H222 | 0.965 | C41—C420 | 1.603 (5) |
C22—C231 | 1.503 (4) | C41—H413 | 0.975 |
C22—H223 | 0.989 | C41—H414 | 0.975 |
C22—H224 | 0.946 | C421—C431 | 1.518 (5) |
C230—C240 | 1.543 (7) | C421—H4211 | 0.963 |
C230—H2301 | 0.959 | C421—H4212 | 0.983 |
C230—H2302 | 0.970 | C431—C441 | 1.485 (5) |
C240—C250 | 1.521 (7) | C431—H4311 | 0.981 |
C240—C260 | 1.533 (7) | C431—H4312 | 0.968 |
C240—H2401 | 0.994 | C441—C451 | 1.508 (5) |
C250—H2501 | 0.969 | C441—C461 | 1.509 (6) |
C250—H2502 | 0.965 | C441—H4411 | 0.965 |
C250—H2503 | 0.970 | C451—H4511 | 0.974 |
C260—H2601 | 0.950 | C451—H4512 | 0.965 |
C260—H2602 | 0.954 | C451—H4513 | 0.957 |
C260—H2603 | 0.947 | C461—H4611 | 0.967 |
C231—C241 | 1.530 (4) | C461—H4612 | 0.962 |
C231—H2311 | 0.949 | C461—H4613 | 0.973 |
C231—H2312 | 0.946 | C420—C430 | 1.520 (5) |
C241—C251 | 1.501 (6) | C420—H4201 | 0.961 |
C241—C261 | 1.561 (6) | C420—H4202 | 0.975 |
C241—H2411 | 0.991 | C430—C440 | 1.522 (6) |
C251—H2511 | 0.974 | C430—H4301 | 0.966 |
C251—H2512 | 0.988 | C430—H4302 | 0.978 |
C251—H2513 | 0.973 | C440—C450 | 1.531 (6) |
C261—H2611 | 0.977 | C440—C460 | 1.521 (6) |
C261—H2612 | 0.958 | C440—H4401 | 0.994 |
C261—H2613 | 0.975 | C450—H4501 | 0.955 |
C31—C32 | 1.505 (3) | C450—H4502 | 0.972 |
C31—H311 | 0.976 | C450—H4503 | 0.966 |
C31—H312 | 0.975 | C460—H4601 | 0.949 |
C32—C33 | 1.524 (3) | C460—H4602 | 0.959 |
C32—H321 | 0.968 | C460—H4603 | 0.960 |
C32—H322 | 0.976 | | |
| | | |
C11—N1—C21 | 105.94 (16) | C32—C33—C340 | 116.05 (7) |
C11—N1—C31 | 110.7 (2) | C32—C33—H331 | 109.2 |
C21—N1—C31 | 111.9 (2) | C340—C33—H331 | 109.0 |
C11—N1—C41 | 109.5 (2) | C32—C33—H332 | 107.6 |
C21—N1—C41 | 112.56 (19) | C340—C33—H332 | 106.1 |
C31—N1—C41 | 106.37 (12) | H331—C33—H332 | 108.8 |
N1—C11—C12 | 115.6 (2) | C32—C33—C341 | 116.02 (7) |
N1—C11—H111 | 109.1 | C32—C33—H333 | 107.9 |
C12—C11—H111 | 109.5 | C341—C33—H333 | 107.6 |
N1—C11—H112 | 107.1 | C32—C33—H334 | 109.7 |
C12—C11—H112 | 109.5 | C341—C33—H334 | 107.4 |
H111—C11—H112 | 105.6 | H333—C33—H334 | 108.0 |
C11—C12—C13 | 110.3 (3) | C33—C340—C350 | 112.92 (7) |
C11—C12—H121 | 107.7 | C33—C340—C360 | 112.93 (7) |
C13—C12—H121 | 111.6 | C350—C340—C360 | 111.31 (7) |
C11—C12—H122 | 109.2 | C33—C340—H3401 | 108.3 |
C13—C12—H122 | 111.0 | C350—C340—H3401 | 105.6 |
H121—C12—H122 | 106.9 | C360—C340—H3401 | 105.1 |
C12—C13—C14 | 114.9 (3) | C340—C350—H3501 | 108.0 |
C12—C13—H131 | 105.8 | C340—C350—H3502 | 105.9 |
C14—C13—H131 | 104.9 | H3501—C350—H3502 | 111.1 |
C12—C13—H132 | 111.0 | C340—C350—H3503 | 108.3 |
C14—C13—H132 | 112.4 | H3501—C350—H3503 | 111.5 |
H131—C13—H132 | 107.3 | H3502—C350—H3503 | 111.8 |
C13—C14—C15 | 110.9 (4) | C340—C360—H3601 | 107.0 |
C13—C14—C16 | 113.5 (4) | C340—C360—H3602 | 104.3 |
C15—C14—C16 | 111.1 (4) | H3601—C360—H3602 | 112.2 |
C13—C14—H141 | 107.1 | C340—C360—H3603 | 106.4 |
C15—C14—H141 | 108.4 | H3601—C360—H3603 | 112.9 |
C16—C14—H141 | 105.4 | H3602—C360—H3603 | 113.2 |
C14—C15—H151 | 110.7 | C33—C341—C351 | 112.93 (7) |
C14—C15—H152 | 107.1 | C33—C341—C361 | 112.95 (7) |
H151—C15—H152 | 108.1 | C351—C341—C361 | 111.33 (7) |
C14—C15—H153 | 110.1 | C33—C341—H3411 | 106.6 |
H151—C15—H153 | 111.1 | C351—C341—H3411 | 108.7 |
H152—C15—H153 | 109.7 | C361—C341—H3411 | 103.7 |
C14—C16—H161 | 107.6 | C341—C351—H3511 | 109.2 |
C14—C16—H162 | 108.1 | C341—C351—H3512 | 113.1 |
H161—C16—H162 | 110.2 | H3511—C351—H3512 | 107.9 |
C14—C16—H163 | 109.2 | C341—C351—H3513 | 111.1 |
H161—C16—H163 | 110.3 | H3511—C351—H3513 | 106.7 |
H162—C16—H163 | 111.4 | H3512—C351—H3513 | 108.6 |
N1—C21—C22 | 115.67 (5) | C341—C361—H3611 | 109.1 |
N1—C21—H211 | 105.7 | C341—C361—H3612 | 109.7 |
C22—C21—H211 | 108.8 | H3611—C361—H3612 | 110.7 |
N1—C21—H212 | 108.4 | C341—C361—H3613 | 108.7 |
C22—C21—H212 | 109.4 | H3611—C361—H3613 | 107.7 |
H211—C21—H212 | 108.6 | H3612—C361—H3613 | 110.9 |
C21—C22—C230 | 110.40 (7) | N1—C41—C421 | 116.00 (7) |
C21—C22—H221 | 108.9 | N1—C41—H411 | 108.3 |
C230—C22—H221 | 109.8 | C421—C41—H411 | 111.2 |
C21—C22—H222 | 110.1 | N1—C41—H412 | 107.0 |
C230—C22—H222 | 108.7 | C421—C41—H412 | 105.1 |
H221—C22—H222 | 108.9 | H411—C41—H412 | 109.0 |
C21—C22—C231 | 110.42 (7) | N1—C41—C420 | 115.39 (7) |
C21—C22—H223 | 109.2 | N1—C41—H413 | 106.3 |
C231—C22—H223 | 110.4 | C420—C41—H413 | 109.0 |
C21—C22—H224 | 110.8 | N1—C41—H414 | 109.1 |
C231—C22—H224 | 108.9 | C420—C41—H414 | 109.2 |
H223—C22—H224 | 107.0 | H413—C41—H414 | 107.6 |
C22—C230—C240 | 116.16 (7) | C41—C421—C431 | 110.12 (7) |
C22—C230—H2301 | 108.3 | C41—C421—H4211 | 107.9 |
C240—C230—H2301 | 106.5 | C431—C421—H4211 | 107.5 |
C22—C230—H2302 | 108.8 | C41—C421—H4212 | 110.8 |
C240—C230—H2302 | 107.0 | C431—C421—H4212 | 112.1 |
H2301—C230—H2302 | 110.0 | H4211—C421—H4212 | 108.2 |
C230—C240—C250 | 112.89 (7) | C421—C431—C441 | 116.17 (7) |
C230—C240—C260 | 112.99 (7) | C421—C431—H4311 | 107.6 |
C250—C240—C260 | 111.29 (7) | C441—C431—H4311 | 106.4 |
C230—C240—H2401 | 105.7 | C421—C431—H4312 | 107.6 |
C250—C240—H2401 | 110.0 | C441—C431—H4312 | 109.6 |
C260—C240—H2401 | 103.4 | H4311—C431—H4312 | 109.3 |
C240—C250—H2501 | 110.4 | C431—C441—C451 | 112.80 (7) |
C240—C250—H2502 | 106.3 | C431—C441—C461 | 112.82 (7) |
H2501—C250—H2502 | 109.0 | C451—C441—C461 | 111.28 (7) |
C240—C250—H2503 | 111.2 | C431—C441—H4411 | 107.3 |
H2501—C250—H2503 | 110.0 | C451—C441—H4411 | 106.5 |
H2502—C250—H2503 | 109.7 | C461—C441—H4411 | 105.6 |
C240—C260—H2601 | 110.1 | C441—C451—H4511 | 109.1 |
C240—C260—H2602 | 111.2 | C441—C451—H4512 | 108.9 |
H2601—C260—H2602 | 109.4 | H4511—C451—H4512 | 109.8 |
C240—C260—H2603 | 108.1 | C441—C451—H4513 | 110.6 |
H2601—C260—H2603 | 108.6 | H4511—C451—H4513 | 109.1 |
H2602—C260—H2603 | 109.4 | H4512—C451—H4513 | 109.4 |
C22—C231—C241 | 115.95 (7) | C441—C461—H4611 | 110.1 |
C22—C231—H2311 | 108.6 | C441—C461—H4612 | 108.6 |
C241—C231—H2311 | 111.8 | H4611—C461—H4612 | 110.1 |
C22—C231—H2312 | 107.0 | C441—C461—H4613 | 109.0 |
C241—C231—H2312 | 104.4 | H4611—C461—H4613 | 109.9 |
H2311—C231—H2312 | 108.6 | H4612—C461—H4613 | 109.1 |
C231—C241—C251 | 112.90 (7) | C41—C420—C430 | 110.55 (7) |
C231—C241—C261 | 112.90 (7) | C41—C420—H4201 | 107.3 |
C251—C241—C261 | 111.32 (7) | C430—C420—H4201 | 109.0 |
C231—C241—H2411 | 107.4 | C41—C420—H4202 | 110.9 |
C251—C241—H2411 | 104.6 | C430—C420—H4202 | 110.3 |
C261—C241—H2411 | 107.1 | H4201—C420—H4202 | 108.6 |
C241—C251—H2511 | 109.0 | C420—C430—C440 | 116.13 (7) |
C241—C251—H2512 | 108.3 | C420—C430—H4301 | 106.6 |
H2511—C251—H2512 | 108.1 | C440—C430—H4301 | 106.4 |
C241—C251—H2513 | 109.4 | C420—C430—H4302 | 109.6 |
H2511—C251—H2513 | 109.7 | C440—C430—H4302 | 109.6 |
H2512—C251—H2513 | 112.2 | H4301—C430—H4302 | 108.2 |
C241—C261—H2611 | 110.3 | C430—C440—C450 | 112.86 (7) |
C241—C261—H2612 | 111.6 | C430—C440—C460 | 112.94 (7) |
H2611—C261—H2612 | 109.0 | C450—C440—C460 | 111.26 (7) |
C241—C261—H2613 | 110.0 | C430—C440—H4401 | 105.0 |
H2611—C261—H2613 | 108.3 | C450—C440—H4401 | 108.4 |
H2612—C261—H2613 | 107.6 | C460—C440—H4401 | 105.8 |
N1—C31—C32 | 115.58 (5) | C440—C450—H4501 | 110.6 |
N1—C31—H311 | 106.5 | C440—C450—H4502 | 110.4 |
C32—C31—H311 | 110.2 | H4501—C450—H4502 | 108.2 |
N1—C31—H312 | 105.6 | C440—C450—H4503 | 110.6 |
C32—C31—H312 | 109.8 | H4501—C450—H4503 | 109.4 |
H311—C31—H312 | 109.0 | H4502—C450—H4503 | 107.7 |
