N,N-Di­methyl­dehydro­abietyl­ammonium chloride ethanol monosolvate

Huang, X.-Z.; Rao, X.-P.; Cui, Y.-J.

doi:10.1107/S1600536813013846

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o959

doi:10.1107/S1600536813013846

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N,N-Dimethyldehydroabietylammonium chloride ethanol monosolvate

Xiu-Zhi Huang,^a Xiao-Ping Rao ^a ^* and Yan-Jie Cui ^a

^aInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, Jiangsu Province, National Engineering Laboratory for Biomass Chemical Utilization, Key Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, People's Republic of China
^*Correspondence e-mail: rxping2001@163.com

(Received 25 April 2013; accepted 20 May 2013; online 25 May 2013)

The title compound {systematic name: 1-[(1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl]-N,N-dimethylmethanaminium chloride ethanol monosolvate}, C₂₂H₃₆N⁺·Cl⁻·C₂H₆O, was synthesized from dehydroabietylamine by N-methylation with formaldehyde/formic acid and transformation into the hydrochloride. The dehydroabietyl moiety exhibits the usual conformation with the two cyclohexane rings in chair and half-chair conformations and a trans-ring junction. The crystal structure is built up from columns of the dehydroabietyl moieties stacked along the a axis. These columns are held together by the chloride ions via N—H⋯Cl and C—H⋯Cl interactions, which establish a two-dimensional network parallel to (010). The ethanol solvent molecules are located between the columns and anchored via O—H⋯Cl hydrogen bonds.

Related literature

For the biological activity of dehydroabietylamine derivatives, see: Goodson et al. (1999 ); Rao et al. (2008 ); Wilkerson et al. (1993 ); For the crystal structures of dehydroabietic acid derivatives, see Rao et al. (2006 , 2009 ).

Experimental

Crystal data

C₂₂H₃₆N⁺·Cl⁻·C₂H₆O
M_r = 396.04
Monoclinic, P 2₁
a = 6.0560 (12) Å
b = 10.963 (2) Å
c = 18.554 (4) Å
β = 98.62 (3)°
V = 1217.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.951, T_max = 0.983
4924 measured reflections
4476 independent reflections
2605 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.190
S = 0.99
4476 reflections
250 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 2102 Friedel pairs
Flack parameter: −0.02 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0B⋯Cl	0.91	2.27	3.097 (4)	152
O—H0A⋯Cl	0.82	2.27	3.092 (9)	178
C18—H18B⋯Clⁱ	0.96	2.78	3.694 (6)	160
C18—H18C⋯Clⁱⁱ	0.96	2.84	3.693 (6)	149
C2—H2B⋯Cl	0.97	2.86	3.775 (5)	158
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813013846/qk2059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813013846/qk2059Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813013846/qk2059Isup3.cml

checkCIF report

Comment top

Dehydroabietylamine is widely used as starting material for design and synthesis of biological compounds (Goodson et al., 1999; Rao et al., 2008; Wilkerson et al., 1993). In continuation of previous investigations (Rao et al., 2006, 2009) the title compound was studied. The overall geometry of dehydroabietyl moiety in the title compound is comparable to that found for dehydroabietic acid and related compounds (Rao et al., 2009). There are three six-membered rings, which form planar, half-chair and chair conformations, respectively. The absolute structure of the title compound could be secured via anomalous dispersion effects (Flack parameter -0.02 (13)) and is in accordance with expectations. Thus the three chiral centers in the molecule have R–, S– and R–configurations, respectively.

Related literature top

For the biological activity of dehydroabietylamine derivatives, see: Goodson et al. (1999); Rao et al. (2008); Wilkerson et al. (1993); For the crystal structures of dehydroabietic acid derivatives, see Rao et al. (2006, 2009).

Experimental top

Dehydroabietylamine (13.57 g, 0.05 mol, Hangzhou Wanjing Company), formaldehyde (11.95 g, 36%) and formic acid (12.83 g, 85%) were added to ethanol solution (13.6 g, 95%), the mixture was stirred for 4h at 60–70 °C to form N,N-dimethydehydroabietylamine. 4.0 ml concentrated hydrochloric acid was added to a solution (10.0 g, 0.032 mol) of N,N-dimethydehydroabietylamine in 50 ml water and the mixture was stirred for 4h at 60–70 °C. After cooling to room temperature, the solvent was distilled off under vacuum. Crystals were obtained by recrystallization from ethanol.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound, with H atoms represented by small spheres of arbitrary radius and displacement ellipsoids at the 30% probability level.

