4-[(2'-Cyano-biphenyl-4-yl)meth-yl]morpholin-4-ium hexa-fluoridophosphate.

In the cation of the title compound, C(18)H(19)N(2)O(+)·PF(6) (-), the morpholine ring adopts the usual chair conformation and the dihedral angle between the benzene rings is 67.55 (11)°. The F atoms of the anion are disordered over two orientations with a refined occupancy ratio of 0.65 (2):0.35 (2). In the crystal, inter-molecular N-H⋯N hydrogen bonds link the cations into chains parallel to the c axis. The crystal packing is further enforced by inter-ionic C-H⋯F hydrogen bonds.

Related literature

For the screening of mol­ecular salts with physicochemical properties, see: Tong & Whitesell (1998 ▶); Shanker (1994 ▶). For the structures of related salts, see: SiMa (2010 ▶); Li et al. (2011 ▶).

Experimental

Crystal data

C18H19N2O+·PF6 −

M = 424.32

Monoclinic,

a = 24.912 (11) Å

b = 10.757 (5) Å

c = 14.925 (7) Å

β = 91.07 (3)°

V = 3999 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.813, T max = 1.000

21155 measured reflections

4512 independent reflections

3216 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.084

wR(F 2) = 0.218

S = 1.19

4512 reflections

308 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201358X/rz2727sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201358X/rz2727Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681201358X/rz2727Isup3.cml

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

C18H19N2O+·PF6−	F(000) = 1744
Mr = 424.32	Dx = 1.410 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4512 reflections
a = 24.912 (11) Å	θ = 2.6–27.4°
b = 10.757 (5) Å	µ = 0.20 mm−1
c = 14.925 (7) Å	T = 293 K
β = 91.07 (3)°	Prism, colourless
V = 3999 (3) Å3	0.20 × 0.20 × 0.20 mm
Z = 8

Rigaku Mercury2 diffractometer	4512 independent reflections
Radiation source: fine-focus sealed tube	3216 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 13.6612 pixels mm-1	θmax = 27.4°, θmin = 2.1°
CCD_Profile_fitting scans	h = −32→31
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.813, Tmax = 1.000	l = −19→19
21155 measured reflections