C31—C32—C33 | 110.43 (5) | C440—C460—H4601 | 107.9 |
C31—C32—H321 | 109.0 | C440—C460—H4602 | 110.4 |
C33—C32—H321 | 108.0 | H4601—C460—H4602 | 109.5 |
C31—C32—H322 | 110.4 | C440—C460—H4603 | 110.4 |
C33—C32—H322 | 110.1 | H4601—C460—H4603 | 108.5 |
H321—C32—H322 | 108.8 | H4602—C460—H4603 | 110.1 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C230—H2302···C261 | 0.97 | 1.57 | 2.360 (10) | 136 |
C250—H2502···C250i | 0.97 | 2.08 | 2.841 (10) | 135 |
C260—H2601···C260ii | 0.95 | 1.79 | 2.545 (10) | 134 |
Symmetry codes: (i) y, x, −z+1; (ii) x−y, −y, −z+4/3. |
(I_250K) tetrakis(4-methylpentyl)azanium bromide
top
Crystal data top
C24H52N+·Br− | Dx = 0.985 Mg m−3 |
Mr = 434.59 | Cu Kα radiation, λ = 1.54184 Å |
Trigonal, P3221 | Cell parameters from 18120 reflections |
Hall symbol: P 32 2" | θ = 3–77° |
a = 15.4995 (2) Å | µ = 1.93 mm−1 |
c = 21.1346 (3) Å | T = 250 K |
V = 4397.06 (12) Å3 | Plate, colourless |
Z = 6 | 0.15 × 0.14 × 0.07 mm |
F(000) = 1428 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 4391 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 76.9°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | h = −19→19 |
Tmin = 0.60, Tmax = 0.87 | k = −19→19 |
94951 measured reflections | l = −26→26 |
6128 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.049 | Method = Modified Sheldrick
w = 1/[σ2(F2) + (0.12P)2 + 0.13P], where P = [max(Fo2,0) + 2Fc2]/3 |
wR(F2) = 0.178 | (Δ/σ)max = 0.004 |
S = 0.96 | Δρmax = 0.21 e Å−3 |
6128 reflections | Δρmin = −0.24 e Å−3 |
366 parameters | Absolute structure: Flack (1983), with 2710 Friedel pairs |
864 restraints | Absolute structure parameter: −0.03 (3) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C24H52N+·Br− | Z = 6 |
Mr = 434.59 | Cu Kα radiation |
Trigonal, P3221 | µ = 1.93 mm−1 |
a = 15.4995 (2) Å | T = 250 K |
c = 21.1346 (3) Å | 0.15 × 0.14 × 0.07 mm |
V = 4397.06 (12) Å3 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 6128 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 4391 reflections with I > 2σ(I) |
Tmin = 0.60, Tmax = 0.87 | Rint = 0.037 |
94951 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.178 | Δρmax = 0.21 e Å−3 |
S = 0.96 | Δρmin = −0.24 e Å−3 |
6128 reflections | Absolute structure: Flack (1983), with 2710 Friedel pairs |
366 parameters | Absolute structure parameter: −0.03 (3) |
864 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.85154 (4) | 0.51981 (5) | 0.71443 (2) | 0.1359 | |
N1 | 0.58832 (17) | 0.43385 (19) | 0.59685 (11) | 0.1058 | |
C11 | 0.6112 (2) | 0.5404 (2) | 0.58831 (18) | 0.1124 | |
C12 | 0.7076 (3) | 0.6194 (2) | 0.6178 (2) | 0.1353 | |
C13 | 0.7278 (4) | 0.7217 (3) | 0.5993 (3) | 0.1600 | |
C140 | 0.8029 (7) | 0.8080 (5) | 0.6372 (4) | 0.1924 | 0.382 (14) |
C150 | 0.8116 (16) | 0.9046 (7) | 0.6191 (10) | 0.2076 | 0.382 (14) |
C160 | 0.9014 (10) | 0.8133 (12) | 0.6416 (12) | 0.1978 | 0.382 (14) |
C141 | 0.8325 (5) | 0.8076 (4) | 0.6082 (3) | 0.1898 | 0.618 (14) |
C151 | 0.8489 (8) | 0.9039 (6) | 0.5809 (7) | 0.2033 | 0.618 (14) |
C161 | 0.8700 (10) | 0.8184 (8) | 0.6740 (6) | 0.2234 | 0.618 (14) |
C21 | 0.4895 (2) | 0.3702 (2) | 0.56421 (18) | 0.1131 | |
C22 | 0.4489 (3) | 0.2587 (3) | 0.5675 (2) | 0.1369 | |
C23 | 0.3425 (3) | 0.2035 (3) | 0.5452 (3) | 0.1556 | |
C240 | 0.2666 (5) | 0.1273 (11) | 0.5886 (5) | 0.1984 | 0.248 (8) |
C250 | 0.1624 (7) | 0.088 (2) | 0.5672 (11) | 0.2119 | 0.248 (8) |
C260 | 0.2878 (15) | 0.0474 (14) | 0.6066 (14) | 0.2026 | 0.248 (8) |
C241 | 0.2913 (4) | 0.0922 (4) | 0.5430 (3) | 0.1883 | 0.752 (8) |
C251 | 0.1839 (5) | 0.0438 (5) | 0.5245 (6) | 0.2215 | 0.752 (8) |
C261 | 0.3467 (6) | 0.0533 (5) | 0.5068 (6) | 0.2153 | 0.752 (8) |
C31 | 0.6710 (3) | 0.4197 (3) | 0.56948 (14) | 0.1125 | |
C32 | 0.6976 (3) | 0.4511 (4) | 0.50075 (15) | 0.1282 | |
C33 | 0.7777 (3) | 0.4306 (4) | 0.47896 (17) | 0.1460 | |
C340 | 0.7969 (5) | 0.4342 (7) | 0.4095 (3) | 0.1915 | 0.466 (18) |
C350 | 0.8944 (10) | 0.4438 (17) | 0.3935 (4) | 0.2035 | 0.466 (18) |
C360 | 0.7780 (16) | 0.5065 (15) | 0.3747 (5) | 0.2027 | 0.466 (18) |
C341 | 0.8079 (5) | 0.4499 (6) | 0.4113 (3) | 0.1721 | 0.534 (18) |
C351 | 0.8729 (10) | 0.4103 (11) | 0.3913 (4) | 0.1807 | 0.534 (18) |
C361 | 0.8466 (14) | 0.5541 (10) | 0.3918 (6) | 0.1903 | 0.534 (18) |
C41 | 0.5848 (2) | 0.4104 (4) | 0.66678 (14) | 0.1222 | |
C421 | 0.4977 (7) | 0.4011 (9) | 0.7020 (2) | 0.1279 | 0.545 (12) |
C431 | 0.4890 (6) | 0.3529 (6) | 0.7654 (3) | 0.1339 | 0.545 (12) |
C441 | 0.4225 (6) | 0.3577 (5) | 0.8116 (2) | 0.1459 | 0.545 (12) |
C451 | 0.4296 (9) | 0.3212 (10) | 0.8757 (3) | 0.1740 | 0.545 (12) |
C461 | 0.3189 (7) | 0.3143 (11) | 0.7894 (5) | 0.1707 | 0.545 (12) |
C420 | 0.5238 (8) | 0.4444 (9) | 0.7091 (3) | 0.1382 | 0.455 (12) |
C430 | 0.5085 (6) | 0.3992 (8) | 0.7751 (3) | 0.1693 | 0.455 (12) |
C440 | 0.4167 (8) | 0.3005 (7) | 0.7864 (4) | 0.1871 | 0.455 (12) |
C450 | 0.4077 (11) | 0.2626 (12) | 0.8528 (7) | 0.1947 | 0.455 (12) |
C460 | 0.3236 (8) | 0.2956 (13) | 0.7635 (7) | 0.1897 | 0.455 (12) |
H111 | 0.5542 | 0.5424 | 0.6072 | 0.1331* | |
H112 | 0.6096 | 0.5501 | 0.5424 | 0.1313* | |
H121 | 0.7036 | 0.6124 | 0.6632 | 0.1605* | |
H122 | 0.7609 | 0.6091 | 0.6017 | 0.1613* | |
H131 | 0.6649 | 0.7203 | 0.5996 | 0.1879* | 0.382 (14) |
H132 | 0.7546 | 0.7337 | 0.5569 | 0.1880* | 0.382 (14) |
H1401 | 0.7784 | 0.7939 | 0.6812 | 0.2248* | 0.382 (14) |
H1501 | 0.8448 | 0.9538 | 0.6545 | 0.3120* | 0.382 (14) |
H1502 | 0.7424 | 0.8915 | 0.6125 | 0.3122* | 0.382 (14) |
H1503 | 0.8510 | 0.9297 | 0.5792 | 0.3121* | 0.382 (14) |
H1601 | 0.9459 | 0.8642 | 0.6710 | 0.2899* | 0.382 (14) |
H1602 | 0.8959 | 0.7497 | 0.6530 | 0.2897* | 0.382 (14) |
H1603 | 0.9276 | 0.8324 | 0.5988 | 0.2901* | 0.382 (14) |
H133 | 0.6887 | 0.7371 | 0.6276 | 0.1880* | 0.618 (14) |
H134 | 0.7055 | 0.7185 | 0.5567 | 0.1881* | 0.618 (14) |
H1411 | 0.8747 | 0.7896 | 0.5840 | 0.2223* | 0.618 (14) |
H1511 | 0.9202 | 0.9519 | 0.5793 | 0.3010* | 0.618 (14) |
H1512 | 0.8160 | 0.9301 | 0.6064 | 0.3014* | 0.618 (14) |
H1513 | 0.8214 | 0.8924 | 0.5382 | 0.3008* | 0.618 (14) |
H1611 | 0.9243 | 0.8858 | 0.6801 | 0.3262* | 0.618 (14) |
H1612 | 0.8129 | 0.8048 | 0.7009 | 0.3259* | 0.618 (14) |
H1613 | 0.8922 | 0.7713 | 0.6816 | 0.3258* | 0.618 (14) |
H211 | 0.4422 | 0.3860 | 0.5821 | 0.1333* | |
H212 | 0.5011 | 0.3915 | 0.5200 | 0.1349* | |
H221 | 0.4547 | 0.2441 | 0.6123 | 0.1624* | |
H222 | 0.4870 | 0.2387 | 0.5411 | 0.1625* | |
H231 | 0.3248 | 0.2536 | 0.5347 | 0.1830* | 0.248 (8) |
H232 | 0.3383 | 0.1649 | 0.5082 | 0.1832* | 0.248 (8) |
H2401 | 0.2751 | 0.1648 | 0.6279 | 0.2330* | 0.248 (8) |
H2501 | 0.1176 | 0.0281 | 0.5915 | 0.3141* | 0.248 (8) |
H2502 | 0.1445 | 0.1394 | 0.5734 | 0.3140* | 0.248 (8) |
H2503 | 0.1593 | 0.0717 | 0.5220 | 0.3140* | 0.248 (8) |
H2601 | 0.2260 | −0.0152 | 0.6022 | 0.2941* | 0.248 (8) |
H2602 | 0.3125 | 0.0551 | 0.6500 | 0.2942* | 0.248 (8) |
H2603 | 0.3365 | 0.0469 | 0.5771 | 0.2939* | 0.248 (8) |
H233 | 0.3064 | 0.2279 | 0.5701 | 0.1831* | 0.752 (8) |
H234 | 0.3448 | 0.2223 | 0.5018 | 0.1832* | 0.752 (8) |
H2411 | 0.2891 | 0.0701 | 0.5870 | 0.2282* | 0.752 (8) |
H2511 | 0.1641 | −0.0239 | 0.5045 | 0.3411* | 0.752 (8) |
H2512 | 0.1384 | 0.0347 | 0.5618 | 0.3414* | 0.752 (8) |
H2513 | 0.1801 | 0.0899 | 0.4911 | 0.3407* | 0.752 (8) |
