Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803002022/cf6234sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803002022/cf6234Isup2.hkl |
CCDC reference: 204723
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (N-C) = 0.008 Å
- Disorder in solvent or counterion
- R factor = 0.033
- wR factor = 0.072
- Data-to-parameter ratio = 21.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 25.00 Perc.
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound, (I), was obtained by stirring a solution of 0.107 g 1-(dibromoboryl)ferrocene–dimethylethylamine (1/1) in 10 ml CH2Cl2 in the presence of 0.05 ml H2O at ambient temperature. The solution was subjected to gas-phase diffusion of diethyl ether, to yield colourless crystals of [HNEtMe2]Br. The NMR spectra were recorded on a Bruker AM 250 spectrometer. [HNEtMe2]Br: 1H NMR (CDCl3, internal TMS): δ 1.45 (t, CH3, 3J = 7.2 Hz), 2.78 (d, 2 NCH3, 3J = 5.3 Hz), 3.14 (dq, NCH2, 3J = 7.2 Hz, 3J = 5.3 Hz), 11.26 (m, NH). 13C{1H} NMR (CDCl3, internal TMS): δ 10.0 (s, CH3), 42.6 (s, 2 NCH3), 53.3 (s, NCH2).
The initial cell determination yielded an orthorhombic C-centred cell with a = 18.197 Å, b = 21.698 Å, c = 7.335 Å and V = 2896.1 Å3. After data collection, the Rint value for the orthorhombic setting (0.474) indicated that the symmetry should be lowered to monoclinic P with an Rint of 0.063. Structure solution and refinement was successful in P21/c. The ethyl group is disorded over two sites. The site-occupation factors refined to 0.54 (1):0.46 (1). H atoms bonded to C atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl)], using a riding model, with C—H = 0.99 Å and methyl C—H = 0.98 Å. The H atom bonded to the N atom was freely refined.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
C4H12N+·Br− | F(000) = 312 |
Mr = 154.06 | Dx = 1.413 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0797 (8) Å | Cell parameters from 1423 reflections |
b = 7.3352 (9) Å | θ = 3.5–24.2° |
c = 14.1594 (15) Å | µ = 5.57 mm−1 |
β = 100.030 (9)° | T = 173 K |
V = 724.07 (14) Å3 | Block, colourless |
Z = 4 | 0.19 × 0.17 × 0.13 mm |
Stoe IPDS-II two-circle diffractometer | 1675 independent reflections |
Radiation source: fine-focus sealed tube | 1171 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans | θmax = 27.8°, θmin = 4.0° |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | h = −9→9 |
Tmin = 0.381, Tmax = 0.485 | k = −8→9 |
5255 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | w = 1/[σ2(Fo2) + (0.032P)2] where P = (Fo2 + 2Fc2)/3 |
1675 reflections | (Δ/σ)max = 0.029 |
78 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
C4H12N+·Br− | V = 724.07 (14) Å3 |
Mr = 154.06 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.0797 (8) Å | µ = 5.57 mm−1 |
b = 7.3352 (9) Å | T = 173 K |
c = 14.1594 (15) Å | 0.19 × 0.17 × 0.13 mm |
β = 100.030 (9)° |
Stoe IPDS-II two-circle diffractometer | 1675 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | 1171 reflections with I > 2σ(I) |
