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The title compound, C4H12N+·Br, is a hydro­lysis product of the 1-(di­bromo­boryl)­ferrocene–di­methyl­ethyl­amine (1/1) adduct. The metric symmetry is apparently orthorhombic C-centred, but the intensity statistics indicate unambigously the correct Laue symmetry, viz. primitive monoclinic. The ethyl group is disordered over two sites. In addition to the hydrogen bond from the NH group to the Br ion, the packing is stabilized by several weak C—H...Br hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803002022/cf6234sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803002022/cf6234Isup2.hkl
Contains datablock I

CCDC reference: 204723

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](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


Red Alert 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.
Yellow Alert 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

Comment top

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.

Experimental top

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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are drawn at the 50% probability level. The major component of the disordered ethyl group (C3 and C4) is drawn with full bonds, the minor component (C3' and C4') with open bonds.
(I) top
Crystal data top
C4H12N+·BrF(000) = 312
Mr = 154.06Dx = 1.413 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.0797 (8) ÅCell parameters from 1423 reflections
b = 7.3352 (9) Åθ = 3.5–24.2°
c = 14.1594 (15) ŵ = 5.57 mm1
β = 100.030 (9)°T = 173 K
V = 724.07 (14) Å3Block, colourless
Z = 40.19 × 0.17 × 0.13 mm
Data collection top
Stoe IPDS-II two-circle
diffractometer
1675 independent reflections
Radiation source: fine-focus sealed tube1171 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω scansθmax = 27.8°, θmin = 4.0°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 99
Tmin = 0.381, Tmax = 0.485k = 89
5255 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H 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 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
C4H12N+·BrV = 724.07 (14) Å3
Mr = 154.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0797 (8) ŵ = 5.57 mm1
b = 7.3352 (9) ÅT = 173 K
c = 14.1594 (15) Å0.19 × 0.17 × 0.13 mm
β = 100.030 (9)°
Data collection top
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 = 0.485Rint = 0.063
5255 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 0.85Δρmax = 0.32 e Å3
1675 reflectionsΔρmin = 0.56 e Å3
78 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.20077 (5)0.69673 (5)0.40160 (3)0.04008 (12)
N10.2062 (8)0.2582 (4)0.4001 (4)0.0633 (12)
H10.215 (8)0.374 (8)0.404 (4)0.076 (15)*
C20.0083 (8)0.1991 (7)0.3659 (3)0.0658 (12)
H2A0.03220.23820.29930.099*
H2B0.07620.25360.40610.099*
H2C0.00110.06590.36960.099*
C10.2685 (6)0.1997 (7)0.5000 (4)0.0657 (13)
H1A0.40060.24000.52250.099*
H1B0.26230.06650.50370.099*
H1C0.18410.25350.54050.099*
C30.3888 (11)0.1976 (11)0.3623 (6)0.040 (2)0.544 (12)
H3A0.50520.24950.40220.048*0.544 (12)
H3B0.39990.06300.36270.048*0.544 (12)
C40.3632 (15)0.2706 (11)0.2610 (7)0.050 (3)0.544 (12)
H4A0.47470.23730.23230.075*0.544 (12)
