N,N,N-Tri-butyl-butan-1-aminium (T-4)-(cyano-κC)tri-hydro-borate.

In the crystal structure of the title salt, C16H36N(+)·CH3BN(-), the tetra-n-butyl-ammonium cations and [BH3(CN)](-) anions are connected via weak C-H⋯N inter-actions, forming chains along the b-axis direction. The anion is almost linear with an N-C-B angle of 178.7 (2)°. The C-N-C angle values at the core of the tetra-n-butyl-ammonium cation range from 105.74 (11) to 111.35 (11)° with an average of 109.49 (11)°, close to the ideal tetra-hedral value.

Related literature

For the use of the title compound as a reducing agent, see: Hutchins & Kandasamy (1973 ▶). It is also a selective reagent for reductive amination (Hutchins & Markovitz, 1981 ▶) and has been used as a radical mediator for hy­droxy­methyl­ation reactions (Kawamoto et al., 2012 ▶). For the structure of related borohydride salts, see: Jaroń & Grochala (2011 ▶) (tetra­methyl­ammonium) and Jaroń et al. (2012 ▶) (tetra-n-butyl­ammonium). For the ability of cyano­borohydride anions to form di­hydrogen bonds, see: Custelcean & Jackson (1998 ▶). For the most usual conformations of quaternary ammonium cations, see: Alder et al. (1990 ▶).

Experimental

Crystal data

C16H36N+·CH3BN−

M = 282.31

Monoclinic,

a = 7.8312 (5) Å

b = 13.9334 (9) Å

c = 9.6313 (6) Å

β = 112.269 (2)°

V = 972.54 (11) Å3

Z = 2

Cu Kα radiation

μ = 0.40 mm−1

T = 100 K

0.25 × 0.2 × 0.15 mm

Data collection

Bruker Microstar X8 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2012 ▶) T min = 0.590, T max = 0.753

18043 measured reflections

3520 independent reflections

3510 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.092

S = 1.03

3520 reflections

186 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack parameter determined using 1596 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons & Flack, 2004 ▶)

Absolute structure parameter: 0.14 (12)

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813028924/sj5361sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028924/sj5361Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813028924/sj5361Isup3.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H36N+·CH3BN−	F(000) = 320
Mr = 282.31	Dx = 0.964 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 7.8312 (5) Å	Cell parameters from 9860 reflections
b = 13.9334 (9) Å	θ = 5.0–70.0°
c = 9.6313 (6) Å	µ = 0.40 mm−1
β = 112.269 (2)°	T = 100 K
V = 972.54 (11) Å3	Block, clear light colourless
Z = 2	0.25 × 0.2 × 0.15 mm

Bruker Microstar X8 diffractometer	3520 independent reflections
Radiation source: Rotating-anode X-ray tube, Bruker Microstar/FR591 generator	3510 reflections with I > 2σ(I)
Helios Mirror Optics monochromator	Rint = 0.041
Detector resolution: 8.3 pixels mm-1	θmax = 70.2°, θmin = 5.0°
ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	k = −16→17
Tmin = 0.590, Tmax = 0.753	l = −11→11
18043 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035	w = 1/[σ2(Fo2) + (0.059P)2 + 0.1174P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.17 e Å−3
3520 reflections	Δρmin = −0.16 e Å−3
186 parameters	Absolute structure: Flack parameter determined using 1596 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
1 restraint	Absolute structure parameter: 0.14 (12)
Primary atom site location: structure-invariant direct methods

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker microstar diffractometer equipped with a Platinum 135 CCD Detector, a Helios optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 110.0 degree scan in 110 frames over three different parts of the reciprocal space

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. 1. Fixed Uiso At 1.2 times of: All C(H,H) groups At 1.5 times of: All B(H,H,H) groups, All C(H,H,H) groups 2.a Secondary CH2 refined with riding coordinates: C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B) 2.b Idealized Me refined as rotating group: C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C4(H4A,H4B,H4C), B1(H1C,H1D,H1E)

