Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614022621/sk3567sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022621/sk3567Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022621/sk3567IIsup3.hkl |
CCDC references: 1029250; 1029251
In the course of our investigations of low-coordinate triele compounds (Wiberg et al., 1998; Budanow et al., 2012), we prepared (tBu3Si)2ECl from ECl3 (E = Al, Ga) and tri-tert-butylsilanide (supersilanide) Na[SitBu3] (Lerner, 2005). When ECl3 (E = Al, Ga) in pentane was treated with one or two molar equivalents of Na[SitBu3] (Lerner, 2005), the reaction mixture underwent a colour change to bright yellow (Wiberg et al., 1998). It is worth mentioning that in both cases we isolated colourless crystals of (tBu3Si)2ECl. Therefore, we suggested that in solution an equilibrium of (tBu3Si)2ECl and ECl3 (E = Al, Ga) with the related ion pairs [tBu3Si–E–SitBu3][ECl4] exists and the yellow colour proceeds from the cation [tBu3Si–E–SitBu3]+. However, up to now we could not isolate the ion pairs [tBu3Si–E–SitBu3][ECl4]. Very recently, we synthesized the two-coordinate cations [tBu3Si–E–SitBu3][Al{OC(CF3)3}4] (E = Al, Ga) (Budanow et al., 2012; Budanow, 2014). As a consequence thereof, the synthesis of [tBu3Si–E–SitBu3][ECl4] (E = Al, Ga) is now possible by the reaction of [tBu3Si–E–SitBu3][Al{OC(CF3)3}4] with [nBu4N][ECl4]. For this approach we synthesized [nBu4N][AlCl4] as a starting material. Apart from the benzene-free pseudopolymorph of (I), there is no structure in the Cambridge Crystallographic Database (Groom & Allen, 2014) containing the AlCl4 anion and an ammonium cation with the N atom bonded to four C atoms.
All experiments were carried out using standard Schlenk techniques. The ammonium salts were obtained from commercial sources and used as purchased. AlCl3 was prepared from Al and HCl gas. C6H6 was dried over Na and CH2Cl2 was dried over CaH2. The solvents were freshly distilled prior to use.
Compound (I) was crystallized from a 1:1 mixture of Bu4NCl and AlCl3 in C6H6. The mixture was stirred for 1 h and filtered through a paper filter. The crystals grew on the paper at the upper rim of the filter. Crystals of (II) grew when the solvent of a clear and colourless solution of Et4NCl and AlCl3 (1:1) in CH2Cl2 was evaporated slowly.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were refined using a riding model, with aromatic C—H = 0.95 Å, methyl C—H = 0.98 Å and methylene C—H = 0.99 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise.
Compound (II) is a nonmerohedral twin. The initial cell determination gave a trigonal cell (a = b = 16.242 Å, c = 12.902 Å, α = β = 90°, γ = 120°). However, since the Rint value (0.399) for merging the data in this setting was rather high, the data were transformed to an orthorhombic C-centred lattice with a = 16.242 Å, b = 28.131 Å and c = 12.902 Å, and α = β = γ = 90°, leading to an acceptable Rint value of 0.060. However, the space group extinctions (h0l for h=2n weak and h0l for h + l=2n weak) did not match any space group. A thorough inspection of the reflection data revealed that all reflections with an odd sum of h + k were significantly weaker [mean I/σ(I) = 4.2] than the remaining [mean I/σ(I) = 22.2] reflections. Thus, the cell was transformed by (0.5 0.5 0/0 0 1/-0.5 0.5 0) to an orthorhombic primitive one with a = 8.119 Å, b = 12.902 Å and c = 14.063 Å, and α = β = γ = 90°. Now the systematic absence exceptions pointed to the space group Pc21b which is just another setting of Pca21 (transformation matrix: 001/100/010). In this space group, the structure could be solved, but refinement did not proceed satisfactorily (wR2 = 0.374, R1 = 0.121 for all data; one nonpositive definite atom). As a result, it became obvious that the structure was twinned. A test for twinning with the TWINROTMAT option in PLATON (Spek, 2009) gave two twin laws, i.e. (0.503 1.491 0.000/0.501 -0.503 0.000/0.000 0.000 -1.000) and (-0.497 1.497 0.000/0.503 0.497 0.000/0.000 0.000 -1.000).
For the refinement, the reflection data have to be read in via the HKLF 5 option in SHELXL (Sheldrick, 2008) and two additional parameters, called BASF, describing the fractional contribution of the twin domains had to be introduced. With these modifications, the structure can be satisfactorily refined (Table 1). The fractional contributions of the two minor twin domains refined to 0.1622 (16) and 0.1636 (19).
Tetrabutylammonium tetrachloridoaluminate benzene hemisolvate, (I) crystallizes with discrete cations and anions and solvent molecules (Fig. 1). The benzene molecule is located on a centre of inversion. The four Al—Cl distances do not vary markedly [2.1195 (10)–2.1389 (11) Å; Table 2] and the six bond angles at Al are close to ideal tetrahedral values [108.12 (5)–111.33 (5)°] (Table 2). All four butyl chains of the cation display an all-trans conformation. The packing diagram (Fig. 2) shows that the three entities are located in layers parallel to the bc plane. There are two Al···N distances below 6 Å [N1···Al1 = 5.5296 (18) Å and N1···Al1i = 5.5764 (18) Å; symmetry code: (i) -x+1/2, y+1/2, -z+1/2] and five N···Cl contacts below 5 Å [N1···Cl3ii = 4.4060 (18) Å, N1···Cl1 = 4.4814 (18) Å, N1···Cl2i = 4.7479 (18) Å, N1···Cl4i = 4.753 (2) Å and N1···Cl2 = 4.8726 (18) Å; symmetry codes: (i) -x+1/2, y+1/2, -z+1/2; (ii) x+1, y, z]. The shortest Al···Al and N···N distances are listed in Table 3.