H2611 | 0.3175 | −0.0179 | 0.5152 | 0.3261* | 0.752 (8) |
H2612 | 0.4161 | 0.0900 | 0.5207 | 0.3262* | 0.752 (8) |
H2613 | 0.3422 | 0.0636 | 0.4619 | 0.3259* | 0.752 (8) |
H311 | 0.7307 | 0.4616 | 0.5946 | 0.1344* | |
H312 | 0.6523 | 0.3493 | 0.5754 | 0.1333* | |
H321 | 0.7233 | 0.5219 | 0.4960 | 0.1531* | |
H322 | 0.6397 | 0.4172 | 0.4739 | 0.1533* | |
H331 | 0.8395 | 0.4814 | 0.4984 | 0.1764* | 0.466 (18) |
H332 | 0.7636 | 0.3664 | 0.4955 | 0.1764* | 0.466 (18) |
H3401 | 0.7448 | 0.3689 | 0.3925 | 0.2312* | 0.466 (18) |
H3501 | 0.8953 | 0.4241 | 0.3502 | 0.3081* | 0.466 (18) |
H3502 | 0.9451 | 0.5118 | 0.4003 | 0.3080* | 0.466 (18) |
H3503 | 0.9055 | 0.4021 | 0.4225 | 0.3079* | 0.466 (18) |
H3601 | 0.7955 | 0.5092 | 0.3303 | 0.3048* | 0.466 (18) |
H3602 | 0.8213 | 0.5702 | 0.3950 | 0.3050* | 0.466 (18) |
H3603 | 0.7080 | 0.4888 | 0.3781 | 0.3049* | 0.466 (18) |
H333 | 0.8366 | 0.4719 | 0.5048 | 0.1763* | 0.534 (18) |
H334 | 0.7564 | 0.3615 | 0.4877 | 0.1766* | 0.534 (18) |
H3411 | 0.7458 | 0.4142 | 0.3859 | 0.2023* | 0.534 (18) |
H3511 | 0.9056 | 0.4404 | 0.3518 | 0.2661* | 0.534 (18) |
H3512 | 0.9214 | 0.4269 | 0.4252 | 0.2658* | 0.534 (18) |
H3513 | 0.8335 | 0.3387 | 0.3863 | 0.2660* | 0.534 (18) |
H3611 | 0.8736 | 0.5642 | 0.3499 | 0.2799* | 0.534 (18) |
H3612 | 0.8982 | 0.5930 | 0.4221 | 0.2800* | 0.534 (18) |
H3613 | 0.7957 | 0.5727 | 0.3925 | 0.2799* | 0.534 (18) |
H411 | 0.6468 | 0.4614 | 0.6857 | 0.1437* | 0.477 (12) |
H412 | 0.5801 | 0.3462 | 0.6702 | 0.1442* | 0.477 (12) |
H4211 | 0.5081 | 0.4671 | 0.7108 | 0.1508* | 0.545 (12) |
H4212 | 0.4366 | 0.3628 | 0.6779 | 0.1507* | 0.545 (12) |
H4311 | 0.5541 | 0.3821 | 0.7848 | 0.1585* | 0.545 (12) |
H4312 | 0.4650 | 0.2829 | 0.7573 | 0.1583* | 0.545 (12) |
H4411 | 0.4459 | 0.4281 | 0.8164 | 0.1728* | 0.545 (12) |
H4511 | 0.4088 | 0.3518 | 0.9098 | 0.2608* | 0.545 (12) |
H4512 | 0.5009 | 0.3410 | 0.8818 | 0.2608* | 0.545 (12) |
H4513 | 0.3865 | 0.2466 | 0.8760 | 0.2609* | 0.545 (12) |
H4611 | 0.2767 | 0.3276 | 0.8228 | 0.2550* | 0.545 (12) |
H4612 | 0.2954 | 0.2378 | 0.7854 | 0.2546* | 0.545 (12) |
H4613 | 0.3197 | 0.3462 | 0.7447 | 0.2550* | 0.545 (12) |
H413 | 0.6534 | 0.4438 | 0.6825 | 0.1434* | 0.523 (12) |
H414 | 0.5546 | 0.3393 | 0.6710 | 0.1441* | 0.523 (12) |
H4201 | 0.5623 | 0.5160 | 0.7142 | 0.1651* | 0.455 (12) |
H4202 | 0.4596 | 0.4268 | 0.6903 | 0.1648* | 0.455 (12) |
H4301 | 0.5023 | 0.4435 | 0.8047 | 0.1978* | 0.455 (12) |
H4302 | 0.5660 | 0.3932 | 0.7865 | 0.1983* | 0.455 (12) |
H4401 | 0.4228 | 0.2534 | 0.7580 | 0.2233* | 0.455 (12) |
H4501 | 0.3675 | 0.1909 | 0.8533 | 0.2928* | 0.455 (12) |
H4502 | 0.3755 | 0.2899 | 0.8784 | 0.2930* | 0.455 (12) |
H4503 | 0.4728 | 0.2822 | 0.8700 | 0.2929* | 0.455 (12) |
H4601 | 0.2655 | 0.2364 | 0.7786 | 0.2879* | 0.455 (12) |
H4602 | 0.3265 | 0.3551 | 0.7812 | 0.2881* | 0.455 (12) |
H4603 | 0.3218 | 0.2976 | 0.7180 | 0.2882* | 0.455 (12) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.1074 (3) | 0.1872 (5) | 0.1140 (3) | 0.0744 (3) | −0.00544 (19) | 0.0263 (3) |
N1 | 0.1075 (14) | 0.1332 (17) | 0.0954 (13) | 0.0743 (13) | −0.0073 (11) | 0.0078 (13) |
C11 | 0.126 (2) | 0.128 (2) | 0.1037 (18) | 0.0787 (18) | −0.0133 (16) | −0.0008 (16) |
C12 | 0.148 (3) | 0.136 (2) | 0.131 (2) | 0.078 (2) | −0.032 (2) | −0.011 (2) |
C13 | 0.182 (3) | 0.137 (3) | 0.163 (3) | 0.082 (3) | −0.040 (3) | −0.015 (2) |
C140 | 0.205 (7) | 0.155 (5) | 0.193 (7) | 0.072 (6) | −0.046 (6) | −0.033 (5) |
C150 | 0.220 (9) | 0.159 (7) | 0.213 (10) | 0.071 (8) | −0.048 (9) | −0.032 (8) |
C160 | 0.203 (8) | 0.166 (8) | 0.197 (9) | 0.072 (7) | −0.036 (8) | −0.042 (7) |
C141 | 0.213 (6) | 0.146 (4) | 0.184 (6) | 0.070 (4) | −0.041 (5) | −0.009 (4) |
C151 | 0.228 (8) | 0.147 (5) | 0.194 (8) | 0.063 (6) | −0.029 (7) | −0.002 (5) |
C161 | 0.238 (8) | 0.174 (7) | 0.193 (7) | 0.053 (7) | −0.057 (7) | −0.008 (6) |
C21 | 0.1073 (19) | 0.137 (2) | 0.1053 (18) | 0.0691 (18) | −0.0092 (15) | 0.0082 (16) |
C22 | 0.126 (2) | 0.140 (2) | 0.145 (3) | 0.067 (2) | −0.013 (2) | 0.011 (2) |
C23 | 0.132 (3) | 0.150 (3) | 0.167 (3) | 0.057 (2) | −0.015 (3) | 0.002 (3) |
C240 | 0.165 (7) | 0.170 (7) | 0.194 (7) | 0.035 (6) | −0.007 (6) | 0.002 (6) |
C250 | 0.168 (9) | 0.181 (10) | 0.204 (10) | 0.026 (9) | −0.005 (9) | −0.008 (9) |
C260 | 0.176 (9) | 0.163 (9) | 0.195 (10) | 0.029 (8) | −0.005 (9) | 0.010 (9) |
C241 | 0.157 (4) | 0.151 (4) | 0.223 (6) | 0.051 (3) | −0.016 (4) | −0.003 (4) |
C251 | 0.163 (5) | 0.180 (6) | 0.262 (8) | 0.041 (5) | −0.009 (6) | −0.018 (6) |
C261 | 0.188 (6) | 0.162 (6) | 0.270 (8) | 0.068 (5) | −0.016 (6) | −0.010 (5) |
C31 | 0.1097 (18) | 0.130 (2) | 0.1150 (18) | 0.0729 (18) | −0.0025 (15) | 0.0010 (18) |
C32 | 0.121 (2) | 0.148 (3) | 0.118 (2) | 0.069 (2) | 0.0064 (18) | −0.010 (2) |
C33 | 0.133 (3) | 0.152 (3) | 0.155 (3) | 0.072 (2) | 0.021 (2) | −0.009 (2) |
C340 | 0.176 (6) | 0.192 (6) | 0.175 (5) | 0.068 (6) | 0.050 (5) | −0.015 (5) |
C350 | 0.183 (7) | 0.200 (8) | 0.194 (8) | 0.070 (7) | 0.064 (7) | −0.017 (7) |
C360 | 0.194 (8) | 0.195 (8) | 0.173 (7) | 0.062 (7) | 0.062 (7) | 0.005 (6) |
C341 | 0.146 (5) | 0.188 (5) | 0.180 (5) | 0.081 (4) | 0.041 (4) | −0.020 (5) |
C351 | 0.149 (6) | 0.179 (7) | 0.205 (7) | 0.075 (5) | 0.054 (6) | −0.024 (6) |
C361 | 0.166 (8) | 0.203 (7) | 0.187 (7) | 0.080 (6) | 0.028 (6) | −0.007 (6) |
C41 | 0.118 (2) | 0.160 (3) | 0.0991 (17) | 0.078 (2) | −0.0048 (16) | 0.0232 (18) |
C421 | 0.137 (4) | 0.167 (5) | 0.096 (3) | 0.088 (4) | 0.002 (3) | 0.016 (3) |
C431 | 0.158 (5) | 0.165 (6) | 0.097 (3) | 0.095 (4) | −0.006 (3) | 0.015 (3) |
C441 | 0.190 (5) | 0.181 (6) | 0.090 (3) | 0.110 (5) | 0.009 (3) | 0.015 (4) |
C451 | 0.222 (8) | 0.202 (8) | 0.104 (5) | 0.111 (6) | −0.001 (5) | 0.026 (5) |
C461 | 0.190 (6) | 0.205 (8) | 0.110 (5) | 0.093 (6) | 0.032 (5) | 0.019 (5) |
C420 | 0.123 (5) | 0.184 (6) | 0.111 (4) | 0.080 (4) | −0.004 (4) | 0.013 (4) |
C430 | 0.155 (6) | 0.210 (7) | 0.121 (5) | 0.074 (5) | −0.007 (5) | 0.012 (5) |
C440 | 0.185 (6) | 0.211 (8) | 0.135 (6) | 0.077 (6) | 0.011 (5) | 0.012 (6) |
C450 | 0.204 (9) | 0.211 (10) | 0.141 (7) | 0.083 (8) | 0.003 (7) | 0.014 (7) |
C460 | 0.180 (8) | 0.219 (10) | 0.134 (7) | 0.073 (7) | 0.026 (6) | 0.005 (7) |
Geometric parameters (Å, º) top
N1—C11 | 1.517 (3) | C31—H311 | 0.978 |
N1—C21 | 1.511 (3) | C31—H312 | 0.987 |
N1—C31 | 1.519 (3) | C32—C33 | 1.499 (4) |
N1—C41 | 1.516 (3) | C32—H321 | 0.966 |
C11—C12 | 1.513 (4) | C32—H322 | 0.966 |
C11—H111 | 0.984 | C33—C340 | 1.493 (6) |
C11—H112 | 0.985 | C33—H331 | 0.976 |
C12—C13 | 1.506 (4) | C33—H332 | 0.971 |
C12—H121 | 0.964 | C33—C341 | 1.488 (6) |
C12—H122 | 0.977 | C33—H333 | 0.978 |
C13—C140 | 1.492 (6) | C33—H334 | 0.968 |
C13—H131 | 0.964 | C340—C350 | 1.483 (7) |
C13—H132 | 0.966 | C340—C360 | 1.488 (7) |
C13—C141 | 1.510 (6) | C340—H3401 | 0.994 |
C13—H133 | 0.962 | C350—H3501 | 0.965 |
C13—H134 | 0.958 | C350—H3502 | 0.960 |
C140—C150 | 1.485 (7) | C350—H3503 | 0.966 |
C140—C160 | 1.489 (7) | C360—H3601 | 0.972 |
C140—H1401 | 0.989 | C360—H3602 | 0.974 |
C150—H1501 | 1.007 | C360—H3603 | 0.979 |
C150—H1502 | 0.996 | C341—C351 | 1.479 (6) |
C150—H1503 | 0.999 | C341—C361 | 1.473 (7) |
C160—H1601 | 0.970 | C341—H3411 | 0.993 |
C160—H1602 | 0.976 | C351—H3511 | 0.967 |
C160—H1603 | 0.975 | C351—H3512 | 0.976 |
C141—C151 | 1.497 (6) | C351—H3513 | 0.967 |
