(3R,4S)-3-Methyl-4-phenyl-2-[(R)-1-phenyl-eth-yl]-3,4-di-hydro-isoquinolin-2-ium tetra-fluorido-borate.

The title salt, C24H24N(+)·BF4 (-), is one of two possible dias-tereoisomers having a different configuration of the asymmetric centre in the α-phenyl-ethyl substituent, whose absolute configuration was established to be R. The two phenyl substituents of the cation have a cofacial orientation, albeit with a long centroid-centroid separation of 4.129 (3) Å. The crystal structure exhibits numerous C-H⋯F contacts between counter-ions, with the tetra-fluorido-borate anion surrounded by five iminium cations.

Related literature

For related literature, see: Adam et al. (2001 ▶); Bohé et al. (1999 ▶); Cremer & Pople (1975 ▶); Davies & Coote (1988 ▶)

Experimental

Crystal data

C24H24N+·BF4 −

M = 413.25

Tetragonal,

a = 9.367 (4) Å

c = 49.137 (14) Å

V = 4311 (3) Å3

Z = 8

Cu Kα radiation

μ = 0.81 mm−1

T = 293 K

0.33 × 0.26 × 0.26 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

10992 measured reflections

2353 independent reflections

1192 reflections with I > 2σ(I)

R int = 0.092

3 standard reflections every 60 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.215

S = 1.08

2353 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.18 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: NONIUS (Riche, 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP (Johnson, 1965 ▶), PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681400230X/ld2119sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400230X/ld2119Isup2.hkl

CCDC reference:

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

C24H24N+·BF4−	Dx = 1.273 Mg m−3
Mr = 413.25	Cu Kα radiation, λ = 1.5418 Å
Tetragonal, P41212	Cell parameters from 25 reflections
Hall symbol: P 4abw 2nw	θ = 7.9–13.4°
a = 9.367 (4) Å	µ = 0.81 mm−1
c = 49.137 (14) Å	T = 293 K
V = 4311 (3) Å3	Prism, colourless
Z = 8	0.33 × 0.26 × 0.26 mm
F(000) = 1728