The structure of the benzene-free pseudo-polymorph of (I) has already been determined (Kanazawa et al., 2012), hereafter (Ia). It crystallizes with two half ions in the asymmetric unit, both of which are located on a twofold rotation axis parallel to [100]. The crystal packing (Fig. 3) shows that every cation is surrounded by six anions and vice versa. As a result, cations and anions are perfectly shielded from each other. There are two Al···N distances below 6 Å (5.766 Å) and four N···Cl contacts below 5 Å (4.471–4.523 Å). The shortest Al···Al and N···N distances are in the same range as for (I).
It is noteworthy, that tetra-n-butylammonium tetrabromidoaluminate (Rudawska-Frąckiewicz & Siekierski, 2004) is isomorphous (orthorhombic space group Pnna) with (Ia), whereas tetra-n-butylammonium tetraiodidoaluminate (Rogers et al., 1984) crystallizes in a different crystal system, i.e. monoclinic P21/n.
The crystal packing patterns of (I) and (Ia) resemble each other. The only difference is that in (I) additional solvent molecules are included in the crystal. Comparing the selected short distances in Table 3, there is only a difference for the N···N distances; the N···Al, N···Cl and Al···Al distances are in the same range.
Tetraethylammonium tetrachloridoaluminate, (II), also crystallizes with discrete cations and anions. The AlCl42- anion is essentially tetrahedral, with Al—Cl bond distances ranging from 2.1313 (14) Å for Al1—Cl3 to 2.1383 (14) Å for Al1—Cl4 (Table 4). The bond angles at Al are almost equal [108.14 (6)–110.38 (6)°; Table 4]. The bond lengths and angles at atom N1 differ slightly more from ideal tetrahedral values [1.503 (5)–1.524 (4) Å and 107.7 (3)–111.6 (3)°; Table 4]. The ions form layers in the ac plane.
There are five N···Al distances below 6 Å ranging from 5.537 (8) [symmetry code for Al1 (x, y-1, z)] to 5.832 (8) Å [symmetry code for Al1 (-x+1/2, y, z-1/2)] and 11 N···Cl distances below 5 Å ranging from 4.460 (9) (N1···Cl1) to 4.999 Å [N1···Cl1(x, -y+1, z-1/2)].
Due to the change of butyl chains to ethyl chains, the cations of (II) are smaller than in (I) and (Ia). As a result, the Al···Al and N···N distances become significantly shorter (Table 3). On the other hand, the shortest N···Al and N···Cl distances do not show marked differences.
For both compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SHELXS97(Sheldrick, 2008) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(C16H36N)[AlCl4]·0.5C6H6 | F(000) = 964 |
Mr = 450.29 | Dx = 1.154 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6887 (5) Å | Cell parameters from 29120 reflections |
b = 13.8505 (5) Å | θ = 1.9–26.7° |
c = 17.5554 (10) Å | µ = 0.49 mm−1 |
β = 93.926 (4)° | T = 173 K |
V = 2592.9 (2) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.30 × 0.30 mm |
Stoe IPDS II two-circle diffractometer | 4643 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.072 |
ω scans | θmax = 26.2°, θmin = 2.3° |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −13→13 |
Tmin = 0.781, Tmax = 0.844 | k = −16→17 |
20778 measured reflections | l = −21→21 |
5137 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.0825P)2 + 1.8021P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
5137 reflections | Δρmax = 1.15 e Å−3 |
226 parameters | Δρmin = −0.66 e Å−3 |
(C16H36N)[AlCl4]·0.5C6H6 | V = 2592.9 (2) Å3 |
Mr = 450.29 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.6887 (5) Å | µ = 0.49 mm−1 |
