Crystal structure of borated N,N,N',N'-tetra-methyldi-amino-methane.

In the title compound, {[(di-methyl-amino)-meth-yl]di-methyl-amine}-trihydridoboron, C5H17BN2, the tetra-hedral geometry of the N-C-N unit is slightly disorted. As a result of the bulky amine substituents, a wider N-C-N angle of 113.6 (1)° is observed. The bond lengths between the N atom and methyl groups are slighly elongated to 1.481 (2) and 1.482 (2) Å at the borated N atom, whereas the distances between the other N atom and its methyl groups are only 1.461 (2) and 1.462 (2) Å. The studied crystal was twinned. The twin data refinement was subsequently carried out with a scale factor of 0.263 (1). The two lattices of the twin domains were rotated by 179.84°.

Related literature

For background to boranes, see: Falbe & Regitz (1999 ▸). Burg & Schlesinger (1937 ▸) reported the first borane amine complex. A feature of boranes is their metal character and pronounced Lewis acidity (Huheey et al., 1995 ▸). This Lewis acidity is used to enable the α-deprotonation of tertiary amines (Kessar et al., 1991 ▸; Ebden et al., 1995 ▸). Our group frequently uses methods to deprotonate compounds in α-position (Strohmann & Gessner, 2007 ▸; Gessner & Strohmann, 2012 ▸). For crystal structures containing the borated N,N,N′,N′-tetra­methyldi­amino­methane motif, see: Fang et al. (1994 ▸); Hanic & Šubrtová (1969 ▸); Flores-Parra et al. (1999 ▸); Rojas-Lima et al. (2000 ▸). For comparison with other structures with di­methyl­amino­borane moiety, see: Gollas et al. (2013 ▸); Bera et al. (2011 ▸); Ramachandran et al. (2004 ▸); Netz et al. (2005 ▸). For diborated tetra­methyl­ethylenedi­amine, see: Chitsaz et al. (2001 ▸).

Experimental

Crystal data

C5H17BN2

M = 116.01

Triclinic,

a = 6.0464 (8) Å

b = 7.6987 (9) Å

c = 9.5896 (11) Å

α = 69.602 (10)°

β = 76.519 (11)°

γ = 74.912 (10)°

V = 398.95 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.06 mm−1

T = 173 K

0.2 × 0.15 × 0.15 mm

Data collection

AgilentXcalibur, Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸) T min = 0.983, T max = 1.000

3232 measured reflections

3232 independent reflections

1828 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 0.87

3232 reflections

90 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS96 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL96 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015016813/zq2234sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016813/zq2234Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015016813/zq2234fig1.tif

Mol­ecular structure of the title compound with displacement ellipsoids drawn at 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015016813/zq2234fig2.tif

Mol­ecular packing viewed along the a axis.

CCDC reference: 1422998

Additional supporting information: crystallographic information; 3D view; checkCIF report

C5H17BN2	Z = 2
Mr = 116.01	F(000) = 132
Triclinic, P1	Dx = 0.966 Mg m−3
a = 6.0464 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6987 (9) Å	Cell parameters from 1858 reflections
c = 9.5896 (11) Å	θ = 3.0–28.3°
α = 69.602 (10)°	µ = 0.06 mm−1
β = 76.519 (11)°	T = 173 K
γ = 74.912 (10)°	Block, clear light colourless
V = 398.95 (9) Å3	0.2 × 0.15 × 0.15 mm

AgilentXcalibur, Sapphire3 diffractometer	3232 measured reflections
Radiation source: Enhance (Mo) X-ray Source	3232 independent reflections
Graphite monochromator	1828 reflections with I > 2σ(I)
Detector resolution: 16.0560 pixels mm-1	θmax = 27.0°, θmin = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −9→9
Tmin = 0.983, Tmax = 1.000	l = −12→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/3
S = 0.87	(Δ/σ)max = 0.001
3232 reflections	Δρmax = 0.18 e Å−3
90 parameters	Δρmin = −0.22 e Å−3
0 restraints

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 2-component twin. 1. Twinned data refinement Scales: 0.7367 (11) 0.2633 (11) 2. Fixed Uiso At 1.2 times of: All C(H,H) groups At 1.5 times of: All C(H,H,H) groups 3.a Secondary CH2 refined with riding coordinates: C3(H3A,H3B) 3.b Idealized Me refined as rotating group: C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C4(H4A,H4B,H4C)