H4B0.35130.40370.26220.075*0.544 (12)
H4C0.24700.21820.22290.075*0.544 (12)
C3'0.2803 (16)0.1902 (13)0.3073 (8)0.044 (3)0.456 (12)
H3'10.28730.05540.30580.053*0.456 (12)
H3'20.19570.23330.24840.053*0.456 (12)
C4'0.4782 (18)0.2742 (15)0.3169 (10)0.057 (3)0.456 (12)
H4'10.53690.23840.26190.085*0.456 (12)
H4'20.55820.23130.37620.085*0.456 (12)
H4'30.46750.40730.31870.085*0.456 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.04661 (18)0.02729 (15)0.0499 (2)0.00288 (19)0.01842 (14)0.0016 (2)
N10.090 (3)0.0260 (14)0.093 (3)0.0066 (18)0.069 (3)0.007 (2)
C20.105 (4)0.047 (2)0.044 (2)0.005 (3)0.009 (2)0.001 (2)
C10.042 (2)0.048 (2)0.107 (4)0.001 (2)0.012 (2)0.011 (3)
C30.039 (4)0.038 (3)0.048 (5)0.004 (3)0.021 (4)0.002 (4)
C40.056 (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)
Geometric parameters (Å, º) top
N1—C21.466 (7)C3—H3A0.990
N1—C11.471 (8)C3—H3B0.990
N1—C31.548 (7)C4—H4A0.980
N1—C3'1.578 (10)C4—H4B0.980
N1—H10.85 (6)C4—H4C0.980
C2—H2A0.980C3'—C4'1.515 (17)
C2—H2B0.980C3'—H3'10.990
C2—H2C0.980C3'—H3'20.990
C1—H1A0.980C4'—H4'10.980
C1—H1B0.980C4'—H4'20.980
C1—H1C0.980C4'—H4'30.980
C3—C41.512 (14)
C2—N1—C1109.9 (4)N1—C3—H3A110.8
C2—N1—C3127.5 (5)C4—C3—H3B110.8
C1—N1—C396.9 (5)N1—C3—H3B110.8
C2—N1—C3'94.0 (6)H3A—C3—H3B108.9
C1—N1—C3'128.4 (5)C3—C4—H4A109.5
C2—N1—H1112 (4)C3—C4—H4B109.5
C1—N1—H1103 (4)H4A—C4—H4B109.5
C3—N1—H1105 (4)C3—C4—H4C109.5
C3'—N1—H1110 (4)H4A—C4—H4C109.5
N1—C2—H2A109.5H4B—C4—H4C109.5
N1—C2—H2B109.5C4'—C3'—N1103.5 (9)
H2A—C2—H2B109.5C4'—C3'—H3'1111.1
N1—C2—H2C109.5N1—C3'—H3'1111.1
H2A—C2—H2C109.5C4'—C3'—H3'2111.1
H2B—C2—H2C109.5N1—C3'—H3'2111.1
N1—C1—H1A109.5H3'1—C3'—H3'2109.0
N1—C1—H1B109.5C3'—C4'—H4'1109.5
H1A—C1—H1B109.5C3'—C4'—H4'2109.5
N1—C1—H1C109.5H4'1—C4'—H4'2109.5
H1A—C1—H1C109.5C3'—C4'—H4'3109.5
H1B—C1—H1C109.5H4'1—C4'—H4'3109.5
C4—C3—N1104.8 (7)H4'2—C4'—H4'3109.5
C4—C3—H3A110.8
C2—N1—C3—C465.8 (8)C2—N1—C3'—C4'168.2 (8)
C1—N1—C3—C4172.5 (6)C1—N1—C3'—C4'72.5 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.85 (6)2.37 (6)3.217 (3)173 (5)
C2—H2A···Br1i0.982.903.819 (5)156
C1—H1A···Br1ii0.982.883.849 (4)171
C2—H2B···Br1iii0.983.033.913 (5)151
C2—H2C···Br1iv0.983.053.931 (5)150
C1—H1C···Br1iii0.983.003.895 (5)152
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1; (iv) x, y1, z.

Experimental details

Crystal data
Chemical formulaC4H12N+·Br
Mr154.06
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)7.0797 (8), 7.3352 (9), 14.1594 (15)
β (°) 100.030 (9)
V3)724.07 (14)
Z4
Radiation typeMo Kα
µ (mm1)5.57
Crystal size (mm)0.19 × 0.17 × 0.13
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.381, 0.485
No. of measured, independent and
observed [I > 2σ(I)] reflections
5255, 1675, 1171
Rint0.063
(sin θ/λ)max1)0.655
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.072, 0.85
No. of reflections1675
No. of parameters78
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.85 (6)2.37 (6)3.217 (3)173 (5)
C2—H2A···Br1i0.982.903.819 (5)156
C1—H1A···Br1ii0.982.883.849 (4)171
C2—H2B···Br1iii0.983.033.913 (5)151
C2—H2C···Br1iv0.983.053.931 (5)150
C1—H1C···Br1iii0.983.003.895 (5)152
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1; (iv) x, y1, z.
 

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