b = 13.8505 (5) Å | T = 173 K |
c = 17.5554 (10) Å | 0.40 × 0.30 × 0.30 mm |
β = 93.926 (4)° |
Stoe IPDS II two-circle diffractometer | 5137 independent reflections |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | 4643 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.844 | Rint = 0.072 |
20778 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.15 e Å−3 |
5137 reflections | Δρmin = −0.66 e Å−3 |
226 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Al1 | 0.04187 (7) | 0.64919 (5) | 0.23509 (4) | 0.0440 (2) | |
Cl1 | 0.14201 (7) | 0.77756 (5) | 0.21111 (4) | 0.0557 (2) | |
Cl2 | 0.17312 (6) | 0.54100 (5) | 0.27113 (5) | 0.0612 (2) | |
Cl3 | −0.07795 (8) | 0.67600 (6) | 0.32452 (6) | 0.0748 (3) | |
Cl4 | −0.06447 (10) | 0.59758 (8) | 0.13572 (6) | 0.0954 (4) | |
N1 | 0.52474 (15) | 0.75811 (12) | 0.33139 (10) | 0.0306 (4) | |
C1 | 0.6011 (2) | 0.81451 (15) | 0.27622 (12) | 0.0337 (4) | |
H1A | 0.6239 | 0.8776 | 0.2997 | 0.040* | |
H1B | 0.6800 | 0.7789 | 0.2698 | 0.040* | |
C2 | 0.5368 (2) | 0.83264 (17) | 0.19788 (13) | 0.0412 (5) | |
H2A | 0.5244 | 0.7706 | 0.1704 | 0.049* | |
H2B | 0.4534 | 0.8620 | 0.2033 | 0.049* | |
C3 | 0.6156 (3) | 0.8996 (2) | 0.15254 (14) | 0.0504 (6) | |
H3A | 0.6954 | 0.8671 | 0.1428 | 0.061* | |
H3B | 0.6360 | 0.9583 | 0.1831 | 0.061* | |
C4 | 0.5489 (3) | 0.9287 (3) | 0.07683 (16) | 0.0649 (8) | |
H4A | 0.6030 | 0.9719 | 0.0495 | 0.097* | |
H4B | 0.4706 | 0.9621 | 0.0862 | 0.097* | |
H4C | 0.5301 | 0.8709 | 0.0460 | 0.097* | |
C5 | 0.47169 (19) | 0.66614 (14) | 0.29444 (13) | 0.0345 (4) | |
H5A | 0.4280 | 0.6295 | 0.3331 | 0.041* | |
H5B | 0.4083 | 0.6842 | 0.2531 | 0.041* | |
C6 | 0.5675 (2) | 0.60024 (16) | 0.26130 (16) | 0.0438 (5) | |
H6A | 0.6155 | 0.6369 | 0.2247 | 0.053* | |
H6B | 0.6272 | 0.5767 | 0.3028 | 0.053* | |
C7 | 0.5038 (2) | 0.51476 (16) | 0.22092 (14) | 0.0415 (5) | |
H7A | 0.4625 | 0.4751 | 0.2588 | 0.050* | |
H7B | 0.4379 | 0.5388 | 0.1833 | 0.050* | |
C8 | 0.5933 (3) | 0.4524 (2) | 0.1806 (2) | 0.0659 (8) | |
H8A | 0.5474 | 0.3983 | 0.1559 | 0.099* | |
H8B | 0.6580 | 0.4274 | 0.2176 | 0.099* | |
H8C | 0.6327 | 0.4907 | 0.1419 | 0.099* | |
C9 | 0.41782 (19) | 0.82216 (15) | 0.35351 (13) | 0.0354 (4) | |
H9A | 0.3642 | 0.8369 | 0.3067 | 0.042* | |
H9B | 0.4539 | 0.8840 | 0.3729 | 0.042* | |
C10 | 0.3346 (2) | 0.78246 (17) | 0.41280 (14) | 0.0408 (5) | |
H10A | 0.3866 | 0.7620 | 0.4588 | 0.049* | |
H10B | 0.2878 | 0.7255 | 0.3920 | 0.049* | |
C11 | 0.2432 (3) | 0.8606 (2) | 0.43385 (17) | 0.0541 (6) | |
H11A | 0.2911 | 0.9159 | 0.4566 | 0.065* | |
H11B | 0.1961 | 0.8837 | 0.3869 | 0.065* | |
C12 | 0.1513 (3) | 0.8257 (3) | 0.4897 (2) | 0.0723 (9) | |
H12A | 0.0949 | 0.8787 | 0.5014 | 0.109* | |
H12B | 0.1973 | 0.8039 | 0.5367 | 0.109* | |
H12C | 0.1020 | 0.7720 | 0.4669 | 0.109* | |
C13 | 0.61026 (19) | 0.73041 (15) | 0.40056 (12) | 0.0337 (4) | |
H13A | 0.5636 | 0.6866 | 0.4330 | 0.040* | |
H13B | 0.6822 | 0.6937 | 0.3828 | 0.040* | |
C14 | 0.6609 (2) | 0.81388 (17) | 0.44949 (13) | 0.0396 (5) | |
H14A | 0.6981 | 0.8629 | 0.4168 | 0.048* | |
H14B | 0.5916 | 0.8446 | 0.4752 | 0.048* | |
C15 | 0.7598 (3) | 0.7778 (2) | 0.50888 (14) | 0.0508 (6) | |
H15A | 0.7218 | 0.7289 | 0.5414 | 0.061* | |
H15B | 0.8279 | 0.7461 | 0.4828 | 0.061* | |
C16 | 0.8147 (3) | 0.8585 (2) | 0.55898 (16) | 0.0570 (7) | |
H16A | 0.8784 | 0.8320 | 0.5961 | 0.085* | |
