(R,E)-[4-(Benz­yloxy)-2-(cinnamo­yloxy)-4-oxobut­yl]trimethylammonium chloride hydro­chloride

The title compound, C₂₃H₂₈NO₄⁺·Cl⁻·HCl, is a quaternary ammonium salt with a scaffold similar to that of acetyl-L-carnitine hydro­chloride. The two Cl atoms in the structure are tightly bonded by a strong Cl—H...Cl hydrogen bond with a Cl...Cl separation of 3.068 (2) Å. The cations are held together partly by a range of C—H...O and C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.049
• wR factor = 0.206
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.09 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.61
           From the CIF: _reflns_number_total               5648
           Count of symmetry unique reflns         3202
           Completeness (_total/calc)            176.39%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2446
           Fraction of Friedel pairs measured     0.764
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

L-carnitine and cinnamic acid are reported to have some pharmaceutical applications (Crill & Helms, 2007; Christov et al., 2006; Kim et al., 2006). In order to study the biological activities of novel synthetic L-carnitine derivatives, a cinnamoyl L-carnitine benzoate was prepared and its crystal structure (Fig. 1) is reported here.

The title compound is a quaternary ammonium salt with a scaffold similar to that of acetyl-L-carnitine hydrochloride (Destro & Heyda, 1977; Weber et al., 1995). C16—C17 (1.332 Å) and C15—C16 and C17—C18 (1.467 and 1.466 Å) have bond lengths typical for partially delocalized C—C single and C=C double bonds, thus pointing towards the existence of a conjugated system along the chain O3—C15—C16—C17—C18. All other bond distances and angles are well within the expected ranges.

The compound is a hydrochloride solvate and the two chlorine atoms in the structure are tightly bonded by a strong Cl—H···Cl hydrogen bond as is evident from the small separation of the two chlorine atoms (3.068 (2) Å), which is very close to the standard value of 3.11 Å in hydrogen dichloride ions (Atwood et al., 1990). Cl···Cl nonbonding contacts other than Cl—H···Cl hydrogen bonds exhibit values usually larger than 3.36 Å (Stoyanov et al., 2006). The hydrogen atom was tentatively localized in a difference density map, and the values are in agreement with previously reported data when taking the accuracy of the X-ray experiment for the determination of hydrogen atoms into account. The refined H—Cl distance of 1.37 Å is slightly longer than that reported for the covalent HCl molecule in the gaseous state without a Cl—H···Cl bond (1.28 Å, Luo et al., 2002), and the H···Cl separation of 1.70 Å is slightly longer than the previously reported values (1.65 Å, Atwood et al., 1990).

The molecules are held together partly by a range of two C—H···O and, owing to the existence of two benzene rings, two C—H···π interactions. (see the Hydrogen-bond geometry table), which contribute to the stabilization of the molecular geometry and the crystal strucuture.

Related literature

Adams & Ulich (1920) report the synthesis of cinnamoyl chloride. Pharmaceutical applications of L-carnitine and cinnamic acid are described by Christov et al. (2006), Crill & Helms (2007) and Kim et al. (2006). Acetyl-L-carnitine hydrochloride is described by Destro & Heyda (1977) and Weber et al. (1995). Background information related to Cl—H···Cl hydrogen bonds is given by Stoyanov et al. (2006), Atwood et al. (1990) and Luo et al. (2002).

S2. Experimental

1. Preparation of cinnamoyl chloride: Cinnamoyl chloride was prepared according to the reported method (Adams & Ulich, 1920).

2. Preparation of (R,E)-3-carboxy-2-(cinnamoyloxy) -N,N,N-trimethylpropan-1-ammonium chloride:

L-carnitine hydrochloride (30.06 g, 0.125 mol) was dissolved in anhydrous trifluoroacetic acid (100 ml), followed by the addition of excess cinnamoyl chloride in an ice bath. The resulting mixture was stirred at 318–323 K until the starting material disappeared as evidenced by TLC (about 20 h). After the reaction was completed, the solvent was removed in vacuo and 400 ml acetone were added. The mixture was stirred for another 2 h, the white precipitate was removed, and then 800 ml diethyl ether were added to the filtrate. The resultant mixture was cooled to room temperature and filtered, the white precipitate obtained was then collected and recrystallized from ethanol-diethyl ether (V:V=1:4) to afford the target compound as colourless needles (36.30 g, 76.0% yield).