1-[(1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl]-N,N-dimethylmethanaminium chloride ethanol monosolvate top

Crystal data top

C₂₂H₃₆N⁺·Cl⁻·C₂H₆O	F(000) = 436
M_r = 396.04	D_x = 1.080 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 6.0560 (12) Å	θ = 9–13°
b = 10.963 (2) Å	µ = 0.17 mm⁻¹
c = 18.554 (4) Å	T = 293 K
β = 98.62 (3)°	Block, white
V = 1217.9 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	2605 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.4°, θ_min = 1.1°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
T_min = 0.951, T_max = 0.983	l = −22→22
4924 measured reflections	3 standard reflections every 200 reflections
4476 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.074	H-atom parameters constrained
wR(F²) = 0.190	w = 1/[σ²(F_o²) + (0.080P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
4476 reflections	Δρ_max = 0.27 e Å⁻³
250 parameters	Δρ_min = −0.20 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 2102 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (13)

Crystal data top

C₂₂H₃₆N⁺·Cl⁻·C₂H₆O	V = 1217.9 (4) Å³
M_r = 396.04	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.0560 (12) Å	µ = 0.17 mm⁻¹
b = 10.963 (2) Å	T = 293 K
c = 18.554 (4) Å	0.30 × 0.20 × 0.10 mm
β = 98.62 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2605 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.951, T_max = 0.983	3 standard reflections every 200 reflections
4924 measured reflections	intensity decay: 1%
4476 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	H-atom parameters constrained
wR(F²) = 0.190	Δρ_max = 0.27 e Å⁻³
S = 0.99	Δρ_min = −0.20 e Å⁻³
4476 reflections	Absolute structure: Flack (1983), 2102 Friedel pairs
250 parameters	Absolute structure parameter: −0.02 (13)
2 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl	0.1469 (2)	0.07595 (14)	0.50514 (8)	0.0890 (5)
C1	0.4016 (7)	0.1919 (4)	0.3221 (2)	0.0511 (11)
C2	0.4933 (8)	0.0669 (5)	0.3522 (2)	0.0642 (12)
H2A	0.6522	0.0747	0.3689	0.077*
H2B	0.4221	0.0456	0.3939	0.077*
C3	0.4563 (11)	−0.0354 (5)	0.2971 (3)	0.0810 (17)
H3A	0.2973	−0.0480	0.2826	0.097*
H3B	0.5197	−0.1103	0.3191	0.097*
C4	0.5646 (9)	−0.0053 (4)	0.2303 (3)	0.0669 (14)
H4A	0.5429	−0.0730	0.1963	0.080*
H4B	0.7239	0.0056	0.2449	0.080*
C5	0.4646 (7)	0.1118 (4)	0.1920 (3)	0.0554 (12)
C6	0.5008 (8)	0.2166 (4)	0.2491 (2)	0.0567 (11)
H6A	0.6628	0.2228	0.2635	0.068*
C7	0.5873 (8)	0.1477 (5)	0.1286 (3)	0.0652 (13)
C8	0.6409 (8)	0.2667 (5)	0.1122 (3)	0.0654 (13)
C9	0.5920 (11)	0.3702 (5)	0.1597 (3)	0.0817 (17)
H9A	0.5321	0.4376	0.1290	0.098*
H9B	0.7310	0.3974	0.1881	0.098*
C10	0.4279 (9)	0.3391 (5)	0.2118 (3)	0.0700 (14)
H10A	0.2779	0.3322	0.1851	0.084*
H10B	0.4284	0.4028	0.2481	0.084*
C11	0.6423 (9)	0.0552 (5)	0.0795 (3)	0.0705 (14)
H11A	0.6097	−0.0259	0.0881	0.085*
C12	0.7413 (8)	0.0836 (6)	0.0204 (3)	0.0741 (14)
H12A	0.7769	0.0214	−0.0099	0.089*
C13	0.7905 (9)	0.2049 (6)	0.0044 (3)	0.0745 (15)
C14	0.7355 (9)	0.2915 (5)	0.0515 (3)	0.0710 (14)
H14A	0.7643	0.3726	0.0416	0.085*
C15	0.2191 (8)	0.0887 (6)	0.1565 (3)	0.0806 (15)
H15A	0.2172	0.0378	0.1144	0.121*
H15B	0.1484	0.1652	0.1423	0.121*
H15C	0.1400	0.0490	0.1911	0.121*