C141—C161 | 1.485 (7) | C361—H3611 | 0.959 |
C141—H1411 | 0.975 | C361—H3612 | 0.966 |
C151—H1511 | 0.977 | C361—H3613 | 0.966 |
C151—H1512 | 0.961 | C41—C421 | 1.485 (5) |
C151—H1513 | 0.975 | C41—H411 | 0.974 |
C161—H1611 | 0.968 | C41—H412 | 0.963 |
C161—H1612 | 0.982 | C41—C420 | 1.572 (6) |
C161—H1613 | 0.963 | C41—H413 | 0.978 |
C21—C22 | 1.517 (4) | C41—H414 | 0.962 |
C21—H211 | 0.960 | C421—C431 | 1.507 (5) |
C21—H212 | 0.976 | C421—H4211 | 0.970 |
C22—C23 | 1.503 (4) | C421—H4212 | 0.972 |
C22—H221 | 0.988 | C431—C441 | 1.449 (6) |
C22—H222 | 0.969 | C431—H4311 | 0.967 |
C23—C240 | 1.494 (7) | C431—H4312 | 0.970 |
C23—H231 | 0.970 | C441—C451 | 1.493 (6) |
C23—H232 | 0.967 | C441—C461 | 1.473 (7) |
C23—C241 | 1.497 (6) | C441—H4411 | 0.967 |
C23—H233 | 0.971 | C451—H4511 | 1.001 |
C23—H234 | 0.957 | C451—H4512 | 0.996 |
C240—C250 | 1.483 (7) | C451—H4513 | 1.005 |
C240—C260 | 1.481 (7) | C461—H4611 | 1.050 |
C240—H2401 | 0.985 | C461—H4612 | 1.056 |
C250—H2501 | 0.982 | C461—H4613 | 1.064 |
C250—H2502 | 0.975 | C420—C430 | 1.525 (6) |
C250—H2503 | 0.984 | C420—H4201 | 0.969 |
C260—H2601 | 0.968 | C420—H4202 | 0.976 |
C260—H2602 | 0.978 | C430—C440 | 1.499 (7) |
C260—H2603 | 0.980 | C430—H4301 | 0.968 |
C241—C251 | 1.496 (6) | C430—H4302 | 0.971 |
C241—C261 | 1.486 (7) | C440—C450 | 1.501 (7) |
C241—H2411 | 0.984 | C440—C460 | 1.487 (7) |
C251—H2511 | 1.026 | C440—H4401 | 0.986 |
C251—H2512 | 1.019 | C450—H4501 | 0.964 |
C251—H2513 | 1.026 | C450—H4502 | 0.966 |
C261—H2611 | 0.977 | C450—H4503 | 0.967 |
C261—H2612 | 0.977 | C460—H4601 | 0.964 |
C261—H2613 | 0.971 | C460—H4602 | 0.976 |
C31—C32 | 1.522 (4) | C460—H4603 | 0.964 |
| | | |
C11—N1—C21 | 105.39 (13) | N1—C31—H312 | 108.0 |
C11—N1—C31 | 110.9 (2) | C32—C31—H312 | 111.0 |
C21—N1—C31 | 112.6 (3) | H311—C31—H312 | 108.8 |
C11—N1—C41 | 109.8 (3) | C31—C32—C33 | 110.25 (5) |
C21—N1—C41 | 112.7 (2) | C31—C32—H321 | 110.8 |
C31—N1—C41 | 105.54 (13) | C33—C32—H321 | 107.0 |
N1—C11—C12 | 115.51 (5) | C31—C32—H322 | 110.9 |
N1—C11—H111 | 105.2 | C33—C32—H322 | 110.3 |
C12—C11—H111 | 110.3 | H321—C32—H322 | 107.4 |
N1—C11—H112 | 105.9 | C32—C33—C340 | 117.70 (7) |
C12—C11—H112 | 111.9 | C32—C33—H331 | 106.4 |
H111—C11—H112 | 107.6 | C340—C33—H331 | 106.8 |
C11—C12—C13 | 110.30 (5) | C32—C33—H332 | 108.7 |
C11—C12—H121 | 109.7 | C340—C33—H332 | 109.3 |
C13—C12—H121 | 110.1 | H331—C33—H332 | 107.6 |
C11—C12—H122 | 107.4 | C32—C33—C341 | 117.62 (7) |
C13—C12—H122 | 109.5 | C32—C33—H333 | 106.9 |
H121—C12—H122 | 109.8 | C341—C33—H333 | 108.0 |
C12—C13—C140 | 117.62 (7) | C32—C33—H334 | 108.4 |
C12—C13—H131 | 107.4 | C341—C33—H334 | 107.7 |
C140—C13—H131 | 110.1 | H333—C33—H334 | 107.9 |
C12—C13—H132 | 106.6 | C33—C340—C350 | 113.73 (7) |
C140—C13—H132 | 104.9 | C33—C340—C360 | 113.80 (7) |
H131—C13—H132 | 110.0 | C350—C340—C360 | 112.74 (7) |
C12—C13—C141 | 117.59 (7) | C33—C340—H3401 | 105.8 |
C12—C13—H133 | 106.0 | C350—C340—H3401 | 106.8 |
C141—C13—H133 | 103.7 | C360—C340—H3401 | 102.8 |
C12—C13—H134 | 108.0 | C340—C350—H3501 | 111.0 |
C141—C13—H134 | 111.2 | C340—C350—H3502 | 108.0 |
H133—C13—H134 | 110.0 | H3501—C350—H3502 | 110.9 |
C13—C140—C150 | 113.76 (7) | C340—C350—H3503 | 107.5 |
C13—C140—C160 | 113.74 (7) | H3501—C350—H3503 | 110.8 |
C150—C140—C160 | 112.73 (7) | H3502—C350—H3503 | 108.5 |
C13—C140—H1401 | 105.4 | C340—C360—H3601 | 110.8 |
C150—C140—H1401 | 107.2 | C340—C360—H3602 | 104.5 |
C160—C140—H1401 | 102.9 | H3601—C360—H3602 | 110.2 |
C140—C150—H1501 | 109.1 | C340—C360—H3603 | 111.1 |
C140—C150—H1502 | 106.6 | H3601—C360—H3603 | 109.3 |
H1501—C150—H1502 | 110.4 | H3602—C360—H3603 | 110.9 |
C140—C150—H1503 | 109.8 | C33—C341—C351 | 113.75 (7) |
H1501—C150—H1503 | 110.5 | C33—C341—C361 | 113.78 (7) |
H1502—C150—H1503 | 110.4 | C351—C341—C361 | 112.76 (7) |
C140—C160—H1601 | 112.2 | C33—C341—H3411 | 106.7 |
C140—C160—H1602 | 112.9 | C351—C341—H3411 | 106.7 |
H1601—C160—H1602 | 109.2 | C361—C341—H3411 | 102.0 |
C140—C160—H1603 | 102.6 | C341—C351—H3511 | 110.4 |
H1601—C160—H1603 | 109.3 | C341—C351—H3512 | 106.0 |
H1602—C160—H1603 | 110.5 | H3511—C351—H3512 | 111.0 |
C13—C141—C151 | 113.81 (7) | C341—C351—H3513 | 109.6 |
C13—C141—C161 | 113.73 (7) | H3511—C351—H3513 | 109.7 |
C151—C141—C161 | 112.76 (7) | H3512—C351—H3513 | 110.1 |
C13—C141—H1411 | 105.2 | C341—C361—H3611 | 110.1 |
C151—C141—H1411 | 106.3 | C341—C361—H3612 | 104.7 |
C161—C141—H1411 | 104.0 | H3611—C361—H3612 | 110.7 |
C141—C151—H1511 | 109.7 | C341—C361—H3613 | 112.2 |
C141—C151—H1512 | 110.1 | H3611—C361—H3613 | 108.7 |
H1511—C151—H1512 | 109.6 | H3612—C361—H3613 | 110.4 |
C141—C151—H1513 | 109.4 | N1—C41—C421 | 115.66 (7) |
H1511—C151—H1513 | 109.4 | N1—C41—H411 | 107.7 |
H1512—C151—H1513 | 108.7 | C421—C41—H411 | 110.6 |
C141—C161—H1611 | 109.1 | N1—C41—H412 | 107.2 |
C141—C161—H1612 | 104.9 | C421—C41—H412 | 105.5 |
H1611—C161—H1612 | 111.0 | H411—C41—H412 | 110.1 |
C141—C161—H1613 | 109.8 | N1—C41—C420 | 115.44 (7) |
H1611—C161—H1613 | 110.4 | N1—C41—H413 | 107.8 |
H1612—C161—H1613 | 111.5 | C420—C41—H413 | 107.7 |
N1—C21—C22 | 115.54 (5) | N1—C41—H414 | 107.6 |
N1—C21—H211 | 108.0 | C420—C41—H414 | 107.6 |
C22—C21—H211 | 109.7 | H413—C41—H414 | 110.7 |
N1—C21—H212 | 105.1 | C41—C421—C431 | 110.18 (7) |
C22—C21—H212 | 109.2 | C41—C421—H4211 | 109.3 |
H211—C21—H212 | 109.0 | C431—C421—H4211 | 106.1 |
C21—C22—C23 | 110.26 (5) | C41—C421—H4212 | 110.9 |
C21—C22—H221 | 105.7 | C431—C421—H4212 | 110.2 |
C23—C22—H221 | 111.7 | H4211—C421—H4212 | 110.1 |
C21—C22—H222 | 111.4 | C421—C431—C441 | 117.63 (7) |
C23—C22—H222 | 108.0 | C421—C431—H4311 | 109.4 |
H221—C22—H222 | 109.8 | C441—C431—H4311 | 107.1 |
C22—C23—C240 | 117.63 (7) | C421—C431—H4312 | 106.7 |
C22—C23—H231 | 106.6 | C441—C431—H4312 | 107.0 |
C240—C23—H231 | 110.3 | H4311—C431—H4312 | 108.9 |
C22—C23—H232 | 108.7 | C431—C441—C451 | 113.72 (7) |
C240—C23—H232 | 102.9 | C431—C441—C461 | 113.71 (7) |
H231—C23—H232 | 110.6 | C451—C441—C461 | 112.74 (7) |
C22—C23—C241 | 117.66 (7) | C431—C441—H4411 | 104.7 |
C22—C23—H233 | 106.9 | C451—C441—H4411 | 106.0 |
C241—C23—H233 | 112.9 | C461—C441—H4411 | 104.9 |
C22—C23—H234 | 105.3 | C441—C451—H4511 | 111.7 |
C241—C23—H234 | 103.8 | C441—C451—H4512 | 106.4 |
H233—C23—H234 | 109.9 | H4511—C451—H4512 | 109.3 |
C23—C240—C250 | 113.76 (7) | C441—C451—H4513 | 108.0 |
C23—C240—C260 | 113.76 (7) | H4511—C451—H4513 | 110.7 |
C250—C240—C260 | 112.75 (7) | H4512—C451—H4513 | 110.6 |
C23—C240—H2401 | 103.3 | C441—C461—H4611 | 109.8 |
C250—C240—H2401 | 107.2 | C441—C461—H4612 | 103.0 |
C260—C240—H2401 | 104.9 | H4611—C461—H4612 | 112.0 |
C240—C250—H2501 | 109.8 | C441—C461—H4613 | 108.3 |
C240—C250—H2502 | 108.7 | H4611—C461—H4613 | 111.6 |
H2501—C250—H2502 | 110.3 | H4612—C461—H4613 | 111.6 |
C240—C250—H2503 | 107.8 | C41—C420—C430 | 110.36 (7) |
H2501—C250—H2503 | 110.2 | C41—C420—H4201 | 108.6 |
H2502—C250—H2503 | 110.1 | C430—C420—H4201 | 106.9 |
C240—C260—H2601 | 106.9 | C41—C420—H4202 | 112.0 |
C240—C260—H2602 | 112.1 | C430—C420—H4202 | 109.9 |
H2601—C260—H2602 | 110.0 | H4201—C420—H4202 | 108.9 |
C240—C260—H2603 | 109.7 | C420—C430—C440 | 117.67 (7) |
H2601—C260—H2603 | 108.2 | C420—C430—H4301 | 108.2 |
H2602—C260—H2603 | 109.9 | C440—C430—H4301 | 103.9 |
C23—C241—C251 | 113.73 (7) | C420—C430—H4302 | 109.4 |