3. Preparation of (R,E)-4-chloro-2-(cinnamoyloxy)- N,N,N-trimethyl-4-oxobutan-1-ammonium chloride:

(R,E)-3-carboxy-2-(cinnamoyloxy)-N,N,N-trimethylpropan -1-ammonium chloride (26.4 g, 0.09 mol) was dissolved in 100 ml of dichlormethane at 273 K, to which freshly distilled oxalyl chloride (15 ml, 0.12 mol) was added dropwise. The resulting mixture was reacted at 318–323 K for 4 h. The solvent was removed in vacuo and the white residue obtained was directly used in the following reaction without further purification.

4. Synthesis of the title compound

The above intermediate was dissolved in 100 ml of anhydrous dimethyl sulfoxide (DMSO) followed by the addition of phenylmethanol (20 ml, 0.18 mol) at room temperature. The resulting mixture was reacted at 323 K for 5 h. After adding 80 ml of diethyl ether and stirring for another 2 h, a white precipitate was collected and dried in vacuo at 313 K. The crude product was recrystallized from a mixture of acetic ether/diethyl ether (V:V=1:2, 75 ml) to give the title compound as colourless crystals (21.80 g, 58.0% yield).

m.p. 363–365 K; IR (KBr, ν cm^-1): 3067, 3027(CH), 1729, 1695(C=O), 1669, 1628(C=C), 1504, 1588(Ar—C), 1486, 1431(CH₂, CH₃), 1208(C—N) 681, 695, 723, 758, 917(Ar); ¹H NMR (MeOD, p.p.m.): 2.71–2.76(m, 2H, –CH₂), 2.98(s, 9H, –CH₃), 3.58, 3.60 (d, 2H, N—CH₂), 3.71–3.76 (dd, 1H, J=5.7; 13.2 Hz, N—CH₂), 4.79(d, 2H, O—CH₂), 5.60–5.64(m, 1H, –CH—O), 6.05, 6.10 (1H, d, J=4.8 Hz, CH=), 6.34, 6.40 (1H, d, J=4.8 Hz, =CH), 6.84–7.00 (m, 5H, CH₂C₆H₅), 7.10–7.40 (m, 5H, CH—C₆H₅); ¹³C NMR (MeOD, p.p.m.): 26.45(C7), 129.0(C1), 127.7(C2,C4,C6), 129.0(C3), 141.2(C5), 68.4(C7), 167.1(C8), 37.2(C9), 63.6(C10), 70.2(C11), 54.7(C12,C13,C14), 158.5(C15), 128.2(C16), 136.2(C17), 135.2(C18), 126.4(C19, C23), 128.7(C20, C21, C22); ESI-MS (m/z): 436.2 [M+H]⁺; Analysis found: C 61.28, H 6.83, N 3.01%; calculated for C₂₃H₂₉O₄Cl₂N: C 60.74, H 6.38, N 3.08%.

20 mg of the title compound were dissolved in 5 ml of 95% methanol, then a mixture of acetic acid and diethyl ether (V:V=1:2, 15 ml) was added slowly, the resulting slightly cloudy solution was kept at 263 K for 24 h. Slow evaporation gave colourless single crystals, which were suitable for X-Ray analysis.

S3. Refinement

All H atoms except H1A bound to the Cl atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97 Å (for CH₂ groups) and 0.96 Å (for CH₃ groups). Their isotropic displacement parameters U_iso were set to 1.2 times (1.5 times for CH₃ groups) the equivalent displacement parameter U_eq of their parent atoms.

In the refinement, the H atom attached to Cl atom was obtained from a difference density map as the highest peak after assignement of all other hydrogen atoms. The peak (0.32 e Å^-3 at 0.2314 0.4121 0.2017) was localized 0.68 Å from Cl(2) and 1.32 Å from Cl(1), respectively. Considering the charge equilibrium, the H atom attached to the Cl atom could be suitable for the peak. Upon refinement the R factor dropped from 0.0511 to 0.0489, and the equivalent dispalcement parameter of the H atom refined to 0.091. In the final model the U_iso value was set to be 1.5 times U_eq of that of the closest Cl atom.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of the molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing diagram viewed along the b axis. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 3. Stereoview of part of the crystal structure of the title compound, showing the formation of hydrogen bonds. Dashed lines indicate the hydrogen bonding interactions.

