Bis(2-pyridyl­methyl)­amine–borane

Sanchez Ballester, N.; Barreira Fontecha, J.; Wikaira, J.; McKee, V.

doi:10.1107/S1600536805001728

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o567-o568

https://doi.org/10.1107/S1600536805001728

Bis(2-pyridylmethyl)amine–borane

Noelia Sanchez Ballester,^a Julia Barreira Fontecha,^a Jan Wikaira ^b ^* and Vickie McKee ^a

^aChemistry Department, Loughborough University, Loughborough, Leics LE11 3TU, England, and ^bChemistry Department, Canterbury University, Christchurch, PB 4800, New Zealand
^*Correspondence e-mail: jan.wikaira@canterbury.ac.nz

(Received 22 December 2004; accepted 18 January 2005; online 5 February 2005)

The title compound, C₁₂H₁₂N₃·BH₃ or C₁₂H₁₅BN₃, contains a BH₃ group and two picolyl groups attached to a central N atom. Both edge-to-face and face-to-face π-stacking interactions are found.

Comment

The asymmetric unit of the title compound, (I), contains one molecule. The two planar pyridyl rings are twisted (Fig. 1) about the central N atom, with an interplanar angle of 110.9°. The amine N atom is not involved in any hydrogen bonding but pyridyl atom N1 interacts with atom C3 in an adjacent ring (Table 1).

An edge-to-face interaction is found between the H atom on C2 and the plane of the pyridine ring containing atom N3 (Fig. 2). This H atom is 2.806 Å from the mean plane of the pyridine ring at (½ + x, ½ − y, ½ + z). The pyridine ring containing atom N3 is π-stacked with its symmetry equivalent by inversion (symmetry code: 2 − x, −y, 1 − z). The interplanar and the centroid-to-centroid distances are 3.496 (2) and 3.971 Å respectively (Fig. 2).

Figure 1
Perspective view of (I

), showing 50% probability displacement ellipsoids.

Figure 2
View showing the C—H⋯N bond (C3 and N1), the interaction between the H atom bonded to C2 and the pyridyl ring, and the π-stacking of the N3-containing pyridine rings [symmetry codes: (i) ½ + x, ½ − y, z − ½; (ii) 2 − x, −y, 1 − z; (iii) ½ + x, ½ − y, ½ + z.]

Experimental

2-(Aminomethyl)pyridine (4.95 g, 44.77 mmol) and pyridine-2-carboxaldehyde (4.96 g, 46.31 mmol) were dissolved in methanol (150 ml) (Lambert et al., 1997 ). The solution was stirred for 2 h at room temperature (yellow–orange solution). After slow addition of an excess of sodium borohydride, stirring was continued for 1 h (pale-yellow solution). The solvent was removed by rotary evaporation to give bis(pyridin-2-ylmethyl)amine (6.43 g, 73%) as an orange oil. Colourless crystals of the borane adduct appeared as a minor product after the oil was stored in a freezer overnight.

Crystal data

C₁₂H₁₅BN₃
M_r = 213.09
Monoclinic, P2₁/n
a = 5.3172 (4) Å
b = 24.8494 (19) Å
c = 9.3896 (7) Å
β = 102.938 (1)°
V = 1209.14 (16) Å³
Z = 4
D_x = 1.171 Mg m⁻³
Mo Kα radiation
Cell parameters from 3633 reflections
θ = 2.4–27.5°
μ = 0.07 mm⁻¹
T = 150 (2) K
Needle, colourless
0.55 × 0.17 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.946, T_max = 0.990
10293 measured reflections
2860 independent reflections
2156 reflections with I > 2σ(I)
R_int = 0.023
θ_max = 28.8°
h = −7 → 6
k = −32 → 32
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.116
S = 1.02
2860 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0526P)² + 0.3966P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.66	3.5215 (19)	150
Symmetry code: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ .

H atoms bonded to C and B atoms were placed at calculated positions; the constrained C—H distances were 0.95, 0.98 and 0.99 Å for H atoms bonded to Csp², Bsp³ and methylene C atoms, respectively. They were refined using a riding model, with U_iso(H) = 1.2U_eq(B,C). The H atom bonded to the amine N atom was located in a difference map and the coordinates freely refined with a fixed U_iso value of 0.03 Å.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805001728/sj6040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805001728/sj6040Isup2.hkl

Computing details top

Data collection: SMART (Bruker 1998); cell refinement: SMART; data reduction: SAINT (Bruker 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2001); software used to prepare material for publication: SHELXTL.