C16	0.1456 (8)	0.1985 (5)	0.3140 (3)	0.0741 (14)
H16A	0.1003	0.1992	0.3614	0.111*
H16B	0.0821	0.1287	0.2872	0.111*
H16C	0.0945	0.2716	0.2882	0.111*
C17	0.5076 (9)	0.2897 (4)	0.3771 (2)	0.0643 (13)
H17A	0.6689	0.2834	0.3819	0.077*
H17B	0.4655	0.3699	0.3577	0.077*
N	0.4394 (6)	0.2782 (3)	0.4510 (2)	0.0579 (10)
H0B	0.3563	0.2090	0.4508	0.069*
C18	0.6406 (8)	0.2623 (6)	0.5085 (3)	0.0756 (15)
H18A	0.5928	0.2483	0.5549	0.113*
H18B	0.7308	0.3346	0.5111	0.113*
H18C	0.7265	0.1937	0.4963	0.113*
C19	0.3003 (9)	0.3800 (5)	0.4710 (3)	0.0760 (15)
H19A	0.1697	0.3878	0.4349	0.114*
H19B	0.3847	0.4544	0.4733	0.114*
H19C	0.2561	0.3640	0.5176	0.114*
C20	0.9025 (11)	0.2391 (7)	−0.0617 (3)	0.0890 (18)
H20A	0.9040	0.3285	−0.0630	0.107*
C21	0.7518 (13)	0.1982 (8)	−0.1330 (4)	0.124 (3)
H21A	0.8099	0.2308	−0.1744	0.186*
H21B	0.6026	0.2277	−0.1330	0.186*
H21C	0.7499	0.1107	−0.1357	0.186*
C22	1.1396 (12)	0.2007 (9)	−0.0568 (4)	0.136 (3)
H22A	1.2276	0.2417	−0.0167	0.204*
H22B	1.1939	0.2214	−0.1013	0.204*
H22C	1.1503	0.1141	−0.0494	0.204*
O	0.1487 (19)	0.0080 (8)	0.6670 (5)	0.246 (5)
H0A	0.1446	0.0264	0.6239	0.295*
C23	0.117 (4)	0.2011 (17)	0.6937 (7)	0.332 (14)
H23A	0.0267	0.2620	0.7123	0.498*
H23B	0.1269	0.2182	0.6436	0.498*
H23C	0.2642	0.2020	0.7216	0.498*
C24	0.022 (3)	0.0876 (13)	0.6992 (7)	0.255 (8)
H24B	0.0224	0.0660	0.7499	0.306*
H24A	−0.1309	0.0870	0.6744	0.306*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0935 (10)	0.0739 (8)	0.1121 (11)	−0.0040 (8)	0.0564 (9)	0.0053 (9)
C1	0.044 (2)	0.047 (3)	0.063 (3)	0.003 (2)	0.013 (2)	−0.001 (2)
C2	0.069 (3)	0.062 (3)	0.065 (3)	0.017 (3)	0.021 (2)	0.015 (3)
C3	0.108 (5)	0.055 (3)	0.083 (4)	0.004 (3)	0.022 (4)	0.001 (3)
C4	0.083 (4)	0.055 (3)	0.066 (3)	0.006 (3)	0.021 (3)	−0.006 (2)
C5	0.052 (3)	0.055 (3)	0.059 (3)	0.000 (2)	0.007 (2)	−0.003 (2)
C6	0.070 (3)	0.050 (2)	0.052 (2)	0.009 (2)	0.015 (2)	0.005 (2)
C7	0.062 (3)	0.072 (3)	0.061 (3)	0.010 (3)	0.008 (3)	0.003 (3)
C8	0.073 (3)	0.064 (3)	0.062 (3)	0.010 (3)	0.020 (3)	0.013 (3)
C9	0.118 (5)	0.062 (3)	0.073 (3)	0.006 (3)	0.039 (3)	0.011 (3)
C10	0.077 (4)	0.064 (3)	0.070 (3)	0.017 (3)	0.015 (3)	0.007 (3)
C11	0.087 (4)	0.061 (3)	0.067 (3)	0.001 (3)	0.023 (3)	−0.004 (3)
C12	0.070 (3)	0.089 (4)	0.061 (3)	0.007 (4)	0.006 (3)	−0.013 (3)
C13	0.068 (3)	0.088 (4)	0.068 (3)	0.003 (3)	0.011 (3)	0.020 (3)
C14	0.077 (4)	0.071 (3)	0.067 (3)	−0.003 (3)	0.016 (3)	0.005 (3)
C15	0.071 (3)	0.093 (4)	0.076 (3)	−0.015 (3)	0.007 (3)	−0.008 (3)
C16	0.053 (3)	0.084 (4)	0.084 (3)	0.005 (3)	0.007 (3)	−0.007 (3)
C17	0.078 (3)	0.060 (3)	0.061 (3)	−0.013 (3)	0.028 (3)	0.004 (2)
N	0.053 (2)	0.052 (2)	0.070 (2)	0.0007 (18)	0.015 (2)	−0.0016 (19)
C18	0.067 (3)	0.087 (4)	0.070 (3)	0.009 (3)	0.000 (3)	0.008 (3)
C19	0.070 (4)	0.070 (3)	0.091 (4)	0.016 (3)	0.022 (3)	−0.015 (3)
C20	0.094 (4)	0.109 (5)	0.069 (3)	0.006 (4)	0.026 (3)	0.020 (3)
C21	0.113 (5)	0.172 (8)	0.081 (4)	−0.020 (5)	−0.001 (4)	0.028 (5)
C22	0.099 (5)	0.192 (9)	0.124 (6)	0.007 (6)	0.043 (5)	0.050 (6)
O	0.380 (14)	0.188 (7)	0.170 (7)	0.130 (8)	0.042 (8)	0.004 (6)
C23	0.54 (3)	0.29 (2)	0.171 (12)	−0.32 (2)	0.062 (15)	−0.073 (12)
C24	0.45 (3)	0.182 (13)	0.162 (10)	0.083 (18)	0.139 (14)	0.020 (10)