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.218	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.0935P)2 + 1.2795P] where P = (Fo2 + 2Fc2)/3
4512 reflections	(Δ/σ)max < 0.001
308 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.17 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	Occ. (<1)
N2	0.32167 (9)	0.0538 (2)	0.37953 (14)	0.0586 (6)
H2A	0.3533	0.0143	0.3918	0.070*
C11	0.36122 (12)	0.1175 (3)	0.23215 (17)	0.0587 (7)
C2	0.49042 (11)	0.2243 (3)	−0.01594 (18)	0.0597 (7)
C8	0.44407 (11)	0.2199 (3)	0.13211 (17)	0.0568 (7)
N1	0.42775 (12)	0.0475 (3)	−0.07023 (19)	0.0804 (8)
C1	0.48586 (12)	0.2708 (3)	0.07186 (18)	0.0598 (7)
C3	0.52800 (13)	0.2724 (3)	−0.0749 (2)	0.0750 (9)
H3A	0.5302	0.2411	−0.1328	0.090*
C15	0.27767 (13)	−0.0213 (3)	0.4206 (2)	0.0729 (9)
H15A	0.2431	0.0145	0.4041	0.088*
H15B	0.2787	−0.1056	0.3977	0.088*
C7	0.45498 (12)	0.1267 (3)	−0.04641 (19)	0.0624 (7)
C10	0.40494 (13)	0.0482 (3)	0.21080 (19)	0.0679 (8)
H10A	0.4072	−0.0341	0.2296	0.082*
C9	0.44606 (13)	0.0986 (3)	0.16145 (19)	0.0685 (8)
H9A	0.4756	0.0497	0.1478	0.082*
C14	0.31444 (13)	0.0585 (3)	0.27939 (19)	0.0697 (8)
H14A	0.2821	0.1050	0.2649	0.084*
H14B	0.3095	−0.0255	0.2570	0.084*
C12	0.35927 (15)	0.2401 (3)	0.2056 (3)	0.0877 (11)
H12A	0.3301	0.2892	0.2210	0.105*
O1	0.28375 (13)	0.0972 (4)	0.55657 (19)	0.1302 (13)
C13	0.40029 (15)	0.2908 (3)	0.1561 (3)	0.0877 (11)
H13A	0.3984	0.3738	0.1388	0.105*
C6	0.52083 (15)	0.3653 (3)	0.0969 (2)	0.0810 (10)
H6A	0.5191	0.3980	0.1545	0.097*
C4	0.56173 (15)	0.3664 (3)	−0.0467 (3)	0.0850 (10)
H4A	0.5869	0.3986	−0.0856	0.102*
C18	0.32429 (16)	0.1780 (4)	0.4223 (3)	0.0940 (12)
H18A	0.2924	0.2252	0.4062	0.113*
H18B	0.3553	0.2229	0.4009	0.113*
C16	0.28390 (18)	−0.0235 (5)	0.5209 (2)	0.1058 (14)
H16A	0.2547	−0.0710	0.5462	0.127*
H16B	0.3174	−0.0644	0.5373	0.127*
C5	0.55830 (15)	0.4125 (4)	0.0386 (3)	0.0916 (11)
H5A	0.5813	0.4759	0.0574	0.110*
C17	0.3284 (2)	0.1644 (5)	0.5233 (3)	0.140 (2)
H17A	0.3613	0.1211	0.5394	0.168*
H17B	0.3296	0.2461	0.5507	0.168*
P1	0.15365 (4)	0.14226 (9)	0.20740 (6)	0.0750 (3)
F1	0.1241 (5)	0.2534 (10)	0.2540 (7)	0.141 (3)	0.65 (2)
F2	0.1364 (4)	0.1889 (13)	0.1147 (8)	0.152 (4)	0.65 (2)
F3	0.2064 (5)	0.2159 (11)	0.2041 (10)	0.136 (4)	0.65 (2)
F4	0.0987 (4)	0.0652 (11)	0.2203 (5)	0.113 (2)	0.65 (2)
F5	0.1803 (6)	0.0238 (11)	0.1705 (8)	0.135 (4)	0.65 (2)
F6	0.1702 (3)	0.0918 (8)	0.3061 (6)	0.108 (2)	0.65 (2)
F1'	0.1419 (7)	0.2894 (14)	0.208 (3)	0.161 (9)	0.35 (2)
F2'	0.1432 (9)	0.147 (2)	0.1016 (11)	0.144 (8)	0.35 (2)
F3'	0.2163 (6)	0.186 (2)	0.1825 (12)	0.106 (5)	0.35 (2)
F4'	0.0981 (6)	0.116 (3)	0.2162 (15)	0.168 (10)	0.35 (2)
F5'	0.1754 (15)	0.0133 (19)	0.192 (2)	0.183 (12)	0.35 (2)
F6'	0.1687 (9)	0.147 (4)	0.3025 (11)	0.185 (10)	0.35 (2)