C23—C241—C261 | 113.74 (7) | C440—C430—H4302 | 108.1 |
C251—C241—C261 | 112.70 (7) | H4301—C430—H4302 | 109.2 |
C23—C241—H2411 | 106.1 | C430—C440—C450 | 113.77 (7) |
C251—C241—H2411 | 103.7 | C430—C440—C460 | 113.79 (7) |
C261—C241—H2411 | 105.7 | C450—C440—C460 | 112.75 (7) |
C241—C251—H2511 | 108.0 | C430—C440—H4401 | 105.3 |
C241—C251—H2512 | 112.7 | C450—C440—H4401 | 107.6 |
H2511—C251—H2512 | 110.2 | C460—C440—H4401 | 102.4 |
C241—C251—H2513 | 105.5 | C440—C450—H4501 | 110.0 |
H2511—C251—H2513 | 109.7 | C440—C450—H4502 | 108.6 |
H2512—C251—H2513 | 110.6 | H4501—C450—H4502 | 108.7 |
C241—C261—H2611 | 109.3 | C440—C450—H4503 | 110.6 |
C241—C261—H2612 | 107.4 | H4501—C450—H4503 | 109.3 |
H2611—C261—H2612 | 110.9 | H4502—C450—H4503 | 109.7 |
C241—C261—H2613 | 109.5 | C440—C460—H4601 | 111.3 |
H2611—C261—H2613 | 109.4 | C440—C460—H4602 | 104.0 |
H2612—C261—H2613 | 110.4 | H4601—C460—H4602 | 110.6 |
N1—C31—C32 | 115.52 (5) | C440—C460—H4603 | 111.5 |
N1—C31—H311 | 106.5 | H4601—C460—H4603 | 109.5 |
C32—C31—H311 | 106.8 | H4602—C460—H4603 | 109.8 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C150—H1501···C150i | 1.01 | 2.29 | 3.256 (15) | 161 |
C23—H232···C261 | 0.97 | 1.80 | 2.497 (15) | 126 |
C250—H2502···C161ii | 0.98 | 2.60 | 3.367 (15) | 136 |
C260—H2602···C260iii | 0.98 | 2.15 | 2.841 (15) | 126 |
C260—H2603···C261 | 0.98 | 1.49 | 2.281 (15) | 133 |
C251—H2513···C250iv | 1.03 | 2.53 | 3.475 (15) | 152 |
Symmetry codes: (i) x−y+1, −y+2, −z+4/3; (ii) x−y, −y+1, −z+4/3; (iii) x−y, −y, −z+4/3; (iv) y, x, −z+1. |
(I_100KC) tetrakis(4-methylpentyl)azanium bromide
top
Crystal data top
C24H52N+·Br− | Dx = 1.043 Mg m−3 |
Mr = 434.59 | Cu Kα radiation, λ = 1.54184 Å |
Trigonal, P3221 | Cell parameters from 30678 reflections |
Hall symbol: P 32 2" | θ = 3–76° |
a = 15.1327 (3) Å | µ = 2.05 mm−1 |
c = 20.9326 (4) Å | T = 100 K |
V = 4151.30 (13) Å3 | Plate, colourless |
Z = 6 | 0.15 × 0.14 × 0.07 mm |
F(000) = 1428 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5336 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 76.6°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | h = −18→18 |
Tmin = 0.59, Tmax = 0.87 | k = −19→19 |
88138 measured reflections | l = −26→26 |
5768 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.041 | Method = Modified Sheldrick
w = 1/[σ2(F2) + (0.09P)2 + 1.26P], where P = [max(Fo2,0) + 2Fc2]/3 |
wR(F2) = 0.128 | (Δ/σ)max = 0.003 |
S = 0.98 | Δρmax = 0.42 e Å−3 |
5768 reflections | Δρmin = −0.44 e Å−3 |
347 parameters | Absolute structure: Flack (1983), with 2546 Friedel pairs |
648 restraints | Absolute structure parameter: −0.01 (3) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C24H52N+·Br− | Z = 6 |
Mr = 434.59 | Cu Kα radiation |
Trigonal, P3221 | µ = 2.05 mm−1 |
a = 15.1327 (3) Å | T = 100 K |
c = 20.9326 (4) Å | 0.15 × 0.14 × 0.07 mm |
V = 4151.30 (13) Å3 | |
Data collection top
Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | 5768 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 5336 reflections with I > 2σ(I) |
Tmin = 0.59, Tmax = 0.87 | Rint = 0.040 |
88138 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.128 | Δρmax = 0.42 e Å−3 |
S = 0.98 | Δρmin = −0.44 e Å−3 |
5768 reflections | Absolute structure: Flack (1983), with 2546 Friedel pairs |
347 parameters | Absolute structure parameter: −0.01 (3) |
648 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.84910 (3) | 0.52779 (3) | 0.717639 (16) | 0.0708 | |
N1 | 0.58292 (18) | 0.42813 (19) | 0.59830 (11) | 0.0597 | |
C11 | 0.6078 (2) | 0.5379 (2) | 0.58733 (15) | 0.0562 | |
C12 | 0.7105 (3) | 0.6199 (3) | 0.61142 (17) | 0.0654 | |
C13 | 0.7233 (3) | 0.7250 (3) | 0.60066 (18) | 0.0715 | |
C14 | 0.8317 (4) | 0.8128 (3) | 0.6056 (2) | 0.0853 | |
C15 | 0.8367 (5) | 0.9129 (4) | 0.5891 (3) | 0.1042 | |
C16 | 0.8822 (4) | 0.8187 (4) | 0.6672 (3) | 0.1063 | |
C21 | 0.4809 (2) | 0.3607 (2) | 0.56551 (14) | 0.0618 | |
C22 | 0.4398 (2) | 0.2472 (2) | 0.57046 (18) | 0.0750 | |
C230 | 0.3394 (6) | 0.1880 (4) | 0.5326 (4) | 0.0987 | 0.272 (7) |
C240 | 0.2454 (6) | 0.1122 (7) | 0.5713 (6) | 0.1182 | 0.272 (7) |
C250 | 0.1500 (9) | 0.0558 (13) | 0.5307 (10) | 0.1141 | 0.272 (7) |
C260 | 0.2638 (10) | 0.0384 (10) | 0.6107 (7) | 0.0969 | 0.272 (7) |
C231 | 0.3301 (3) | 0.1888 (3) | 0.5483 (2) | 0.0736 | 0.728 (7) |
C241 | 0.2840 (3) | 0.0737 (3) | 0.54184 (18) | 0.0907 | 0.728 (7) |
C251 | 0.1716 (5) | 0.0191 (4) | 0.5286 (4) | 0.1279 | 0.728 (7) |
C261 | 0.3410 (5) | 0.0437 (4) | 0.4932 (3) | 0.1087 | 0.728 (7) |
C31 | 0.6670 (2) | 0.4121 (3) | 0.57097 (12) | 0.0647 | |
C32 | 0.6922 (2) | 0.4400 (3) | 0.50194 (13) | 0.0692 | |
C33 | 0.7766 (3) | 0.4200 (3) | 0.48021 (15) | 0.0844 | |
C340 | 0.7886 (7) | 0.4150 (10) | 0.4082 (3) | 0.1042 | 0.235 (14) |
C350 | 0.8907 (13) | 0.427 (2) | 0.3893 (4) | 0.1107 | 0.235 (14) |
C360 | 0.7663 (19) | 0.4883 (18) | 0.3713 (5) | 0.1086 | 0.235 (14) |
C341 | 0.8028 (3) | 0.4361 (4) | 0.4100 (2) | 0.1019 | 0.765 (14) |
C351 | 0.8816 (5) | 0.4067 (7) | 0.3908 (3) | 0.1122 | 0.765 (14) |
C361 | 0.8325 (8) | 0.5404 (7) | 0.3879 (3) | 0.1221 | 0.765 (14) |
C41 | 0.5799 (2) | 0.4083 (3) | 0.66950 (13) | 0.0702 | |
C421 | 0.4941 (5) | 0.3990 (7) | 0.7027 (2) | 0.0629 | 0.451 (8) |
C431 | 0.4846 (5) | 0.3504 (5) | 0.7677 (2) | 0.0626 | 0.451 (8) |
C441 | 0.4185 (4) | 0.3629 (4) | 0.8146 (2) | 0.0622 | 0.451 (8) |
C451 | 0.4193 (6) | 0.3197 (7) | 0.8796 (3) | 0.0799 | 0.451 (8) |
C461 | 0.3111 (5) | 0.3227 (7) | 0.7909 (3) | 0.0697 | 0.451 (8) |
C420 | 0.5196 (5) | 0.4493 (6) | 0.7114 (2) | 0.0712 | 0.549 (8) |
C430 | 0.4995 (4) | 0.4038 (5) | 0.7788 (2) | 0.0880 | 0.549 (8) |
C440 | 0.4069 (5) | 0.2967 (5) | 0.7861 (3) | 0.0958 | 0.549 (8) |
C450 | 0.3956 (6) | 0.2539 (8) | 0.8534 (4) | 0.1118 | 0.549 (8) |
C460 | 0.3084 (5) | 0.2896 (7) | 0.7634 (4) | 0.0991 | 0.549 (8) |
H111 | 0.5544 | 0.5471 | 0.6067 | 0.0670* | |
H112 | 0.6029 | 0.5462 | 0.5425 | 0.0656* | |
H121 | 0.7153 | 0.6067 | 0.6572 | 0.0791* | |
H122 | 0.7644 | 0.6135 | 0.5893 | 0.0793* | |
H131 | 0.6874 | 0.7356 | 0.6360 | 0.0859* | |
H132 | 0.6905 | 0.7267 | 0.5622 | 0.0854* | |
H141 | 0.8717 | 0.8004 | 0.5744 | 0.1021* | |
H151 | 0.9074 | 0.9697 | 0.5920 | 0.1558* | |
H152 | 0.7959 | 0.9239 | 0.6212 | 0.1561* | |
H153 | 0.8086 | 0.9093 | 0.5473 | 0.1558* | |
H161 | 0.9502 | 0.8787 | 0.6662 | 0.1585* | |
H162 | 0.8417 | 0.8258 | 0.7000 | 0.1589* | |
H163 | 0.8866 | 0.7575 | 0.6732 | 0.1584* | |
H211 | 0.4333 | 0.3767 | 0.5856 | 0.0742* | |
H212 | 0.4872 | 0.3804 | 0.5207 | 0.0733* | |
H221 | 0.4272 | 0.2271 | 0.6153 | 0.0902* | 0.272 (7) |
H222 | 0.4889 | 0.2304 | 0.5537 | 0.0899* | 0.272 (7) |
H2301 | 0.3233 | 0.2365 | 0.5146 | 0.1172* | 0.272 (7) |
H2302 | 0.3493 | 0.1498 | 0.4991 | 0.1172* | 0.272 (7) |
H2401 | 0.2334 | 0.1536 | 0.6031 | 0.1391* | 0.272 (7) |
H2501 | 0.1100 | −0.0143 | 0.5451 | 0.1700* | 0.272 (7) |
H2502 | 0.1101 | 0.0891 | 0.5357 | 0.1701* | 0.272 (7) |
H2503 | 0.1685 | 0.0575 | 0.4864 | 0.1700* | 0.272 (7) |
H2601 | 0.2441 | 0.0397 | 0.6534 | 0.1409* | 0.272 (7) |
H2602 | 0.3340 | 0.0567 | 0.6095 | 0.1408* | 0.272 (7) |
H2603 | 0.2233 | −0.0285 | 0.5945 | 0.1410* | 0.272 (7) |
H223 | 0.4452 | 0.2295 | 0.6150 | 0.0902* | 0.728 (7) |
H224 | 0.4790 | 0.2275 | 0.5454 | 0.0894* | 0.728 (7) |
H2311 | 0.2904 | 0.2060 | 0.5749 | 0.0886* | 0.728 (7) |