Geometric parameters (Å, º) top

C1—C16	1.537 (6)	C15—H15B	0.9600
C1—C2	1.551 (6)	C15—H15C	0.9600
C1—C17	1.551 (6)	C16—H16A	0.9600
C1—C6	1.585 (6)	C16—H16B	0.9600
C2—C3	1.511 (7)	C16—H16C	0.9600
C2—H2A	0.9700	C17—N	1.496 (5)
C2—H2B	0.9700	C17—H17A	0.9700
C3—C4	1.523 (7)	C17—H17B	0.9700
C3—H3A	0.9700	N—C19	1.479 (6)
C3—H3B	0.9700	N—C18	1.505 (6)
C4—C5	1.547 (6)	N—H0B	0.9100
C4—H4A	0.9700	C18—H18A	0.9600
C4—H4B	0.9700	C18—H18B	0.9600
C5—C7	1.533 (7)	C18—H18C	0.9600
C5—C15	1.554 (6)	C19—H19A	0.9600
C5—C6	1.556 (6)	C19—H19B	0.9600
C6—C10	1.544 (6)	C19—H19C	0.9600
C6—H6A	0.9800	C20—C22	1.486 (9)
C7—C8	1.390 (7)	C20—C21	1.557 (9)
C7—C11	1.436 (7)	C20—H20A	0.9800
C8—C14	1.365 (7)	C21—H21A	0.9600
C8—C9	1.494 (7)	C21—H21B	0.9600
C9—C10	1.524 (7)	C21—H21C	0.9600
C9—H9A	0.9700	C22—H22A	0.9600
C9—H9B	0.9700	C22—H22B	0.9600
C10—H10A	0.9700	C22—H22C	0.9600
C10—H10B	0.9700	O—C24	1.358 (13)
C11—C12	1.361 (7)	O—H0A	0.8200
C11—H11A	0.9300	C23—C24	1.382 (13)
C12—C13	1.404 (8)	C23—H23A	0.9600
C12—H12A	0.9300	C23—H23B	0.9600
C13—C14	1.365 (7)	C23—H23C	0.9600
C13—C20	1.534 (7)	C24—H24B	0.9700
C14—H14A	0.9300	C24—H24A	0.9700
C15—H15A	0.9600