	U11	U22	U33	U12	U13	U23
N2	0.0516 (13)	0.0768 (16)	0.0475 (12)	0.0046 (12)	0.0073 (9)	0.0004 (11)
C11	0.0619 (17)	0.0708 (18)	0.0434 (14)	0.0016 (14)	0.0008 (12)	0.0058 (12)
C2	0.0577 (16)	0.0639 (17)	0.0575 (16)	0.0037 (13)	0.0061 (13)	0.0023 (13)
C8	0.0634 (17)	0.0610 (17)	0.0461 (14)	0.0001 (13)	0.0020 (12)	0.0002 (12)
N1	0.0799 (19)	0.094 (2)	0.0675 (17)	−0.0107 (16)	−0.0001 (14)	−0.0165 (15)
C1	0.0620 (17)	0.0611 (17)	0.0566 (16)	−0.0026 (14)	0.0022 (13)	0.0024 (13)
C3	0.072 (2)	0.084 (2)	0.070 (2)	−0.0006 (17)	0.0195 (16)	0.0039 (16)
C15	0.071 (2)	0.085 (2)	0.0637 (18)	−0.0106 (17)	0.0155 (15)	0.0033 (15)
C7	0.0638 (18)	0.076 (2)	0.0481 (15)	0.0040 (16)	0.0055 (13)	−0.0039 (14)
C10	0.087 (2)	0.0641 (17)	0.0537 (16)	0.0120 (16)	0.0176 (15)	0.0115 (13)
C9	0.077 (2)	0.0720 (19)	0.0575 (17)	0.0198 (16)	0.0156 (15)	0.0090 (14)
C14	0.0677 (19)	0.091 (2)	0.0504 (16)	−0.0039 (17)	−0.0038 (13)	0.0087 (15)
C12	0.078 (2)	0.085 (2)	0.101 (3)	0.0250 (19)	0.032 (2)	0.026 (2)
O1	0.123 (2)	0.188 (3)	0.0812 (18)	−0.057 (2)	0.0535 (16)	−0.049 (2)
C13	0.097 (3)	0.0618 (19)	0.106 (3)	0.0170 (18)	0.034 (2)	0.0198 (18)
C6	0.091 (2)	0.083 (2)	0.069 (2)	−0.0196 (19)	−0.0070 (18)	−0.0045 (17)
C4	0.077 (2)	0.085 (2)	0.094 (3)	−0.0058 (19)	0.0180 (19)	0.017 (2)
C18	0.095 (3)	0.093 (3)	0.096 (3)	−0.028 (2)	0.040 (2)	−0.034 (2)
C16	0.103 (3)	0.153 (4)	0.062 (2)	−0.017 (3)	0.027 (2)	0.012 (2)
C5	0.080 (2)	0.088 (3)	0.107 (3)	−0.029 (2)	−0.001 (2)	0.011 (2)
C17	0.140 (4)	0.196 (5)	0.085 (3)	−0.075 (4)	0.052 (3)	−0.065 (3)
P1	0.0695 (6)	0.0775 (6)	0.0778 (6)	0.0104 (4)	−0.0032 (4)	−0.0038 (4)
F1	0.158 (7)	0.082 (4)	0.184 (7)	0.038 (4)	0.042 (4)	−0.015 (4)
F2	0.140 (5)	0.199 (9)	0.116 (7)	0.038 (6)	−0.024 (4)	0.072 (6)
F3	0.095 (5)	0.089 (4)	0.223 (10)	−0.024 (4)	−0.005 (5)	0.038 (5)
F4	0.097 (4)	0.146 (6)	0.096 (4)	−0.045 (4)	−0.004 (3)	−0.003 (3)
F5	0.157 (6)	0.112 (7)	0.138 (5)	0.028 (6)	0.075 (5)	−0.029 (5)
F6	0.095 (4)	0.136 (5)	0.093 (4)	0.011 (3)	−0.012 (2)	0.032 (4)
F1'	0.129 (10)	0.071 (7)	0.28 (3)	0.023 (6)	0.021 (10)	−0.022 (10)
F2'	0.167 (14)	0.198 (15)	0.068 (6)	−0.089 (13)	0.002 (7)	−0.033 (9)
F3'	0.061 (5)	0.143 (13)	0.113 (7)	0.024 (6)	−0.004 (5)	0.031 (7)
F4'	0.059 (6)	0.22 (3)	0.224 (16)	−0.005 (9)	0.043 (7)	−0.003 (13)
F5'	0.22 (2)	0.063 (8)	0.27 (3)	0.026 (9)	0.080 (17)	0.050 (12)
F6'	0.195 (14)	0.30 (3)	0.059 (8)	0.041 (16)	−0.016 (7)	−0.055 (11)