(R,E)-[4-(Benzyloxy)-2-(cinnamoyloxy)- 4-oxobutyl]trimethylammonium chloride hydrochloride

Crystal data

C23H28NO4^+·Cl^−·HCl	Dx = 1.236 Mg m^−3
Mr = 454.37	Melting point: 363-365K K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 10.1670 (4) Å	Cell parameters from 3797 reflections
b = 10.4488 (4) Å	θ = 2.6–21.0°
c = 22.9795 (11) Å	µ = 0.29 mm^−1
V = 2441.18 (18) Å^3	T = 293 K
Z = 4	Prism, colourless
F(000) = 960	0.41 × 0.26 × 0.23 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5648 independent reflections
Radiation source: fine-focus sealed tube	3350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −13→10
Tmin = 0.889, Tmax = 0.935	k = −13→13
19537 measured reflections	l = −29→29

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1668P)^2 + 0.001P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.049	(Δ/σ)max < 0.001
wR(F^2) = 0.206	Δρmax = 0.24 e Å^−3
S = 0.81	Δρmin = −0.25 e Å^−3
5648 reflections	Absolute structure: Flack (1983), 2454 Friedel pairs
279 parameters	Absolute structure parameter: −0.01 (11)
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	1.5794 (5)	0.6771 (5)	0.3970 (3)	0.0975 (15)
H1	1.6264	0.7037	0.3645	0.117*
C2	1.6308 (5)	0.6890 (5)	0.4490 (3)	0.108 (2)
H2	1.7145	0.7239	0.4527	0.130*
C3	1.5644 (7)	0.6513 (5)	0.4982 (3)	0.109 (2)
H3	1.6028	0.6603	0.5347	0.131*
C4	1.4367 (5)	0.5985 (4)	0.49251 (19)	0.0781 (11)
H4	1.3891	0.5742	0.5252	0.094*
C5	1.3849 (3)	0.5841 (4)	0.43810 (15)	0.0598 (8)
C6	1.4565 (5)	0.6255 (4)	0.39051 (19)	0.0771 (11)
H6	1.4205	0.6182	0.3535	0.093*
C7	1.2561 (5)	0.5165 (5)	0.4303 (2)	0.0883 (14)
H7A	1.2715	0.4291	0.4179	0.106*
H7B	1.2092	0.5142	0.4671	0.106*
C8	1.0922 (3)	0.5120 (3)	0.35739 (15)	0.0540 (7)
C9	1.0245 (3)	0.5897 (3)	0.31191 (15)	0.0551 (7)
H9A	1.0902	0.6249	0.2859	0.066*
H9B	0.9803	0.6609	0.3306	0.066*
C10	0.9248 (3)	0.5160 (3)	0.27626 (13)	0.0484 (7)
H10	0.9662	0.4409	0.2585	0.058*
C11	0.8743 (3)	0.6043 (3)	0.23001 (14)	0.0594 (8)
H11A	0.9495	0.6339	0.2078	0.071*
H11B	0.8372	0.6785	0.2493	0.071*
C12	0.7716 (6)	0.6435 (6)	0.1363 (2)	0.113 (2)
H12A	0.7571	0.7297	0.1494	0.170*
H12B	0.7022	0.6189	0.1103	0.170*
H12C	0.8544	0.6387	0.1164	0.170*
C13	0.8013 (5)	0.4216 (5)	0.1668 (2)	0.0918 (13)
H13A	0.7359	0.3963	0.1390	0.138*
H13B	0.7994	0.3642	0.1994	0.138*
H13C	0.8866	0.4189	0.1489	0.138*
C14	0.6389 (4)	0.5535 (6)	0.2142 (2)	0.0973 (15)
H14A	0.6177	0.6371	0.2287	0.146*
H14B	0.6376	0.4931	0.2457	0.146*
H14C	0.5754	0.5288	0.1854	0.146*
C15	0.7964 (3)	0.3504 (3)	0.32137 (13)	0.0478 (7)
C16	0.6979 (3)	0.3258 (3)	0.36670 (13)	0.0460 (6)
H16	0.6558	0.3936	0.3852	0.055*
C17	0.6692 (3)	0.2054 (3)	0.38118 (13)	0.0472 (7)
H17	0.7132	0.1416	0.3608	0.057*
C18	0.5758 (3)	0.1630 (3)	0.42578 (13)	0.0482 (7)
C19	0.5485 (3)	0.0341 (3)	0.43073 (15)	0.0553 (8)
H19	0.5914	−0.0241	0.4067	0.066*
C20	0.4571 (4)	−0.0096 (4)	0.47148 (17)	0.0682 (10)