Tmin = 0.381, Tmax = 0.485 | Rint = 0.063 |
5255 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.32 e Å−3 |
1675 reflections | Δρmin = −0.56 e Å−3 |
78 parameters |
Experimental. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.20077 (5) | 0.69673 (5) | 0.40160 (3) | 0.04008 (12) | |
N1 | 0.2062 (8) | 0.2582 (4) | 0.4001 (4) | 0.0633 (12) | |
H1 | 0.215 (8) | 0.374 (8) | 0.404 (4) | 0.076 (15)* | |
C2 | 0.0083 (8) | 0.1991 (7) | 0.3659 (3) | 0.0658 (12) | |
H2A | −0.0322 | 0.2382 | 0.2993 | 0.099* | |
H2B | −0.0762 | 0.2536 | 0.4061 | 0.099* | |
H2C | 0.0011 | 0.0659 | 0.3696 | 0.099* | |
C1 | 0.2685 (6) | 0.1997 (7) | 0.5000 (4) | 0.0657 (13) | |
H1A | 0.4006 | 0.2400 | 0.5225 | 0.099* | |
H1B | 0.2623 | 0.0665 | 0.5037 | 0.099* | |
H1C | 0.1841 | 0.2535 | 0.5405 | 0.099* | |
C3 | 0.3888 (11) | 0.1976 (11) | 0.3623 (6) | 0.040 (2) | 0.544 (12) |
H3A | 0.5052 | 0.2495 | 0.4022 | 0.048* | 0.544 (12) |
H3B | 0.3999 | 0.0630 | 0.3627 | 0.048* | 0.544 (12) |
C4 | 0.3632 (15) | 0.2706 (11) | 0.2610 (7) | 0.050 (3) | 0.544 (12) |
H4A | 0.4747 | 0.2373 | 0.2323 | 0.075* | 0.544 (12) |
H4B | 0.3513 | 0.4037 | 0.2622 | 0.075* | 0.544 (12) |
H4C | 0.2470 | 0.2182 | 0.2229 | 0.075* | 0.544 (12) |
C3' | 0.2803 (16) | 0.1902 (13) | 0.3073 (8) | 0.044 (3) | 0.456 (12) |
H3'1 | 0.2873 | 0.0554 | 0.3058 | 0.053* | 0.456 (12) |
H3'2 | 0.1957 | 0.2333 | 0.2484 | 0.053* | 0.456 (12) |
C4' | 0.4782 (18) | 0.2742 (15) | 0.3169 (10) | 0.057 (3) | 0.456 (12) |
H4'1 | 0.5369 | 0.2384 | 0.2619 | 0.085* | 0.456 (12) |
H4'2 | 0.5582 | 0.2313 | 0.3762 | 0.085* | 0.456 (12) |
H4'3 | 0.4675 | 0.4073 | 0.3187 | 0.085* | 0.456 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.04661 (18) | 0.02729 (15) | 0.0499 (2) | 0.00288 (19) | 0.01842 (14) | 0.0016 (2) |
N1 | 0.090 (3) | 0.0260 (14) | 0.093 (3) | 0.0066 (18) | 0.069 (3) | 0.007 (2) |
C2 | 0.105 (4) | 0.047 (2) | 0.044 (2) | 0.005 (3) | 0.009 (2) | −0.001 (2) |
C1 | 0.042 (2) | 0.048 (2) | 0.107 (4) | 0.001 (2) | 0.012 (2) | 0.011 (3) |
C3 | 0.039 (4) | 0.038 (3) | 0.048 (5) | 0.004 (3) | 0.021 (4) | 0.002 (4) |
C4 | 0.056 (5) | 0.047 (5) | 0.053 (6) | 0.008 (4) | 0.029 (5) | 0.001 (4) |
C3' | 0.056 (6) | 0.036 (4) | 0.045 (6) | 0.000 (5) | 0.025 (5) | −0.001 (5) |
C4' | 0.057 (7) | 0.055 (6) | 0.062 (7) | −0.002 (5) | 0.025 (6) | −0.015 (5) |
N1—C2 | 1.466 (7) | C3—H3A | 0.990 |
N1—C1 | 1.471 (8) | C3—H3B | 0.990 |
N1—C3 | 1.548 (7) | C4—H4A | 0.980 |
N1—C3' | 1.578 (10) | C4—H4B | 0.980 |
N1—H1 | 0.85 (6) | C4—H4C | 0.980 |
C2—H2A | 0.980 | C3'—C4' | 1.515 (17) |
C2—H2B | 0.980 | C3'—H3'1 | 0.990 |
C2—H2C | 0.980 | C3'—H3'2 | 0.990 |
C1—H1A | 0.980 | C4'—H4'1 | 0.980 |
C1—H1B | 0.980 | C4'—H4'2 | 0.980 |
C1—H1C | 0.980 | C4'—H4'3 | 0.980 |
C3—C4 | 1.512 (14) | ||
C2—N1—C1 | 109.9 (4) | N1—C3—H3A | 110.8 |
C2—N1—C3 | 127.5 (5) | C4—C3—H3B | 110.8 |
C1—N1—C3 | 96.9 (5) | N1—C3—H3B | 110.8 |
C2—N1—C3' | 94.0 (6) | H3A—C3—H3B | 108.9 |
C1—N1—C3' | 128.4 (5) | C3—C4—H4A | 109.5 |