H2312 | 0.3287 | 0.2112 | 0.5065 | 0.0890* | 0.728 (7) |
H2411 | 0.2895 | 0.0474 | 0.5839 | 0.1099* | 0.728 (7) |
H2511 | 0.1484 | −0.0523 | 0.5193 | 0.1930* | 0.728 (7) |
H2512 | 0.1359 | 0.0218 | 0.5673 | 0.1931* | 0.728 (7) |
H2513 | 0.1588 | 0.0507 | 0.4922 | 0.1930* | 0.728 (7) |
H2611 | 0.3151 | −0.0298 | 0.4950 | 0.1651* | 0.728 (7) |
H2612 | 0.4129 | 0.0790 | 0.5013 | 0.1653* | 0.728 (7) |
H2613 | 0.3308 | 0.0611 | 0.4502 | 0.1652* | 0.728 (7) |
H311 | 0.7273 | 0.4520 | 0.5973 | 0.0777* | |
H312 | 0.6436 | 0.3398 | 0.5768 | 0.0780* | |
H321 | 0.7161 | 0.5121 | 0.4968 | 0.0830* | |
H322 | 0.6317 | 0.4013 | 0.4755 | 0.0832* | |
H331 | 0.8416 | 0.4729 | 0.4978 | 0.1010* | 0.235 (14) |
H332 | 0.7616 | 0.3538 | 0.4975 | 0.1011* | 0.235 (14) |
H3401 | 0.7367 | 0.3456 | 0.3938 | 0.1250* | 0.235 (14) |
H3501 | 0.8772 | 0.3671 | 0.3578 | 0.1659* | 0.235 (14) |
H3502 | 0.9310 | 0.4988 | 0.3664 | 0.1659* | 0.235 (14) |
H3503 | 0.9279 | 0.4248 | 0.4310 | 0.1660* | 0.235 (14) |
H3601 | 0.8372 | 0.5394 | 0.3421 | 0.1620* | 0.235 (14) |
H3602 | 0.7512 | 0.5320 | 0.4087 | 0.1620* | 0.235 (14) |
H3603 | 0.6973 | 0.4389 | 0.3408 | 0.1620* | 0.235 (14) |
H333 | 0.8410 | 0.4680 | 0.5051 | 0.1010* | 0.765 (14) |
H334 | 0.7583 | 0.3499 | 0.4906 | 0.1016* | 0.765 (14) |
H3411 | 0.7362 | 0.3894 | 0.3856 | 0.1232* | 0.765 (14) |
H3511 | 0.8947 | 0.4176 | 0.3456 | 0.1669* | 0.765 (14) |
H3512 | 0.9455 | 0.4466 | 0.4127 | 0.1670* | 0.765 (14) |
H3513 | 0.8574 | 0.3355 | 0.3985 | 0.1667* | 0.765 (14) |
H3611 | 0.8677 | 0.5530 | 0.3471 | 0.1837* | 0.765 (14) |
H3612 | 0.8756 | 0.5900 | 0.4189 | 0.1838* | 0.765 (14) |
H3613 | 0.7705 | 0.5435 | 0.3810 | 0.1842* | 0.765 (14) |
H411 | 0.6437 | 0.4601 | 0.6882 | 0.0839* | 0.488 (8) |
H412 | 0.5746 | 0.3417 | 0.6744 | 0.0838* | 0.488 (8) |
H4211 | 0.5063 | 0.4671 | 0.7098 | 0.0752* | 0.451 (8) |
H4212 | 0.4314 | 0.3617 | 0.6774 | 0.0760* | 0.451 (8) |
H4311 | 0.5531 | 0.3822 | 0.7864 | 0.0761* | 0.451 (8) |
H4312 | 0.4598 | 0.2785 | 0.7609 | 0.0761* | 0.451 (8) |
H4411 | 0.4458 | 0.4353 | 0.8206 | 0.0746* | 0.451 (8) |
H4511 | 0.3658 | 0.3187 | 0.9059 | 0.1207* | 0.451 (8) |
H4512 | 0.4850 | 0.3624 | 0.8991 | 0.1210* | 0.451 (8) |
H4513 | 0.4075 | 0.2516 | 0.8756 | 0.1211* | 0.451 (8) |
H4611 | 0.2701 | 0.3296 | 0.8236 | 0.1047* | 0.451 (8) |
H4612 | 0.2832 | 0.2520 | 0.7797 | 0.1044* | 0.451 (8) |
H4613 | 0.3125 | 0.3608 | 0.7532 | 0.1047* | 0.451 (8) |
H413 | 0.6506 | 0.4414 | 0.6837 | 0.0835* | 0.512 (8) |
H414 | 0.5500 | 0.3352 | 0.6763 | 0.0837* | 0.512 (8) |
H4201 | 0.5618 | 0.5222 | 0.7142 | 0.0850* | 0.549 (8) |
H4202 | 0.4552 | 0.4334 | 0.6912 | 0.0847* | 0.549 (8) |
H4301 | 0.4878 | 0.4486 | 0.8057 | 0.1051* | 0.549 (8) |
H4302 | 0.5607 | 0.4039 | 0.7940 | 0.1050* | 0.549 (8) |
H4401 | 0.4191 | 0.2526 | 0.7565 | 0.1143* | 0.549 (8) |
H4501 | 0.3669 | 0.1815 | 0.8524 | 0.1669* | 0.549 (8) |
H4502 | 0.3512 | 0.2693 | 0.8787 | 0.1667* | 0.549 (8) |
H4503 | 0.4613 | 0.2848 | 0.8742 | 0.1669* | 0.549 (8) |
H4601 | 0.2601 | 0.2199 | 0.7557 | 0.1480* | 0.549 (8) |
H4602 | 0.2826 | 0.3158 | 0.7955 | 0.1482* | 0.549 (8) |
H4603 | 0.3192 | 0.3269 | 0.7245 | 0.1479* | 0.549 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.05383 (18) | 0.1000 (3) | 0.06365 (19) | 0.04236 (18) | −0.00084 (13) | 0.01809 (16) |
N1 | 0.0543 (12) | 0.0671 (14) | 0.0655 (13) | 0.0362 (11) | −0.0038 (10) | 0.0074 (11) |
C11 | 0.0595 (16) | 0.0649 (17) | 0.0546 (15) | 0.0389 (14) | −0.0084 (12) | −0.0027 (13) |
C12 | 0.0685 (19) | 0.070 (2) | 0.0667 (17) | 0.0412 (17) | −0.0158 (15) | −0.0052 (15) |
C13 | 0.080 (2) | 0.067 (2) | 0.075 (2) | 0.0423 (18) | −0.0225 (18) | −0.0114 (16) |
C14 | 0.091 (3) | 0.073 (2) | 0.089 (3) | 0.039 (2) | −0.020 (2) | −0.002 (2) |
C15 | 0.120 (4) | 0.070 (3) | 0.110 (3) | 0.038 (3) | −0.038 (3) | −0.007 (2) |
C16 | 0.101 (3) | 0.081 (3) | 0.122 (4) | 0.034 (3) | −0.048 (3) | −0.009 (3) |
C21 | 0.0563 (15) | 0.0679 (15) | 0.0657 (15) | 0.0345 (12) | −0.0042 (12) | 0.0035 (13) |
C22 | 0.076 (2) | 0.0672 (17) | 0.0778 (19) | 0.0332 (16) | −0.0108 (17) | 0.0090 (15) |
C230 | 0.095 (5) | 0.084 (6) | 0.086 (6) | 0.022 (5) | −0.023 (5) | 0.022 (5) |
C240 | 0.112 (6) | 0.090 (6) | 0.107 (6) | 0.016 (5) | −0.024 (5) | 0.027 (5) |
C250 | 0.112 (8) | 0.085 (8) | 0.115 (8) | 0.026 (7) | −0.025 (7) | 0.025 (7) |
C260 | 0.103 (8) | 0.066 (6) | 0.086 (7) | 0.016 (6) | −0.025 (6) | 0.018 (6) |
C231 | 0.072 (3) | 0.069 (3) | 0.059 (2) | 0.020 (2) | −0.001 (2) | 0.007 (2) |
C241 | 0.101 (3) | 0.060 (2) | 0.076 (3) | 0.014 (2) | −0.013 (2) | 0.006 (2) |
C251 | 0.107 (4) | 0.091 (4) | 0.119 (5) | 0.000 (4) | 0.015 (4) | −0.004 (4) |
C261 | 0.119 (5) | 0.073 (3) | 0.120 (4) | 0.037 (3) | −0.009 (4) | 0.002 (3) |
C31 | 0.0572 (15) | 0.0610 (16) | 0.0839 (17) | 0.0356 (13) | 0.0019 (13) | 0.0048 (15) |
C32 | 0.0604 (15) | 0.0688 (18) | 0.0818 (18) | 0.0348 (14) | 0.0004 (14) | −0.0093 (15) |
C33 | 0.079 (2) | 0.0601 (17) | 0.117 (2) | 0.0366 (16) | 0.0243 (19) | −0.0037 (18) |
C340 | 0.104 (6) | 0.071 (5) | 0.124 (5) | 0.034 (5) | 0.037 (6) | −0.007 (5) |
C350 | 0.105 (8) | 0.079 (8) | 0.129 (9) | 0.031 (7) | 0.040 (8) | −0.020 (8) |
C360 | 0.113 (8) | 0.071 (7) | 0.127 (8) | 0.035 (7) | 0.049 (7) | 0.003 (7) |
C341 | 0.088 (3) | 0.104 (3) | 0.117 (3) | 0.050 (3) | 0.022 (3) | −0.023 (3) |
C351 | 0.080 (4) | 0.109 (5) | 0.141 (5) | 0.042 (4) | 0.030 (4) | −0.025 (4) |
C361 | 0.119 (5) | 0.118 (4) | 0.127 (5) | 0.057 (4) | 0.030 (4) | −0.011 (4) |
C41 | 0.0549 (15) | 0.092 (2) | 0.0662 (16) | 0.0381 (15) | −0.0039 (13) | 0.0171 (15) |
C421 | 0.057 (3) | 0.071 (4) | 0.056 (3) | 0.029 (3) | −0.008 (3) | 0.008 (3) |
C431 | 0.067 (3) | 0.070 (4) | 0.051 (3) | 0.034 (3) | −0.014 (3) | 0.002 (3) |
C441 | 0.074 (3) | 0.075 (4) | 0.047 (3) | 0.044 (3) | −0.007 (2) | 0.003 (3) |
C451 | 0.098 (5) | 0.088 (5) | 0.051 (3) | 0.045 (4) | −0.010 (3) | 0.012 (3) |
C461 | 0.070 (4) | 0.085 (5) | 0.054 (4) | 0.038 (4) | 0.006 (3) | 0.002 (3) |
C420 | 0.054 (3) | 0.107 (4) | 0.059 (3) | 0.045 (3) | −0.003 (2) | 0.005 (3) |
C430 | 0.085 (4) | 0.121 (5) | 0.057 (3) | 0.051 (4) | −0.005 (3) | −0.001 (3) |
C440 | 0.101 (4) | 0.122 (5) | 0.074 (3) | 0.062 (4) | 0.009 (3) | 0.015 (4) |
C450 | 0.116 (5) | 0.142 (7) | 0.089 (5) | 0.073 (5) | 0.006 (4) | 0.029 (5) |
C460 | 0.094 (5) | 0.119 (6) | 0.083 (5) | 0.052 (4) | 0.007 (4) | 0.021 (4) |
Geometric parameters (Å, º) top
N1—C11 | 1.526 (4) | C33—C340 | 1.524 (7) |
N1—C21 | 1.524 (3) | C33—H331 | 0.978 |
N1—C31 | 1.521 (3) | C33—H332 | 0.979 |
N1—C41 | 1.516 (3) | C33—C341 | 1.509 (5) |
C11—C12 | 1.510 (5) | C33—H333 | 1.021 |
C11—H111 | 0.975 | C33—H334 | 0.977 |
C11—H112 | 0.954 | C340—C350 | 1.514 (7) |
C12—C13 | 1.519 (5) | C340—C360 | 1.521 (7) |
C12—H121 | 0.989 | C340—H3401 | 0.993 |
C12—H122 | 0.983 | C350—H3501 | 1.058 |
C13—C14 | 1.512 (6) | C350—H3502 | 1.055 |
C13—H131 | 0.978 | C350—H3503 | 1.049 |
C13—H132 | 0.953 | C360—H3601 | 1.137 |
C14—C15 | 1.517 (6) | C360—H3602 | 1.120 |
C14—C16 | 1.478 (6) | C360—H3603 | 1.130 |
C14—H141 | 0.970 | C341—C351 | 1.520 (5) |
C15—H151 | 0.984 | C341—C361 | 1.483 (6) |
C15—H152 | 0.982 | C341—H3411 | 1.031 |
C15—H153 | 0.963 | C351—H3511 | 0.962 |
C16—H161 | 0.974 | C351—H3512 | 0.963 |
C16—H162 | 0.961 | C351—H3513 | 0.963 |
C16—H163 | 0.971 | C361—H3611 | 0.974 |