H16B | 0.7480 | 0.8890 | 0.5861 | 0.085* | |
H16C | 0.8534 | 0.9067 | 0.5271 | 0.085* | |
C21 | −0.0328 (4) | 0.9353 (2) | 0.05424 (18) | 0.0691 (9) | |
H21 | −0.0565 | 0.8904 | 0.0915 | 0.083* | |
C22 | −0.1185 (3) | 0.9645 (2) | −0.0030 (2) | 0.0713 (9) | |
H22 | −0.2015 | 0.9396 | −0.0051 | 0.086* | |
C23 | −0.0848 (4) | 1.0298 (2) | −0.05744 (18) | 0.0659 (8) | |
H23 | −0.1444 | 1.0499 | −0.0969 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Al1 | 0.0351 (4) | 0.0420 (4) | 0.0545 (4) | −0.0019 (3) | 0.0003 (3) | −0.0010 (3) |
Cl1 | 0.0558 (4) | 0.0428 (3) | 0.0686 (4) | −0.0031 (3) | 0.0066 (3) | 0.0098 (3) |
Cl2 | 0.0422 (3) | 0.0436 (4) | 0.0982 (6) | 0.0037 (3) | 0.0086 (3) | 0.0057 (3) |
Cl3 | 0.0619 (5) | 0.0603 (5) | 0.1069 (7) | 0.0075 (3) | 0.0408 (4) | −0.0004 (4) |
Cl4 | 0.0945 (7) | 0.1003 (7) | 0.0853 (6) | −0.0225 (6) | −0.0387 (5) | −0.0065 (5) |
N1 | 0.0276 (8) | 0.0271 (8) | 0.0367 (9) | −0.0008 (6) | 0.0003 (6) | 0.0025 (7) |
C1 | 0.0328 (10) | 0.0321 (10) | 0.0360 (10) | −0.0044 (8) | 0.0003 (8) | 0.0061 (8) |
C2 | 0.0447 (12) | 0.0425 (12) | 0.0357 (11) | −0.0014 (10) | −0.0023 (9) | 0.0032 (9) |
C3 | 0.0538 (14) | 0.0565 (15) | 0.0411 (12) | 0.0021 (12) | 0.0040 (11) | 0.0157 (11) |
C4 | 0.077 (2) | 0.077 (2) | 0.0408 (13) | 0.0145 (16) | 0.0046 (13) | 0.0165 (13) |
C5 | 0.0305 (10) | 0.0277 (10) | 0.0449 (11) | −0.0034 (8) | −0.0002 (8) | 0.0002 (8) |
C6 | 0.0326 (11) | 0.0345 (11) | 0.0640 (15) | 0.0007 (9) | 0.0021 (10) | −0.0071 (10) |
C7 | 0.0397 (11) | 0.0339 (11) | 0.0504 (13) | 0.0017 (9) | −0.0013 (9) | −0.0033 (9) |
C8 | 0.0523 (15) | 0.0499 (16) | 0.096 (2) | 0.0045 (13) | 0.0076 (15) | −0.0250 (15) |
C9 | 0.0306 (10) | 0.0299 (10) | 0.0454 (11) | 0.0034 (8) | 0.0011 (8) | 0.0045 (8) |
C10 | 0.0351 (11) | 0.0385 (11) | 0.0494 (13) | 0.0016 (9) | 0.0074 (9) | 0.0039 (9) |
C11 | 0.0426 (13) | 0.0542 (15) | 0.0669 (16) | 0.0105 (11) | 0.0146 (12) | 0.0021 (13) |
C12 | 0.0513 (16) | 0.089 (2) | 0.080 (2) | 0.0063 (16) | 0.0264 (15) | −0.0020 (18) |
C13 | 0.0312 (10) | 0.0336 (10) | 0.0359 (10) | 0.0028 (8) | 0.0002 (8) | 0.0067 (8) |
C14 | 0.0401 (11) | 0.0393 (11) | 0.0389 (11) | −0.0018 (9) | −0.0017 (9) | 0.0022 (9) |
C15 | 0.0565 (15) | 0.0523 (14) | 0.0417 (12) | 0.0092 (12) | −0.0095 (11) | −0.0022 (11) |
C16 | 0.0571 (16) | 0.0672 (17) | 0.0447 (13) | 0.0022 (13) | −0.0107 (11) | −0.0068 (12) |
C21 | 0.106 (3) | 0.0486 (15) | 0.0554 (16) | 0.0004 (17) | 0.0273 (17) | −0.0043 (13) |
C22 | 0.0611 (18) | 0.0637 (19) | 0.091 (2) | −0.0059 (15) | 0.0170 (17) | −0.0332 (18) |
C23 | 0.084 (2) | 0.0569 (17) | 0.0552 (16) | 0.0186 (16) | −0.0095 (15) | −0.0169 (13) |
Al1—Cl2 | 2.1195 (10) | C9—C10 | 1.518 (3) |
Al1—Cl3 | 2.1257 (11) | C9—H9A | 0.9900 |
Al1—Cl1 | 2.1321 (10) | C9—H9B | 0.9900 |
Al1—Cl4 | 2.1389 (11) | C10—C11 | 1.520 (3) |
N1—C9 | 1.518 (3) | C10—H10A | 0.9900 |
N1—C13 | 1.518 (3) | C10—H10B | 0.9900 |
N1—C5 | 1.521 (3) | C11—C12 | 1.514 (4) |
N1—C1 | 1.524 (3) | C11—H11A | 0.9900 |
C1—C2 | 1.516 (3) | C11—H11B | 0.9900 |
C1—H1A | 0.9900 | C12—H12A | 0.9800 |
C1—H1B | 0.9900 | C12—H12B | 0.9800 |
C2—C3 | 1.515 (3) | C12—H12C | 0.9800 |
C2—H2A | 0.9900 | C13—C14 | 1.518 (3) |
C2—H2B | 0.9900 | C13—H13A | 0.9900 |
C3—C4 | 1.519 (4) | C13—H13B | 0.9900 |
C3—H3A | 0.9900 | C14—C15 | 1.517 (3) |
C3—H3B | 0.9900 | C14—H14A | 0.9900 |
C4—H4A | 0.9800 | C14—H14B | 0.9900 |
