Monolayer effect of a gemini surfactant with a rigid biphenyl spacer on its self-crystallization at the air/liquid interface

A gemini surfactant with a biphenyl spacer can spontaneously generate crystals at the air/solution interface. X-ray crystallography reveals that surfactant molecules exhibit an almost fully extended conformation with interdigitating alkyl chains, together with an approximate co-planarity of two C—C—C planes in two alkyl chains of one gemini molecule, and a prominent dihedral angle between the benzene rings and C—C—C planes of the alkyl chains. Infrared reflection–absorption spectroscopy shows that the gemini surfactant was stretched at the air/water interface, with the hydrocarbon chains oriented at a tilt angle of ∼75° with respect to the surface normal. In particular, the biphenyl group is more or less perpendicular to the water surface, and the C—C—C plane of the alkyl chain tends to be parallel to the water surface. Both results point out a remarkable similarity in the molecular conformation between the crystal and the monolayer. Meanwhile, dynamic light scattering and transmission electron microscopy results indicate that the crystallization of such gemini surfactants at the interface is contrary to the crystallization behavior in the bulk phase, meaning that the surfactant solution can only form a supersaturated solution as it is cooled, though the crystallization temperature of 296 K is lower than the Krafft temperature (∼303 K). Therefore, our findings indicate that the Gibbs monolayer of the gemini surfactant plays a critical role in its interfacial crystallization. Additionally, multiple weak intermolecular interactions, involving van der Waals interaction, π–π stacking and cationic–π interactions, as well as the hydrophobic effect during the aggregation of the gemini molecule in solution, are responsible for the formation of the interfacial crystal.

Computing details

Data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(I)

Crystal data

C42H80Br2N2O3	F(000) = 3520
Mr = 820.90	Dx = 1.196 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 54.695 (2) Å	Cell parameters from 4665 reflections
b = 9.8891 (4) Å	θ = 6.5–134.4°
c = 16.8770 (6) Å	µ = 2.52 mm^−1
β = 92.628 (5)°	T = 140 K
V = 9118.9 (6) Å^3	Plate, colorless
Z = 8	0.35 × 0.20 × 0.02 mm

Data collection

Bruker APEX-II CCD diffractometer	7273 independent reflections
Radiation source: fine-focus sealed tube	5507 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.172
φ and ω scans	θmax = 64.0°, θmin = 1.6°