C21—C22 | 1.510 (3) | C361—H3612 | 0.959 |
C21—H211 | 0.962 | C361—H3613 | 0.974 |
C21—H212 | 0.973 | C41—C421 | 1.416 (5) |
C22—C230 | 1.542 (7) | C41—H411 | 0.972 |
C22—H221 | 0.975 | C41—H412 | 0.976 |
C22—H222 | 0.965 | C41—C420 | 1.597 (5) |
C22—C231 | 1.511 (5) | C41—H413 | 0.975 |
C22—H223 | 0.985 | C41—H414 | 0.975 |
C22—H224 | 0.945 | C421—C431 | 1.518 (5) |
C230—C240 | 1.536 (7) | C421—H4211 | 0.963 |
C230—H2301 | 0.959 | C421—H4212 | 0.982 |
C230—H2302 | 0.968 | C431—C441 | 1.480 (6) |
C240—C250 | 1.517 (7) | C431—H4311 | 0.980 |
C240—C260 | 1.522 (7) | C431—H4312 | 0.968 |
C240—H2401 | 0.992 | C441—C451 | 1.511 (5) |
C250—H2501 | 0.969 | C441—C461 | 1.506 (6) |
C250—H2502 | 0.965 | C441—H4411 | 0.966 |
C250—H2503 | 0.966 | C451—H4511 | 0.973 |
C260—H2601 | 0.946 | C451—H4512 | 0.965 |
C260—H2602 | 0.955 | C451—H4513 | 0.958 |
C260—H2603 | 0.946 | C461—H4611 | 0.965 |
C231—C241 | 1.524 (5) | C461—H4612 | 0.962 |
C231—H2311 | 0.948 | C461—H4613 | 0.971 |
C231—H2312 | 0.942 | C420—C430 | 1.532 (5) |
C241—C251 | 1.499 (6) | C420—H4201 | 0.961 |
C241—C261 | 1.541 (6) | C420—H4202 | 0.975 |
C241—H2411 | 0.988 | C430—C440 | 1.530 (6) |
C251—H2511 | 0.974 | C430—H4301 | 0.964 |
C251—H2512 | 0.985 | C430—H4302 | 0.978 |
C251—H2513 | 0.971 | C440—C450 | 1.524 (6) |
C261—H2611 | 0.977 | C440—C460 | 1.516 (6) |
C261—H2612 | 0.958 | C440—H4401 | 0.993 |
C261—H2613 | 0.971 | C450—H4501 | 0.956 |
C31—C32 | 1.500 (3) | C450—H4502 | 0.971 |
C31—H311 | 0.975 | C450—H4503 | 0.965 |
C31—H312 | 0.975 | C460—H4601 | 0.949 |
C32—C33 | 1.522 (3) | C460—H4602 | 0.957 |
C32—H321 | 0.968 | C460—H4603 | 0.958 |
C32—H322 | 0.975 | | |
| | | |
C11—N1—C21 | 106.09 (17) | C32—C33—C340 | 115.95 (7) |
C11—N1—C31 | 110.2 (2) | C32—C33—H331 | 108.9 |
C21—N1—C31 | 111.9 (2) | C340—C33—H331 | 108.4 |
C11—N1—C41 | 109.2 (2) | C32—C33—H332 | 107.7 |
C21—N1—C41 | 112.9 (2) | C340—C33—H332 | 106.8 |
C31—N1—C41 | 106.47 (12) | H331—C33—H332 | 108.9 |
N1—C11—C12 | 115.9 (2) | C32—C33—C341 | 115.92 (7) |
N1—C11—H111 | 108.8 | C32—C33—H333 | 107.7 |
C12—C11—H111 | 109.2 | C341—C33—H333 | 107.5 |
N1—C11—H112 | 107.3 | C32—C33—H334 | 109.9 |
C12—C11—H112 | 109.7 | C341—C33—H334 | 107.5 |
H111—C11—H112 | 105.4 | H333—C33—H334 | 108.1 |
C11—C12—C13 | 110.5 (3) | C33—C340—C350 | 113.05 (7) |
C11—C12—H121 | 107.9 | C33—C340—C360 | 113.07 (7) |
C13—C12—H121 | 111.8 | C350—C340—C360 | 111.25 (7) |
C11—C12—H122 | 109.0 | C33—C340—H3401 | 107.6 |
C13—C12—H122 | 110.8 | C350—C340—H3401 | 105.5 |
H121—C12—H122 | 106.7 | C360—C340—H3401 | 105.7 |
C12—C13—C14 | 115.1 (3) | C340—C350—H3501 | 108.2 |
C12—C13—H131 | 105.6 | C340—C350—H3502 | 106.0 |
C14—C13—H131 | 104.6 | H3501—C350—H3502 | 111.3 |
C12—C13—H132 | 111.0 | C340—C350—H3503 | 108.2 |
C14—C13—H132 | 112.6 | H3501—C350—H3503 | 111.3 |
H131—C13—H132 | 107.1 | H3502—C350—H3503 | 111.6 |
C13—C14—C15 | 110.7 (4) | C340—C360—H3601 | 107.0 |
C13—C14—C16 | 114.4 (4) | C340—C360—H3602 | 105.0 |
C15—C14—C16 | 111.8 (4) | H3601—C360—H3602 | 112.1 |
C13—C14—H141 | 106.9 | C340—C360—H3603 | 105.8 |
C15—C14—H141 | 108.4 | H3601—C360—H3603 | 113.1 |
C16—C14—H141 | 104.2 | H3602—C360—H3603 | 113.1 |
C14—C15—H151 | 110.4 | C33—C341—C351 | 113.06 (7) |
C14—C15—H152 | 107.1 | C33—C341—C361 | 113.08 (7) |
H151—C15—H152 | 108.1 | C351—C341—C361 | 111.28 (7) |
C14—C15—H153 | 110.5 | C33—C341—H3411 | 106.5 |
H151—C15—H153 | 111.2 | C351—C341—H3411 | 107.9 |
H152—C15—H153 | 109.4 | C361—C341—H3411 | 104.4 |
C14—C16—H161 | 108.2 | C341—C351—H3511 | 109.6 |
C14—C16—H162 | 106.9 | C341—C351—H3512 | 112.3 |
H161—C16—H162 | 110.3 | H3511—C351—H3512 | 107.7 |
C14—C16—H163 | 109.6 | C341—C351—H3513 | 111.6 |
H161—C16—H163 | 110.3 | H3511—C351—H3513 | 106.7 |
H162—C16—H163 | 111.5 | H3512—C351—H3513 | 108.6 |
N1—C21—C22 | 115.72 (5) | C341—C361—H3611 | 109.2 |
N1—C21—H211 | 105.6 | C341—C361—H3612 | 110.3 |
C22—C21—H211 | 108.7 | H3611—C361—H3612 | 110.5 |
N1—C21—H212 | 108.5 | C341—C361—H3613 | 108.1 |
C22—C21—H212 | 109.6 | H3611—C361—H3613 | 107.8 |
H211—C21—H212 | 108.5 | H3612—C361—H3613 | 110.9 |
C21—C22—C230 | 110.58 (7) | N1—C41—C421 | 115.98 (7) |
C21—C22—H221 | 109.0 | N1—C41—H411 | 108.5 |
C230—C22—H221 | 109.3 | C421—C41—H411 | 112.0 |
C21—C22—H222 | 110.0 | N1—C41—H412 | 106.6 |
C230—C22—H222 | 109.0 | C421—C41—H412 | 104.4 |
H221—C22—H222 | 108.8 | H411—C41—H412 | 109.0 |
C21—C22—C231 | 110.57 (7) | N1—C41—C420 | 115.47 (7) |
C21—C22—H223 | 109.4 | N1—C41—H413 | 106.4 |
C231—C22—H223 | 110.4 | C420—C41—H413 | 109.1 |
C21—C22—H224 | 110.7 | N1—C41—H414 | 108.7 |
C231—C22—H224 | 108.9 | C420—C41—H414 | 109.3 |
H223—C22—H224 | 106.8 | H413—C41—H414 | 107.6 |
C22—C230—C240 | 116.03 (7) | C41—C421—C431 | 110.34 (7) |
C22—C230—H2301 | 108.1 | C41—C421—H4211 | 107.1 |
C240—C230—H2301 | 106.5 | C431—C421—H4211 | 107.5 |
C22—C230—H2302 | 108.5 | C41—C421—H4212 | 111.5 |
C240—C230—H2302 | 107.3 | C431—C421—H4212 | 111.9 |
H2301—C230—H2302 | 110.2 | H4211—C421—H4212 | 108.2 |
C230—C240—C250 | 113.02 (7) | C421—C431—C441 | 116.02 (7) |
C230—C240—C260 | 113.10 (7) | C421—C431—H4311 | 107.5 |
C250—C240—C260 | 111.23 (7) | C441—C431—H4311 | 106.7 |
C230—C240—H2401 | 106.0 | C421—C431—H4312 | 107.6 |
C250—C240—H2401 | 107.9 | C441—C431—H4312 | 109.6 |
C260—C240—H2401 | 104.9 | H4311—C431—H4312 | 109.3 |
C240—C250—H2501 | 109.9 | C431—C441—C451 | 112.96 (7) |
C240—C250—H2502 | 108.3 | C431—C441—C461 | 112.97 (7) |
H2501—C250—H2502 | 109.0 | C451—C441—C461 | 111.23 (7) |
C240—C250—H2503 | 109.9 | C431—C441—H4411 | 107.3 |
H2501—C250—H2503 | 110.0 | C451—C441—H4411 | 106.5 |
H2502—C250—H2503 | 109.8 | C461—C441—H4411 | 105.3 |
C240—C260—H2601 | 108.8 | C441—C451—H4511 | 109.3 |
C240—C260—H2602 | 111.1 | C441—C451—H4512 | 108.6 |
H2601—C260—H2602 | 109.5 | H4511—C451—H4512 | 110.0 |
C240—C260—H2603 | 109.5 | C441—C451—H4513 | 110.5 |
H2601—C260—H2603 | 108.5 | H4511—C451—H4513 | 109.1 |
H2602—C260—H2603 | 109.4 | H4512—C451—H4513 | 109.4 |
C22—C231—C241 | 115.87 (7) | C441—C461—H4611 | 110.1 |
C22—C231—H2311 | 108.7 | C441—C461—H4612 | 108.4 |
C241—C231—H2311 | 112.1 | H4611—C461—H4612 | 110.1 |
C22—C231—H2312 | 106.9 | C441—C461—H4613 | 109.3 |
C241—C231—H2312 | 104.5 | H4611—C461—H4613 | 109.7 |
H2311—C231—H2312 | 108.4 | H4612—C461—H4613 | 109.3 |
C231—C241—C251 | 113.03 (7) | C41—C420—C430 | 110.73 (7) |
C231—C241—C261 | 113.03 (7) | C41—C420—H4201 | 107.3 |
C251—C241—C261 | 111.26 (7) | C430—C420—H4201 | 109.2 |
C231—C241—H2411 | 107.5 | C41—C420—H4202 | 111.1 |
C251—C241—H2411 | 104.1 | C430—C420—H4202 | 109.8 |
C261—C241—H2411 | 107.3 | H4201—C420—H4202 | 108.6 |
C241—C251—H2511 | 109.2 | C420—C430—C440 | 116.01 (7) |
C241—C251—H2512 | 108.7 | C420—C430—H4301 | 106.6 |
H2511—C251—H2512 | 108.0 | C440—C430—H4301 | 107.0 |
C241—C251—H2513 | 108.9 | C420—C430—H4302 | 109.0 |
H2511—C251—H2513 | 109.9 | C440—C430—H4302 | 109.6 |
H2512—C251—H2513 | 112.0 | H4301—C430—H4302 | 108.3 |
C241—C261—H2611 | 110.2 | C430—C440—C450 | 113.01 (7) |
C241—C261—H2612 | 111.4 | C430—C440—C460 | 113.08 (7) |
H2611—C261—H2612 | 109.0 | C450—C440—C460 | 111.22 (7) |
C241—C261—H2613 | 110.2 | C430—C440—H4401 | 105.6 |
H2611—C261—H2613 | 108.4 | C450—C440—H4401 | 108.0 |
H2612—C261—H2613 | 107.6 | C460—C440—H4401 | 105.3 |
N1—C31—C32 | 115.62 (5) | C440—C450—H4501 | 111.0 |