C4—H4B | 0.9800 | C15—C16 | 1.516 (4) |
C4—H4C | 0.9800 | C15—H15A | 0.9900 |
C5—C6 | 1.517 (3) | C15—H15B | 0.9900 |
C5—H5A | 0.9900 | C16—H16A | 0.9800 |
C5—H5B | 0.9900 | C16—H16B | 0.9800 |
C6—C7 | 1.517 (3) | C16—H16C | 0.9800 |
C6—H6A | 0.9900 | C21—C23i | 1.344 (5) |
C6—H6B | 0.9900 | C21—C22 | 1.373 (5) |
C7—C8 | 1.502 (4) | C21—H21 | 0.9500 |
C7—H7A | 0.9900 | C22—C23 | 1.382 (5) |
C7—H7B | 0.9900 | C22—H22 | 0.9500 |
C8—H8A | 0.9800 | C23—C21i | 1.344 (5) |
C8—H8B | 0.9800 | C23—H23 | 0.9500 |
C8—H8C | 0.9800 | ||
Cl2—Al1—Cl3 | 108.84 (5) | H8B—C8—H8C | 109.5 |
Cl2—Al1—Cl1 | 108.52 (4) | N1—C9—C10 | 116.78 (17) |
Cl3—Al1—Cl1 | 109.64 (5) | N1—C9—H9A | 108.1 |
Cl2—Al1—Cl4 | 108.12 (5) | C10—C9—H9A | 108.1 |
Cl3—Al1—Cl4 | 110.33 (5) | N1—C9—H9B | 108.1 |
Cl1—Al1—Cl4 | 111.33 (5) | C10—C9—H9B | 108.1 |
C9—N1—C13 | 111.45 (16) | H9A—C9—H9B | 107.3 |
C9—N1—C5 | 109.46 (15) | C9—C10—C11 | 108.97 (19) |
C13—N1—C5 | 108.41 (15) | C9—C10—H10A | 109.9 |
C9—N1—C1 | 107.96 (15) | C11—C10—H10A | 109.9 |
C13—N1—C1 | 108.56 (15) | C9—C10—H10B | 109.9 |
C5—N1—C1 | 111.01 (16) | C11—C10—H10B | 109.9 |
C2—C1—N1 | 115.61 (17) | H10A—C10—H10B | 108.3 |
C2—C1—H1A | 108.4 | C12—C11—C10 | 112.7 (2) |
N1—C1—H1A | 108.4 | C12—C11—H11A | 109.0 |
C2—C1—H1B | 108.4 | C10—C11—H11A | 109.0 |
N1—C1—H1B | 108.4 | C12—C11—H11B | 109.0 |
H1A—C1—H1B | 107.4 | C10—C11—H11B | 109.0 |
C3—C2—C1 | 110.15 (19) | H11A—C11—H11B | 107.8 |
C3—C2—H2A | 109.6 | C11—C12—H12A | 109.5 |
C1—C2—H2A | 109.6 | C11—C12—H12B | 109.5 |
C3—C2—H2B | 109.6 | H12A—C12—H12B | 109.5 |
C1—C2—H2B | 109.6 | C11—C12—H12C | 109.5 |
H2A—C2—H2B | 108.1 | H12A—C12—H12C | 109.5 |
C2—C3—C4 | 112.2 (2) | H12B—C12—H12C | 109.5 |
C2—C3—H3A | 109.2 | C14—C13—N1 | 115.60 (17) |
C4—C3—H3A | 109.2 | C14—C13—H13A | 108.4 |
C2—C3—H3B | 109.2 | N1—C13—H13A | 108.4 |
C4—C3—H3B | 109.2 | C14—C13—H13B | 108.4 |
H3A—C3—H3B | 107.9 | N1—C13—H13B | 108.4 |
C3—C4—H4A | 109.5 | H13A—C13—H13B | 107.4 |
C3—C4—H4B | 109.5 | C15—C14—C13 | 110.05 (19) |
H4A—C4—H4B | 109.5 | C15—C14—H14A | 109.7 |
C3—C4—H4C | 109.5 | C13—C14—H14A | 109.7 |
H4A—C4—H4C | 109.5 | C15—C14—H14B | 109.7 |
H4B—C4—H4C | 109.5 | C13—C14—H14B | 109.7 |
C6—C5—N1 | 115.19 (17) | H14A—C14—H14B | 108.2 |
C6—C5—H5A | 108.5 | C16—C15—C14 | 112.3 (2) |
N1—C5—H5A | 108.5 | C16—C15—H15A | 109.1 |
C6—C5—H5B | 108.5 | C14—C15—H15A | 109.1 |
N1—C5—H5B | 108.5 | C16—C15—H15B | 109.1 |
H5A—C5—H5B | 107.5 | C14—C15—H15B | 109.1 |
C7—C6—C5 | 110.83 (18) | H15A—C15—H15B | 107.9 |
C7—C6—H6A | 109.5 | C15—C16—H16A | 109.5 |
C5—C6—H6A | 109.5 | C15—C16—H16B | 109.5 |
C7—C6—H6B | 109.5 | H16A—C16—H16B | 109.5 |
C5—C6—H6B | 109.5 | C15—C16—H16C | 109.5 |
H6A—C6—H6B | 108.1 | H16A—C16—H16C | 109.5 |
C8—C7—C6 | 112.9 (2) | H16B—C16—H16C | 109.5 |
C8—C7—H7A | 109.0 | C23i—C21—C22 | 120.0 (3) |
C6—C7—H7A | 109.0 | C23i—C21—H21 | 120.0 |
C8—C7—H7B | 109.0 | C22—C21—H21 | 120.0 |
C6—C7—H7B | 109.0 | C21—C22—C23 | 120.5 (3) |
H7A—C7—H7B | 107.8 | C21—C22—H22 | 119.8 |
C7—C8—H8A | 109.5 | C23—C22—H22 | 119.8 |
C7—C8—H8B | 109.5 | C21i—C23—C22 | 119.6 (3) |
H8A—C8—H8B | 109.5 | C21i—C23—H23 | 120.2 |
C7—C8—H8C | 109.5 | C22—C23—H23 | 120.2 |
H8A—C8—H8C | 109.5 | ||
C9—N1—C1—C2 | −69.5 (2) | C5—N1—C9—C10 | 63.2 (2) |
C13—N1—C1—C2 | 169.55 (18) | C1—N1—C9—C10 | −175.89 (18) |
C5—N1—C1—C2 | 50.5 (2) | N1—C9—C10—C11 | 173.7 (2) |
N1—C1—C2—C3 | 172.87 (19) | C9—C10—C11—C12 | 176.8 (2) |