C2—N1—H1 | 112 (4) | C3—C4—H4B | 109.5 |
C1—N1—H1 | 103 (4) | H4A—C4—H4B | 109.5 |
C3—N1—H1 | 105 (4) | C3—C4—H4C | 109.5 |
C3'—N1—H1 | 110 (4) | H4A—C4—H4C | 109.5 |
N1—C2—H2A | 109.5 | H4B—C4—H4C | 109.5 |
N1—C2—H2B | 109.5 | C4'—C3'—N1 | 103.5 (9) |
H2A—C2—H2B | 109.5 | C4'—C3'—H3'1 | 111.1 |
N1—C2—H2C | 109.5 | N1—C3'—H3'1 | 111.1 |
H2A—C2—H2C | 109.5 | C4'—C3'—H3'2 | 111.1 |
H2B—C2—H2C | 109.5 | N1—C3'—H3'2 | 111.1 |
N1—C1—H1A | 109.5 | H3'1—C3'—H3'2 | 109.0 |
N1—C1—H1B | 109.5 | C3'—C4'—H4'1 | 109.5 |
H1A—C1—H1B | 109.5 | C3'—C4'—H4'2 | 109.5 |
N1—C1—H1C | 109.5 | H4'1—C4'—H4'2 | 109.5 |
H1A—C1—H1C | 109.5 | C3'—C4'—H4'3 | 109.5 |
H1B—C1—H1C | 109.5 | H4'1—C4'—H4'3 | 109.5 |
C4—C3—N1 | 104.8 (7) | H4'2—C4'—H4'3 | 109.5 |
C4—C3—H3A | 110.8 | ||
C2—N1—C3—C4 | 65.8 (8) | C2—N1—C3'—C4' | 168.2 (8) |
C1—N1—C3—C4 | −172.5 (6) | C1—N1—C3'—C4' | −72.5 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.85 (6) | 2.37 (6) | 3.217 (3) | 173 (5) |
C2—H2A···Br1i | 0.98 | 2.90 | 3.819 (5) | 156 |
C1—H1A···Br1ii | 0.98 | 2.88 | 3.849 (4) | 171 |
C2—H2B···Br1iii | 0.98 | 3.03 | 3.913 (5) | 151 |
C2—H2C···Br1iv | 0.98 | 3.05 | 3.931 (5) | 150 |
C1—H1C···Br1iii | 0.98 | 3.00 | 3.895 (5) | 152 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C4H12N+·Br− |
Mr | 154.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 7.0797 (8), 7.3352 (9), 14.1594 (15) |
β (°) | 100.030 (9) |
V (Å3) | 724.07 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.57 |
Crystal size (mm) | 0.19 × 0.17 × 0.13 |
Data collection | |
Diffractometer | Stoe IPDS-II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.381, 0.485 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5255, 1675, 1171 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.655 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.072, 0.85 |
No. of reflections | 1675 |
No. of parameters | 78 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.56 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.85 (6) | 2.37 (6) | 3.217 (3) | 173 (5) |
C2—H2A···Br1i | 0.98 | 2.90 | 3.819 (5) | 156 |
C1—H1A···Br1ii | 0.98 | 2.88 | 3.849 (4) | 171 |
C2—H2B···Br1iii | 0.98 | 3.03 | 3.913 (5) | 151 |
C2—H2C···Br1iv | 0.98 | 3.05 | 3.931 (5) | 150 |
C1—H1C···Br1iii | 0.98 | 3.00 | 3.895 (5) | 152 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z. |
Recently, our group reported the properties and X-ray crystal structure determination of triferrocenylboroxine (Ma et al., 2002). We report here the hydrolysis of the 1-(dibromoboryl)ferrocene–dimethylethylamine (1/1) adduct and the X-ray crystal structure analysis of the resulting dimethylethylammonium bromide, [HNEtMe2]Br. The synthesis of triferrocenylboroxine and of the title compound, (I), was achieved by the hydrolysis of the 1-(dibromoboryl)ferrocene–dimethylethylammonium adduct, as indicated in the reaction Scheme below. There is a strong hydrogen bond linking the NH group and the Br− ion. Furthermore, the packing is stabilized by several weak C—H···Br hydrogen bonds.