N2—C18	1.482 (4)	O1—C16	1.403 (5)
N2—C15	1.502 (4)	O1—C17	1.423 (5)
N2—C14	1.503 (3)	C13—H13A	0.9300
N2—H2A	0.9100	C6—C5	1.385 (5)
C11—C10	1.362 (4)	C6—H6A	0.9300
C11—C12	1.378 (4)	C4—C5	1.370 (5)
C11—C14	1.513 (4)	C4—H4A	0.9300
C2—C3	1.396 (4)	C18—C17	1.516 (5)
C2—C1	1.409 (4)	C18—H18A	0.9700
C2—C7	1.440 (4)	C18—H18B	0.9700
C8—C9	1.377 (4)	C16—H16A	0.9700
C8—C13	1.384 (4)	C16—H16B	0.9700
C8—C1	1.492 (4)	C5—H5A	0.9300
N1—C7	1.142 (4)	C17—H17A	0.9700
C1—C6	1.386 (4)	C17—H17B	0.9700
C3—C4	1.375 (5)	P1—F4'	1.421 (17)
C3—H3A	0.9300	P1—F6'	1.463 (16)
C15—C16	1.502 (5)	P1—F5'	1.51 (2)
C15—H15A	0.9700	P1—F2	1.527 (8)
C15—H15B	0.9700	P1—F3	1.536 (9)
C10—C9	1.384 (4)	P1—F5	1.543 (9)
C10—H10A	0.9300	P1—F1	1.574 (7)
C9—H9A	0.9300	P1—F2'	1.597 (15)
C14—H14A	0.9700	P1—F1'	1.610 (14)
C14—H14B	0.9700	P1—F4	1.615 (9)
C12—C13	1.384 (5)	P1—F6	1.616 (7)
C12—H12A	0.9300	P1—F3'	1.678 (17)
C18—N2—C15	109.6 (2)	C6—C5—H5A	119.8
C18—N2—C14	113.7 (3)	O1—C17—C18	111.0 (3)
C15—N2—C14	110.5 (2)	O1—C17—H17A	109.4
C18—N2—H2A	107.6	C18—C17—H17A	109.4
C15—N2—H2A	107.6	O1—C17—H17B	109.4
C14—N2—H2A	107.6	C18—C17—H17B	109.4
C10—C11—C12	118.7 (3)	H17A—C17—H17B	108.0
C10—C11—C14	120.4 (3)	F4'—P1—F6'	98.6 (13)
C12—C11—C14	120.8 (3)	F4'—P1—F5'	100.7 (18)
C3—C2—C1	121.4 (3)	F6'—P1—F5'	95.1 (17)
C3—C2—C7	119.0 (3)	F4'—P1—F2	83.7 (11)
C1—C2—C7	119.5 (3)	F6'—P1—F2	158.7 (14)
C9—C8—C13	117.6 (3)	F5'—P1—F2	105.3 (13)
C9—C8—C1	121.2 (3)	F4'—P1—F3	160.1 (12)
C13—C8—C1	121.1 (3)	F6'—P1—F3	79.0 (11)
C6—C1—C2	116.7 (3)	F5'—P1—F3	99.2 (14)
C6—C1—C8	123.3 (3)	F2—P1—F3	91.6 (6)
C2—C1—C8	120.0 (3)	F4'—P1—F5	107.3 (14)
C4—C3—C2	119.5 (3)	F6'—P1—F5	105.6 (15)
C4—C3—H3A	120.2	F2—P1—F5	93.7 (7)
C2—C3—H3A	120.2	F3—P1—F5	92.3 (8)
C16—C15—N2	110.7 (3)	F4'—P1—F1	69.1 (11)
C16—C15—H15A	109.5	F6'—P1—F1	70.1 (14)
N2—C15—H15A	109.5	F5'—P1—F1	159.6 (10)
C16—C15—H15B	109.5	F2—P1—F1	91.4 (6)
N2—C15—H15B	109.5	F3—P1—F1	91.8 (5)
H15A—C15—H15B	108.1	F5—P1—F1	173.4 (5)
N1—C7—C2	178.5 (3)	F4'—P1—F2'	87.5 (11)
C11—C10—C9	120.9 (3)	F6'—P1—F2'	173.3 (14)
C11—C10—H10A	119.6	F5'—P1—F2'	86.4 (14)
C9—C10—H10A	119.6	F3—P1—F2'	94.3 (8)
C8—C9—C10	121.2 (3)	F5—P1—F2'	74.8 (10)
C8—C9—H9A	119.4	F1—P1—F2'	110.0 (9)