Absorption correction: multi-scan sadabs	h = −63→62
Tmin = 0.473, Tmax = 0.951	k = −11→11
27794 measured reflections	l = −15→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.124	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.330	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.1017P)^2 + 134.7655P] where P = (Fo^2 + 2Fc^2)/3
7273 reflections	(Δ/σ)max = 0.015
448 parameters	Δρmax = 1.57 e Å^−3
65 restraints	Δρmin = −0.90 e Å^−3

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. This crystals with plate-like (dimensions of ca 0.35x0.25x0.02 mm) was weakly diffractive, which forced the use of sealed-tube Cu Ka radiation and a measurement at 140 K and long exposure times. The R_int is still large (0.1724). This is evidenced in large atomic displacement parameters for many of the long carbon chains. It was necessary to constrain or restrain a number of bond lengths and angles in the structure in order get a stable refinement and chemically reasonable model. All carbon atoms from the long chains were restrained to have similar ADP's as their neighbors with simu and isor command in the refinement. The thereby used constraints are given below: mpla c7 > c12 mpla c1 > c6 DFIX 0.85 H2SA O2S DFIX 1.55 0.02 C40 C41 C41 C42 C31 C32 DFIX 1.55 0.02 C33 C34 C34 C35 C35 C36 C36 C37 C37 C38 C38 C39 C39 C40 SIMU 0.01 C37 C38 SIMU 0.01 C39 C40 ISOR 0.01 C34 C42 ISOR 0.01 C33 C36 C38 C37 C41

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	Occ. (<1)
Br1	0.421270 (17)	0.46907 (9)	0.45941 (5)	0.0536 (2)
Br2	0.391295 (16)	0.02297 (10)	0.26314 (5)	0.0561 (3)
N1	0.39511 (10)	−0.1283 (7)	0.4923 (3)	0.0363 (14)
N2	0.57036 (11)	0.3549 (6)	0.8060 (3)	0.0393 (15)
O1S	0.43206 (14)	0.2766 (7)	0.3002 (4)	0.073 (2)
H1SA	0.4259	0.3287	0.3340	0.088*
H1SB	0.4206	0.2262	0.2811	0.088*
O2S	0.48248 (14)	0.4190 (7)	0.4629 (4)	0.077 (2)
H2SA	0.4670	0.4296	0.4667	0.092*
H2SB	0.4873	0.4289	0.4161	0.092*
O3S	0.48267 (15)	0.3217 (7)	0.3092 (4)	0.081 (2)
H3SA	0.4653	0.3167	0.2927	0.097*
H3SB	0.4916	0.3695	0.2687	0.097*	0.50
H3SC	0.4988	0.2941	0.2921	0.097*	0.50
C1	0.47073 (11)	0.0983 (6)	0.5211 (3)	0.0273 (14)
H1	0.4769	0.1806	0.5011	0.033*
C2	0.45063 (12)	0.0383 (7)	0.4837 (4)	0.0320 (15)
H2	0.4429	0.0820	0.4391	0.038*
C3	0.44129 (11)	−0.0850 (7)	0.5093 (4)	0.0330 (16)
C4	0.45320 (12)	−0.1459 (7)	0.5737 (4)	0.0357 (16)
H4	0.4476	−0.2316	0.5907	0.043*
C5	0.47313 (12)	−0.0866 (7)	0.6149 (4)	0.0351 (16)
H5	0.4805	−0.1301	0.6601	0.042*
C6	0.48219 (11)	0.0380 (6)	0.5891 (4)	0.0277 (14)
C7	0.50360 (11)	0.1063 (6)	0.6284 (3)	0.0238 (13)
C8	0.50765 (13)	0.2439 (7)	0.6195 (4)	0.0343 (16)