	x	y	z	Uiso*/Ueq
N1	0.37329 (16)	0.60490 (9)	0.25684 (14)	0.0171 (3)
C1	0.35569 (19)	0.67475 (12)	0.37167 (17)	0.0186 (3)
H1A	0.2313	0.6701	0.3698	0.022*
H1B	0.3712	0.7393	0.3405	0.022*
C2	0.4898 (2)	0.66116 (12)	0.53249 (16)	0.0209 (3)
H2A	0.6134	0.6790	0.5418	0.025*
H2B	0.4914	0.5944	0.5616	0.025*
C3	0.4275 (2)	0.72452 (12)	0.63373 (17)	0.0246 (4)
H3A	0.4305	0.7911	0.6052	0.030*
H3B	0.3008	0.7088	0.6178	0.030*
C5	0.56503 (19)	0.61031 (11)	0.25259 (17)	0.0183 (3)
H5A	0.5705	0.5666	0.1761	0.022*
H5B	0.6538	0.5883	0.3483	0.022*
C6	0.6223 (2)	0.70965 (12)	0.22094 (18)	0.0215 (3)
H6A	0.6227	0.7536	0.2992	0.026*
H6B	0.5336	0.7330	0.1262	0.026*
C7	0.8133 (2)	0.70710 (12)	0.2143 (2)	0.0252 (3)
H7A	0.9020	0.6845	0.3097	0.030*
H7B	0.8131	0.6622	0.1373	0.030*
C8	0.8715 (2)	0.80552 (13)	0.1804 (2)	0.0286 (4)
H8A	0.7902	0.8255	0.0822	0.043*
H8B	0.9956	0.8024	0.1840	0.043*
H8C	0.8655	0.8508	0.2536	0.043*
C9	0.2259 (2)	0.63434 (11)	0.10726 (17)	0.0193 (3)
H9A	0.1081	0.6354	0.1187	0.023*
H9B	0.2520	0.6995	0.0857	0.023*
C10	0.2053 (2)	0.57252 (12)	−0.02823 (17)	0.0224 (3)
H10A	0.1533	0.5106	−0.0197	0.027*
H10B	0.3249	0.5620	−0.0338	0.027*
C11	0.0779 (2)	0.62444 (14)	−0.16886 (18)	0.0274 (4)
H11A	−0.0376	0.6389	−0.1581	0.033*
H11B	0.1343	0.6848	−0.1782	0.033*
C12	0.0379 (3)	0.56601 (14)	−0.31121 (18)	0.0319 (4)
H12A	−0.0299	0.6046	−0.3970	0.048*
H12B	−0.0337	0.5105	−0.3090	0.048*
H12C	0.1520	0.5460	−0.3175	0.048*
C13	0.3451 (2)	0.50172 (11)	0.29578 (16)	0.0187 (3)
H13A	0.3467	0.4603	0.2153	0.022*
H13B	0.4484	0.4835	0.3859	0.022*
C14	0.1676 (2)	0.48347 (12)	0.32089 (18)	0.0222 (3)
H14A	0.0628	0.5025	0.2323	0.027*
H14B	0.1668	0.5219	0.4046	0.027*
C15	0.1506 (2)	0.37789 (13)	0.3535 (2)	0.0276 (4)
H15A	0.2592	0.3582	0.4385	0.033*
H15B	0.1452	0.3399	0.2675	0.033*
C16	−0.0207 (3)	0.35851 (13)	0.3874 (2)	0.0310 (4)
H16A	−0.1288	0.3712	0.2996	0.047*
H16B	−0.0202	0.3995	0.4677	0.047*
H16C	−0.0211	0.2926	0.4165	0.047*
C4	0.5460 (2)	0.71352 (15)	0.79966 (19)	0.0313 (4)
H4A	0.6699	0.7334	0.8177	0.047*
H4B	0.5462	0.6475	0.8284	0.047*
H4C	0.4965	0.7527	0.8576	0.047*
N2	0.5861 (3)	0.42280 (13)	0.66014 (18)	0.0418 (4)
C17	0.6380 (2)	0.42768 (13)	0.7884 (2)	0.0297 (4)
B1	0.7120 (3)	0.43232 (17)	0.9652 (2)	0.0332 (4)
H1C	0.6112	0.4235	0.9975	0.050*
H1D	0.7681	0.4937	0.9987	0.050*
H1E	0.8018	0.3826	1.0069	0.050*