Bis(2-pyridylmethyl)amine–borane top

Crystal data top

C₁₂H₁₃N₃·BH₃	F(000) = 456
M_r = 213.09	D_x = 1.171 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.3172 (4) Å	Cell parameters from 3633 reflections
b = 24.8494 (19) Å	θ = 2.4–27.5°
c = 9.3896 (7) Å	µ = 0.07 mm⁻¹
β = 102.938 (1)°	T = 150 K
V = 1209.14 (16) Å³	Needles, colourless
Z = 4	0.55 × 0.17 × 0.09 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2860 independent reflections
Radiation source: normal-focus sealed tube	2156 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 28.8°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −7→6
T_min = 0.946, T_max = 0.990	k = −32→32
10293 measured reflections	l = −12→12

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: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0526P)² + 0.3966P] where P = (F_o² + 2F_c²)/3
2860 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

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
N1	0.7734 (2)	0.21154 (5)	0.06397 (12)	0.0294 (3)
C1	0.7038 (3)	0.26208 (6)	0.02464 (16)	0.0330 (3)
H1	0.5762	0.2787	0.0663	0.040*
C2	0.8076 (3)	0.29147 (6)	−0.07349 (16)	0.0364 (3)
H2	0.7520	0.3273	−0.0985	0.044*
C3	0.9934 (3)	0.26772 (6)	−0.13425 (17)	0.0391 (4)
H3	1.0690	0.2869	−0.2016	0.047*
C4	1.0676 (3)	0.21532 (6)	−0.09506 (16)	0.0323 (3)
H4	1.1947	0.1979	−0.1354	0.039*
C5	0.9533 (3)	0.18883 (5)	0.00379 (14)	0.0249 (3)
C6	1.0282 (3)	0.13226 (5)	0.05302 (14)	0.0268 (3)
H6A	1.1212	0.1153	−0.0157	0.032*
H6B	1.1461	0.1331	0.1509	0.032*
N2	0.7962 (2)	0.09966 (4)	0.05927 (12)	0.0247 (3)
C7	0.8683 (3)	0.05115 (5)	0.15252 (14)	0.0315 (3)
H7A	1.0137	0.0326	0.1235	0.038*
H7B	0.7201	0.0260	0.1365	0.038*
C8	0.9453 (3)	0.06549 (5)	0.31264 (14)	0.0261 (3)
C9	1.1746 (3)	0.04780 (5)	0.40128 (15)	0.0303 (3)
H9	1.2931	0.0271	0.3618	0.036*
C10	1.2282 (3)	0.06080 (6)	0.54864 (15)	0.0327 (3)
H10	1.3837	0.0491	0.6121	0.039*
C11	1.0516 (3)	0.09103 (6)	0.60112 (15)	0.0320 (3)
H11	1.0821	0.1003	0.7017	0.038*
C12	0.8290 (3)	0.10767 (6)	0.50462 (15)	0.0320 (3)
H12	0.7091	0.1288	0.5415	0.038*
N3	0.7732 (2)	0.09558 (5)	0.36190 (13)	0.0305 (3)
B1	0.6297 (3)	0.08390 (7)	−0.10096 (17)	0.0302 (3)
H13A	0.5839	0.1167	−0.1591	0.045*
H13B	0.4720	0.0652	−0.0916	0.045*
H13C	0.7321	0.0603	−0.1495	0.045*
H1N	0.700 (3)	0.1212 (6)	0.1050 (17)	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0338 (6)	0.0275 (6)	0.0291 (6)	0.0024 (5)	0.0116 (5)	0.0003 (5)
C1	0.0376 (8)	0.0296 (7)	0.0338 (7)	0.0037 (6)	0.0125 (6)	−0.0006 (6)
C2	0.0500 (9)	0.0249 (7)	0.0345 (8)	−0.0005 (6)	0.0100 (7)	0.0020 (6)
C3	0.0540 (10)	0.0337 (8)	0.0345 (8)	−0.0076 (7)	0.0201 (7)	0.0014 (6)
C4	0.0362 (8)	0.0322 (7)	0.0319 (7)	−0.0047 (6)	0.0148 (6)	−0.0039 (6)
C5	0.0260 (7)	0.0266 (7)	0.0217 (6)	−0.0024 (5)	0.0044 (5)	−0.0030 (5)
C6	0.0249 (6)	0.0301 (7)	0.0251 (6)	0.0018 (5)	0.0048 (5)	−0.0018 (5)
N2	0.0294 (6)	0.0220 (5)	0.0227 (5)	0.0020 (4)	0.0057 (4)	−0.0023 (4)
C7	0.0448 (8)	0.0217 (6)	0.0259 (7)	0.0020 (6)	0.0035 (6)	−0.0013 (5)
C8	0.0339 (7)	0.0192 (6)	0.0249 (6)	−0.0031 (5)	0.0059 (5)	0.0021 (5)
C9	0.0334 (7)	0.0252 (7)	0.0325 (7)	0.0010 (6)	0.0077 (6)	0.0011 (5)
C10	0.0324 (8)	0.0325 (8)	0.0302 (7)	−0.0014 (6)	0.0005 (6)	0.0054 (6)
C11	0.0399 (8)	0.0337 (7)	0.0222 (6)	−0.0078 (6)	0.0066 (6)	0.0008 (5)
C12	0.0346 (8)	0.0340 (8)	0.0291 (7)	0.0000 (6)	0.0108 (6)	0.0001 (6)
N3	0.0315 (6)	0.0308 (6)	0.0283 (6)	0.0009 (5)	0.0051 (5)	−0.0001 (5)
B1	0.0334 (8)	0.0297 (8)	0.0248 (7)	0.0011 (6)	0.0012 (6)	−0.0048 (6)