C16—C1—C2	112.2 (4)	C5—C15—H15B	109.5
C16—C1—C17	110.1 (4)	H15A—C15—H15B	109.5
C2—C1—C17	106.4 (4)	C5—C15—H15C	109.5
C16—C1—C6	114.5 (4)	H15A—C15—H15C	109.5
C2—C1—C6	107.3 (3)	H15B—C15—H15C	109.5
C17—C1—C6	105.8 (3)	C1—C16—H16A	109.5
C3—C2—C1	113.8 (4)	C1—C16—H16B	109.5
C3—C2—H2A	108.8	H16A—C16—H16B	109.5
C1—C2—H2A	108.8	C1—C16—H16C	109.5
C3—C2—H2B	108.8	H16A—C16—H16C	109.5
C1—C2—H2B	108.8	H16B—C16—H16C	109.5
H2A—C2—H2B	107.7	N—C17—C1	113.7 (4)
C2—C3—C4	110.5 (4)	N—C17—H17A	108.8
C2—C3—H3A	109.5	C1—C17—H17A	108.8
C4—C3—H3A	109.5	N—C17—H17B	108.8
C2—C3—H3B	109.5	C1—C17—H17B	108.8
C4—C3—H3B	109.5	H17A—C17—H17B	107.7
H3A—C3—H3B	108.1	C19—N—C17	114.3 (4)
C3—C4—C5	111.6 (4)	C19—N—C18	109.9 (4)
C3—C4—H4A	109.3	C17—N—C18	110.8 (4)
C5—C4—H4A	109.3	C19—N—H0B	107.1
C3—C4—H4B	109.3	C17—N—H0B	107.1
C5—C4—H4B	109.3	C18—N—H0B	107.1
H4A—C4—H4B	108.0	N—C18—H18A	109.5
C7—C5—C4	111.3 (4)	N—C18—H18B	109.5
C7—C5—C15	105.1 (4)	H18A—C18—H18B	109.5
C4—C5—C15	110.1 (4)	N—C18—H18C	109.5
C7—C5—C6	107.3 (4)	H18A—C18—H18C	109.5
C4—C5—C6	107.1 (4)	H18B—C18—H18C	109.5
C15—C5—C6	115.9 (4)	N—C19—H19A	109.5
C10—C6—C5	109.6 (4)	N—C19—H19B	109.5
C10—C6—C1	114.3 (4)	H19A—C19—H19B	109.5
C5—C6—C1	115.0 (4)	N—C19—H19C	109.5
C10—C6—H6A	105.7	H19A—C19—H19C	109.5
C5—C6—H6A	105.7	H19B—C19—H19C	109.5
C1—C6—H6A	105.7	C22—C20—C13	114.9 (5)
C8—C7—C11	116.1 (5)	C22—C20—C21	114.0 (6)
C8—C7—C5	124.4 (4)	C13—C20—C21	109.6 (5)
C11—C7—C5	119.5 (4)	C22—C20—H20A	105.8
C14—C8—C7	120.6 (5)	C13—C20—H20A	105.8
C14—C8—C9	118.7 (5)	C21—C20—H20A	105.8
C7—C8—C9	120.7 (4)	C20—C21—H21A	109.5
C8—C9—C10	114.2 (5)	C20—C21—H21B	109.5
C8—C9—H9A	108.7	H21A—C21—H21B	109.5
C10—C9—H9A	108.7	C20—C21—H21C	109.5
C8—C9—H9B	108.7	H21A—C21—H21C	109.5
C10—C9—H9B	108.7	H21B—C21—H21C	109.5
H9A—C9—H9B	107.6	C20—C22—H22A	109.5
C9—C10—C6	108.0 (4)	C20—C22—H22B	109.5
C9—C10—H10A	110.1	H22A—C22—H22B	109.5
C6—C10—H10A	110.1	C20—C22—H22C	109.5
C9—C10—H10B	110.1	H22A—C22—H22C	109.5
C6—C10—H10B	110.1	H22B—C22—H22C	109.5
H10A—C10—H10B	108.4	C24—O—H0A	109.5
C12—C11—C7	121.5 (5)	C24—C23—H23A	109.5
C12—C11—H11A	119.3	C24—C23—H23B	109.5
C7—C11—H11A	119.3	H23A—C23—H23B	109.5
C11—C12—C13	121.3 (5)	C24—C23—H23C	109.5
C11—C12—H12A	119.3	H23A—C23—H23C	109.5
C13—C12—H12A	119.3	H23B—C23—H23C	109.5
C14—C13—C12	116.3 (5)	O—C24—C23	106.1 (17)
C14—C13—C20	121.4 (5)	O—C24—H24B	110.5
C12—C13—C20	122.3 (5)	C23—C24—H24B	110.5
C8—C14—C13	124.2 (5)	O—C24—H24A	110.5
C8—C14—H14A	117.9	C23—C24—H24A	110.5
C13—C14—H14A	117.9	H24B—C24—H24A	108.7
C5—C15—H15A	109.5