C10—C9—H9A	119.4	F4'—P1—F1'	90.9 (12)
N2—C14—C11	113.5 (2)	F6'—P1—F1'	90.5 (12)
N2—C14—H14A	108.9	F5'—P1—F1'	166.2 (12)
C11—C14—H14A	108.9	F2—P1—F1'	68.3 (10)
N2—C14—H14B	108.9	F3—P1—F1'	69.4 (7)
C11—C14—H14B	108.9	F5—P1—F1'	153.1 (13)
H14A—C14—H14B	107.7	F2'—P1—F1'	86.7 (11)
C11—C12—C13	120.6 (3)	F6'—P1—F4	96.0 (13)
C11—C12—H12A	119.7	F5'—P1—F4	81.5 (13)
C13—C12—H12A	119.7	F2—P1—F4	93.0 (6)
C16—O1—C17	109.3 (3)	F3—P1—F4	175.0 (6)
C8—C13—C12	120.9 (3)	F5—P1—F4	89.4 (7)
C8—C13—H13A	119.5	F1—P1—F4	86.1 (6)
C12—C13—H13A	119.5	F2'—P1—F4	90.7 (7)
C5—C6—C1	121.8 (3)	F1'—P1—F4	110.5 (8)
C5—C6—H6A	119.1	F4'—P1—F6	94.7 (11)
C1—C6—H6A	119.1	F5'—P1—F6	74.9 (13)
C5—C4—C3	120.1 (3)	F2—P1—F6	178.3 (5)
C5—C4—H4A	119.9	F3—P1—F6	90.0 (5)
C3—C4—H4A	119.9	F5—P1—F6	86.8 (6)
N2—C18—C17	110.0 (3)	F1—P1—F6	88.0 (4)
N2—C18—H18A	109.7	F2'—P1—F6	161.3 (9)
C17—C18—H18A	109.7	F1'—P1—F6	111.8 (12)
N2—C18—H18B	109.7	F4—P1—F6	85.4 (4)
C17—C18—H18B	109.7	F4'—P1—F3'	170.8 (13)
H18A—C18—H18B	108.2	F6'—P1—F3'	89.0 (11)
O1—C16—C15	111.3 (3)	F5'—P1—F3'	83.6 (14)
O1—C16—H16A	109.4	F2—P1—F3'	87.4 (7)
C15—C16—H16A	109.4	F5—P1—F3'	75.2 (9)
O1—C16—H16B	109.4	F1—P1—F3'	109.2 (8)
C15—C16—H16B	109.4	F2'—P1—F3'	84.6 (9)
H16A—C16—H16B	108.0	F1'—P1—F3'	83.9 (9)
C4—C5—C6	120.4 (3)	F4—P1—F3'	164.7 (8)
C4—C5—H5A	119.8	F6—P1—F3'	94.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.91	2.04	2.942 (4)	171
C10—H10A···F1ii	0.93	2.43	3.296 (9)	155
C14—H14A···F3	0.97	2.39	3.355 (12)	171
C15—H15A···F6	0.97	2.46	3.377 (8)	158
C15—H15B···F3ii	0.97	2.48	3.412 (10)	161
C15—H15B···F3′ii	0.97	2.54	3.51 (2)	172
C10—H10A···F1′ii	0.93	2.45	3.26 (2)	145
C14—H14B···F1′ii	0.97	2.38	3.097 (16)	130
C5—H5A···F2′iii	0.93	2.48	3.41 (2)	178
C17—H17B···F6′iv	0.97	2.47	3.29 (3)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.91	2.04	2.942 (4)	171
C10—H10A⋯F1ii	0.93	2.43	3.296 (9)	155
C14—H14A⋯F3	0.97	2.39	3.355 (12)	171
C15—H15A⋯F6	0.97	2.46	3.377 (8)	158
C15—H15B⋯F3ii	0.97	2.48	3.412 (10)	161
C15—H15B⋯F3′ii	0.97	2.54	3.51 (2)	172
C10—H10A⋯F1′ii	0.93	2.45	3.26 (2)	145
C14—H14B⋯F1′ii	0.97	2.38	3.097 (16)	130
C5—H5A⋯F2′iii	0.93	2.48	3.41 (2)	178
C17—H17B⋯F6′iv	0.97	2.47	3.29 (3)	143

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