(S,E)-N-Methyl-4-[(S)2,6,6-trimethyl-4-oxocyclo­hex-2-en­yl]but-3-en-2-aminium chloride

Chang, L.-S.; Duan, H.-Q.

doi:10.1107/S1600536811015297

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1289

doi:10.1107/S1600536811015297

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(S,E)-N-Methyl-4-[(S)2,6,6-trimethyl-4-oxocyclohex-2-enyl]but-3-en-2-aminium chloride

Liu-Shuan Chang ^a and Hong-Quan Duan ^a ^*

^aSchool of Pharmaceutical Sciences, Research Center of Basic Medical Sciences, Tianjin Medical University, Tianjin 300070, People's Republic of China
^*Correspondence e-mail: duanhq@tijmu.edu.cn

(Received 18 March 2011; accepted 22 April 2011; online 7 May 2011)

The title compound, C₁₄H₂₄NO⁺·Cl⁻, crystallizes with four independent molecules in the asymmetric unit. It was isolated from plant Pachysandra terminalis Siebold & Zucc. The six-membered ring has a conformation close to an envelope. In the crystal, N—H⋯Cl hydrogen-bonding interactions exist between secondary ammonium groups and free chloride anions, resulting in a one-dimensional supramolecular structure oriented along [100]. The crystal studied was found to be a two-component non-merohedral twin with twin law [ $[\overline{1}]$ 00/0 $[\overline{1}]$ 0/101], the fractional contribution of the minor component being approximately 33%.

Related literature

For a general background to Pachysandra terminalis Siebold & Zucc., see: Kikuchi & Uyeo (1965 , 1967a ,b ); Kikuchi et al. (1981 ); Chiu et al. (1990 , 1992 ). For the determination of the twin law, see: Spek (2009 ).

Experimental

Crystal data

C₁₄H₂₄NO⁺·Cl⁻
M_r = 257.79
Monoclinic, P 2₁
a = 14.547 (3) Å
b = 12.247 (2) Å
c = 19.035 (4) Å
β = 112.46 (3)°
V = 3134.0 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 113 K
0.20 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.955, T_max = 0.977
30954 measured reflections
12371 independent reflections
10363 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.092
S = 1.01
12371 reflections
658 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ), 4816 Friedel pairs
Flack parameter: 0.03 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.93 (2)	2.19 (2)	3.109 (3)	173 (3)
N1—H1B⋯Cl4ⁱ	0.93 (2)	2.17 (2)	3.069 (4)	163 (3)
N2—H2A⋯Cl2	0.94 (2)	2.17 (2)	3.105 (3)	171 (3)
N2—H2B⋯Cl1	0.91 (2)	2.19 (2)	3.089 (4)	175 (4)
N3—H3A⋯Cl3ⁱⁱ	0.93 (2)	2.18 (2)	3.108 (3)	175 (3)
N3—H3B⋯Cl2ⁱ	0.92 (2)	2.18 (2)	3.088 (4)	171 (3)
N4—H4A⋯Cl4ⁱⁱⁱ	0.85 (3)	2.28 (4)	3.117 (4)	169 (4)
N4—H4B⋯Cl3ⁱⁱⁱ	0.96 (4)	2.13 (4)	3.083 (4)	172 (4)
Symmetry codes: (i) x, y, z-1; (ii) x+1, y, z-1; (iii) x+1, y, z.

Data collection: CrystalClear (Rigaku/MSC, 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: CrystalStructure (Rigaku/MSC, 2005) and SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015297/bh2347sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015297/bh2347Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015297/bh2347Isup3.cml

checkCIF report

Comment top

The title substance is a new alkaloid skeleton from natural source, which is isolated from the n-butanol soluble fraction of Pachysandra terminalis Sieb. & Zucc. The plant P. terminalis is mainly distributed in Japan and Hubei Province of China. The whole plant of P. terminalis has been used in Chinese folk medicine to treat rheumatism, spasm of calf and abnormal menstruation. A series of alkaloids and triterpenoids have been isolated from Pachysandra terminalis Sieb. & Zucc. (Kikuchi & Uyeo, 1965, 1967a,b; Kikuchi et al., 1981; Chiu et al., 1990, 1992). In order to find its bioactive ingredients we studied the chemical constituents and found the title compound.

Four independent molecules can be observed in an asymmetric unit (Fig. 1). The NH₂⁺ groups in the molecules act as an hydrogen-bond donors to Cl^- ions, forming N—H···Cl hydrogen bonds, resulting in a one-dimensional supramolecular structure (Fig. 2).

Related literature top

For a general background to Pachysandra terminalis Siebold & Zucc., see: Kikuchi & Uyeo (1965, 1967a,b); Kikuchi et al. (1981); Chiu et al. (1990, 1992). For the determination of the twin law, see: Spek (2009).

Experimental top

Plant material: Pachysandra terminalis Sieb. & Zucc. was collected from the Hefeng area in Hubei Province of China and authenticated by Professor Ding-Rong Wan (School of Life Sciences, South-Central University For Nationalities). Extraction and Isolation: The dry powders (8 kg) of the whole plant of P. terminalis were refluxed for 6 h with 95% EtOH three times. After removal of the EtOH under reduced pressure, the extract was suspended in water and then partitioned with petroleum ether, EtOAc and n-butanol. The n-butanol soluble fraction (360 g) was subjected to macroporous resin column chromatography with a gradient of EtOH-H₂O (1:9 → 19:1 v/v) to afford five fractions (F₁ to F₅), pooled by common TLC characteristics. F₂ (9.6 g) was separated by a Toyopeal HW-40 column (CH₂Cl₂—MeOH, 1:1 v/v) to afford four fractions (F_2.1 to F_2.4). F_2.2 was separated by preparative HPLC with MeOH to give three fractions (F_2.2.1 to F_2.2.3). F_2.2.1 was separated by preparative HPLC (MeOH-H₂O, 3:7 v/v) to afford the title compound. Colourless block crystals were obtained by slow evaporation from a methanol solution of the product, at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: CrystalStructure (Rigaku/MSC, 2005) and SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radius. There are four independent molecules in an asymmetric unit.
	Fig. 2. The packing of the title compound, showing the one-dimensional structure. Hydrogen bonds are drawn as dashed lines. For clarity H atoms have been omitted.