C16—C1—C2—C3	74.3 (5)	C5—C7—C8—C14	−175.0 (5)
C17—C1—C2—C3	−165.2 (4)	C11—C7—C8—C9	−179.8 (5)
C6—C1—C2—C3	−52.3 (5)	C5—C7—C8—C9	3.7 (8)
C1—C2—C3—C4	58.2 (6)	C14—C8—C9—C10	162.8 (5)
C2—C3—C4—C5	−60.7 (6)	C7—C8—C9—C10	−16.0 (7)
C3—C4—C5—C7	175.3 (4)	C8—C9—C10—C6	47.1 (6)
C3—C4—C5—C15	−68.6 (5)	C5—C6—C10—C9	−68.4 (5)
C3—C4—C5—C6	58.2 (5)	C1—C6—C10—C9	160.8 (4)
C7—C5—C6—C10	54.1 (5)	C8—C7—C11—C12	0.0 (7)
C4—C5—C6—C10	173.8 (4)	C5—C7—C11—C12	176.7 (4)
C15—C5—C6—C10	−63.0 (5)	C7—C11—C12—C13	−1.0 (8)
C7—C5—C6—C1	−175.4 (4)	C11—C12—C13—C14	0.5 (7)
C4—C5—C6—C1	−55.8 (5)	C11—C12—C13—C20	179.8 (5)
C15—C5—C6—C1	67.5 (5)	C7—C8—C14—C13	−2.1 (8)
C16—C1—C6—C10	55.3 (5)	C9—C8—C14—C13	179.1 (5)
C2—C1—C6—C10	−179.4 (4)	C12—C13—C14—C8	1.0 (8)
C17—C1—C6—C10	−66.1 (5)	C20—C13—C14—C8	−178.3 (5)
C16—C1—C6—C5	−72.8 (5)	C16—C1—C17—N	57.9 (5)
C2—C1—C6—C5	52.5 (5)	C2—C1—C17—N	−64.0 (5)
C17—C1—C6—C5	165.8 (4)	C6—C1—C17—N	−178.0 (4)
C4—C5—C7—C8	−139.8 (5)	C1—C17—N—C19	−113.0 (5)
C15—C5—C7—C8	101.1 (6)	C1—C17—N—C18	122.1 (4)
C6—C5—C7—C8	−22.8 (6)	C14—C13—C20—C22	110.1 (7)
C4—C5—C7—C11	43.9 (6)	C12—C13—C20—C22	−69.2 (8)
C15—C5—C7—C11	−75.3 (5)	C14—C13—C20—C21	−120.0 (6)
C6—C5—C7—C11	160.8 (4)	C12—C13—C20—C21	60.8 (8)
C11—C7—C8—C14	1.5 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0B···Cl	0.91	2.27	3.097 (4)	152
O—H0A···Cl	0.82	2.27	3.092 (9)	178
C18—H18B···Clⁱ	0.96	2.78	3.694 (6)	160
C18—H18C···Clⁱⁱ	0.96	2.84	3.693 (6)	149
C2—H2B···Cl	0.97	2.86	3.775 (5)	158

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₃₆N⁺·Cl⁻·C₂H₆O
M_r	396.04
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.0560 (12), 10.963 (2), 18.554 (4)
β (°)	98.62 (3)
V (Å³)	1217.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.951, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	4924, 4476, 2605
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.190, 0.99
No. of reflections	4476
No. of parameters	250
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20
Absolute structure	Flack (1983), 2102 Friedel pairs
Absolute structure parameter	−0.02 (13)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0B···Cl	0.91	2.27	3.097 (4)	151.7
O—H0A···Cl	0.82	2.27	3.092 (9)	177.9
C18—H18B···Clⁱ	0.96	2.78	3.694 (6)	160.2
C18—H18C···Clⁱⁱ	0.96	2.84	3.693 (6)	148.9
C2—H2B···Cl	0.97	2.86	3.775 (5)	157.7

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z.

Acknowledgements

This research was supported financially by grants from the National Forestry Bureau 948 (2012–4–13).

References

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