C1—C2—C3—C4 | −173.9 (2) | C9—N1—C13—C14 | −53.3 (2) |
C9—N1—C5—C6 | 173.39 (19) | C5—N1—C13—C14 | −173.80 (18) |
C13—N1—C5—C6 | −64.8 (2) | C1—N1—C13—C14 | 65.5 (2) |
C1—N1—C5—C6 | 54.3 (2) | N1—C13—C14—C15 | −171.30 (19) |
N1—C5—C6—C7 | −175.83 (18) | C13—C14—C15—C16 | 179.4 (2) |
C5—C6—C7—C8 | 174.4 (2) | C23i—C21—C22—C23 | −0.1 (5) |
C13—N1—C9—C10 | −56.7 (2) | C21—C22—C23—C21i | 0.1 (5) |
Symmetry code: (i) −x, −y+2, −z. |
(C8H20N)[AlCl4] | Dx = 1.349 Mg m−3 |
Mr = 299.03 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 13398 reflections |
a = 14.0348 (10) Å | θ = 3.2–26.4° |
b = 8.1362 (7) Å | µ = 0.83 mm−1 |
c = 12.8892 (12) Å | T = 173 K |
V = 1471.8 (2) Å3 | Block, colourless |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
F(000) = 624 |
Stoe IPDS II two-circle- diffractometer | 2423 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.028 |
ω scans | θmax = 25.8°, θmin = 4.0° |
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001) | h = 0→15 |
Tmin = 0.897, Tmax = 0.904 | k = −4→9 |
6472 measured reflections | l = −15→15 |
2522 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0263P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.052 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.20 e Å−3 |
2522 reflections | Δρmin = −0.15 e Å−3 |
129 parameters | Absolute structure: Flack x determined using 1046 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: −0.04 (5) |
(C8H20N)[AlCl4] | V = 1471.8 (2) Å3 |
Mr = 299.03 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 14.0348 (10) Å | µ = 0.83 mm−1 |
b = 8.1362 (7) Å | T = 173 K |
c = 12.8892 (12) Å | 0.10 × 0.10 × 0.10 mm |
Stoe IPDS II two-circle- diffractometer | 2522 independent reflections |
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001) | 2423 reflections with I > 2σ(I) |
Tmin = 0.897, Tmax = 0.904 | Rint = 0.028 |
6472 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.052 | Δρmax = 0.20 e Å−3 |
S = 1.10 | Δρmin = −0.15 e Å−3 |
2522 reflections | Absolute structure: Flack x determined using 1046 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
129 parameters | Absolute structure parameter: −0.04 (5) |
1 restraint |
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. Refined as a 3-component twin. |
x | y | z | Uiso*/Ueq | ||
Al1 | 0.24065 (8) | 0.72153 (13) | 0.52107 (7) | 0.0232 (2) | |
Cl1 | 0.10146 (7) | 0.69274 (11) | 0.45644 (7) | 0.0306 (2) | |
Cl2 | 0.23073 (8) | 0.72358 (13) | 0.68639 (6) | 0.0335 (2) | |
Cl3 | 0.32847 (7) | 0.52335 (10) | 0.47060 (7) | 0.0309 (2) | |
Cl4 | 0.30042 (7) | 0.95065 (10) | 0.47242 (7) | 0.0334 (2) | |
N1 | 0.0859 (2) | 0.2192 (4) | 0.2809 (2) | 0.0203 (6) | |
C1 | 0.0915 (3) | 0.0357 (4) | 0.2601 (3) | 0.0253 (8) | |
H1A | 0.1239 | 0.0186 | 0.1927 | 0.030* | |
H1B | 0.1315 | −0.0154 | 0.3145 | 0.030* | |
C2 | −0.0035 (3) | −0.0524 (5) | 0.2574 (3) | 0.0315 (9) | |
H2A | 0.0069 | −0.1695 | 0.2435 | 0.047* | |
H2B | −0.0356 | −0.0394 | 0.3244 | 0.047* | |
H2C | −0.0433 | −0.0053 | 0.2024 | 0.047* | |
C3 | 0.1843 (3) | 0.2859 (5) | 0.2990 (3) | 0.0262 (8) | |
H3A | 0.2099 | 0.2359 | 0.3632 | 0.031* | |
H3B | 0.1793 | 0.4057 | 0.3110 | 0.031* | |
C4 | 0.2555 (4) | 0.2571 (5) | 0.2122 (4) | 0.0392 (10) | |
H4A | 0.3171 | 0.3049 | 0.2314 | 0.059* | |
H4B | 0.2630 | 0.1387 | 0.2007 | 0.059* | |
H4C | 0.2323 | 0.3091 | 0.1484 | 0.059* | |
C5 | 0.0245 (3) | 0.2566 (4) | 0.3755 (3) | 0.0253 (8) | |
