Dichloridobis(methyl­amine-κN)boron(III) chloride

Weinmann, M.; Nuss, J.; Jansen, M.

doi:10.1107/S1600536808003589

organic compounds

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Volume 64| Part 3| March 2008| Page o583

doi:10.1107/S1600536808003589

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Dichloridobis(methylamine-κN)boron(III) chloride

Markus Weinmann,^a Jürgen Nuss ^a and Martin Jansen ^a ^*

^aMax-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70569 Stuttgart, Germany
^*Correspondence e-mail: m.jansen@fkf.mpg.de

(Received 30 January 2008; accepted 1 February 2008; online 13 February 2008)

The title compound, C₂H₁₀BCl₂N₂⁺·Cl⁻ or [BCl₂(H₃CNH₂)₂]⁺·Cl⁻, is the first crystallographically characterized di(alkylamine)–BCl₂⁺ salt. The B atom is tetrahedrally coordinated by two Cl and two methylamine N atoms. In the crystal structure, the cations and anions interact via N—H⋯Cl hydrogen bonds (mean H⋯Cl = 2.40 Å), resulting in a layered structure.

Related literature

For more details of the synthesis and background, see Weinmann, Nuss et al. (2007 ); Weinmann, Kroschel et al. (2007 ). For related structures, see: Nöth & Lukas (1962 ); Mikhailov et al. (1964 ); Nöth et al. (1966 ); Ryschkewitz & Myers (1975 ).

Experimental

Crystal data

C₂H₁₀BCl₂N₂⁺·Cl⁻
M_r = 179.28
Orthorhombic, P b c a
a = 9.9881 (11) Å
b = 11.8071 (13) Å
c = 14.1039 (15) Å
V = 1663.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 100 (2) K
0.30 × 0.02 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.751, T_max = 0.980
19044 measured reflections
2430 independent reflections
2123 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.089
S = 1.22
2430 reflections
113 parameters
All H-atom parameters refined
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.89 (3)	2.39 (3)	3.2232 (18)	156 (2)
N1—H1B⋯Cl1ⁱ	0.85 (3)	2.34 (3)	3.1862 (18)	173 (2)
N2—H2A⋯Cl1	0.86 (3)	2.46 (3)	3.2168 (18)	148 (2)
N2—H2B⋯Cl1ⁱⁱ	0.86 (3)	2.36 (3)	3.2016 (18)	165 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003589/hb2697sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808003589/hb2697Isup2.hkl

checkCIF report

Comment top

Borazonium cations BCl₂⁺ coordinated by secondary amines R₂NH are very few in number whereas those coordinated by primary amines are more or less unknown. To our knowledge, there has appeared so far no publication dealing with H₃CNH₂-coordinated BCl₂⁺ cations.

We recently published the continuous synthesis of Cl₃Si-NCH₃—BCl₂ (DMTA) by a two-step gas phase synthesis. This reaction proceeds with the formation of solid by-products which are separated from the desired product by filtration. The solid mainly consists of MeNH₃Cl. Moreover we observed formation of crystalline 2,4,6-trichloro-1,3,5-trimethylborazine, (CH₃NBCl)₃ (Weinmann, Nuss et al., 2007). Re-crystallization of the solid from THF/n-pentane now additionally afforded crystals of the title compound, (I) (Fig. 1).

The boron atom in the BCl₂L₂⁺ cation in (I) is tetrahedrally coordinated by two chlorine atoms Cl2 and Cl3 and two nitrogen atoms N1 and N2 of the methylamine ligands. The smallest angle (N2—B—Cl2) measures 106.38 (13)°, while the biggest (Cl2—B—Cl3) amounts to 113.08 (11)°. The B—Cl bond distances are 1.837 (2) and 1.841 (2) Å whereas the B—N bond lengths measure 1.566 (3) and 1.562 (3) Å. These are values typically found in tetrachloroborate (BCl₄^-) or tetraaminoborate (B(NR₂)₄^-) anions, respectively.

The chloride counter anions are associated with the cations via N—H···Cl hydrogen bonds (Table 1). From Figure 2 it is evident that the anions are each connetcted to four hydrogen atoms, thereby linking three cations. Consequently all the N-bonded H atoms contribute to hydrogen-bond bridges.

A further special feature is the formation of a layered structure in (001) which results from the H-bridge formation. The layers, which are stacked in [001] are connected via less polar van-der-Vaals interactions.