H20	0.4374	−0.0964	0.4737	0.082*
C21	0.3967 (4)	0.0752 (4)	0.50804 (17)	0.0734 (11)
H21	0.3367	0.0459	0.5355	0.088*
C22	0.4246 (4)	0.2045 (4)	0.50423 (18)	0.0758 (11)
H22	0.3829	0.2619	0.5291	0.091*
C23	0.5146 (4)	0.2490 (4)	0.46349 (15)	0.0634 (9)
H23	0.5340	0.3359	0.4614	0.076*
Cl2	0.34728 (19)	0.4253 (2)	0.25740 (8)	0.1340 (6)
N1	0.7733 (3)	0.5557 (3)	0.18732 (12)	0.0619 (7)
O1	1.1776 (3)	0.5832 (2)	0.38699 (11)	0.0688 (7)
O2	1.0754 (3)	0.4004 (2)	0.36643 (13)	0.0726 (7)
O3	0.81958 (19)	0.47657 (18)	0.31532 (9)	0.0479 (5)
O4	0.8494 (3)	0.2695 (2)	0.29206 (11)	0.0683 (7)
Cl1	0.15256 (13)	0.39911 (12)	0.15612 (6)	0.0978 (4)
H1A	0.2369	0.4149	0.2018	0.147*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.070 (3)	0.079 (3)	0.144 (5)	−0.001 (2)	0.023 (3)	−0.009 (3)
C2	0.071 (3)	0.066 (3)	0.187 (7)	0.001 (2)	−0.032 (4)	0.007 (4)
C3	0.124 (4)	0.074 (3)	0.130 (5)	0.010 (3)	−0.081 (4)	−0.003 (3)
C4	0.095 (3)	0.065 (2)	0.075 (2)	0.016 (2)	−0.020 (2)	0.0058 (19)
C5	0.0508 (18)	0.064 (2)	0.064 (2)	0.0027 (16)	−0.0048 (15)	−0.0002 (16)
C6	0.077 (3)	0.074 (2)	0.081 (3)	−0.006 (2)	0.006 (2)	−0.017 (2)
C7	0.066 (2)	0.111 (3)	0.088 (3)	−0.018 (2)	−0.023 (2)	0.038 (3)
C8	0.0402 (15)	0.0566 (18)	0.0652 (19)	−0.0015 (13)	0.0066 (14)	0.0054 (15)
C9	0.0482 (16)	0.0491 (15)	0.0681 (19)	−0.0052 (14)	−0.0019 (15)	0.0114 (15)
C10	0.0399 (14)	0.0460 (15)	0.0593 (17)	−0.0063 (13)	0.0092 (13)	0.0046 (13)
C11	0.0593 (19)	0.0567 (18)	0.0623 (19)	−0.0174 (16)	−0.0050 (15)	0.0104 (16)
C12	0.129 (4)	0.124 (4)	0.086 (3)	−0.052 (4)	−0.041 (3)	0.049 (3)
C13	0.097 (3)	0.088 (3)	0.091 (3)	−0.004 (3)	−0.017 (3)	−0.018 (2)
C14	0.053 (2)	0.140 (5)	0.100 (3)	0.003 (3)	−0.006 (2)	0.014 (3)
C15	0.0490 (17)	0.0421 (14)	0.0524 (16)	−0.0023 (13)	0.0060 (13)	−0.0033 (13)
C16	0.0440 (15)	0.0473 (15)	0.0466 (14)	−0.0017 (12)	0.0046 (12)	0.0005 (12)
C17	0.0445 (15)	0.0454 (15)	0.0517 (15)	−0.0005 (13)	0.0039 (13)	−0.0024 (12)
C18	0.0408 (14)	0.0533 (16)	0.0505 (15)	0.0009 (13)	−0.0002 (13)	0.0099 (13)
C19	0.0486 (17)	0.0518 (16)	0.0654 (19)	0.0045 (15)	0.0097 (15)	0.0088 (15)
C20	0.063 (2)	0.059 (2)	0.082 (2)	−0.0047 (18)	0.0094 (19)	0.0221 (18)
C21	0.066 (2)	0.085 (3)	0.069 (2)	−0.010 (2)	0.0172 (19)	0.019 (2)
C22	0.076 (2)	0.084 (3)	0.068 (2)	−0.004 (2)	0.028 (2)	−0.0030 (19)
C23	0.068 (2)	0.057 (2)	0.065 (2)	−0.0015 (17)	0.0157 (18)	−0.0021 (16)
Cl2	0.1186 (12)	0.1575 (15)	0.1259 (11)	−0.0422 (12)	0.0160 (10)	−0.0017 (11)
N1	0.0561 (16)	0.0646 (17)	0.0651 (17)	−0.0086 (13)	−0.0024 (13)	0.0080 (14)
O1	0.0624 (14)	0.0648 (14)	0.0792 (16)	−0.0067 (12)	−0.0189 (12)	0.0145 (12)
O2	0.0708 (16)	0.0542 (14)	0.0927 (17)	−0.0047 (13)	−0.0099 (14)	0.0186 (13)
O3	0.0420 (11)	0.0416 (10)	0.0601 (11)	−0.0014 (8)	0.0139 (9)	0.0014 (9)
O4	0.0802 (16)	0.0450 (11)	0.0795 (15)	−0.0014 (12)	0.0327 (14)	−0.0070 (11)
Cl1	0.0803 (7)	0.0913 (8)	0.1218 (9)	−0.0201 (6)	0.0286 (7)	−0.0118 (7)