H5A | 0.0255 | 0.3767 | 0.3878 | 0.030* | |
H5B | −0.0421 | 0.2254 | 0.3596 | 0.030* | |
C6 | 0.0545 (3) | 0.1703 (5) | 0.4745 (3) | 0.0353 (9) | |
H6A | 0.0113 | 0.2014 | 0.5309 | 0.053* | |
H6B | 0.0519 | 0.0511 | 0.4641 | 0.053* | |
H6C | 0.1197 | 0.2028 | 0.4924 | 0.053* | |
C7 | 0.0390 (3) | 0.2995 (4) | 0.1872 (3) | 0.0247 (8) | |
H7A | 0.0794 | 0.2792 | 0.1255 | 0.030* | |
H7B | −0.0232 | 0.2453 | 0.1748 | 0.030* | |
C8 | 0.0225 (3) | 0.4827 (5) | 0.1968 (3) | 0.0318 (9) | |
H8A | −0.0078 | 0.5237 | 0.1333 | 0.048* | |
H8B | −0.0191 | 0.5045 | 0.2563 | 0.048* | |
H8C | 0.0837 | 0.5385 | 0.2069 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Al1 | 0.0224 (7) | 0.0241 (5) | 0.0232 (4) | −0.0009 (5) | 0.0001 (4) | 0.0001 (4) |
Cl1 | 0.0257 (5) | 0.0346 (4) | 0.0316 (4) | −0.0019 (4) | −0.0057 (4) | −0.0010 (4) |
Cl2 | 0.0347 (6) | 0.0432 (6) | 0.0227 (4) | −0.0013 (4) | 0.0002 (4) | −0.0022 (4) |
Cl3 | 0.0305 (5) | 0.0293 (4) | 0.0329 (4) | 0.0041 (3) | 0.0020 (5) | −0.0020 (4) |
Cl4 | 0.0309 (5) | 0.0267 (4) | 0.0426 (5) | −0.0040 (3) | 0.0023 (5) | 0.0043 (4) |
N1 | 0.0194 (18) | 0.0185 (14) | 0.0230 (13) | 0.0018 (13) | −0.0014 (11) | −0.0014 (11) |
C1 | 0.030 (2) | 0.0179 (16) | 0.0279 (16) | 0.0030 (15) | −0.0003 (15) | −0.0033 (13) |
C2 | 0.036 (3) | 0.0228 (18) | 0.035 (2) | −0.0044 (16) | −0.0038 (17) | −0.0036 (15) |
C3 | 0.022 (2) | 0.0243 (17) | 0.0325 (19) | 0.0016 (16) | −0.0056 (15) | −0.0012 (13) |
C4 | 0.026 (3) | 0.042 (2) | 0.050 (3) | −0.003 (2) | 0.0057 (16) | 0.0025 (18) |
C5 | 0.025 (3) | 0.026 (2) | 0.0249 (18) | 0.0024 (14) | 0.0027 (15) | −0.0054 (12) |
C6 | 0.040 (3) | 0.041 (2) | 0.0251 (18) | 0.0050 (17) | 0.0029 (18) | −0.0042 (18) |
C7 | 0.022 (2) | 0.0283 (18) | 0.0235 (15) | 0.0045 (15) | −0.0027 (14) | 0.0022 (15) |
C8 | 0.033 (3) | 0.023 (2) | 0.0388 (19) | 0.0018 (17) | −0.0032 (17) | 0.0071 (16) |
Al1—Cl3 | 2.1313 (14) | C3—H3B | 0.9900 |
Al1—Cl2 | 2.1354 (11) | C4—H4A | 0.9800 |
Al1—Cl1 | 2.1365 (14) | C4—H4B | 0.9800 |
Al1—Cl4 | 2.1383 (14) | C4—H4C | 0.9800 |
N1—C3 | 1.503 (5) | C5—C6 | 1.516 (5) |
N1—C1 | 1.519 (4) | C5—H5A | 0.9900 |
N1—C5 | 1.523 (4) | C5—H5B | 0.9900 |
N1—C7 | 1.524 (4) | C6—H6A | 0.9800 |
C1—C2 | 1.514 (5) | C6—H6B | 0.9800 |
C1—H1A | 0.9900 | C6—H6C | 0.9800 |
C1—H1B | 0.9900 | C7—C8 | 1.513 (5) |
C2—H2A | 0.9800 | C7—H7A | 0.9900 |
C2—H2B | 0.9800 | C7—H7B | 0.9900 |
C2—H2C | 0.9800 | C8—H8A | 0.9800 |
C3—C4 | 1.518 (6) | C8—H8B | 0.9800 |
C3—H3A | 0.9900 | C8—H8C | 0.9800 |
Cl3—Al1—Cl2 | 110.38 (6) | C3—C4—H4A | 109.5 |
Cl3—Al1—Cl1 | 109.08 (6) | C3—C4—H4B | 109.5 |
Cl2—Al1—Cl1 | 109.29 (7) | H4A—C4—H4B | 109.5 |
Cl3—Al1—Cl4 | 110.07 (6) | C3—C4—H4C | 109.5 |
Cl2—Al1—Cl4 | 108.14 (6) | H4A—C4—H4C | 109.5 |
Cl1—Al1—Cl4 | 109.87 (6) | H4B—C4—H4C | 109.5 |
C3—N1—C1 | 109.5 (3) | C6—C5—N1 | 115.0 (3) |
C3—N1—C5 | 108.9 (3) | C6—C5—H5A | 108.5 |
C1—N1—C5 | 111.6 (3) | N1—C5—H5A | 108.5 |
C3—N1—C7 | 111.4 (3) | C6—C5—H5B | 108.5 |
C1—N1—C7 | 107.7 (3) | N1—C5—H5B | 108.5 |
C5—N1—C7 | 107.7 (3) | H5A—C5—H5B | 107.5 |
C2—C1—N1 | 115.1 (3) | C5—C6—H6A | 109.5 |
C2—C1—H1A | 108.5 | C5—C6—H6B | 109.5 |
N1—C1—H1A | 108.5 | H6A—C6—H6B | 109.5 |
C2—C1—H1B | 108.5 | C5—C6—H6C | 109.5 |
N1—C1—H1B | 108.5 | H6A—C6—H6C | 109.5 |
H1A—C1—H1B | 107.5 | H6B—C6—H6C | 109.5 |
C1—C2—H2A | 109.5 | C8—C7—N1 | 115.1 (3) |
C1—C2—H2B | 109.5 | C8—C7—H7A | 108.5 |
H2A—C2—H2B | 109.5 | N1—C7—H7A | 108.5 |