N1—C31—H311 | 106.7 | C440—C450—H4502 | 110.3 |
C32—C31—H311 | 110.1 | H4501—C450—H4502 | 108.2 |
N1—C31—H312 | 105.6 | C440—C450—H4503 | 110.0 |
C32—C31—H312 | 109.6 | H4501—C450—H4503 | 109.4 |
H311—C31—H312 | 109.0 | H4502—C450—H4503 | 107.8 |
C31—C32—C33 | 110.61 (5) | C440—C460—H4601 | 108.3 |
C31—C32—H321 | 108.9 | C440—C460—H4602 | 109.9 |
C33—C32—H321 | 108.2 | H4601—C460—H4602 | 109.5 |
C31—C32—H322 | 110.3 | C440—C460—H4603 | 110.6 |
C33—C32—H322 | 109.9 | H4601—C460—H4603 | 108.6 |
H321—C32—H322 | 108.9 | H4602—C460—H4603 | 109.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C230—H2302···C261 | 0.97 | 1.55 | 2.346 (11) | 136 |
C250—H2502···C250i | 0.97 | 2.05 | 2.784 (11) | 131 |
C260—H2601···C260ii | 0.95 | 1.80 | 2.552 (11) | 134 |
Symmetry codes: (i) y, x, −z+1; (ii) x−y, −y, −z+4/3. |
Experimental details
| (I_100KQ) | (I_250K) | (I_100KC) |
Crystal data |
Chemical formula | C24H52N+·Br− | C24H52N+·Br− | C24H52N+·Br− |
Mr | 434.59 | 434.59 | 434.59 |
Crystal system, space group | Trigonal, P3221 | Trigonal, P3221 | Trigonal, P3221 |
Temperature (K) | 100 | 250 | 100 |
a, c (Å) | 15.12762 (13), 21.0223 (2) | 15.4995 (2), 21.1346 (3) | 15.1327 (3), 20.9326 (4) |
V (Å3) | 4166.31 (6) | 4397.06 (12) | 4151.30 (13) |
Z | 6 | 6 | 6 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 2.04 | 1.93 | 2.05 |
Crystal size (mm) | 0.15 × 0.14 × 0.07 | 0.15 × 0.14 × 0.07 | 0.15 × 0.14 × 0.07 |
|
Data collection |
Diffractometer | Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector | Oxford SuperNova Dual diffractometer with Cu at zero and Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) | Multi-scan (CrysAlis PRO; Agilent, 2011) | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.57, 0.87 | 0.60, 0.87 | 0.59, 0.87 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 89102, 5781, 5591 | 94951, 6128, 4391 | 88138, 5768, 5336 |
Rint | 0.033 | 0.037 | 0.040 |
(sin θ/λ)max (Å−1) | 0.631 | 0.632 | 0.631 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.114, 1.02 | 0.049, 0.178, 0.96 | 0.041, 0.128, 0.98 |
No. of reflections | 5781 | 6128 | 5768 |
No. of parameters | 347 | 366 | 347 |
No. of restraints | 648 | 864 | 648 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.60 | 0.21, −0.24 | 0.42, −0.44 |
Absolute structure | Flack (1983), with 2550 Friedel pairs | Flack (1983), with 2710 Friedel pairs | Flack (1983), with 2546 Friedel pairs |
Absolute structure parameter | −0.02 (2) | −0.03 (3) | −0.01 (3) |
Gas hydrates are ice-like clathrates that are formed at high pressure and low temperature from water or water/hydrocarbon mixtures, and are a serious problem in the oil and gas industry due to their ability to cause blockages. Low-dosage hydrate inhibitors are a recent alternative to thermodynamic hydrate inhibitors and can be divided into two classes: kinetic inhibitors and anti-agglomerants. A major breakthrough in this area of research was the development of quaternary ammonium surfactant anti-agglomerants with tributyl or tripentyl head-groups (Kelland, 2006). Searches of the Cambridge Structural Database (CSD, Version 5.32 including November 2010 and February 2011 updates; Allen, 2002; Bruno et al., 2002) show that many quaternary ammonium halide structures have been reported, both as hydrate clathrates (e.g. Feil & Jeffrey, 1961; McMullan et al., 1963; Lipkowski et al., 1994, 2002; Shimada et al., 2005; Komarov et al., 2007; Wang et al., 2009) and without solvent as n-propyl (Yoshida et al., 1994), n-butyl (Wang et al., 1995; Prukała et al., 2007), n-pentyl (Szafranska et al., 2000), n-dodecyl, n-hexadecyl and n-octadecyl (Abdallah et al., 1999) ammonium halides. However, despite its industrial importance, the structure of the title compound, (I), has never been reported and, remarkably, the tetrakis(isohexyl)ammonium cation does not appear in the CSD at all. The most closely related compound is tetrakis(isopentyl) ammonium bromide, which is reported as the hydrate clathrate (Wang et al., 2009).
Compound (I), was found to form soft greasy soap-like crystals which gave poor-quality diffraction data and were consequently challenging to work with. Almost no diffraction was seen with a conventional Mo radiation X-ray source. However, reasonable data could be obtained using a Cu microfocus instrument. Initially, the chosen crystal was placed directly in a cold stream (Cosier & Glazer, 1986) at 100 K. The space group was determined to be P3221 and the structure was solved. Examination of the difference map indicated disorder in three of the four alkyl chains.
It is often postulated that rapid or `quench' cooling can cause dynamic motion to freeze in multiple disordered components to form a metastable structure, whereas slow cooling in such systems enables dynamic components to find a single global optimum position and achieve a more stable state. To test this in (I), the single crystal was warmed to 300 K and after a few minutes was cooled back to 250 K (at 120 K h-1), where data were collected. The crystal was then further cooled to 100 K (at 120 K h-1), where a third data collection was carried out for comparison. All three data collections were carried out in an identical manner and indexed on the same orientation matrix so that the first structure solution at 100 K could be used as the starting point for all refinements.
The structure consists of one ammonium cation and one bromide anion in the asymmetric unit (Fig. 1), both on general positions. Each bromide anion is surrounded by three cations, two of which are related by a twofold screw axis and the third related to the other two by a twofold rotor and a threefold screw axis, respectively (Fig. 2). Initially, each structure was refined without disorder and with anisotropic displacement parameters (ADPs) for each isohexyl group. The two structures at 100 K showed very little difference, so the disorder was modelled for the first 100 K data set and the model transferred to the other 100 K refinement. This model consisted of one ordered alkyl group (C11–C16), two where the terminal 3–5 atoms wagged (C31–C36 and C41–C46), and one where the end group wagged and is also rotated (C21–C26). On refinement against the data at 250 K, it was clear that the alkyl group that was ordered at 100 K (C11–C16) also appeared disordered. Although all of the ADPs increased in size between 100 and 250 K, the nature of the disorder showed little sign of change in the two wagging alkyl chains (C31–C36 and C41–C46; Fig. 3). A slight change in the orientation of the chain defined by atoms C21–C26 was observed. It is of note that the highest density of short contacts is between the minor component of the terminal methyl groups of this chain and their symmetry equivalents, suggesting that there is a correlation between the disorder in neighbouring molecules. At 250 K, there are additional contacts between the C21–C26 chain and the C11–C16 chain that is ordered at 100 K. It is possible, therefore, that the disorder seen in the C11–C16 chain at 250 K is correlated with increased motion in the C21–C26 chain.
In conclusion, in the case of this compound, the structure accessed by flash cooling to 100 K is the same as that achieved by a slower cooling regime. This suggests that the disorder at 100 K is dynamic in nature.