Geometric parameters (Å, º)

C1—C2	1.310 (8)	C12—H12C	0.9600
C1—C6	1.368 (7)	C13—N1	1.506 (6)
C1—H1	0.9300	C13—H13A	0.9600
C2—C3	1.374 (9)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.416 (9)	C14—N1	1.499 (6)
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.365 (5)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.383 (6)	C15—O4	1.208 (4)
C5—C7	1.499 (6)	C15—O3	1.347 (3)
C6—H6	0.9300	C15—C16	1.468 (4)
C7—O1	1.454 (5)	C16—C17	1.333 (4)
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	C17—C18	1.466 (4)
C8—O2	1.197 (4)	C17—H17	0.9300
C8—O1	1.330 (4)	C18—C19	1.379 (5)
C8—C9	1.492 (5)	C18—C23	1.395 (5)
C9—C10	1.514 (4)	C19—C20	1.396 (5)
C9—H9A	0.9700	C19—H19	0.9300
C9—H9B	0.9700	C20—C21	1.367 (6)
C10—O3	1.456 (3)	C20—H20	0.9300
C10—C11	1.497 (4)	C21—C22	1.383 (7)
C10—H10	0.9800	C21—H21	0.9300
C11—N1	1.508 (4)	C22—C23	1.390 (5)
C11—H11A	0.9700	C22—H22	0.9300
C11—H11B	0.9700	C23—H23	0.9300
C12—N1	1.488 (5)	Cl2—H1A	1.7033
C12—H12A	0.9600	Cl1—H1A	1.3661
C12—H12B	0.9600
C2—C1—C6	120.1 (6)	H12A—C12—H12C	109.5
C2—C1—H1	119.9	H12B—C12—H12C	109.5
C6—C1—H1	119.9	N1—C13—H13A	109.5
C1—C2—C3	121.8 (5)	N1—C13—H13B	109.5
C1—C2—H2	119.1	H13A—C13—H13B	109.5
C3—C2—H2	119.1	N1—C13—H13C	109.5
C2—C3—C4	119.0 (5)	H13A—C13—H13C	109.5
C2—C3—H3	120.5	H13B—C13—H13C	109.5
C4—C3—H3	120.5	N1—C14—H14A	109.5
C5—C4—C3	118.8 (5)	N1—C14—H14B	109.5
C5—C4—H4	120.6	H14A—C14—H14B	109.5
C3—C4—H4	120.6	N1—C14—H14C	109.5
C4—C5—C6	119.1 (4)	H14A—C14—H14C	109.5
C4—C5—C7	119.9 (4)	H14B—C14—H14C	109.5
C6—C5—C7	120.9 (4)	O4—C15—O3	123.3 (3)
C1—C6—C5	121.1 (5)	O4—C15—C16	125.3 (3)
C1—C6—H6	119.4	O3—C15—C16	111.4 (2)
C5—C6—H6	119.4	C17—C16—C15	119.4 (3)
O1—C7—C5	109.6 (3)	C17—C16—H16	120.3
O1—C7—H7A	109.8	C15—C16—H16	120.3
C5—C7—H7A	109.8	C16—C17—C18	127.0 (3)
O1—C7—H7B	109.8	C16—C17—H17	116.5
C5—C7—H7B	109.8	C18—C17—H17	116.5
H7A—C7—H7B	108.2	C19—C18—C23	119.2 (3)
O2—C8—O1	123.3 (3)	C19—C18—C17	118.9 (3)
O2—C8—C9	125.9 (3)	C23—C18—C17	121.9 (3)
O1—C8—C9	110.8 (3)	C18—C19—C20	120.6 (3)
C8—C9—C10	114.3 (3)	C18—C19—H19	119.7
C8—C9—H9A	108.7	C20—C19—H19	119.7
C10—C9—H9A	108.7	C21—C20—C19	120.0 (3)
C8—C9—H9B	108.7	C21—C20—H20	120.0