C1—C2—H2C | 109.5 | C8—C7—H7B | 108.5 |
H2A—C2—H2C | 109.5 | N1—C7—H7B | 108.5 |
H2B—C2—H2C | 109.5 | H7A—C7—H7B | 107.5 |
N1—C3—C4 | 115.8 (3) | C7—C8—H8A | 109.5 |
N1—C3—H3A | 108.3 | C7—C8—H8B | 109.5 |
C4—C3—H3A | 108.3 | H8A—C8—H8B | 109.5 |
N1—C3—H3B | 108.3 | C7—C8—H8C | 109.5 |
C4—C3—H3B | 108.3 | H8A—C8—H8C | 109.5 |
H3A—C3—H3B | 107.4 | H8B—C8—H8C | 109.5 |
C3—N1—C1—C2 | 170.8 (3) | C3—N1—C5—C6 | −65.5 (4) |
C5—N1—C1—C2 | 50.1 (4) | C1—N1—C5—C6 | 55.6 (4) |
C7—N1—C1—C2 | −67.9 (4) | C7—N1—C5—C6 | 173.6 (3) |
C1—N1—C3—C4 | 57.0 (4) | C3—N1—C7—C8 | −63.0 (4) |
C5—N1—C3—C4 | 179.3 (3) | C1—N1—C7—C8 | 176.8 (3) |
C7—N1—C3—C4 | −62.0 (4) | C5—N1—C7—C8 | 56.4 (4) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C16H36N)[AlCl4]·0.5C6H6 | (C8H20N)[AlCl4] |
Mr | 450.29 | 299.03 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pca21 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 10.6887 (5), 13.8505 (5), 17.5554 (10) | 14.0348 (10), 8.1362 (7), 12.8892 (12) |
α, β, γ (°) | 90, 93.926 (4), 90 | 90, 90, 90 |
V (Å3) | 2592.9 (2) | 1471.8 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.49 | 0.83 |
Crystal size (mm) | 0.40 × 0.30 × 0.30 | 0.10 × 0.10 × 0.10 |
Data collection | ||
Diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle- diffractometer |
Absorption correction | Multi-scan (X-AREA; Stoe & Cie, 2001) | Multi-scan X-AREA (Stoe & Cie, 2001) |
Tmin, Tmax | 0.781, 0.844 | 0.897, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20778, 5137, 4643 | 6472, 2522, 2423 |
Rint | 0.072 | 0.028 |
(sin θ/λ)max (Å−1) | 0.621 | 0.613 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.162, 1.04 | 0.023, 0.052, 1.10 |
No. of reflections | 5137 | 2522 |
No. of parameters | 226 | 129 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.15, −0.66 | 0.20, −0.15 |
Absolute structure | ? | Flack x determined using 1046 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | ? | −0.04 (5) |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXS97(Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Al1—Cl2 | 2.1195 (10) | Al1—Cl1 | 2.1321 (10) |
Al1—Cl3 | 2.1257 (11) | Al1—Cl4 | 2.1389 (11) |
Cl2—Al1—Cl3 | 108.84 (5) | Cl2—Al1—Cl4 | 108.12 (5) |
Cl2—Al1—Cl1 | 108.52 (4) | Cl3—Al1—Cl4 | 110.33 (5) |
Cl3—Al1—Cl1 | 109.64 (5) | Cl1—Al1—Cl4 | 111.33 (5) |
Structure | N···Al | N···Cl | Al···Al | N···N |
(I) | 5.5296 (18) | 4.4060 (18)i | 8.2286 (8)ii | 8.981 (3)iii |
(Ia) | 5.766 | 4.471iv | 8.213v | 8.431vi |
(II) | 5.537 (8)vii | 4.460 (9) | 6.4492 (6)viii | 7.748 (9)ix |
Atom name and symmetry operators for generating the equivalent of the second atom: (i) N1···Cl3 (x+1, y , z); (ii) Al1···Al1 (-x+1/2, y+1/2, -z+1/2); (iii) N1···N1 (-x+1, y+2, -z+1); (iv) N1···Cl2 (-x+1, y+1, -z); (v) Al1···Al1 (-x+1, y+1, -z); (vi) N1···N1 (-x+1, y+1, -z); (vii) N1···Al1 (x, y-1, z); (viii) Al1···Al1 (-x+1/2, y, z+1/2); (ix) N1···N1 (-x, -y, z+1/2). |
Al1—Cl3 | 2.1313 (14) | N1—C1 | 1.519 (4) |
Al1—Cl2 | 2.1354 (11) | N1—C5 | 1.523 (4) |
Al1—Cl1 | 2.1365 (14) | N1—C7 | 1.524 (4) |
Al1—Cl4 | 2.1383 (14) | C1—C2 | 1.514 (5) |
N1—C3 | 1.503 (5) | ||
Cl3—Al1—Cl2 | 110.38 (6) | C3—N1—C1 | 109.5 (3) |
Cl3—Al1—Cl1 | 109.08 (6) | C3—N1—C5 | 108.9 (3) |
Cl2—Al1—Cl1 | 109.29 (7) | C1—N1—C5 | 111.6 (3) |
Cl3—Al1—Cl4 | 110.07 (6) | C3—N1—C7 | 111.4 (3) |
Cl2—Al1—Cl4 | 108.14 (6) | C1—N1—C7 | 107.7 (3) |
Cl1—Al1—Cl4 | 109.87 (6) | C5—N1—C7 | 107.7 (3) |