Nonius CAD-4 diffractometer	Rint = 0.092
Radiation source: X-ray tube	θmax = 67.0°, θmin = 3.6°
Graphite monochromator	h = −11→10
θ/2θ scans	k = −3→11
10992 measured reflections	l = 0→58
2353 independent reflections	3 standard reflections every 60 min
1192 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.065	Hydrogen site location: difference Fourier map
wR(F2) = 0.215	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.1069P)2 + 0.3684P] where P = (Fo2 + 2Fc2)/3
2353 reflections	(Δ/σ)max = 0.001
273 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.5567 (6)	0.4341 (7)	0.05389 (13)	0.0603 (17)
H1	0.5550	0.5320	0.0507	0.068*
N2	0.5135 (5)	0.3893 (5)	0.07701 (9)	0.0529 (13)
C3	0.5210 (7)	0.2316 (6)	0.08264 (11)	0.0539 (16)
H3	0.4509	0.2086	0.0968	0.060*
C4	0.4824 (6)	0.1472 (6)	0.05687 (10)	0.0517 (15)
H4	0.5096	0.0477	0.0602	0.058*
C5	0.6173 (8)	0.1095 (8)	0.01273 (13)	0.0717 (19)
H5	0.5933	0.0131	0.0129	0.080*
C6	0.6996 (9)	0.1639 (10)	−0.00821 (14)	0.085 (2)
H6	0.7334	0.1031	−0.0217	0.095*
C7	0.7322 (8)	0.3084 (10)	−0.00929 (14)	0.083 (2)
H7	0.7864	0.3444	−0.0236	0.093*
C8	0.6845 (8)	0.3968 (8)	0.01059 (12)	0.072 (2)
H8	0.7032	0.4941	0.0096	0.081*
C9	0.6083 (6)	0.3428 (7)	0.03230 (11)	0.0565 (16)
C10	0.5708 (6)	0.1985 (7)	0.03335 (12)	0.0552 (16)
C11	0.6686 (7)	0.1929 (8)	0.09325 (14)	0.077 (2)
H11A	0.6783	0.0909	0.0938	0.088*
H11B	0.6806	0.2311	0.1112	0.088*
H11C	0.7399	0.2321	0.0814	0.088*
C12	0.3215 (7)	0.1476 (7)	0.05072 (12)	0.0581 (17)
C13	0.2383 (8)	0.0355 (8)	0.05968 (13)	0.074 (2)
H13	0.2807	−0.0381	0.0695	0.083*
C14	0.0943 (8)	0.0300 (9)	0.05445 (14)	0.085 (2)
H14	0.0411	−0.0479	0.0604	0.095*
C15	0.0293 (8)	0.1376 (11)	0.04074 (16)	0.090 (3)
H15	−0.0683	0.1350	0.0373	0.100*
C16	0.1104 (9)	0.2492 (10)	0.03213 (16)	0.100 (3)
H16	0.0672	0.3234	0.0226	0.113*
C17	0.2526 (8)	0.2549 (9)	0.03710 (15)	0.087 (2)
H17	0.3046	0.3334	0.0311	0.097*
C18	0.4575 (7)	0.4894 (7)	0.09788 (11)	0.0611 (17)
H18	0.4812	0.5856	0.0915	0.068*
C19	0.5320 (8)	0.4718 (8)	0.12507 (14)	0.087 (2)
H19A	0.5069	0.5500	0.1368	0.100*
H19B	0.6335	0.4708	0.1223	0.100*
H19C	0.5027	0.3836	0.1333	0.100*
C20	0.2977 (7)	0.4823 (7)	0.09907 (12)	0.0562 (16)
C21	0.2243 (8)	0.3923 (8)	0.11650 (14)	0.079 (2)
H21	0.2736	0.3317	0.1282	0.088*
C22	0.0726 (9)	0.3937 (11)	0.1163 (2)	0.102 (3)
H22	0.0220	0.3337	0.1279	0.115*
C23	0.0022 (10)	0.4820 (12)	0.09934 (19)	0.102 (3)
H23	−0.0971	0.4827	0.0996	0.114*
C24	0.0700 (10)	0.5679 (12)	0.08225 (19)	0.114 (3)
H24	0.0190	0.6258	0.0703	0.128*
C25	0.2198 (9)	0.5703 (9)	0.08234 (15)	0.089 (2)
H25	0.2675	0.6330	0.0708	0.100*
B26	0.7073 (11)	0.7827 (9)	0.0634 (2)	0.078 (3)
F27	0.5714 (5)	0.7850 (5)	0.05584 (14)	0.151 (3)
F28	0.7744 (6)	0.9020 (6)	0.06260 (15)	0.160 (3)
F29	0.7185 (7)	0.7172 (11)	0.08622 (15)	0.248 (5)
F30	0.7760 (9)	0.6905 (9)	0.0478 (2)	0.237 (5)