(S,E)-N-Methyl-4-[(S)2,6,6-trimethyl- 4-oxocyclohex-2-enyl]but-3-en-2-aminium chloride top

Crystal data top

C₁₄H₂₄NO⁺·Cl⁻	F(000) = 1120
M_r = 257.79	D_x = 1.093 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9688 reflections
a = 14.547 (3) Å	θ = 2.9–27.5°
b = 12.247 (2) Å	µ = 0.23 mm⁻¹
c = 19.035 (4) Å	T = 113 K
β = 112.46 (3)°	Block, colourless
V = 3134.0 (13) Å³	0.20 × 0.12 × 0.10 mm
Z = 8

Data collection top

Rigaku Saturn CCD area-detector diffractometer	12371 independent reflections
Radiation source: rotating anode	10363 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.046
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.5°, θ_min = 1.7°
ω and ϕ scans	h = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −15→14
T_min = 0.955, T_max = 0.977	l = −24→24
30954 measured reflections

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0421P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
12371 reflections	Δρ_max = 0.24 e Å⁻³
658 parameters	Δρ_min = −0.35 e Å⁻³
7 restraints	Absolute structure: Flack (1983), 4816 Friedel pairs
0 constraints	Absolute structure parameter: 0.03 (4)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₂₄NO⁺·Cl⁻	V = 3134.0 (13) Å³
M_r = 257.79	Z = 8
Monoclinic, P2₁	Mo Kα radiation
a = 14.547 (3) Å	µ = 0.23 mm⁻¹
b = 12.247 (2) Å	T = 113 K
c = 19.035 (4) Å	0.20 × 0.12 × 0.10 mm
β = 112.46 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	12371 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	10363 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.977	R_int = 0.046
30954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	Δρ_max = 0.24 e Å⁻³
S = 1.01	Δρ_min = −0.35 e Å⁻³
12371 reflections	Absolute structure: Flack (1983), 4816 Friedel pairs
658 parameters	Absolute structure parameter: 0.03 (4)
7 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.60208 (7)	0.40656 (9)	0.85070 (5)	0.0284 (3)
Cl2	0.75173 (7)	0.36146 (9)	0.65009 (5)	0.0254 (3)
Cl3	0.10038 (7)	0.36764 (9)	0.84472 (5)	0.0276 (3)
Cl4	0.25369 (7)	0.31672 (9)	0.65341 (6)	0.0290 (3)
N1	0.3768 (2)	0.3827 (3)	−0.18164 (19)	0.0237 (8)
H1A	0.4425 (16)	0.392 (3)	−0.176 (2)	0.028*
H1B	0.352 (2)	0.355 (3)	−0.2308 (13)	0.028*
N2	0.5596 (3)	0.3447 (3)	0.68389 (19)	0.0226 (8)
H2A	0.615 (2)	0.356 (3)	0.671 (2)	0.027*
H2B	0.572 (3)	0.359 (3)	0.7333 (12)	0.027*
N3	0.8777 (2)	0.3890 (3)	−0.17864 (18)	0.0219 (8)
H3A	0.9452 (15)	0.386 (3)	−0.169 (2)	0.026*
H3B	0.847 (2)	0.378 (3)	−0.2302 (11)	0.026*
N4	1.0515 (3)	0.3390 (3)	0.6733 (2)	0.0237 (8)
H4A	1.102 (3)	0.329 (3)	0.662 (2)	0.028*
H4B	1.064 (3)	0.355 (3)	0.726 (2)	0.028*
O1	0.1485 (2)	0.2664 (3)	0.13065 (18)	0.0516 (9)
O2	0.0107 (2)	0.3327 (3)	0.3666 (2)	0.0679 (12)
O3	0.6463 (3)	0.3929 (3)	0.1392 (2)	0.0620 (11)
O4	0.5144 (2)	0.4635 (3)	0.36417 (18)	0.0535 (9)
C1	0.4766 (3)	0.1922 (3)	0.1329 (2)	0.0366 (10)
H1C	0.4704	0.1260	0.1598	0.055*
H1D	0.5352	0.2336	0.1650	0.055*
H1E	0.4837	0.1718	0.0855	0.055*
C2	0.3856 (3)	0.2610 (3)	0.1153 (2)	0.0264 (9)
C3	0.3091 (3)	0.2310 (4)	0.1332 (2)	0.0330 (10)
H3	0.3130	0.1635	0.1588	0.040*
C4	0.2191 (3)	0.2975 (4)	0.1151 (2)	0.0332 (10)
C5	0.2141 (3)	0.4036 (3)	0.0735 (2)	0.0288 (9)
H5A	0.1752	0.4568	0.0899	0.035*
H5B	0.1778	0.3908	0.0184	0.035*
C6	0.3160 (3)	0.4543 (3)	0.0858 (2)	0.0269 (9)
C7	0.3836 (3)	0.3657 (4)	0.0718 (2)	0.0240 (8)
H7	0.4529	0.3950	0.0889	0.029*
C8	0.3653 (3)	0.4953 (4)	0.1683 (2)	0.0388 (11)
H8A	0.3754	0.4336	0.2033	0.058*
H8B	0.3222	0.5496	0.1782	0.058*
H8C	0.4297	0.5286	0.1760	0.058*
C9	0.3024 (3)	0.5500 (3)	0.0317 (2)	0.0374 (9)
H9A	0.2632	0.6071	0.0434	0.056*
H9B	0.2675	0.5251	−0.0207	0.056*
H9C	0.3676	0.5793	0.0377	0.056*
C10	0.3498 (3)	0.3350 (3)	−0.0105 (2)	0.0226 (9)
H10	0.2809	0.3207	−0.0366	0.027*
C11	0.4069 (3)	0.3259 (3)	−0.0505 (2)	0.0232 (9)
H11	0.4756	0.3429	−0.0264	0.028*
C12	0.3682 (3)	0.2903 (3)	−0.1310 (2)	0.0241 (9)
H12	0.2963	0.2715	−0.1465	0.029*
C13	0.4215 (3)	0.1921 (4)	−0.1461 (2)	0.0346 (10)
H13A	0.4920	0.2095	−0.1320	0.052*
H13B	0.3918	0.1734	−0.2002	0.052*
H13C	0.4150	0.1300	−0.1159	0.052*
C14	0.3322 (3)	0.4880 (4)	−0.1721 (3)	0.0301 (10)
H14A	0.3730	0.5202	−0.1229	0.045*
H14B	0.2648	0.4751	−0.1740	0.045*
H14C	0.3294	0.5381	−0.2130	0.045*
C15	0.2916 (3)	0.5499 (3)	0.3735 (2)	0.0402 (11)
H15A	0.3446	0.5748	0.4205	0.060*
H15B	0.2413	0.6074	0.3541	0.060*
H15C	0.3199	0.5335	0.3355	0.060*
C16	0.2445 (3)	0.4494 (3)	0.3893 (2)	0.0286 (9)
C17	0.1473 (3)	0.4395 (4)	0.3716 (2)	0.0368 (11)
H17	0.1057	0.4996	0.3480	0.044*
C18	0.1012 (3)	0.3409 (4)	0.3864 (3)	0.0432 (13)
C19	0.1689 (3)	0.2496 (3)	0.4276 (2)	0.0364 (10)
H19A	0.1330	0.1795	0.4117	0.044*
H19B	0.1856	0.2581	0.4828	0.044*
C20	0.2662 (3)	0.2444 (3)	0.4133 (2)	0.0289 (9)
C21	0.3162 (3)	0.3575 (4)	0.4300 (2)	0.0216 (8)
H21	0.3718	0.3574	0.4113	0.026*
C22	0.2423 (3)	0.2147 (4)	0.3300 (2)	0.0356 (10)
H22A	0.1941	0.2669	0.2969	0.053*
H22B	0.2142	0.1409	0.3200	0.053*
H22C	0.3035	0.2172	0.3198	0.053*
C23	0.3339 (3)	0.1579 (3)	0.4649 (2)	0.0340 (9)
H23A	0.3059	0.0853	0.4479	0.051*
H23B	0.3393	0.1699	0.5173	0.051*
H23C	0.4000	0.1629	0.4628	0.051*
C24	0.3593 (3)	0.3841 (3)	0.5135 (2)	0.0207 (8)
H24	0.3143	0.3850	0.5388	0.025*
C25	0.4529 (3)	0.4062 (3)	0.5550 (2)	0.0238 (9)
H25	0.4998	0.4066	0.5313	0.029*
C26	0.4881 (3)	0.4308 (3)	0.6381 (2)	0.0198 (8)
H26	0.4291	0.4307	0.6529	0.024*
C27	0.5398 (3)	0.5411 (3)	0.6596 (2)	0.0288 (9)
H27A	0.4941	0.5991	0.6317	0.043*
H27B	0.5989	0.5421	0.6467	0.043*
H27C	0.5598	0.5530	0.7144	0.043*
C28	0.5207 (3)	0.2325 (3)	0.6718 (3)	0.0302 (10)
H28A	0.5089	0.2095	0.6198	0.045*
H28B	0.4580	0.2297	0.6798	0.045*
H28C	0.5691	0.1833	0.7079	0.045*
C29	0.9222 (3)	0.1765 (4)	0.1326 (3)	0.0425 (11)
H29A	0.8918	0.1190	0.1523	0.064*
H29B	0.9880	0.1945	0.1707	0.064*
H29C	0.9290	0.1509	0.0860	0.064*
C30	0.8585 (3)	0.2750 (3)	0.1154 (2)	0.0281 (9)
C31	0.7785 (3)	0.2854 (4)	0.1344 (2)	0.0365 (10)
H31	0.7606	0.2254	0.1582	0.044*
C32	0.7182 (3)	0.3840 (4)	0.1200 (3)	0.0409 (12)
C33	0.7455 (3)	0.4763 (3)	0.0787 (2)	0.0352 (10)
H33A	0.7268	0.5464	0.0956	0.042*
H33B	0.7059	0.4689	0.0236	0.042*
C34	0.8556 (3)	0.4805 (3)	0.0915 (2)	0.0279 (9)
C35	0.8889 (3)	0.3661 (4)	0.0745 (2)	0.0228 (8)
H35	0.9631	0.3660	0.0925	0.027*
C36	0.9168 (3)	0.5104 (4)	0.1747 (2)	0.0381 (11)
H36A	0.9871	0.5171	0.1824	0.057*
H36B	0.9092	0.4532	0.2081	0.057*
H36C	0.8931	0.5801	0.1868	0.057*
C37	0.8720 (3)	0.5684 (3)	0.0399 (2)	0.0345 (9)
H37A	0.9404	0.5639	0.0423	0.052*
H37B	0.8605	0.6407	0.0570	0.052*
H37C	0.8255	0.5566	−0.0126	0.052*
C38	0.8472 (3)	0.3421 (3)	−0.0090 (2)	0.0219 (9)
H38	0.7768	0.3428	−0.0339	0.026*
C39	0.8991 (3)	0.3197 (3)	−0.0518 (2)	0.0205 (8)
H39	0.9696	0.3167	−0.0282	0.025*
C40	0.8508 (3)	0.2994 (4)	−0.1352 (2)	0.0231 (9)
H40	0.7771	0.3003	−0.1498	0.028*
C41	0.8787 (3)	0.1929 (3)	−0.1608 (2)	0.0316 (10)
H41A	0.8606	0.1326	−0.1348	0.047*
H41B	0.9506	0.1915	−0.1484	0.047*
H41C	0.8432	0.1852	−0.2158	0.047*
C42	0.8539 (3)	0.5010 (3)	−0.1619 (3)	0.0293 (10)
H42A	0.8986	0.5216	−0.1104	0.044*
H42B	0.7849	0.5037	−0.1656	0.044*
H42C	0.8624	0.5520	−0.1987	0.044*
C43	0.8362 (3)	0.5329 (4)	0.3550 (3)	0.0460 (12)
H43A	0.8966	0.5460	0.4002	0.069*
H43B	0.8053	0.6030	0.3340	0.069*
H43C	0.8534	0.4937	0.3168	0.069*
C44	0.7644 (3)	0.4655 (3)	0.3766 (2)	0.0273 (9)
C45	0.6707 (3)	0.4961 (4)	0.3592 (2)	0.0325 (10)
H45	0.6487	0.5624	0.3321	0.039*
C46	0.5998 (3)	0.4324 (4)	0.3800 (2)	0.0334 (10)
C47	0.6372 (3)	0.3269 (3)	0.4227 (2)	0.0300 (10)
H47A	0.5819	0.2735	0.4071	0.036*
H47B	0.6566	0.3409	0.4777	0.036*
C48	0.7266 (3)	0.2755 (3)	0.4099 (2)	0.0262 (9)
C49	0.8074 (3)	0.3643 (4)	0.4227 (2)	0.0228 (8)
H49	0.8594	0.3341	0.4057	0.027*
C50	0.6942 (3)	0.2327 (4)	0.3283 (2)	0.0372 (10)
H50A	0.6652	0.2925	0.2925	0.056*
H50B	0.6447	0.1748	0.3200	0.056*
H50C	0.7522	0.2034	0.3203	0.056*
C51	0.7669 (3)	0.1809 (3)	0.4647 (2)	0.0343 (9)
H51A	0.7173	0.1224	0.4520	0.051*
H51B	0.7816	0.2060	0.5168	0.051*
H51C	0.8280	0.1534	0.4607	0.051*
C52	0.8574 (3)	0.3972 (3)	0.5053 (2)	0.0238 (9)
H52	0.8153	0.4150	0.5314	0.029*
C53	0.9535 (3)	0.4034 (3)	0.5440 (2)	0.0249 (9)
H53	0.9977	0.3878	0.5193	0.030*
C54	0.9954 (3)	0.4344 (4)	0.6264 (2)	0.0253 (9)
H54	0.9389	0.4526	0.6421	0.030*
C55	1.0666 (3)	0.5323 (3)	0.6449 (3)	0.0337 (10)
H55A	1.0318	0.5958	0.6152	0.051*
H55B	1.1239	0.5145	0.6320	0.051*
H55C	1.0894	0.5492	0.6992	0.051*
C56	0.9936 (3)	0.2359 (4)	0.6599 (3)	0.0304 (10)
H56A	0.9828	0.2078	0.6092	0.046*
H56B	0.9292	0.2500	0.6635	0.046*
H56C	1.0305	0.1818	0.6983	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0179 (5)	0.0417 (8)	0.0252 (5)	0.0000 (4)	0.0078 (4)	−0.0020 (4)
Cl2	0.0206 (5)	0.0351 (7)	0.0226 (5)	0.0003 (4)	0.0106 (4)	0.0000 (4)
Cl3	0.0185 (5)	0.0392 (7)	0.0248 (5)	0.0008 (4)	0.0080 (4)	−0.0003 (4)
Cl4	0.0230 (6)	0.0406 (7)	0.0269 (5)	−0.0018 (4)	0.0134 (4)	−0.0010 (4)
N1	0.0176 (18)	0.030 (2)	0.0265 (18)	0.0024 (15)	0.0120 (15)	0.0018 (15)
N2	0.0191 (18)	0.029 (2)	0.0218 (17)	−0.0008 (14)	0.0102 (15)	0.0012 (14)
N3	0.0191 (18)	0.028 (2)	0.0191 (16)	0.0032 (14)	0.0081 (14)	0.0016 (13)
N4	0.0168 (18)	0.033 (2)	0.0254 (18)	0.0012 (14)	0.0129 (15)	−0.0003 (14)
O1	0.0412 (19)	0.064 (2)	0.059 (2)	−0.0070 (17)	0.0292 (18)	0.0095 (16)
O2	0.0257 (19)	0.088 (3)	0.088 (3)	0.0065 (18)	0.0204 (19)	−0.017 (2)
O3	0.041 (2)	0.078 (3)	0.083 (3)	−0.0012 (18)	0.041 (2)	−0.009 (2)
O4	0.0293 (18)	0.066 (2)	0.062 (2)	0.0187 (16)	0.0130 (16)	0.0087 (17)
C1	0.031 (2)	0.034 (2)	0.039 (2)	0.0032 (19)	0.0058 (19)	0.0162 (18)
C2	0.028 (2)	0.028 (2)	0.0179 (18)	−0.0049 (17)	0.0033 (17)	−0.0008 (16)
C3	0.038 (3)	0.030 (2)	0.028 (2)	−0.0030 (19)	0.0090 (19)	0.0056 (17)
C4	0.033 (2)	0.039 (3)	0.029 (2)	−0.007 (2)	0.0120 (19)	−0.0046 (19)
C5	0.026 (2)	0.031 (2)	0.029 (2)	0.0001 (16)	0.0099 (17)	−0.0053 (18)
C6	0.029 (2)	0.027 (2)	0.0215 (18)	−0.0040 (17)	0.0063 (18)	−0.0056 (15)
C7	0.020 (2)	0.026 (2)	0.0244 (19)	−0.0009 (18)	0.0070 (17)	0.0034 (18)
C8	0.038 (3)	0.042 (3)	0.033 (2)	−0.009 (2)	0.010 (2)	−0.011 (2)
C9	0.044 (3)	0.026 (2)	0.039 (2)	0.0007 (18)	0.013 (2)	0.0015 (17)
C10	0.016 (2)	0.024 (2)	0.027 (2)	0.0012 (15)	0.0068 (17)	0.0030 (15)
C11	0.016 (2)	0.027 (2)	0.027 (2)	0.0002 (16)	0.0085 (17)	0.0008 (16)
C12	0.021 (2)	0.027 (2)	0.028 (2)	−0.0018 (17)	0.0133 (18)	0.0032 (16)
C13	0.037 (3)	0.033 (2)	0.038 (2)	0.000 (2)	0.019 (2)	−0.0003 (18)
C14	0.027 (2)	0.029 (2)	0.037 (2)	0.0043 (18)	0.014 (2)	0.0056 (18)
C15	0.050 (3)	0.035 (2)	0.038 (2)	0.010 (2)	0.019 (2)	0.007 (2)
C16	0.036 (3)	0.027 (2)	0.0227 (19)	0.0071 (19)	0.0119 (18)	0.0013 (16)
C17	0.027 (3)	0.044 (3)	0.036 (2)	0.016 (2)	0.0094 (19)	−0.006 (2)
C18	0.026 (3)	0.060 (4)	0.048 (3)	−0.005 (2)	0.019 (2)	−0.017 (2)
C19	0.031 (2)	0.043 (3)	0.035 (2)	−0.0109 (19)	0.0123 (19)	−0.0105 (19)
C20	0.033 (2)	0.023 (2)	0.030 (2)	−0.0011 (17)	0.0111 (18)	−0.0050 (16)
C21	0.022 (2)	0.026 (2)	0.0203 (18)	0.0018 (17)	0.0113 (17)	0.0001 (16)
C22	0.042 (3)	0.032 (2)	0.026 (2)	0.0066 (19)	0.0060 (19)	−0.0070 (19)
C23	0.042 (2)	0.027 (2)	0.032 (2)	0.0025 (18)	0.012 (2)	−0.0025 (16)
C24	0.023 (2)	0.024 (2)	0.0158 (17)	0.0034 (16)	0.0090 (16)	0.0026 (14)
C25	0.028 (2)	0.024 (2)	0.024 (2)	0.0002 (17)	0.0146 (18)	0.0030 (17)
C26	0.014 (2)	0.023 (2)	0.0238 (19)	0.0008 (15)	0.0090 (16)	−0.0020 (16)
C27	0.031 (2)	0.023 (2)	0.030 (2)	−0.0017 (17)	0.0080 (18)	−0.0024 (16)
C28	0.032 (2)	0.024 (2)	0.034 (2)	0.0020 (18)	0.0115 (19)	0.0044 (18)
C29	0.047 (3)	0.034 (3)	0.045 (3)	0.006 (2)	0.016 (2)	0.014 (2)
C30	0.030 (2)	0.030 (2)	0.0215 (18)	−0.0082 (18)	0.0063 (18)	−0.0021 (16)
C31	0.043 (3)	0.038 (3)	0.032 (2)	−0.008 (2)	0.017 (2)	−0.0004 (19)
C32	0.032 (2)	0.054 (3)	0.040 (2)	−0.014 (2)	0.018 (2)	−0.012 (2)
C33	0.031 (2)	0.036 (2)	0.040 (2)	0.0076 (19)	0.015 (2)	−0.0050 (19)
C34	0.032 (2)	0.029 (2)	0.0228 (19)	−0.0003 (17)	0.0109 (18)	−0.0067 (16)
C35	0.022 (2)	0.026 (2)	0.0197 (18)	−0.0029 (18)	0.0071 (16)	0.0013 (17)
C36	0.048 (3)	0.043 (3)	0.023 (2)	−0.015 (2)	0.013 (2)	−0.010 (2)
C37	0.051 (3)	0.023 (2)	0.031 (2)	0.0019 (18)	0.017 (2)	−0.0019 (16)
C38	0.015 (2)	0.024 (2)	0.026 (2)	0.0024 (15)	0.0057 (17)	0.0000 (15)
C39	0.015 (2)	0.022 (2)	0.0227 (19)	0.0016 (16)	0.0058 (16)	0.0011 (16)
C40	0.023 (2)	0.027 (2)	0.0220 (18)	0.0021 (18)	0.0111 (17)	−0.0011 (16)
C41	0.040 (3)	0.028 (2)	0.031 (2)	0.002 (2)	0.018 (2)	−0.0007 (17)
C42	0.029 (2)	0.025 (2)	0.035 (2)	0.0038 (18)	0.014 (2)	−0.0007 (17)
C43	0.051 (3)	0.043 (3)	0.056 (3)	0.011 (2)	0.034 (3)	0.019 (2)
C44	0.031 (2)	0.028 (2)	0.025 (2)	0.0071 (17)	0.0129 (18)	0.0021 (16)
C45	0.035 (2)	0.036 (2)	0.026 (2)	0.0108 (19)	0.0118 (18)	0.0046 (17)
C46	0.031 (2)	0.037 (3)	0.028 (2)	−0.001 (2)	0.0060 (18)	−0.0065 (18)
C47	0.027 (2)	0.035 (3)	0.030 (2)	−0.0069 (17)	0.0123 (18)	−0.0031 (18)
C48	0.032 (2)	0.022 (2)	0.0230 (18)	0.0019 (16)	0.0084 (17)	0.0026 (15)
C49	0.023 (2)	0.027 (2)	0.0200 (18)	−0.0007 (18)	0.0101 (16)	−0.0015 (17)
C50	0.043 (3)	0.039 (3)	0.024 (2)	0.001 (2)	0.007 (2)	−0.0095 (18)
C51	0.042 (2)	0.025 (2)	0.035 (2)	0.0007 (18)	0.014 (2)	0.0021 (17)
C52	0.029 (2)	0.023 (2)	0.0232 (19)	0.0031 (17)	0.0140 (18)	0.0017 (15)
C53	0.026 (2)	0.029 (2)	0.0242 (19)	0.0005 (17)	0.0143 (18)	0.0026 (16)
C54	0.018 (2)	0.032 (2)	0.027 (2)	0.0056 (17)	0.0090 (17)	0.0042 (17)
C55	0.027 (2)	0.026 (2)	0.044 (2)	−0.0027 (18)	0.009 (2)	0.0006 (18)
C56	0.027 (2)	0.032 (2)	0.033 (2)	0.0019 (18)	0.0116 (19)	0.0018 (18)

Geometric parameters (Å, º) top

N1—C14	1.486 (5)	C25—C26	1.495 (5)
N1—C12	1.522 (5)	C25—H25	0.9500
N1—H1A	0.928 (18)	C26—C27	1.524 (6)
N1—H1B	0.927 (18)	C26—H26	1.0000
N2—C28	1.471 (5)	C27—H27A	0.9800
N2—C26	1.504 (5)	C27—H27B	0.9800
N2—H2A	0.940 (18)	C27—H27C	0.9800
N2—H2B	0.905 (18)	C28—H28A	0.9800
N3—C42	1.479 (5)	C28—H28B	0.9800
N3—C40	1.512 (5)	C28—H28C	0.9800
N3—H3A	0.929 (18)	C29—C30	1.480 (6)
N3—H3B	0.921 (18)	C29—H29A	0.9800
N4—C56	1.485 (5)	C29—H29B	0.9800
N4—C54	1.507 (5)	C29—H29C	0.9800
N4—H4A	0.85 (3)	C30—C31	1.349 (6)
N4—H4B	0.96 (4)	C30—C35	1.520 (5)
O1—C4	1.234 (4)	C31—C32	1.456 (7)
O2—C18	1.228 (5)	C31—H31	0.9500
O3—C32	1.237 (5)	C32—C33	1.513 (6)
O4—C46	1.222 (5)	C33—C34	1.527 (6)
C1—C2	1.496 (6)	C33—H33A	0.9900
C1—H1C	0.9800	C33—H33B	0.9900
C1—H1D	0.9800	C34—C37	1.536 (5)
C1—H1E	0.9800	C34—C36	1.537 (5)
C2—C3	1.333 (5)	C34—C35	1.556 (6)
C2—C7	1.521 (6)	C35—C38	1.497 (5)
C3—C4	1.467 (6)	C35—H35	1.0000
C3—H3	0.9500	C36—H36A	0.9800
C4—C5	1.508 (6)	C36—H36B	0.9800
C5—C6	1.540 (5)	C36—H36C	0.9800
C5—H5A	0.9900	C37—H37A	0.9800
C5—H5B	0.9900	C37—H37B	0.9800
C6—C9	1.522 (5)	C37—H37C	0.9800
C6—C8	1.539 (5)	C38—C39	1.335 (5)
C6—C7	1.555 (6)	C38—H38	0.9500
C7—C10	1.499 (5)	C39—C40	1.491 (5)
C7—H7	1.0000	C39—H39	0.9500
C8—H8A	0.9800	C40—C41	1.501 (6)
C8—H8B	0.9800	C40—H40	1.0000
C8—H8C	0.9800	C41—H41A	0.9800
C9—H9A	0.9800	C41—H41B	0.9800
C9—H9B	0.9800	C41—H41C	0.9800
C9—H9C	0.9800	C42—H42A	0.9800
C10—C11	1.328 (5)	C42—H42B	0.9800
C10—H10	0.9500	C42—H42C	0.9800
C11—C12	1.482 (6)	C43—C44	1.506 (6)
C11—H11	0.9500	C43—H43A	0.9800
C12—C13	1.516 (6)	C43—H43B	0.9800
C12—H12	1.0000	C43—H43C	0.9800
C13—H13A	0.9800	C44—C45	1.328 (5)
C13—H13B	0.9800	C44—C49	1.509 (6)
C13—H13C	0.9800	C45—C46	1.464 (6)
C14—H14A	0.9800	C45—H45	0.9500
C14—H14B	0.9800	C46—C47	1.512 (6)
C14—H14C	0.9800	C47—C48	1.545 (5)
C15—C16	1.495 (6)	C47—H47A	0.9900
C15—H15A	0.9800	C47—H47B	0.9900
C15—H15B	0.9800	C48—C51	1.519 (5)
C15—H15C	0.9800	C48—C50	1.533 (5)
C16—C17	1.327 (6)	C48—C49	1.551 (6)
C16—C21	1.529 (6)	C49—C52	1.512 (5)
C17—C18	1.460 (7)	C49—H49	1.0000
C17—H17	0.9500	C50—H50A	0.9800
C18—C19	1.499 (6)	C50—H50B	0.9800
C19—C20	1.542 (5)	C50—H50C	0.9800
C19—H19A	0.9900	C51—H51A	0.9800
C19—H19B	0.9900	C51—H51B	0.9800
C20—C23	1.523 (5)	C51—H51C	0.9800
C20—C22	1.532 (5)	C52—C53	1.309 (6)
C20—C21	1.540 (6)	C52—H52	0.9500
C21—C24	1.506 (5)	C53—C54	1.499 (6)
C21—H21	1.0000	C53—H53	0.9500
C22—H22A	0.9800	C54—C55	1.535 (6)
C22—H22B	0.9800	C54—H54	1.0000
C22—H22C	0.9800	C55—H55A	0.9800
C23—H23A	0.9800	C55—H55B	0.9800
C23—H23B	0.9800	C55—H55C	0.9800
C23—H23C	0.9800	C56—H56A	0.9800
C24—C25	1.315 (6)	C56—H56B	0.9800
C24—H24	0.9500	C56—H56C	0.9800

C14—N1—C12	115.0 (3)	C26—C27—H27A	109.5
C14—N1—H1A	111 (2)	C26—C27—H27B	109.5
C12—N1—H1A	110 (2)	H27A—C27—H27B	109.5
C14—N1—H1B	115 (2)	C26—C27—H27C	109.5
C12—N1—H1B	106 (2)	H27A—C27—H27C	109.5
H1A—N1—H1B	99 (3)	H27B—C27—H27C	109.5
C28—N2—C26	115.1 (3)	N2—C28—H28A	109.5
C28—N2—H2A	115 (2)	N2—C28—H28B	109.5
C26—N2—H2A	102 (2)	H28A—C28—H28B	109.5
C28—N2—H2B	105 (3)	N2—C28—H28C	109.5
C26—N2—H2B	107 (3)	H28A—C28—H28C	109.5
H2A—N2—H2B	114 (3)	H28B—C28—H28C	109.5
C42—N3—C40	115.1 (3)	C30—C29—H29A	109.5
C42—N3—H3A	108 (2)	C30—C29—H29B	109.5
C40—N3—H3A	110 (2)	H29A—C29—H29B	109.5
C42—N3—H3B	108 (2)	C30—C29—H29C	109.5
C40—N3—H3B	111 (2)	H29A—C29—H29C	109.5
H3A—N3—H3B	105 (3)	H29B—C29—H29C	109.5
C56—N4—C54	114.5 (3)	C31—C30—C29	123.4 (4)
C56—N4—H4A	109 (3)	C31—C30—C35	121.2 (4)
C54—N4—H4A	107 (3)	C29—C30—C35	115.5 (3)
C56—N4—H4B	103 (2)	C30—C31—C32	123.2 (4)
C54—N4—H4B	108 (2)	C30—C31—H31	118.4
H4A—N4—H4B	117 (3)	C32—C31—H31	118.4
C2—C1—H1C	109.5	O3—C32—C31	122.3 (4)
C2—C1—H1D	109.5	O3—C32—C33	120.5 (4)
H1C—C1—H1D	109.5	C31—C32—C33	117.3 (3)
C2—C1—H1E	109.5	C32—C33—C34	114.2 (3)
H1C—C1—H1E	109.5	C32—C33—H33A	108.7
H1D—C1—H1E	109.5	C34—C33—H33A	108.7
C3—C2—C1	122.8 (4)	C32—C33—H33B	108.7
C3—C2—C7	121.9 (4)	C34—C33—H33B	108.7
C1—C2—C7	115.3 (3)	H33A—C33—H33B	107.6
C2—C3—C4	122.9 (4)	C33—C34—C37	109.4 (3)
C2—C3—H3	118.5	C33—C34—C36	109.3 (3)
C4—C3—H3	118.5	C37—C34—C36	108.8 (3)
O1—C4—C3	121.5 (4)	C33—C34—C35	109.1 (3)
O1—C4—C5	121.0 (4)	C37—C34—C35	111.2 (3)
C3—C4—C5	117.5 (3)	C36—C34—C35	109.0 (3)
C4—C5—C6	114.7 (3)	C38—C35—C30	108.7 (3)
C4—C5—H5A	108.6	C38—C35—C34	111.4 (3)
C6—C5—H5A	108.6	C30—C35—C34	112.3 (3)
C4—C5—H5B	108.6	C38—C35—H35	108.1
C6—C5—H5B	108.6	C30—C35—H35	108.1
H5A—C5—H5B	107.6	C34—C35—H35	108.1
C9—C6—C8	109.2 (3)	C34—C36—H36A	109.5
C9—C6—C5	109.8 (3)	C34—C36—H36B	109.5
C8—C6—C5	109.5 (3)	H36A—C36—H36B	109.5
C9—C6—C7	110.4 (3)	C34—C36—H36C	109.5
C8—C6—C7	108.9 (3)	H36A—C36—H36C	109.5
C5—C6—C7	109.0 (3)	H36B—C36—H36C	109.5
C10—C7—C2	106.8 (3)	C34—C37—H37A	109.5
C10—C7—C6	112.2 (3)	C34—C37—H37B	109.5
C2—C7—C6	112.1 (3)	H37A—C37—H37B	109.5
C10—C7—H7	108.5	C34—C37—H37C	109.5
C2—C7—H7	108.5	H37A—C37—H37C	109.5
C6—C7—H7	108.5	H37B—C37—H37C	109.5
C6—C8—H8A	109.5	C39—C38—C35	126.4 (4)
C6—C8—H8B	109.5	C39—C38—H38	116.8
H8A—C8—H8B	109.5	C35—C38—H38	116.8
C6—C8—H8C	109.5	C38—C39—C40	122.5 (4)
H8A—C8—H8C	109.5	C38—C39—H39	118.7
H8B—C8—H8C	109.5	C40—C39—H39	118.7
C6—C9—H9A	109.5	C39—C40—C41	114.5 (4)
C6—C9—H9B	109.5	C39—C40—N3	110.2 (3)
H9A—C9—H9B	109.5	C41—C40—N3	107.1 (3)
C6—C9—H9C	109.5	C39—C40—H40	108.3
H9A—C9—H9C	109.5	C41—C40—H40	108.3
H9B—C9—H9C	109.5	N3—C40—H40	108.3
C11—C10—C7	126.3 (4)	C40—C41—H41A	109.5
C11—C10—H10	116.8	C40—C41—H41B	109.5
C7—C10—H10	116.8	H41A—C41—H41B	109.5
C10—C11—C12	123.0 (4)	C40—C41—H41C	109.5
C10—C11—H11	118.5	H41A—C41—H41C	109.5
C12—C11—H11	118.5	H41B—C41—H41C	109.5
C11—C12—C13	114.2 (4)	N3—C42—H42A	109.5
C11—C12—N1	110.3 (3)	N3—C42—H42B	109.5
C13—C12—N1	107.3 (3)	H42A—C42—H42B	109.5
C11—C12—H12	108.3	N3—C42—H42C	109.5
C13—C12—H12	108.3	H42A—C42—H42C	109.5
N1—C12—H12	108.3	H42B—C42—H42C	109.5
C12—C13—H13A	109.5	C44—C43—H43A	109.5
C12—C13—H13B	109.5	C44—C43—H43B	109.5
H13A—C13—H13B	109.5	H43A—C43—H43B	109.5
C12—C13—H13C	109.5	C44—C43—H43C	109.5
H13A—C13—H13C	109.5	H43A—C43—H43C	109.5
H13B—C13—H13C	109.5	H43B—C43—H43C	109.5
N1—C14—H14A	109.5	C45—C44—C43	122.0 (4)
N1—C14—H14B	109.5	C45—C44—C49	122.3 (4)
H14A—C14—H14B	109.5	C43—C44—C49	115.6 (3)
N1—C14—H14C	109.5	C44—C45—C46	123.0 (4)
H14A—C14—H14C	109.5	C44—C45—H45	118.5
H14B—C14—H14C	109.5	C46—C45—H45	118.5
C16—C15—H15A	109.5	O4—C46—C45	121.5 (4)
C16—C15—H15B	109.5	O4—C46—C47	121.4 (4)
H15A—C15—H15B	109.5	C45—C46—C47	117.0 (4)
C16—C15—H15C	109.5	C46—C47—C48	114.5 (3)
H15A—C15—H15C	109.5	C46—C47—H47A	108.6
H15B—C15—H15C	109.5	C48—C47—H47A	108.6
C17—C16—C15	123.4 (4)	C46—C47—H47B	108.6
C17—C16—C21	121.0 (4)	C48—C47—H47B	108.6
C15—C16—C21	115.6 (4)	H47A—C47—H47B	107.6
C16—C17—C18	123.4 (4)	C51—C48—C50	108.8 (3)
C16—C17—H17	118.3	C51—C48—C47	109.3 (3)
C18—C17—H17	118.3	C50—C48—C47	110.3 (3)
O2—C18—C17	121.8 (5)	C51—C48—C49	110.9 (3)
O2—C18—C19	120.8 (4)	C50—C48—C49	108.6 (3)
C17—C18—C19	117.4 (4)	C47—C48—C49	108.9 (3)
C18—C19—C20	113.7 (4)	C44—C49—C52	108.3 (3)
C18—C19—H19A	108.8	C44—C49—C48	111.3 (3)
C20—C19—H19A	108.8	C52—C49—C48	112.6 (3)
C18—C19—H19B	108.8	C44—C49—H49	108.2
C20—C19—H19B	108.8	C52—C49—H49	108.2
H19A—C19—H19B	107.7	C48—C49—H49	108.2
C23—C20—C22	109.7 (3)	C48—C50—H50A	109.5
C23—C20—C21	110.8 (3)	C48—C50—H50B	109.5
C22—C20—C21	109.2 (3)	H50A—C50—H50B	109.5
C23—C20—C19	109.0 (3)	C48—C50—H50C	109.5
C22—C20—C19	109.4 (3)	H50A—C50—H50C	109.5
C21—C20—C19	108.7 (3)	H50B—C50—H50C	109.5
C24—C21—C16	107.7 (3)	C48—C51—H51A	109.5
C24—C21—C20	112.7 (3)	C48—C51—H51B	109.5
C16—C21—C20	112.4 (3)	H51A—C51—H51B	109.5
C24—C21—H21	108.0	C48—C51—H51C	109.5
C16—C21—H21	108.0	H51A—C51—H51C	109.5
C20—C21—H21	108.0	H51B—C51—H51C	109.5
C20—C22—H22A	109.5	C53—C52—C49	126.0 (4)
C20—C22—H22B	109.5	C53—C52—H52	117.0
H22A—C22—H22B	109.5	C49—C52—H52	117.0
C20—C22—H22C	109.5	C52—C53—C54	121.6 (3)
H22A—C22—H22C	109.5	C52—C53—H53	119.2
H22B—C22—H22C	109.5	C54—C53—H53	119.2
C20—C23—H23A	109.5	C53—C54—N4	109.5 (3)
C20—C23—H23B	109.5	C53—C54—C55	114.0 (3)
H23A—C23—H23B	109.5	N4—C54—C55	107.8 (3)
C20—C23—H23C	109.5	C53—C54—H54	108.5
H23A—C23—H23C	109.5	N4—C54—H54	108.5
H23B—C23—H23C	109.5	C55—C54—H54	108.5
C25—C24—C21	126.6 (3)	C54—C55—H55A	109.5
C25—C24—H24	116.7	C54—C55—H55B	109.5
C21—C24—H24	116.7	H55A—C55—H55B	109.5
C24—C25—C26	122.3 (3)	C54—C55—H55C	109.5
C24—C25—H25	118.9	H55A—C55—H55C	109.5
C26—C25—H25	118.9	H55B—C55—H55C	109.5
C25—C26—N2	110.7 (3)	N4—C56—H56A	109.5
C25—C26—C27	113.4 (3)	N4—C56—H56B	109.5
N2—C26—C27	107.7 (3)	H56A—C56—H56B	109.5
C25—C26—H26	108.3	N4—C56—H56C	109.5
N2—C26—H26	108.3	H56A—C56—H56C	109.5
C27—C26—H26	108.3	H56B—C56—H56C	109.5