Related literature top

For more details of the synthesis and background, see Weinmann, Nuss et al. (2007); Weinmann, Kroschel et al. (2007). For related structures, see: Nöth & Lukas (1962); Mikhailov et al. (1964); Nöth et al. (1966); Ryschkewitz & Myers (1975).

Experimental top

[BCl₂(H₃CNH₂)₂]Cl was obtained as a side-product in amounts < 5% during the continuous synthesis of DMTA. Details of the experimental setup are found elsewhere (Weinmann, Nuss et al., 2007; Weinmann, Kroschel et al., 2007). Re-crystallization of the reaction mixture from THF/n-hexane afforded colourless needles of (I).

Computing details top

Data collection: SMART (Bruker 2005); cell refinement: SAINT (Bruker 2005); data reduction: SAINT (Bruker 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms). Hydrogen bonds are indicated by thin red lines.
	Fig. 2. Packing diagram of (I) with hydrogen bonds indicated by dashed lines.

Dichloridobis(methylamine-κN)boron(III) chloride top

Crystal data top

C₂H₁₀BCl₂N₂⁺·Cl⁻	F(000) = 736
M_r = 179.28	D_x = 1.432 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5369 reflections
a = 9.9881 (11) Å	θ = 2.6–34.8°
b = 11.8071 (13) Å	µ = 1.01 mm⁻¹
c = 14.1039 (15) Å	T = 100 K
V = 1663.3 (3) Å³	Needle, colourless
Z = 8	0.30 × 0.02 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2430 independent reflections
Radiation source: fine-focus sealed tube	2123 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 30.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −14→14
T_min = 0.751, T_max = 0.980	k = −16→16
19044 measured reflections	l = −19→19

Refinement top

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F²) = 0.089	All H-atom parameters refined
S = 1.22	w = 1/[σ²(F_o²) + (0.036P)² + 0.6817P] where P = (F_o² + 2F_c²)/3
2430 reflections	(Δ/σ)_max = 0.001
113 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₂H₁₀BCl₂N₂⁺·Cl⁻	V = 1663.3 (3) Å³
M_r = 179.28	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.9881 (11) Å	µ = 1.01 mm⁻¹
b = 11.8071 (13) Å	T = 100 K
c = 14.1039 (15) Å	0.30 × 0.02 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2430 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2123 reflections with I > 2σ(I)
T_min = 0.751, T_max = 0.980	R_int = 0.050
19044 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.089	All H-atom parameters refined
S = 1.22	Δρ_max = 0.62 e Å⁻³
2430 reflections	Δρ_min = −0.28 e Å⁻³
113 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Cl1	0.43797 (5)	0.04596 (4)	0.73581 (4)	0.02091 (13)
Cl2	0.54279 (5)	−0.21105 (4)	0.55584 (3)	0.01808 (12)
Cl3	0.82564 (5)	−0.25006 (4)	0.63429 (4)	0.01710 (12)
B	0.6695 (2)	−0.16781 (17)	0.64305 (15)	0.0120 (4)
N1	0.70412 (17)	−0.03969 (14)	0.62830 (12)	0.0136 (3)
H1A	0.630 (3)	−0.002 (2)	0.6429 (17)	0.021 (6)*
H1B	0.767 (3)	−0.023 (2)	0.6669 (19)	0.024 (7)*
N2	0.60546 (17)	−0.18659 (14)	0.74288 (12)	0.0137 (3)
H2A	0.535 (3)	−0.145 (2)	0.7468 (19)	0.030 (7)*
H2B	0.579 (3)	−0.256 (3)	0.744 (2)	0.028 (7)*
C3	0.7536 (3)	−0.01034 (19)	0.53109 (16)	0.0212 (4)
H3A	0.831 (3)	−0.059 (2)	0.519 (2)	0.032 (7)*
H3B	0.682 (3)	−0.020 (3)	0.488 (2)	0.040 (8)*
H3C	0.782 (3)	0.066 (2)	0.5310 (19)	0.027 (7)*
C4	0.6894 (3)	−0.1676 (2)	0.82892 (16)	0.0253 (5)
H4A	0.636 (3)	−0.178 (2)	0.8830 (19)	0.025 (7)*
H4B	0.766 (4)	−0.218 (3)	0.831 (2)	0.045 (9)*
H4C	0.724 (3)	−0.094 (3)	0.825 (2)	0.034 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0190 (2)	0.0103 (2)	0.0334 (3)	0.00027 (17)	0.0106 (2)	−0.00070 (18)
Cl2	0.0168 (2)	0.0200 (2)	0.0174 (2)	−0.00113 (18)	−0.00353 (18)	−0.00502 (18)
Cl3	0.0131 (2)	0.0133 (2)	0.0249 (3)	0.00233 (17)	0.00170 (18)	−0.00173 (18)
B	0.0121 (9)	0.0100 (9)	0.0140 (10)	−0.0011 (7)	0.0011 (7)	0.0001 (7)
N1	0.0143 (8)	0.0125 (8)	0.0141 (8)	−0.0001 (6)	0.0007 (6)	−0.0001 (6)
N2	0.0144 (8)	0.0105 (7)	0.0161 (8)	−0.0011 (6)	0.0004 (6)	−0.0003 (6)
C3	0.0308 (12)	0.0155 (10)	0.0173 (10)	−0.0007 (9)	0.0065 (9)	0.0034 (8)
C4	0.0299 (12)	0.0321 (13)	0.0140 (10)	−0.0132 (10)	−0.0023 (9)	0.0022 (9)