	x	y	z	Uiso*/Ueq
N1	0.17275 (18)	0.17659 (15)	0.69988 (12)	0.0182 (3)
C3	0.2336 (2)	−0.00477 (18)	0.82279 (15)	0.0214 (3)
H3A	0.2756	0.0246	0.9048	0.026*
H3B	0.0951	−0.0634	0.8648	0.026*
N2	0.42225 (19)	−0.13895 (16)	0.77307 (13)	0.0226 (3)
C2	0.1062 (3)	0.1356 (2)	0.57701 (16)	0.0274 (4)
H2A	0.2389	0.0568	0.5326	0.041*
H2B	0.0591	0.2545	0.4995	0.041*
H2C	−0.0233	0.0685	0.6177	0.041*
C1	0.3751 (2)	0.2702 (2)	0.63738 (18)	0.0293 (4)
H1A	0.4230	0.2959	0.7179	0.044*
H1B	0.3328	0.3894	0.5589	0.044*
H1C	0.5036	0.1873	0.5939	0.044*
C5	0.3510 (3)	−0.3102 (2)	0.78120 (19)	0.0340 (4)
H5A	0.2924	−0.3745	0.8861	0.051*
H5B	0.4844	−0.3946	0.7432	0.051*
H5C	0.2284	−0.2762	0.7197	0.051*
B1	−0.0405 (3)	0.3123 (3)	0.7713 (2)	0.0289 (4)
C4	0.6200 (3)	−0.1878 (2)	0.85213 (18)	0.0333 (4)
H4A	0.6693	−0.0721	0.8429	0.050*
H4B	0.7483	−0.2698	0.8077	0.050*
H4C	0.5749	−0.2542	0.9588	0.050*
H1D	−0.083 (2)	0.4427 (19)	0.6758 (15)	0.032 (4)*
H1E	−0.189 (2)	0.2332 (19)	0.8155 (16)	0.034 (4)*
H1F	0.023 (2)	0.3383 (19)	0.8634 (17)	0.036 (4)*

	U11	U22	U33	U12	U13	U23
N1	0.0196 (6)	0.0158 (6)	0.0184 (6)	−0.0027 (5)	−0.0032 (5)	−0.0047 (5)
C3	0.0245 (8)	0.0191 (7)	0.0183 (7)	−0.0020 (6)	−0.0041 (6)	−0.0041 (6)
N2	0.0222 (7)	0.0187 (6)	0.0260 (7)	−0.0015 (5)	−0.0044 (5)	−0.0072 (5)
C2	0.0311 (9)	0.0279 (9)	0.0229 (8)	0.0000 (7)	−0.0093 (7)	−0.0081 (7)
C1	0.0259 (9)	0.0240 (8)	0.0347 (9)	−0.0071 (7)	0.0007 (7)	−0.0066 (7)
C5	0.0367 (10)	0.0230 (8)	0.0421 (10)	−0.0019 (7)	−0.0055 (8)	−0.0131 (8)
B1	0.0284 (10)	0.0236 (9)	0.0273 (10)	0.0026 (8)	−0.0018 (8)	−0.0063 (8)
C4	0.0255 (9)	0.0317 (9)	0.0404 (10)	0.0024 (7)	−0.0102 (8)	−0.0107 (8)

N1—C3	1.5039 (16)	C1—H1A	0.9800
N1—C2	1.4818 (17)	C1—H1B	0.9800
N1—C1	1.4806 (17)	C1—H1C	0.9800
N1—B1	1.615 (2)	C5—H5A	0.9800
C3—H3A	0.9900	C5—H5B	0.9800
C3—H3B	0.9900	C5—H5C	0.9800
C3—N2	1.4393 (17)	B1—H1D	1.117 (13)
N2—C5	1.4622 (18)	B1—H1E	1.131 (14)
N2—C4	1.4612 (18)	B1—H1F	1.137 (14)
C2—H2A	0.9800	C4—H4A	0.9800
C2—H2B	0.9800	C4—H4B	0.9800
C2—H2C	0.9800	C4—H4C	0.9800
C3—N1—B1	108.16 (10)	N1—C1—H1C	109.5
C2—N1—C3	109.62 (10)	H1A—C1—H1B	109.5
C2—N1—B1	110.43 (11)	H1A—C1—H1C	109.5
C1—N1—C3	110.11 (10)	H1B—C1—H1C	109.5
C1—N1—C2	108.59 (10)	N2—C5—H5A	109.5
C1—N1—B1	109.93 (12)	N2—C5—H5B	109.5
N1—C3—H3A	108.8	N2—C5—H5C	109.5
N1—C3—H3B	108.8	H5A—C5—H5B	109.5
H3A—C3—H3B	107.7	H5A—C5—H5C	109.5
N2—C3—N1	113.61 (10)	H5B—C5—H5C	109.5
N2—C3—H3A	108.8	N1—B1—H1D	105.7 (7)
N2—C3—H3B	108.8	N1—B1—H1E	106.1 (7)
C3—N2—C5	112.85 (12)	N1—B1—H1F	106.4 (7)
C3—N2—C4	112.82 (11)	H1D—B1—H1E	111.1 (10)
C4—N2—C5	110.31 (11)	H1D—B1—H1F	113.7 (10)
N1—C2—H2A	109.5	H1E—B1—H1F	113.2 (10)
N1—C2—H2B	109.5	N2—C4—H4A	109.5
N1—C2—H2C	109.5	N2—C4—H4B	109.5
H2A—C2—H2B	109.5	N2—C4—H4C	109.5
H2A—C2—H2C	109.5	H4A—C4—H4B	109.5
H2B—C2—H2C	109.5	H4A—C4—H4C	109.5
N1—C1—H1A	109.5	H4B—C4—H4C	109.5
N1—C1—H1B	109.5
N1—C3—N2—C5	−114.53 (13)	C1—N1—C3—N2	−60.04 (14)
N1—C3—N2—C4	119.61 (12)	B1—N1—C3—N2	179.82 (13)
C2—N1—C3—N2	59.36 (14)