C1—C2—C3—C4	−179.1 (4)	C29—C30—C31—C32	177.6 (4)
C7—C2—C3—C4	−2.3 (6)	C35—C30—C31—C32	−2.3 (7)
C2—C3—C4—O1	178.2 (4)	C30—C31—C32—O3	−178.4 (4)
C2—C3—C4—C5	0.8 (6)	C30—C31—C32—C33	2.7 (7)
O1—C4—C5—C6	156.5 (4)	O3—C32—C33—C34	152.3 (4)
C3—C4—C5—C6	−26.1 (5)	C31—C32—C33—C34	−28.8 (5)
C4—C5—C6—C9	171.0 (3)	C32—C33—C34—C37	173.5 (3)
C4—C5—C6—C8	−69.2 (4)	C32—C33—C34—C36	−67.5 (4)
C4—C5—C6—C7	49.9 (4)	C32—C33—C34—C35	51.6 (4)
C3—C2—C7—C10	−95.1 (4)	C31—C30—C35—C38	−96.7 (5)
C1—C2—C7—C10	81.9 (4)	C29—C30—C35—C38	83.4 (4)
C3—C2—C7—C6	28.2 (5)	C31—C30—C35—C34	27.1 (5)
C1—C2—C7—C6	−154.8 (3)	C29—C30—C35—C34	−152.9 (4)
C9—C6—C7—C10	−50.5 (4)	C33—C34—C35—C38	72.2 (4)
C8—C6—C7—C10	−170.4 (3)	C37—C34—C35—C38	−48.6 (4)
C5—C6—C7—C10	70.2 (4)	C36—C34—C35—C38	−168.5 (3)
C9—C6—C7—C2	−170.7 (3)	C33—C34—C35—C30	−50.1 (4)
C8—C6—C7—C2	69.4 (4)	C37—C34—C35—C30	−170.8 (3)
C5—C6—C7—C2	−50.0 (4)	C36—C34—C35—C30	69.2 (4)
C2—C7—C10—C11	−103.9 (5)	C30—C35—C38—C39	−114.5 (4)
C6—C7—C10—C11	132.9 (4)	C34—C35—C38—C39	121.2 (4)
C7—C10—C11—C12	177.2 (4)	C35—C38—C39—C40	−178.5 (4)
C10—C11—C12—C13	−124.1 (4)	C38—C39—C40—C41	−124.9 (4)
C10—C11—C12—N1	115.0 (4)	C38—C39—C40—N3	114.2 (4)
C14—N1—C12—C11	−52.5 (5)	C42—N3—C40—C39	−55.9 (4)
C14—N1—C12—C13	−177.5 (3)	C42—N3—C40—C41	179.0 (3)
C15—C16—C17—C18	179.4 (4)	C43—C44—C45—C46	−179.6 (4)
C21—C16—C17—C18	−2.3 (6)	C49—C44—C45—C46	−2.9 (6)
C16—C17—C18—O2	−177.1 (4)	C44—C45—C46—O4	178.9 (4)
C16—C17—C18—C19	3.5 (6)	C44—C45—C46—C47	−0.4 (6)
O2—C18—C19—C20	150.8 (4)	O4—C46—C47—C48	156.0 (4)
C17—C18—C19—C20	−29.8 (5)	C45—C46—C47—C48	−24.6 (5)
C18—C19—C20—C23	173.3 (3)	C46—C47—C48—C51	171.2 (3)
C18—C19—C20—C22	−66.7 (4)	C46—C47—C48—C50	−69.1 (4)
C18—C19—C20—C21	52.5 (4)	C46—C47—C48—C49	50.0 (4)
C17—C16—C21—C24	−97.4 (5)	C45—C44—C49—C52	−94.0 (5)
C15—C16—C21—C24	80.9 (4)	C43—C44—C49—C52	82.8 (4)
C17—C16—C21—C20	27.3 (5)	C45—C44—C49—C48	30.3 (5)
C15—C16—C21—C20	−154.4 (3)	C43—C44—C49—C48	−152.9 (3)
C23—C20—C21—C24	−48.3 (4)	C51—C48—C49—C44	−171.9 (3)
C22—C20—C21—C24	−169.3 (3)	C50—C48—C49—C44	68.6 (4)
C19—C20—C21—C24	71.4 (4)	C47—C48—C49—C44	−51.6 (4)
C23—C20—C21—C16	−170.2 (3)	C51—C48—C49—C52	−50.1 (4)
C22—C20—C21—C16	68.8 (4)	C50—C48—C49—C52	−169.6 (3)
C19—C20—C21—C16	−50.5 (4)	C47—C48—C49—C52	70.2 (4)
C16—C21—C24—C25	−114.8 (4)	C44—C49—C52—C53	−106.0 (5)
C20—C21—C24—C25	120.7 (4)	C48—C49—C52—C53	130.5 (4)
C21—C24—C25—C26	−179.5 (4)	C49—C52—C53—C54	−178.5 (4)
C24—C25—C26—N2	115.7 (4)	C52—C53—C54—N4	114.6 (4)
C24—C25—C26—C27	−123.1 (4)	C52—C53—C54—C55	−124.7 (4)
C28—N2—C26—C25	−57.2 (4)	C56—N4—C54—C53	−53.5 (4)
C28—N2—C26—C27	178.3 (3)	C56—N4—C54—C55	−178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.93 (2)	2.19 (2)	3.109 (3)	173 (3)
N1—H1B···Cl4ⁱ	0.93 (2)	2.17 (2)	3.069 (4)	163 (3)
N2—H2A···Cl2	0.94 (2)	2.17 (2)	3.105 (3)	171 (3)
N2—H2B···Cl1	0.91 (2)	2.19 (2)	3.089 (4)	175 (4)
N3—H3A···Cl3ⁱⁱ	0.93 (2)	2.18 (2)	3.108 (3)	175 (3)
N3—H3B···Cl2ⁱ	0.92 (2)	2.18 (2)	3.088 (4)	171 (3)
N4—H4A···Cl4ⁱⁱⁱ	0.85 (3)	2.28 (4)	3.117 (4)	169 (4)
N4—H4B···Cl3ⁱⁱⁱ	0.96 (4)	2.13 (4)	3.083 (4)	172 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₂₄NO⁺·Cl⁻
M_r	257.79
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	113
a, b, c (Å)	14.547 (3), 12.247 (2), 19.035 (4)
β (°)	112.46 (3)
V (Å³)	3134.0 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.955, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	30954, 12371, 10363
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.092, 1.01
No. of reflections	12371
No. of parameters	658
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.35
Absolute structure	Flack (1983), 4816 Friedel pairs
Absolute structure parameter	0.03 (4)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005) and SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.928 (18)	2.185 (19)	3.109 (3)	173 (3)
N1—H1B···Cl4ⁱ	0.927 (18)	2.17 (2)	3.069 (4)	163 (3)
N2—H2A···Cl2	0.940 (18)	2.172 (19)	3.105 (3)	171 (3)
N2—H2B···Cl1	0.905 (18)	2.186 (19)	3.089 (4)	175 (4)
N3—H3A···Cl3ⁱⁱ	0.929 (18)	2.182 (19)	3.108 (3)	175 (3)
N3—H3B···Cl2ⁱ	0.921 (18)	2.176 (19)	3.088 (4)	171 (3)
N4—H4A···Cl4ⁱⁱⁱ	0.85 (3)	2.28 (4)	3.117 (4)	169 (4)
N4—H4B···Cl3ⁱⁱⁱ	0.96 (4)	2.13 (4)	3.083 (4)	172 (4)

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

Acknowledgements

The authors are very grateful to the Central Laboratory of Nankai University for the X-ray data collection. Special thanks go to Dr Cheng-Zhi Xie (School of Pharmaceutical Sciences, Tianjin Medical University) for his invaluable support.

References

Chiu, M., Nie, R., Li, Z. & Zhou, J. (1990). Phytochemistry, 29, 3927–3930. CAS Google Scholar
Chiu, M., Nie, R., Li, Z. & Zhou, J. (1992). J. Nat. Prod. 55, 25–28. CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kikuchi, T. & Uyeo, S. (1965). Tetrahedron Lett. 39, 3473–3485. CrossRef PubMed Web of Science Google Scholar
Kikuchi, T. & Uyeo, S. (1967a). Chem. Pharm. Bull. 15, 207–213. CrossRef CAS Google Scholar
Kikuchi, T. & Uyeo, S. (1967b). Chem. Pharm. Bull. 15, 302–306. CrossRef CAS PubMed Web of Science Google Scholar
Kikuchi, T., Yokoi, T., Shingu, T. & Niwa, M. (1981). Chem. Pharm. Bull. 29, 2531–2539. CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(S,E)-N-Methyl-4-[(S)2,6,6-tri­methyl-4-oxo­cyclo­hex-2-en­yl]but-3-en-2-aminium chloride

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Experimental

Crystal data

Data collection

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Supporting information

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organic compounds

(S,E)-N-Methyl-4-[(S)2,6,6-trimethyl-4-oxocyclohex-2-enyl]but-3-en-2-aminium chloride