Geometric parameters (Å, º) top

B—Cl2	1.837 (2)	N2—H2A	0.86 (3)
B—Cl3	1.841 (2)	N2—H2B	0.86 (3)
B—N2	1.562 (3)	C3—H3A	0.98 (3)
B—N1	1.566 (3)	C3—H3B	0.95 (3)
N1—C3	1.498 (3)	C3—H3C	0.95 (3)
N1—H1A	0.89 (3)	C4—H4A	0.94 (3)
N1—H1B	0.85 (3)	C4—H4B	0.97 (3)
N2—C4	1.492 (3)	C4—H4C	0.93 (3)

N2—B—N1	110.33 (15)	C4—N2—H2B	107.4 (18)
N2—B—Cl2	106.38 (13)	B—N2—H2B	106.0 (18)
N1—B—Cl2	109.37 (13)	H2A—N2—H2B	107 (3)
N2—B—Cl3	109.41 (13)	N1—C3—H3A	106.6 (16)
N1—B—Cl3	108.27 (13)	N1—C3—H3B	108.3 (18)
Cl2—B—Cl3	113.08 (11)	H3A—C3—H3B	114 (2)
C3—N1—B	114.71 (16)	N1—C3—H3C	108.7 (16)
C3—N1—H1A	111.9 (16)	H3A—C3—H3C	109 (2)
B—N1—H1A	105.4 (17)	H3B—C3—H3C	110 (2)
C3—N1—H1B	106.6 (18)	N2—C4—H4A	108.8 (17)
B—N1—H1B	107.7 (18)	N2—C4—H4B	112.0 (19)
H1A—N1—H1B	110 (2)	H4A—C4—H4B	110 (3)
C4—N2—B	118.80 (16)	N2—C4—H4C	107.7 (18)
C4—N2—H2A	108.7 (18)	H4A—C4—H4C	112 (2)
B—N2—H2A	108.1 (18)	H4B—C4—H4C	106 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89 (3)	2.39 (3)	3.2232 (18)	156 (2)
N1—H1B···Cl1ⁱ	0.85 (3)	2.34 (3)	3.1862 (18)	173 (2)
N2—H2A···Cl1	0.86 (3)	2.46 (3)	3.2168 (18)	148 (2)
N2—H2B···Cl1ⁱⁱ	0.86 (3)	2.36 (3)	3.2016 (18)	165 (2)

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂H₁₀BCl₂N₂⁺·Cl⁻
M_r	179.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	9.9881 (11), 11.8071 (13), 14.1039 (15)
V (Å³)	1663.3 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.30 × 0.02 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.751, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	19044, 2430, 2123
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.089, 1.22
No. of reflections	2430
No. of parameters	113
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.28

Computer programs: SMART (Bruker 2005), SAINT (Bruker 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89 (3)	2.39 (3)	3.2232 (18)	156 (2)
N1—H1B···Cl1ⁱ	0.85 (3)	2.34 (3)	3.1862 (18)	173 (2)
N2—H2A···Cl1	0.86 (3)	2.46 (3)	3.2168 (18)	148 (2)
N2—H2B···Cl1ⁱⁱ	0.86 (3)	2.36 (3)	3.2016 (18)	165 (2)

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1, y−1/2, −z+3/2.

Acknowledgements

The authors acknowledge financial support by the Max Planck Society and the German Research Foundation.

References

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