C10—C9—H9B	108.7	C19—C20—H20	120.0
H9A—C9—H9B	107.6	C20—C21—C22	120.1 (3)
O3—C10—C11	111.1 (3)	C20—C21—H21	119.9
O3—C10—C9	107.6 (2)	C22—C21—H21	119.9
C11—C10—C9	107.5 (2)	C21—C22—C23	120.3 (4)
O3—C10—H10	110.2	C21—C22—H22	119.8
C11—C10—H10	110.2	C23—C22—H22	119.8
C9—C10—H10	110.2	C22—C23—C18	119.8 (3)
C10—C11—N1	119.2 (3)	C22—C23—H23	120.1
C10—C11—H11A	107.5	C18—C23—H23	120.1
N1—C11—H11A	107.5	C12—N1—C14	108.9 (4)
C10—C11—H11B	107.5	C12—N1—C13	109.2 (4)
N1—C11—H11B	107.5	C14—N1—C13	106.7 (4)
H11A—C11—H11B	107.0	C12—N1—C11	108.2 (3)
N1—C12—H12A	109.5	C14—N1—C11	111.0 (3)
N1—C12—H12B	109.5	C13—N1—C11	112.8 (3)
H12A—C12—H12B	109.5	C8—O1—C7	116.1 (3)
N1—C12—H12C	109.5	C15—O3—C10	118.0 (2)
C6—C1—C2—C3	−0.2 (8)	C16—C17—C18—C23	−7.1 (5)
C1—C2—C3—C4	−0.2 (8)	C23—C18—C19—C20	2.4 (5)
C2—C3—C4—C5	1.5 (7)	C17—C18—C19—C20	−178.0 (3)
C3—C4—C5—C6	−2.3 (6)	C18—C19—C20—C21	−1.9 (6)
C3—C4—C5—C7	173.8 (4)	C19—C20—C21—C22	0.9 (6)
C2—C1—C6—C5	−0.6 (7)	C20—C21—C22—C23	−0.3 (7)
C4—C5—C6—C1	1.9 (6)	C21—C22—C23—C18	0.8 (6)
C7—C5—C6—C1	−174.1 (4)	C19—C18—C23—C22	−1.8 (5)
C4—C5—C7—O1	139.3 (4)	C17—C18—C23—C22	178.6 (3)
C6—C5—C7—O1	−44.7 (6)	C10—C11—N1—C12	−162.3 (4)
O2—C8—C9—C10	1.3 (5)	C10—C11—N1—C14	78.3 (4)
O1—C8—C9—C10	−179.7 (3)	C10—C11—N1—C13	−41.3 (4)
C8—C9—C10—O3	64.7 (3)	O2—C8—O1—C7	2.7 (5)
C8—C9—C10—C11	−175.5 (3)	C9—C8—O1—C7	−176.3 (3)
O3—C10—C11—N1	−62.9 (4)	C5—C7—O1—C8	152.0 (3)
C9—C10—C11—N1	179.6 (3)	O4—C15—O3—C10	−7.4 (5)
O4—C15—C16—C17	5.6 (5)	C16—C15—O3—C10	173.8 (2)
O3—C15—C16—C17	−175.6 (3)	C11—C10—O3—C15	122.9 (3)
C15—C16—C17—C18	178.9 (3)	C9—C10—O3—C15	−119.7 (3)
C16—C17—C18—C19	173.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O4^i	0.97	2.42	3.299 (4)	150
C11—H11A···O4^i	0.97	2.49	3.336 (4)	146
C12—H12A···O2^i	0.96	2.49	3.103 (6)	121
C13—H13C···Cl1^ii	0.96	2.72	3.587 (6)	151
C12—H12B···Cg2^iii	0.96	2.62	3.551 (5)	164
C20—H20···Cg1^iv	0.93	2.95	3.776 (4)	148
Cl1—H1A···Cl2	1.37	1.70	3.068 (2)	176
C10—H10···O4	0.98	2.28	2.712 (4)	105
C13—H13B···O4	0.96	2.40	3.324 (6)	161
C14—H14B···O3	0.96	2.45	3.069 (5)	122
C17—H17···O4	0.93	2.49	2.828 (4)	102

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