H8	0.4958	0.2965	0.5904	0.041*
C9	0.52824 (13)	0.3064 (7)	0.6514 (4)	0.0357 (16)
H9	0.5304	0.4007	0.6437	0.043*
C10	0.54614 (11)	0.2322 (7)	0.6952 (3)	0.0281 (14)
C11	0.54227 (11)	0.0969 (7)	0.7065 (4)	0.0322 (16)
H11	0.5540	0.0451	0.7364	0.039*
C12	0.52096 (11)	0.0335 (6)	0.6740 (4)	0.0277 (14)
H12	0.5184	−0.0601	0.6833	0.033*
C13	0.42106 (11)	−0.1523 (8)	0.4627 (4)	0.0355 (16)
H13A	0.4242	−0.2509	0.4628	0.043*
H13B	0.4214	−0.1208	0.4071	0.043*
C14	0.38967 (14)	0.0188 (9)	0.4922 (6)	0.056 (2)
H14A	0.4018	0.0657	0.5267	0.084*
H14B	0.3733	0.0337	0.5119	0.084*
H14C	0.3903	0.0541	0.4381	0.084*
C15	0.39331 (15)	−0.1911 (13)	0.5731 (4)	0.066 (3)
H15A	0.3762	−0.1904	0.5880	0.099*
H15B	0.4033	−0.1393	0.6120	0.099*
H15C	0.3992	−0.2846	0.5717	0.099*
C16	0.37784 (12)	−0.2007 (8)	0.4331 (4)	0.0388 (17)
H16A	0.3811	−0.2991	0.4365	0.047*
H16B	0.3815	−0.1711	0.3789	0.047*
C17	0.35055 (13)	−0.1762 (9)	0.4454 (5)	0.047 (2)
H17A	0.3460	−0.2169	0.4962	0.057*
H17B	0.3473	−0.0778	0.4476	0.057*
C18	0.33534 (13)	−0.2400 (9)	0.3764 (4)	0.046 (2)
H18A	0.3422	−0.2129	0.3255	0.055*
H18B	0.3363	−0.3398	0.3805	0.055*
C19	0.30876 (12)	−0.1955 (9)	0.3776 (5)	0.046 (2)
H19A	0.3080	−0.0956	0.3751	0.055*
H19B	0.3020	−0.2241	0.4283	0.055*
C20	0.29272 (14)	−0.2543 (9)	0.3084 (5)	0.048 (2)
H20A	0.3003	−0.2331	0.2578	0.058*
H20B	0.2922	−0.3539	0.3138	0.058*
C21	0.26687 (13)	−0.1997 (9)	0.3054 (5)	0.047 (2)
H21A	0.2675	−0.1001	0.3000	0.056*
H21B	0.2594	−0.2204	0.3563	0.056*
C22	0.25043 (15)	−0.2565 (9)	0.2377 (5)	0.055 (2)
H22A	0.2489	−0.3556	0.2447	0.066*
H22B	0.2583	−0.2403	0.1869	0.066*
C23	0.22469 (14)	−0.1935 (9)	0.2335 (5)	0.053 (2)
H23A	0.2173	−0.2040	0.2856	0.064*
H23B	0.2261	−0.0955	0.2227	0.064*
C24	0.20762 (16)	−0.2577 (10)	0.1692 (6)	0.064 (3)
H24A	0.2055	−0.3548	0.1813	0.077*
H24B	0.2153	−0.2508	0.1174	0.077*
C25	0.18238 (16)	−0.1894 (10)	0.1633 (7)	0.069 (3)
H25A	0.1744	−0.2005	0.2144	0.083*
H25B	0.1846	−0.0913	0.1543	0.083*
C26	0.1658 (2)	−0.2462 (12)	0.0976 (8)	0.100 (4)
H26A	0.1632	−0.3440	0.1067	0.120*
H26B	0.1736	−0.2354	0.0462	0.120*
C27	0.14061 (19)	−0.1715 (13)	0.0947 (10)	0.114 (5)
H27A	0.1430	−0.0761	0.0813	0.171*
H27B	0.1334	−0.1780	0.1466	0.171*
H27C	0.1296	−0.2135	0.0543	0.171*
C28	0.56920 (12)	0.3042 (8)	0.7215 (4)	0.0365 (17)
H28A	0.5714	0.3823	0.6858	0.044*
H28B	0.5831	0.2421	0.7148	0.044*
C29	0.5481 (2)	0.4454 (10)	0.8193 (5)	0.067 (3)
H29A	0.5475	0.5185	0.7800	0.101*
H29B	0.5495	0.4842	0.8727	0.101*
H29C	0.5331	0.3914	0.8136	0.101*
C30	0.56916 (15)	0.2392 (7)	0.8630 (4)	0.0402 (18)
H30A	0.5716	0.2730	0.9174	0.060*
H30B	0.5820	0.1736	0.8522	0.060*
H30C	0.5531	0.1954	0.8567	0.060*
C31	0.59121 (15)	0.4520 (10)	0.8239 (6)	0.065 (3)
H31A	0.5890	0.5334	0.7902	0.078*
H31B	0.5909	0.4808	0.8800	0.078*
C32	0.61527 (18)	0.3902 (13)	0.8096 (8)	0.107 (4)
H32A	0.6179	0.3851	0.7520	0.128*
H32B	0.6162	0.2976	0.8319	0.128*
C33	0.6347 (2)	0.4827 (14)	0.8514 (9)	0.101 (4)
H33A	0.6354	0.5687	0.8216	0.121*
H33B	0.6293	0.5042	0.9051	0.121*
C34	0.65977 (18)	0.4261 (14)	0.8592 (7)	0.091 (4)
H34A	0.6654	0.4087	0.8052	0.110*
H34B	0.6589	0.3376	0.8863	0.110*
C35	0.67866 (17)	0.5099 (11)	0.9026 (8)	0.087 (4)
H35A	0.6723	0.5352	0.9546	0.104*
H35B	0.6808	0.5945	0.8724	0.104*
C36	0.7034 (2)	0.4459 (15)	0.9172 (9)	0.113 (4)
H36A	0.7010	0.3547	0.9398	0.135*
H36B	0.7109	0.4340	0.8654	0.135*
C37	0.72097 (17)	0.5213 (12)	0.9709 (7)	0.079 (3)
H37A	0.7132	0.5366	1.0220	0.095*
H37B	0.7239	0.6111	0.9472	0.095*
C38	0.74564 (18)	0.4529 (13)	0.9880 (7)	0.091 (3)
H38A	0.7426	0.3631	1.0117	0.110*
H38B	0.7533	0.4374	0.9368	0.110*
C39	0.76320 (16)	0.5262 (12)	1.0408 (7)	0.084 (3)
H39A	0.7550	0.5474	1.0904	0.101*
H39B	0.7670	0.6133	1.0152	0.101*
C40	0.78707 (18)	0.4564 (14)	1.0628 (7)	0.096 (3)
H40A	0.7833	0.3697	1.0888	0.116*
H40B	0.7952	0.4343	1.0131	0.116*
C41	0.80483 (18)	0.5299 (13)	1.1150 (7)	0.091 (4)
H41A	0.8091	0.6140	1.0870	0.110*
H41B	0.7961	0.5575	1.1625	0.110*
C42	0.8279 (2)	0.4680 (18)	1.1436 (9)	0.122 (5)
H42A	0.8393	0.4654	1.1004	0.183*
H42B	0.8248	0.3758	1.1618	0.183*
H42C	0.8351	0.5216	1.1877	0.183*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0761 (6)	0.0504 (5)	0.0348 (4)	−0.0120 (4)	0.0076 (4)	0.0023 (3)
Br2	0.0522 (5)	0.0725 (6)	0.0437 (5)	0.0055 (4)	0.0021 (3)	0.0074 (4)
N1	0.027 (3)	0.053 (4)	0.029 (3)	0.001 (3)	0.004 (2)	−0.005 (3)
N2	0.058 (3)	0.037 (3)	0.023 (3)	−0.020 (3)	0.002 (2)	0.002 (2)
O1S	0.102 (5)	0.057 (4)	0.060 (4)	−0.002 (4)	0.001 (3)	−0.012 (3)
O2S	0.097 (5)	0.060 (4)	0.071 (4)	−0.005 (4)	−0.018 (3)	0.029 (3)
O3S	0.093 (5)	0.063 (4)	0.086 (5)	0.013 (4)	−0.007 (4)	0.008 (4)
C1	0.036 (3)	0.025 (3)	0.021 (3)	0.003 (3)	0.009 (2)	−0.006 (2)
C2	0.036 (3)	0.040 (4)	0.020 (3)	0.010 (3)	0.005 (2)	0.001 (3)
C3	0.026 (3)	0.045 (4)	0.028 (3)	0.005 (3)	0.005 (2)	−0.007 (3)
C4	0.035 (3)	0.034 (4)	0.039 (4)	0.003 (3)	0.005 (3)	0.001 (3)
C5	0.031 (3)	0.039 (4)	0.036 (4)	0.003 (3)	0.000 (3)	0.009 (3)
C6	0.032 (3)	0.022 (3)	0.029 (3)	0.005 (3)	0.009 (2)	0.002 (2)
C7	0.031 (3)	0.024 (3)	0.017 (3)	−0.002 (2)	0.002 (2)	0.001 (2)
C8	0.044 (4)	0.039 (4)	0.019 (3)	0.004 (3)	0.000 (3)	0.005 (3)
C9	0.058 (4)	0.022 (3)	0.028 (3)	−0.011 (3)	0.013 (3)	−0.003 (3)
C10	0.036 (3)	0.035 (3)	0.013 (3)	−0.011 (3)	0.006 (2)	−0.003 (2)
C11	0.024 (3)	0.048 (4)	0.024 (3)	−0.001 (3)	0.000 (2)	−0.007 (3)
C12	0.034 (3)	0.018 (3)	0.031 (3)	−0.003 (3)	0.009 (2)	0.001 (2)
C13	0.028 (3)	0.044 (4)	0.035 (3)	0.007 (3)	0.009 (3)	−0.001 (3)
C14	0.030 (3)	0.069 (5)	0.068 (5)	0.004 (4)	0.001 (3)	−0.027 (4)
C15	0.050 (5)	0.126 (9)	0.021 (4)	−0.007 (5)	0.004 (3)	0.010 (4)
C16	0.038 (4)	0.051 (4)	0.027 (3)	−0.002 (3)	0.000 (3)	−0.010 (3)
C17	0.031 (4)	0.064 (5)	0.046 (4)	0.001 (3)	0.004 (3)	−0.006 (4)
C18	0.038 (4)	0.058 (5)	0.041 (4)	0.001 (4)	0.000 (3)	−0.002 (3)
C19	0.032 (3)	0.060 (5)	0.046 (4)	−0.004 (3)	0.003 (3)	0.004 (4)
C20	0.046 (4)	0.051 (5)	0.047 (4)	0.009 (4)	0.003 (3)	−0.002 (4)
C21	0.033 (4)	0.047 (4)	0.060 (5)	0.000 (3)	−0.004 (3)	−0.008 (4)
C22	0.051 (4)	0.050 (5)	0.063 (5)	0.012 (4)	−0.011 (4)	−0.008 (4)
C23	0.041 (4)	0.047 (5)	0.069 (5)	−0.002 (4)	−0.017 (4)	0.001 (4)
C24	0.058 (5)	0.052 (5)	0.080 (6)	0.008 (4)	−0.022 (4)	−0.005 (5)
C25	0.046 (4)	0.054 (5)	0.104 (7)	0.000 (4)	−0.025 (5)	0.001 (5)
C26	0.079 (6)	0.058 (6)	0.156 (10)	−0.001 (5)	−0.068 (7)	0.014 (7)
C27	0.064 (6)	0.070 (7)	0.201 (13)	−0.013 (5)	−0.070 (7)	0.027 (8)
C28	0.041 (3)	0.049 (4)	0.019 (3)	−0.016 (3)	0.004 (3)	0.000 (3)
C29	0.102 (7)	0.060 (5)	0.040 (5)	0.019 (5)	−0.002 (4)	−0.013 (4)
C30	0.062 (4)	0.032 (4)	0.027 (3)	−0.014 (3)	0.000 (3)	0.007 (3)
C31	0.067 (5)	0.066 (6)	0.060 (5)	−0.023 (5)	−0.009 (4)	0.002 (5)
C32	0.080 (7)	0.098 (8)	0.139 (10)	0.031 (6)	−0.037 (7)	−0.070 (7)
C33	0.097 (6)	0.091 (7)	0.113 (7)	0.000 (6)	0.002 (6)	−0.006 (6)
C34	0.086 (6)	0.102 (7)	0.085 (6)	−0.017 (5)	−0.008 (5)	−0.005 (5)
C35	0.062 (6)	0.061 (6)	0.139 (11)	−0.003 (5)	0.021 (6)	−0.001 (7)
C36	0.112 (7)	0.109 (7)	0.117 (7)	−0.010 (6)	0.005 (6)	0.000 (6)
C37	0.068 (4)	0.084 (5)	0.087 (5)	−0.004 (4)	0.008 (4)	0.006 (4)
C38	0.087 (5)	0.094 (5)	0.093 (5)	−0.006 (5)	0.001 (4)	0.006 (5)
C39	0.056 (5)	0.103 (6)	0.092 (6)	−0.014 (5)	0.009 (4)	0.017 (5)
C40	0.075 (5)	0.121 (7)	0.093 (6)	−0.025 (6)	0.000 (5)	0.020 (6)
C41	0.076 (5)	0.098 (7)	0.101 (6)	−0.005 (5)	0.015 (5)	0.007 (5)
C42	0.114 (7)	0.132 (8)	0.119 (8)	−0.021 (6)	−0.010 (6)	0.015 (6)

Geometric parameters (Å, º)

N1—C14	1.485 (11)	C21—H21B	0.9900
N1—C15	1.506 (10)	C22—C23	1.538 (11)
N1—C16	1.522 (9)	C22—H22A	0.9900
N1—C13	1.544 (8)	C22—H22B	0.9900
N2—C30	1.498 (9)	C23—C24	1.535 (12)
N2—C28	1.511 (8)	C23—H23A	0.9900
N2—C31	1.511 (10)	C23—H23B	0.9900
N2—C29	1.535 (12)	C24—C25	1.536 (12)
O1S—H1SA	0.8502	C24—H24A	0.9900
O1S—H1SB	0.8505	C24—H24B	0.9900
O2S—H2SA	0.8576	C25—C26	1.508 (14)
O2S—H2SB	0.8499	C25—H25A	0.9900
O3S—H3SA	0.9800	C25—H25B	0.9900
O3S—H3SB	0.9800	C26—C27	1.563 (16)
O3S—H3SC	0.9800	C26—H26A	0.9900
C1—C2	1.376 (9)	C26—H26B	0.9900
C1—C6	1.414 (9)	C27—H27A	0.9800
C1—H1	0.9500	C27—H27B	0.9800
C2—C3	1.398 (10)	C27—H27C	0.9800
C2—H2	0.9500	C28—H28A	0.9900
C3—C4	1.380 (9)	C28—H28B	0.9900
C3—C13	1.485 (9)	C29—H29A	0.9800
C4—C5	1.395 (10)	C29—H29B	0.9800
C4—H4	0.9500	C29—H29C	0.9800
C5—C6	1.405 (9)	C30—H30A	0.9800
C5—H5	0.9500	C30—H30B	0.9800
C6—C7	1.482 (8)	C30—H30C	0.9800
C7—C8	1.388 (9)	C31—C32	1.480 (12)
C7—C12	1.395 (8)	C31—H31A	0.9900
C8—C9	1.372 (10)	C31—H31B	0.9900
C8—H8	0.9500	C32—C33	1.549 (17)
C9—C10	1.406 (10)	C32—H32A	0.9900
C9—H9	0.9500	C32—H32B	0.9900
C10—C11	1.370 (10)	C33—C34	1.480 (13)
C10—C28	1.497 (9)	C33—H33A	0.9900
C11—C12	1.412 (9)	C33—H33B	0.9900
C11—H11	0.9500	C34—C35	1.491 (13)
C12—H12	0.9500	C34—H34A	0.9900
C13—H13A	0.9900	C34—H34B	0.9900
C13—H13B	0.9900	C35—C36	1.504 (13)
C14—H14A	0.9800	C35—H35A	0.9900
C14—H14B	0.9800	C35—H35B	0.9900
C14—H14C	0.9800	C36—C37	1.490 (13)
C15—H15A	0.9800	C36—H36A	0.9900
C15—H15B	0.9800	C36—H36B	0.9900
C15—H15C	0.9800	C37—C38	1.525 (12)
C16—C17	1.536 (10)	C37—H37A	0.9900
C16—H16A	0.9900	C37—H37B	0.9900
C16—H16B	0.9900	C38—C39	1.471 (13)
C17—C18	1.535 (11)	C38—H38A	0.9900
C17—H17A	0.9900	C38—H38B	0.9900
C17—H17B	0.9900	C39—C40	1.508 (13)
C18—C19	1.520 (10)	C39—H39A	0.9900
C18—H18A	0.9900	C39—H39B	0.9900
C18—H18B	0.9900	C40—C41	1.474 (13)
C19—C20	1.541 (11)	C40—H40A	0.9900
C19—H19A	0.9900	C40—H40B	0.9900
C19—H19B	0.9900	C41—C42	1.465 (14)
C20—C21	1.512 (10)	C41—H41A	0.9900
C20—H20A	0.9900	C41—H41B	0.9900
C20—H20B	0.9900	C42—H42A	0.9800
C21—C22	1.527 (11)	C42—H42B	0.9800
C21—H21A	0.9900	C42—H42C	0.9800
C14—N1—C15	112.5 (7)	C22—C23—H23B	109.0
C14—N1—C16	110.0 (6)	H23A—C23—H23B	107.8
C15—N1—C16	109.6 (6)	C23—C24—C25	112.3 (8)
C14—N1—C13	109.7 (6)	C23—C24—H24A	109.1
C15—N1—C13	109.1 (6)	C25—C24—H24A	109.1
C16—N1—C13	105.5 (5)	C23—C24—H24B	109.1
C30—N2—C28	110.6 (5)	C25—C24—H24B	109.1
C30—N2—C31	114.3 (6)	H24A—C24—H24B	107.9
C28—N2—C31	113.5 (6)	C26—C25—C24	113.1 (9)
C30—N2—C29	107.0 (6)	C26—C25—H25A	109.0
C28—N2—C29	109.4 (6)	C24—C25—H25A	109.0
C31—N2—C29	101.3 (7)	C26—C25—H25B	109.0
H1SA—O1S—H1SB	107.6	C24—C25—H25B	109.0
H2SA—O2S—H2SB	114.0	H25A—C25—H25B	107.8
H3SA—O3S—H3SB	109.5	C25—C26—C27	110.3 (11)
H3SA—O3S—H3SC	141.1	C25—C26—H26A	109.6
H3SB—O3S—H3SC	56.3	C27—C26—H26A	109.6
C2—C1—C6	120.4 (6)	C25—C26—H26B	109.6
C2—C1—H1	119.8	C27—C26—H26B	109.6
C6—C1—H1	119.8	H26A—C26—H26B	108.1
C1—C2—C3	121.9 (6)	C26—C27—H27A	109.5
C1—C2—H2	119.0	C26—C27—H27B	109.5