	U11	U22	U33	U12	U13	U23
N1	0.0163 (6)	0.0160 (7)	0.0194 (6)	0.0013 (4)	0.0071 (5)	0.0006 (5)
C1	0.0192 (7)	0.0154 (7)	0.0236 (7)	0.0018 (5)	0.0108 (6)	−0.0010 (6)
C2	0.0220 (7)	0.0194 (8)	0.0221 (7)	0.0006 (6)	0.0092 (6)	−0.0012 (6)
C3	0.0262 (7)	0.0248 (9)	0.0251 (8)	0.0011 (6)	0.0122 (6)	−0.0034 (7)
C5	0.0140 (6)	0.0199 (8)	0.0214 (7)	0.0022 (5)	0.0072 (6)	−0.0007 (6)
C6	0.0198 (7)	0.0207 (8)	0.0265 (8)	0.0002 (6)	0.0117 (6)	0.0003 (6)
C7	0.0196 (7)	0.0232 (8)	0.0351 (8)	0.0000 (6)	0.0130 (6)	−0.0007 (7)
C8	0.0257 (8)	0.0270 (9)	0.0367 (9)	−0.0059 (6)	0.0158 (7)	−0.0028 (7)
C9	0.0176 (7)	0.0191 (7)	0.0206 (7)	0.0026 (6)	0.0065 (6)	0.0025 (6)
C10	0.0239 (7)	0.0213 (8)	0.0208 (7)	0.0024 (6)	0.0070 (6)	0.0007 (6)
C11	0.0310 (8)	0.0250 (9)	0.0226 (8)	0.0028 (7)	0.0062 (7)	0.0027 (6)
C12	0.0387 (9)	0.0298 (10)	0.0215 (8)	0.0001 (8)	0.0049 (7)	0.0009 (7)
C13	0.0203 (7)	0.0143 (7)	0.0203 (7)	0.0001 (6)	0.0064 (5)	0.0005 (6)
C14	0.0235 (7)	0.0198 (8)	0.0240 (7)	−0.0014 (6)	0.0099 (6)	0.0005 (6)
C15	0.0274 (8)	0.0209 (8)	0.0336 (8)	−0.0053 (7)	0.0104 (7)	0.0017 (7)
C16	0.0374 (9)	0.0296 (10)	0.0282 (8)	−0.0132 (7)	0.0148 (7)	−0.0027 (7)
C4	0.0336 (8)	0.0383 (10)	0.0243 (8)	−0.0005 (8)	0.0134 (7)	−0.0056 (7)
N2	0.0627 (11)	0.0240 (8)	0.0286 (8)	−0.0016 (8)	0.0059 (7)	0.0025 (7)
C17	0.0335 (8)	0.0164 (8)	0.0341 (9)	0.0002 (7)	0.0070 (7)	0.0010 (7)
B1	0.0389 (10)	0.0263 (10)	0.0306 (10)	0.0033 (9)	0.0088 (8)	−0.0021 (8)