	U11	U22	U33	U12	U13	U23
C1	0.051 (4)	0.063 (4)	0.066 (4)	−0.017 (3)	0.004 (3)	0.003 (3)
N2	0.053 (3)	0.054 (3)	0.052 (3)	0.002 (3)	0.007 (2)	−0.005 (2)
C3	0.056 (4)	0.054 (4)	0.051 (3)	0.004 (3)	−0.006 (3)	0.007 (3)
C4	0.050 (4)	0.051 (4)	0.054 (3)	−0.006 (3)	−0.002 (3)	0.002 (3)
C5	0.072 (5)	0.079 (5)	0.064 (4)	0.000 (4)	−0.002 (4)	−0.013 (4)
C6	0.088 (6)	0.105 (7)	0.062 (4)	0.003 (5)	0.016 (4)	−0.013 (5)
C7	0.075 (5)	0.109 (7)	0.065 (4)	−0.006 (5)	0.021 (4)	−0.001 (5)
C8	0.072 (5)	0.082 (5)	0.063 (4)	−0.013 (4)	0.008 (4)	0.004 (4)
C9	0.052 (4)	0.068 (4)	0.050 (3)	−0.008 (3)	0.010 (3)	0.001 (3)
C10	0.052 (4)	0.061 (4)	0.053 (3)	−0.006 (3)	−0.008 (3)	−0.001 (3)
C11	0.063 (5)	0.095 (6)	0.072 (4)	0.009 (4)	−0.016 (4)	−0.004 (4)
C12	0.054 (4)	0.066 (4)	0.054 (3)	−0.016 (4)	−0.010 (3)	−0.004 (3)
C13	0.074 (5)	0.082 (5)	0.066 (4)	−0.026 (4)	−0.004 (4)	0.004 (4)
C14	0.068 (5)	0.107 (7)	0.079 (5)	−0.043 (5)	0.014 (4)	−0.018 (5)
C15	0.043 (4)	0.135 (8)	0.090 (5)	−0.009 (5)	−0.001 (4)	0.002 (6)
C16	0.067 (6)	0.115 (7)	0.119 (7)	−0.003 (5)	−0.018 (5)	0.024 (6)
C17	0.053 (5)	0.100 (6)	0.107 (5)	−0.014 (4)	−0.012 (4)	0.023 (5)
C18	0.065 (4)	0.060 (4)	0.058 (3)	0.001 (3)	0.007 (3)	−0.007 (3)
C19	0.078 (5)	0.111 (7)	0.072 (4)	0.003 (5)	−0.006 (4)	−0.023 (5)
C20	0.058 (4)	0.050 (4)	0.060 (4)	−0.001 (3)	0.007 (3)	−0.004 (3)
C21	0.075 (5)	0.074 (5)	0.087 (5)	0.005 (4)	0.008 (4)	0.022 (4)
C22	0.066 (6)	0.106 (7)	0.135 (8)	−0.011 (5)	0.030 (5)	0.008 (6)
C23	0.062 (5)	0.133 (9)	0.110 (7)	0.021 (6)	0.008 (5)	−0.015 (6)
C24	0.076 (7)	0.164 (11)	0.103 (7)	0.029 (6)	−0.003 (5)	0.003 (7)
C25	0.088 (6)	0.100 (7)	0.080 (5)	0.008 (5)	0.015 (5)	0.014 (5)
B26	0.078 (7)	0.047 (5)	0.108 (7)	−0.003 (5)	−0.021 (6)	−0.003 (5)
F27	0.085 (4)	0.079 (3)	0.287 (7)	−0.014 (3)	−0.087 (4)	0.040 (4)
F28	0.098 (4)	0.106 (4)	0.277 (7)	−0.051 (3)	−0.015 (4)	−0.001 (5)
F29	0.135 (6)	0.415 (15)	0.194 (6)	−0.101 (7)	−0.062 (5)	0.166 (9)
F30	0.176 (8)	0.193 (8)	0.343 (11)	0.014 (6)	0.014 (7)	−0.147 (8)