Geometric parameters (Å, º) top

N1—C1	1.3375 (18)	C7—C8	1.5097 (18)
N1—C5	1.3396 (17)	C7—H7A	0.9900
C1—C2	1.384 (2)	C7—H7B	0.9900
C1—H1	0.9500	C8—N3	1.3417 (17)
C2—C3	1.379 (2)	C8—C9	1.385 (2)
C2—H2	0.9500	C9—C10	1.387 (2)
C3—C4	1.386 (2)	C9—H9	0.9500
C3—H3	0.9500	C10—C11	1.377 (2)
C4—C5	1.3845 (19)	C10—H10	0.9500
C4—H4	0.9500	C11—C12	1.383 (2)
C5—C6	1.5054 (18)	C11—H11	0.9500
C6—N2	1.4881 (17)	C12—N3	1.3402 (18)
C6—H6A	0.9900	C12—H12	0.9500
C6—H6B	0.9900	B1—H13A	0.9800
N2—C7	1.4887 (17)	B1—H13B	0.9800
N2—B1	1.6138 (18)	B1—H13C	0.9800
N2—H1N	0.910 (16)

C1—N1—C5	117.31 (12)	N2—C7—C8	111.80 (11)
N1—C1—C2	123.53 (14)	N2—C7—H7A	109.3
N1—C1—H1	118.2	C8—C7—H7A	109.3
C2—C1—H1	118.2	N2—C7—H7B	109.3
C3—C2—C1	118.61 (14)	C8—C7—H7B	109.3
C3—C2—H2	120.7	H7A—C7—H7B	107.9
C1—C2—H2	120.7	N3—C8—C9	123.11 (12)
C2—C3—C4	118.67 (13)	N3—C8—C7	114.89 (12)
C2—C3—H3	120.7	C9—C8—C7	121.98 (13)
C4—C3—H3	120.7	C8—C9—C10	118.83 (13)
C5—C4—C3	118.89 (13)	C8—C9—H9	120.6
C5—C4—H4	120.6	C10—C9—H9	120.6
C3—C4—H4	120.6	C11—C10—C9	118.67 (13)
N1—C5—C4	122.98 (13)	C11—C10—H10	120.7
N1—C5—C6	115.40 (11)	C9—C10—H10	120.7
C4—C5—C6	121.61 (12)	C10—C11—C12	118.74 (13)
N2—C6—C5	110.83 (11)	C10—C11—H11	120.6
N2—C6—H6A	109.5	C12—C11—H11	120.6
C5—C6—H6A	109.5	N3—C12—C11	123.60 (14)
N2—C6—H6B	109.5	N3—C12—H12	118.2
C5—C6—H6B	109.5	C11—C12—H12	118.2
H6A—C6—H6B	108.1	C12—N3—C8	117.02 (12)
C6—N2—C7	110.95 (11)	N2—B1—H13A	109.5
C6—N2—B1	112.45 (10)	N2—B1—H13B	109.5
C7—N2—B1	111.54 (10)	H13A—B1—H13B	109.5
C6—N2—H1N	104.8 (10)	N2—B1—H13C	109.5
C7—N2—H1N	107.2 (10)	H13A—B1—H13C	109.5
B1—N2—H1N	109.5 (10)	H13B—B1—H13C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.66	3.5215 (19)	150

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

We are grateful to the Socrates Exchange Programme for support. JW thanks the Erskine fund at the University of Canterbury for support.

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lambert, E., Chabut, B., Chardon-Noblat, S., Deronzier, A., Chottard, G., Bousseksou, A., Tuchages, J.-P., Laugier, J., Bardet, M. & Latour, J.-M. (1997). J. Am. Chem. Soc. 119, 9424–9437. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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