N1—C1	1.5182 (18)	C10—H10B	0.9700
N1—C5	1.5195 (17)	C10—C11	1.526 (2)
N1—C9	1.5216 (18)	C11—H11A	0.9700
N1—C13	1.5229 (19)	C11—H11B	0.9700
C1—H1A	0.9700	C11—C12	1.521 (2)
C1—H1B	0.9700	C12—H12A	0.9600
C1—C2	1.518 (2)	C12—H12B	0.9600
C2—H2A	0.9700	C12—H12C	0.9600
C2—H2B	0.9700	C13—H13A	0.9700
C2—C3	1.526 (2)	C13—H13B	0.9700
C3—H3A	0.9700	C13—C14	1.5192 (19)
C3—H3B	0.9700	C14—H14A	0.9700
C3—C4	1.521 (2)	C14—H14B	0.9700
C5—H5A	0.9700	C14—C15	1.520 (2)
C5—H5B	0.9700	C15—H15A	0.9700
C5—C6	1.521 (2)	C15—H15B	0.9700
C6—H6A	0.9700	C15—C16	1.521 (2)
C6—H6B	0.9700	C16—H16A	0.9600
C6—C7	1.5215 (19)	C16—H16B	0.9600
C7—H7A	0.9700	C16—H16C	0.9600
C7—H7B	0.9700	C4—H4A	0.9600
C7—C8	1.519 (2)	C4—H4B	0.9600
C8—H8A	0.9600	C4—H4C	0.9600
C8—H8B	0.9600	N2—C17	1.147 (2)
C8—H8C	0.9600	C17—B1	1.578 (3)
C9—H9A	0.9700	B1—H1C	0.9600
C9—H9B	0.9700	B1—H1D	0.9600
C9—C10	1.520 (2)	B1—H1E	0.9600
C10—H10A	0.9700
C1—N1—C5	110.57 (11)	C9—C10—H10B	110.0
C1—N1—C9	105.74 (11)	C9—C10—C11	108.33 (13)
C1—N1—C13	111.35 (11)	H10A—C10—H10B	108.4
C5—N1—C9	111.33 (10)	C11—C10—H10A	110.0
C5—N1—C13	106.90 (10)	C11—C10—H10B	110.0
C9—N1—C13	111.03 (11)	C10—C11—H11A	109.0
N1—C1—H1A	108.2	C10—C11—H11B	109.0
N1—C1—H1B	108.2	H11A—C11—H11B	107.8
N1—C1—C2	116.39 (12)	C12—C11—C10	112.85 (15)
H1A—C1—H1B	107.3	C12—C11—H11A	109.0
C2—C1—H1A	108.2	C12—C11—H11B	109.0
C2—C1—H1B	108.2	C11—C12—H12A	109.5
C1—C2—H2A	110.0	C11—C12—H12B	109.5
C1—C2—H2B	110.0	C11—C12—H12C	109.5
C1—C2—C3	108.34 (12)	H12A—C12—H12B	109.5
H2A—C2—H2B	108.4	H12A—C12—H12C	109.5
C3—C2—H2A	110.0	H12B—C12—H12C	109.5
C3—C2—H2B	110.0	N1—C13—H13A	108.5
C2—C3—H3A	108.9	N1—C13—H13B	108.5
C2—C3—H3B	108.9	H13A—C13—H13B	107.5
H3A—C3—H3B	107.7	C14—C13—N1	115.09 (12)
C4—C3—C2	113.43 (13)	C14—C13—H13A	108.5
C4—C3—H3A	108.9	C14—C13—H13B	108.5
C4—C3—H3B	108.9	C13—C14—H14A	109.5
N1—C5—H5A	108.6	C13—C14—H14B	109.5
N1—C5—H5B	108.6	C13—C14—C15	110.59 (13)
N1—C5—C6	114.83 (12)	H14A—C14—H14B	108.1
H5A—C5—H5B	107.5	C15—C14—H14A	109.5
C6—C5—H5A	108.6	C15—C14—H14B	109.5
C6—C5—H5B	108.6	C14—C15—H15A	109.3
C5—C6—H6A	109.5	C14—C15—H15B	109.3
C5—C6—H6B	109.5	C14—C15—C16	111.69 (15)
C5—C6—C7	110.87 (12)	H15A—C15—H15B	107.9
H6A—C6—H6B	108.1	C16—C15—H15A	109.3
C7—C6—H6A	109.5	C16—C15—H15B	109.3
C7—C6—H6B	109.5	C15—C16—H16A	109.5
C6—C7—H7A	109.3	C15—C16—H16B	109.5
C6—C7—H7B	109.3	C15—C16—H16C	109.5
H7A—C7—H7B	108.0	H16A—C16—H16B	109.5
C8—C7—C6	111.58 (13)	H16A—C16—H16C	109.5
C8—C7—H7A	109.3	H16B—C16—H16C	109.5
C8—C7—H7B	109.3	C3—C4—H4A	109.5
C7—C8—H8A	109.5	C3—C4—H4B	109.5
C7—C8—H8B	109.5	C3—C4—H4C	109.5
C7—C8—H8C	109.5	H4A—C4—H4B	109.5
H8A—C8—H8B	109.5	H4A—C4—H4C	109.5
H8A—C8—H8C	109.5	H4B—C4—H4C	109.5
H8B—C8—H8C	109.5	N2—C17—B1	178.7 (2)
N1—C9—H9A	108.0	C17—B1—H1C	109.5
N1—C9—H9B	108.0	C17—B1—H1D	109.5
H9A—C9—H9B	107.3	C17—B1—H1E	109.5
C10—C9—N1	117.12 (12)	H1C—B1—H1D	109.5
C10—C9—H9A	108.0	H1C—B1—H1E	109.5
C10—C9—H9B	108.0	H1D—B1—H1E	109.5
C9—C10—H10A	110.0
N1—C1—C2—C3	−169.39 (12)	C5—N1—C13—C14	174.17 (12)
N1—C5—C6—C7	−178.31 (12)	C5—C6—C7—C8	179.12 (13)
N1—C9—C10—C11	−169.54 (12)	C9—N1—C1—C2	−179.68 (12)
N1—C13—C14—C15	178.00 (12)	C9—N1—C5—C6	60.80 (16)
C1—N1—C5—C6	−56.43 (15)	C9—N1—C13—C14	−64.23 (15)
C1—N1—C9—C10	−176.84 (12)	C9—C10—C11—C12	−176.50 (14)
C1—N1—C13—C14	53.31 (15)	C13—N1—C1—C2	59.62 (15)
C1—C2—C3—C4	177.11 (14)	C13—N1—C5—C6	−177.78 (12)
C5—N1—C1—C2	−59.06 (16)	C13—N1—C9—C10	−55.94 (16)
C5—N1—C9—C10	63.04 (16)	C13—C14—C15—C16	176.90 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···N2i	0.97	2.58	3.515 (2)	162
C2—H2B···N2	0.97	2.58	3.523 (2)	165
C13—H13B···N2	0.97	2.59	3.474 (2)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯N2i	0.97	2.58	3.515 (2)	162
C2—H2B⋯N2	0.97	2.58	3.523 (2)	165
C13—H13B⋯N2	0.97	2.59	3.474 (2)	152

Symmetry code: (i) .