C3—C2—H2	119.0	H27A—C27—H27B	109.5
C4—C3—C2	117.3 (6)	C26—C27—H27C	109.5
C4—C3—C13	122.3 (7)	H27A—C27—H27C	109.5
C2—C3—C13	120.1 (6)	H27B—C27—H27C	109.5
C3—C4—C5	122.6 (7)	C10—C28—N2	115.8 (5)
C3—C4—H4	118.7	C10—C28—H28A	108.3
C5—C4—H4	118.7	N2—C28—H28A	108.3
C4—C5—C6	119.5 (6)	C10—C28—H28B	108.3
C4—C5—H5	120.2	N2—C28—H28B	108.3
C6—C5—H5	120.2	H28A—C28—H28B	107.4
C5—C6—C1	118.1 (6)	N2—C29—H29A	109.5
C5—C6—C7	122.9 (6)	N2—C29—H29B	109.5
C1—C6—C7	118.9 (5)	H29A—C29—H29B	109.5
C8—C7—C12	117.3 (6)	N2—C29—H29C	109.5
C8—C7—C6	121.7 (5)	H29A—C29—H29C	109.5
C12—C7—C6	121.0 (5)	H29B—C29—H29C	109.5
C9—C8—C7	122.1 (6)	N2—C30—H30A	109.5
C9—C8—H8	119.0	N2—C30—H30B	109.5
C7—C8—H8	119.0	H30A—C30—H30B	109.5
C8—C9—C10	120.7 (6)	N2—C30—H30C	109.5
C8—C9—H9	119.7	H30A—C30—H30C	109.5
C10—C9—H9	119.6	H30B—C30—H30C	109.5
C11—C10—C9	118.3 (6)	C32—C31—N2	111.9 (8)
C11—C10—C28	123.9 (6)	C32—C31—H31A	109.2
C9—C10—C28	117.7 (6)	N2—C31—H31A	109.2
C10—C11—C12	120.7 (6)	C32—C31—H31B	109.2
C10—C11—H11	119.7	N2—C31—H31B	109.2
C12—C11—H11	119.7	H31A—C31—H31B	107.9
C7—C12—C11	120.9 (6)	C31—C32—C33	106.2 (9)
C7—C12—H12	119.5	C31—C32—H32A	110.5
C11—C12—H12	119.5	C33—C32—H32A	110.5
C3—C13—N1	115.7 (5)	C31—C32—H32B	110.5
C3—C13—H13A	108.4	C33—C32—H32B	110.5
N1—C13—H13A	108.4	H32A—C32—H32B	108.7
C3—C13—H13B	108.4	C34—C33—C32	115.5 (11)
N1—C13—H13B	108.4	C34—C33—H33A	108.4
H13A—C13—H13B	107.4	C32—C33—H33A	108.4
N1—C14—H14A	109.5	C34—C33—H33B	108.4
N1—C14—H14B	109.5	C32—C33—H33B	108.4
H14A—C14—H14B	109.5	H33A—C33—H33B	107.5
N1—C14—H14C	109.5	C33—C34—C35	116.8 (11)
H14A—C14—H14C	109.5	C33—C34—H34A	108.1
H14B—C14—H14C	109.5	C35—C34—H34A	108.1
N1—C15—H15A	109.5	C33—C34—H34B	108.1
N1—C15—H15B	109.5	C35—C34—H34B	108.1
H15A—C15—H15B	109.5	H34A—C34—H34B	107.3
N1—C15—H15C	109.5	C34—C35—C36	116.4 (10)
H15A—C15—H15C	109.5	C34—C35—H35A	108.2
H15B—C15—H15C	109.5	C36—C35—H35A	108.2
N1—C16—C17	114.5 (6)	C34—C35—H35B	108.2
N1—C16—H16A	108.6	C36—C35—H35B	108.2
C17—C16—H16A	108.6	H35A—C35—H35B	107.3
N1—C16—H16B	108.6	C37—C36—C35	116.0 (11)
C17—C16—H16B	108.6	C37—C36—H36A	108.3
H16A—C16—H16B	107.6	C35—C36—H36A	108.3
C18—C17—C16	109.2 (6)	C37—C36—H36B	108.3
C18—C17—H17A	109.8	C35—C36—H36B	108.3
C16—C17—H17A	109.8	H36A—C36—H36B	107.4
C18—C17—H17B	109.8	C36—C37—C38	115.6 (10)
C16—C17—H17B	109.8	C36—C37—H37A	108.4
H17A—C17—H17B	108.3	C38—C37—H37A	108.4
C19—C18—C17	110.9 (6)	C36—C37—H37B	108.4
C19—C18—H18A	109.5	C38—C37—H37B	108.4
C17—C18—H18A	109.5	H37A—C37—H37B	107.4
C19—C18—H18B	109.5	C39—C38—C37	116.3 (10)
C17—C18—H18B	109.5	C39—C38—H38A	108.2
H18A—C18—H18B	108.0	C37—C38—H38A	108.2
C18—C19—C20	113.1 (7)	C39—C38—H38B	108.2
C18—C19—H19A	108.9	C37—C38—H38B	108.2
C20—C19—H19A	108.9	H38A—C38—H38B	107.4
C18—C19—H19B	108.9	C38—C39—C40	117.2 (10)
C20—C19—H19B	108.9	C38—C39—H39A	108.0
H19A—C19—H19B	107.8	C40—C39—H39A	108.0
C21—C20—C19	113.0 (7)	C38—C39—H39B	108.0
C21—C20—H20A	109.0	C40—C39—H39B	108.0
C19—C20—H20A	109.0	H39A—C39—H39B	107.2
C21—C20—H20B	109.0	C41—C40—C39	117.5 (11)
C19—C20—H20B	109.0	C41—C40—H40A	107.9
H20A—C20—H20B	107.8	C39—C40—H40A	107.9
C20—C21—C22	114.3 (7)	C41—C40—H40B	107.9
C20—C21—H21A	108.7	C39—C40—H40B	107.9
C22—C21—H21A	108.7	H40A—C40—H40B	107.2
C20—C21—H21B	108.7	C42—C41—C40	121.7 (12)
C22—C21—H21B	108.7	C42—C41—H41A	106.9
H21A—C21—H21B	107.6	C40—C41—H41A	106.9
C21—C22—C23	113.1 (7)	C42—C41—H41B	106.9
C21—C22—H22A	109.0	C40—C41—H41B	106.9
C23—C22—H22A	109.0	H41A—C41—H41B	106.7
C21—C22—H22B	109.0	C41—C42—H42A	109.5
C23—C22—H22B	109.0	C41—C42—H42B	109.5
H22A—C22—H22B	107.8	H42A—C42—H42B	109.5
C24—C23—C22	113.0 (7)	C41—C42—H42C	109.5
C24—C23—H23A	109.0	H42A—C42—H42C	109.5
C22—C23—H23A	109.0	H42B—C42—H42C	109.5
C24—C23—H23B	109.0
C6—C1—C2—C3	−2.1 (9)	C15—N1—C16—C17	69.5 (8)
C1—C2—C3—C4	−0.6 (9)	C13—N1—C16—C17	−173.1 (6)
C1—C2—C3—C13	−174.2 (6)	N1—C16—C17—C18	173.1 (6)
C2—C3—C4—C5	2.7 (10)	C16—C17—C18—C19	−169.1 (7)
C13—C3—C4—C5	176.2 (6)	C17—C18—C19—C20	178.8 (7)
C3—C4—C5—C6	−2.1 (10)	C18—C19—C20—C21	−174.7 (7)
C4—C5—C6—C1	−0.6 (9)	C19—C20—C21—C22	−179.7 (7)
C4—C5—C6—C7	−178.6 (6)	C20—C21—C22—C23	−176.9 (7)
C2—C1—C6—C5	2.7 (9)	C21—C22—C23—C24	−175.9 (8)
C2—C1—C6—C7	−179.2 (6)	C22—C23—C24—C25	−177.5 (8)
C5—C6—C7—C8	−159.4 (6)	C23—C24—C25—C26	177.0 (9)
C1—C6—C7—C8	22.6 (9)	C24—C25—C26—C27	−179.6 (10)
C5—C6—C7—C12	22.7 (9)	C11—C10—C28—N2	−86.3 (8)
C1—C6—C7—C12	−155.3 (6)	C9—C10—C28—N2	98.7 (7)
C12—C7—C8—C9	2.3 (9)	C30—N2—C28—C10	62.6 (8)
C6—C7—C8—C9	−175.6 (6)	C31—N2—C28—C10	−167.4 (7)
C7—C8—C9—C10	−0.4 (10)	C29—N2—C28—C10	−55.0 (8)
C8—C9—C10—C11	−1.1 (9)	C30—N2—C31—C32	69.3 (10)
C8—C9—C10—C28	174.2 (6)	C28—N2—C31—C32	−58.8 (11)
C9—C10—C11—C12	0.7 (9)	C29—N2—C31—C32	−175.9 (9)
C28—C10—C11—C12	−174.3 (6)	N2—C31—C32—C33	−164.7 (10)
C8—C7—C12—C11	−2.8 (9)	C31—C32—C33—C34	167.9 (12)
C6—C7—C12—C11	175.2 (6)	C32—C33—C34—C35	−177.1 (12)
C10—C11—C12—C7	1.3 (9)	C33—C34—C35—C36	174.2 (12)
C4—C3—C13—N1	89.2 (8)	C34—C35—C36—C37	−171.1 (12)
C2—C3—C13—N1	−97.6 (7)	C35—C36—C37—C38	177.6 (11)
C14—N1—C13—C3	58.6 (8)	C36—C37—C38—C39	179.9 (11)
C15—N1—C13—C3	−65.1 (8)	C37—C38—C39—C40	176.1 (10)
C16—N1—C13—C3	177.2 (6)	C38—C39—C40—C41	179.4 (11)
C14—N1—C16—C17	−54.8 (8)	C39—C40—C41—C42	176.4 (12)