C1—N2	1.277 (7)	C14—C15	1.356 (10)
C1—C9	1.446 (8)	C14—H14	0.9300
C1—H1	0.9300	C15—C16	1.360 (11)
N2—C18	1.485 (7)	C15—H15	0.9300
N2—C3	1.505 (7)	C16—C17	1.356 (10)
C3—C11	1.521 (8)	C16—H16	0.9300
C3—C4	1.536 (8)	C17—H17	0.9300
C3—H3	0.9800	C18—C20	1.500 (9)
C4—C10	1.500 (8)	C18—C19	1.516 (9)
C4—C12	1.537 (8)	C18—H18	0.9800
C4—H4	0.9800	C19—H19A	0.9600
C5—C10	1.383 (9)	C19—H19B	0.9600
C5—C6	1.383 (9)	C19—H19C	0.9600
C5—H5	0.9300	C20—C25	1.374 (9)
C6—C7	1.389 (10)	C20—C21	1.385 (9)
C6—H6	0.9300	C21—C22	1.421 (11)
C7—C8	1.356 (9)	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.347 (11)
C8—C9	1.379 (8)	C22—H22	0.9300
C8—H8	0.9300	C23—C24	1.325 (12)
C9—C10	1.398 (8)	C23—H23	0.9300
C11—H11A	0.9600	C24—C25	1.403 (11)
C11—H11B	0.9600	C24—H24	0.9300
C11—H11C	0.9600	C25—H25	0.9300
C12—C17	1.369 (10)	B26—F29	1.281 (10)
C12—C13	1.380 (9)	B26—F28	1.283 (9)
C13—C14	1.374 (10)	B26—F30	1.323 (11)
C13—H13	0.9300	B26—F27	1.327 (10)
N2—C1—C9	124.4 (6)	C15—C14—C13	120.4 (8)
N2—C1—H1	117.8	C15—C14—H14	119.8
C9—C1—H1	117.8	C13—C14—H14	119.8
C1—N2—C18	121.3 (5)	C14—C15—C16	118.3 (7)
C1—N2—C3	118.1 (5)	C14—C15—H15	120.8
C18—N2—C3	120.6 (5)	C16—C15—H15	120.8
N2—C3—C11	109.9 (5)	C17—C16—C15	121.5 (8)
N2—C3—C4	110.0 (4)	C17—C16—H16	119.2
C11—C3—C4	112.0 (5)	C15—C16—H16	119.2
N2—C3—H3	108.3	C16—C17—C12	121.5 (8)
C11—C3—H3	108.3	C16—C17—H17	119.2
C4—C3—H3	108.3	C12—C17—H17	119.2
C10—C4—C3	109.9 (5)	N2—C18—C20	110.6 (5)
C10—C4—C12	112.9 (5)	N2—C18—C19	112.2 (5)
C3—C4—C12	113.1 (5)	C20—C18—C19	114.8 (5)
C10—C4—H4	106.9	N2—C18—H18	106.2
C3—C4—H4	106.9	C20—C18—H18	106.2
C12—C4—H4	106.9	C19—C18—H18	106.2
C10—C5—C6	119.9 (7)	C18—C19—H19A	109.5
C10—C5—H5	120.0	C18—C19—H19B	109.5
C6—C5—H5	120.0	H19A—C19—H19B	109.5
C5—C6—C7	120.7 (7)	C18—C19—H19C	109.5
C5—C6—H6	119.7	H19A—C19—H19C	109.5
C7—C6—H6	119.7	H19B—C19—H19C	109.5
C8—C7—C6	119.7 (7)	C25—C20—C21	118.2 (7)
C8—C7—H7	120.2	C25—C20—C18	118.7 (6)
C6—C7—H7	120.2	C21—C20—C18	123.1 (6)
C7—C8—C9	120.2 (7)	C20—C21—C22	119.1 (7)
C7—C8—H8	119.9	C20—C21—H21	120.4
C9—C8—H8	119.9	C22—C21—H21	120.4
C8—C9—C10	120.9 (6)	C23—C22—C21	120.0 (8)
C8—C9—C1	121.6 (6)	C23—C22—H22	120.0
C10—C9—C1	117.4 (5)	C21—C22—H22	120.0
C5—C10—C9	118.5 (6)	C24—C23—C22	122.0 (9)
C5—C10—C4	123.0 (6)	C24—C23—H23	119.0
C9—C10—C4	118.5 (5)	C22—C23—H23	119.0
C3—C11—H11A	109.5	C23—C24—C25	119.2 (9)
C3—C11—H11B	109.5	C23—C24—H24	120.4
H11A—C11—H11B	109.5	C25—C24—H24	120.4
C3—C11—H11C	109.5	C20—C25—C24	121.5 (8)
H11A—C11—H11C	109.5	C20—C25—H25	119.2
H11B—C11—H11C	109.5	C24—C25—H25	119.2
C17—C12—C13	116.6 (6)	F29—B26—F28	113.9 (9)
C17—C12—C4	124.1 (6)	F29—B26—F30	98.9 (9)
C13—C12—C4	119.3 (6)	F28—B26—F30	108.2 (9)
C14—C13—C12	121.5 (8)	F29—B26—F27	109.4 (9)
C14—C13—H13	119.2	F28—B26—F27	116.6 (8)
C12—C13—H13	119.2	F30—B26—F27	108.3 (8)
C9—C1—N2—C18	−178.0 (5)	C3—C4—C12—C17	83.7 (7)
C9—C1—N2—C3	2.2 (9)	C10—C4—C12—C13	139.5 (6)
C1—N2—C3—C11	85.5 (6)	C3—C4—C12—C13	−95.0 (7)
C18—N2—C3—C11	−94.3 (6)	C17—C12—C13—C14	1.9 (10)
C1—N2—C3—C4	−38.2 (7)	C4—C12—C13—C14	−179.3 (6)
C18—N2—C3—C4	141.9 (5)	C12—C13—C14—C15	−1.5 (11)
N2—C3—C4—C10	51.8 (6)	C13—C14—C15—C16	0.7 (12)
C11—C3—C4—C10	−70.7 (6)	C14—C15—C16—C17	−0.4 (13)
N2—C3—C4—C12	−75.3 (6)	C15—C16—C17—C12	0.8 (14)
C11—C3—C4—C12	162.2 (6)	C13—C12—C17—C16	−1.5 (11)
C10—C5—C6—C7	−2.2 (11)	C4—C12—C17—C16	179.7 (7)
C5—C6—C7—C8	0.9 (12)	C1—N2—C18—C20	103.3 (7)
C6—C7—C8—C9	2.3 (11)	C3—N2—C18—C20	−76.9 (7)
C7—C8—C9—C10	−4.3 (10)	C1—N2—C18—C19	−127.1 (6)
C7—C8—C9—C1	179.6 (6)	C3—N2—C18—C19	52.7 (8)
N2—C1—C9—C8	−164.3 (6)	N2—C18—C20—C25	−88.9 (7)
N2—C1—C9—C10	19.5 (9)	C19—C18—C20—C25	142.9 (7)
C6—C5—C10—C9	0.3 (10)	N2—C18—C20—C21	91.9 (7)
C6—C5—C10—C4	−179.4 (6)	C19—C18—C20—C21	−36.3 (9)
C8—C9—C10—C5	2.9 (9)	C25—C20—C21—C22	0.4 (11)
C1—C9—C10—C5	179.2 (6)	C18—C20—C21—C22	179.6 (7)
C8—C9—C10—C4	−177.4 (6)	C20—C21—C22—C23	−0.1 (13)
C1—C9—C10—C4	−1.1 (9)	C21—C22—C23—C24	0.9 (15)
C3—C4—C10—C5	146.2 (6)	C22—C23—C24—C25	−2.0 (16)
C12—C4—C10—C5	−86.6 (7)	C21—C20—C25—C24	−1.5 (12)
C3—C4—C10—C9	−33.5 (8)	C18—C20—C25—C24	179.3 (7)
C12—C4—C10—C9	93.7 (7)	C23—C24—C25—C20	2.3 (15)
C10—C4—C12—C17	−41.8 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F27	0.93	2.39	3.292 (9)	164
C1—H1···F30	0.93	2.55	3.170 (12)	125
C18—H18···F29	0.98	2.55	3.292 (10)	132
C24—H24···F30i	0.93	2.60	3.430 (15)	148
C4—H4···F27ii	0.98	2.54	3.498 (8)	165
C11—H11A···F28ii	0.96	2.50	3.268 (11)	137
C14—H14···F28iii	0.93	2.54	3.249 (10)	133
C7—H7···F27iv	0.93	2.65	3.399 (10)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F27	0.93	2.39	3.292 (9)	164
C1—H1⋯F30	0.93	2.55	3.170 (12)	125
C18—H18⋯F29	0.98	2.55	3.292 (10)	132
C24—H24⋯F30i	0.93	2.60	3.430 (15)	148
C4—H4⋯F27ii	0.98	2.54	3.498 (8)	165
C11—H11A⋯F28ii	0.96	2.50	3.268 (11)	137
C14—H14⋯F28iii	0.93	2.54	3.249 (10)	133
C7—H7⋯F27iv	0.93	2.65	3.399 (10)	138

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .