(R)-1-Phenyl­ethyl­ammonium N-tetra­deca­noyl-L-phenyl­alaninate monohydrate

The title compound, C₈H₁₂N⁺·C₂₃H₃₆NO₃⁻·H₂O, has one mol­ecule of N-tetra­deca­noyl-L-phenyl­alanine and one mol­ecule of (R)-1-phenyl­ethyl­amine as a diastereoisomeric salt, and a water mol­ecule in the asymmetric unit. In the crystal structure, the packing of the mol­ecules is stabilized by N—H...O and O—H...O hydrogen bonds involving the amide, ammonium and carboxyl­ate groups, and the solvent water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.068
• wR factor = 0.151
• Data-to-parameter ratio = 10.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O4     -   H50    ...       1.05 Ang.

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           27.50
           From the CIF: _reflns_number_total               3774
           Count of symmetry unique reflns         3905
           Completeness (_total/calc)             96.65%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

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

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

---

S1. Comment

N-Acyl amino acids are generally formed by condensation of amino acids with fatty acids and produce water-soluble anionic surfactants when their acid moieties are neutralized with a range of bases. These compounds are widely used as additives, dispersants and detergents in a variety of industrial and commercial applications due to their biodegradability and low toxicity (Takehara, 1984). There are also growing concerns over the molecular associations of chiral surfactants (Shinitzky & Haimovitz, 1993; Parazak et al., 1994; Ohta et al., 2003) and their applications to chiral analytical techniques such as electrophoresis (Taurus et al., 2003). When N-acyl amino acids are neutralized with optically active bases, diastereoisomeric surfactant salts are formed. Structural studies on these diastereomeric salts may provide the basis for understanding the mechanism of chiral discrimination of N-acyl amino acid surfactants. In this work, we have prepared a diastereomeric salt, (I), from N-tetradecanoyl-L-phenylalanine and (R)-1-phenylethylamine as a model of chiral discrimination of N-acyl amino acids and determined its structure.

The conformation of the tetradecanoyl chain is as most often found for larger alkanes, i.e. staggered with the largest substituents at any C—C bond antiperiplanar with respect to each other (Fig. 1). The C—C bond lengths within the chain range from 1.518 (6) to 1.533 (5) Å and the anglesfrom 112.8 (3) to 114.1 (3)°. These values are similar to those found in a related fatty acid (Amai et al., 1998).

The molecular packing is such that the hydrocarbon chains lie side by side, with neighboring hydrophillic heads pointing in opposite directions. The hydrophilic heads are connected by a network of hydrogen bonds involving the carboxylate group of N-tetradecanoyl-L-phenylalanine, the ammonium group of (R)-1-phenylethylamine and the water molecule (Table 1 and Fig. 2). The amide linkages of N-tetradecanoyl-L-phenylalanine molecules form a N—H···O hydrogen-bondied chain running along the b axis.

S2. Experimental

N-tetradecanoyl-l-phenylalanine was prepared by the reaction of l-phenylalanine with tetradecanoyl chloride as described previously (Miyagishi & Nishida, 1978) and was recrystallized from an acetone/methanol solution three times. The purity was checked by HPLC and DSC and by observing no minimum on the surface tension vs concentration curves at 298.15 K. The title compound was obtained by neutralization of N-tetradecanoyl-l-phenylalanine with equimolar of (R)-1-phenylethylamine in methanol. After evaporation of the solvent, the residue was recrystallized from a methanol/water solution to obtain suitable crystals for X-ray diffraction (m.p. 374–376 K).

S3. Refinement

H atoms involved in hydrogen bonds were located in a difference map, and their positional parameters were refined. The U_iso(H) values were set at 1.2U_eq(N or O). Other H atoms were included in calculated positions using a riding-model approximation, with C—H distances in the range 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C). Due to the absence of any significant anomalous scatterers in the crystal, Friedel pairs were merged before the final refinement. The absolute configuration has been assigned on the basis of the known configuration of the reagents.

Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: MITHRIL90 (Gilmore, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPIII (Johnson & Burnett, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular packing of (I), viewed along the b axis. Dashed lines indicate the hydrogen-bonding interactions. H atoms have been omitted for clarity.

(R)-1-Phenylethylammonium N-tetradecanoyl-L-phenylalaninate monohydrate

Crystal data

C8H12N^+·C23H36NO3^−·H2O	F(000) = 564
Mr = 514.73	Dx = 1.126 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2yb	Cell parameters from 5442 reflections
a = 10.920 (4) Å	θ = 7.2–27.5°
b = 4.9902 (17) Å	µ = 0.07 mm^−1
c = 27.926 (10) Å	T = 123 K
β = 94.085 (8)°	Plate, colorless
V = 1517.9 (9) Å^3	0.50 × 0.20 × 0.10 mm
Z = 2

Data collection

Rigaku/MSC Mercury CCD diffractometer	Rint = 0.100
Detector resolution: 14.63 pixels mm^-1	θmax = 27.5°
ω scans	h = −13→14
16351 measured reflections	k = −6→6
3774 independent reflections	l = −35→35
2920 reflections with I > 2σ(I)

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.068	w = 1/[σ^2(Fo^2) + (0.0384P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.151	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.20 e Å^−3
3774 reflections	Δρmin = −0.23 e Å^−3
352 parameters

Special details

Refinement. Refinement using reflections with F² > −10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
O1	0.2957 (2)	1.0792 (7)	0.41845 (10)	0.0360 (7)
O2	0.4593 (2)	0.9265 (5)	0.38397 (8)	0.0217 (5)
O3	0.3805 (2)	1.2925 (5)	0.28462 (10)	0.0275 (6)
O4	0.5634 (3)	0.5884 (6)	0.49885 (10)	0.0270 (6)
N1	0.3314 (3)	0.8609 (6)	0.29735 (10)	0.0196 (6)
N2	0.4315 (3)	0.9376 (7)	0.59795 (12)	0.0210 (6)
C1	0.3455 (3)	0.9770 (7)	0.38413 (13)	0.0211 (7)
C2	0.2615 (3)	0.9225 (7)	0.33811 (12)	0.0187 (7)
C3	0.1674 (3)	0.7025 (8)	0.34547 (12)	0.0219 (7)
C4	0.0711 (3)	0.6899 (8)	0.30375 (13)	0.0236 (7)
C5	−0.0296 (3)	0.8655 (8)	0.30198 (14)	0.0303 (9)
C6	−0.1155 (4)	0.8644 (9)	0.26247 (16)	0.0360 (10)
C7	−0.1032 (4)	0.6868 (10)	0.22508 (15)	0.0350 (9)
C8	−0.0052 (4)	0.5129 (9)	0.22649 (15)	0.0341 (9)
C9	0.0817 (4)	0.5123 (8)	0.26557 (14)	0.0297 (9)
C10	0.3875 (3)	1.0526 (7)	0.27413 (13)	0.0216 (7)
C11	0.4583 (3)	0.9621 (8)	0.23226 (13)	0.0251 (8)
C12	0.3802 (4)	0.8076 (8)	0.19401 (13)	0.0252 (8)
C13	0.2637 (3)	0.9523 (8)	0.17555 (12)	0.0236 (7)
C14	0.1933 (4)	0.8035 (8)	0.13483 (13)	0.0265 (8)
C15	0.0744 (3)	0.9407 (8)	0.11627 (13)	0.0242 (7)
C16	0.0052 (4)	0.7932 (8)	0.07511 (13)	0.0275 (8)
C17	−0.1135 (4)	0.9302 (8)	0.05686 (13)	0.0272 (8)
C18	−0.1797 (4)	0.7899 (8)	0.01355 (13)	0.0261 (8)
C19	−0.2992 (3)	0.9248 (8)	−0.00424 (13)	0.0250 (7)
C20	−0.3640 (3)	0.7883 (8)	−0.04777 (12)	0.0246 (8)
C21	−0.4838 (3)	0.9219 (8)	−0.06560 (13)	0.0269 (8)
C22	−0.5478 (4)	0.7807 (8)	−0.10908 (13)	0.0307 (9)
C23	−0.6651 (4)	0.9180 (9)	−0.12842 (17)	0.0390 (10)
C24	0.3100 (3)	0.9530 (8)	0.61958 (13)	0.0212 (7)
C25	0.2150 (3)	0.7917 (7)	0.59119 (12)	0.0210 (7)
C26	0.0915 (3)	0.8420 (8)	0.59840 (13)	0.0249 (8)
C27	−0.0017 (3)	0.6921 (9)	0.57536 (14)	0.0272 (8)
C28	0.0271 (3)	0.4880 (8)	0.54484 (14)	0.0267 (8)
C29	0.1480 (3)	0.4365 (8)	0.53622 (14)	0.0258 (8)
C30	0.2418 (3)	0.5884 (8)	0.55977 (13)	0.0235 (8)
C31	0.3274 (4)	0.8684 (9)	0.67217 (14)	0.0325 (10)
H1	0.347 (4)	0.681 (9)	0.2894 (14)	0.0233*
H2	0.2173	1.0789	0.3307	0.0225*
H3	0.2082	0.5310	0.3483	0.0257*
H4	0.1280	0.7347	0.3741	0.0257*
H5	−0.0395	0.9813	0.3278	0.0364*
H6	−0.1826	0.9860	0.2613	0.0436*
H7	−0.1627	0.6807	0.1984	0.0422*
H8	0.0032	0.3871	0.2006	0.0399*
H9	0.1489	0.3869	0.2661	0.0351*
H10	0.5236	0.8455	0.2442	0.0301*
H11	0.4909	1.1120	0.2177	0.0301*
H12	0.3574	0.6372	0.2073	0.0294*
H13	0.4282	0.7720	0.1675	0.0294*
H14	0.2122	0.9670	0.2013	0.0284*
H15	0.2854	1.1202	0.1644	0.0284*
H16	0.1736	0.6257	0.1459	0.0314*
H17	0.2447	0.7838	0.1089	0.0314*
H18	0.0224	0.9499	0.1420	0.0290*
H19	0.0937	1.1109	0.1055	0.0290*
H20	−0.0139	0.6140	0.0859	0.0326*
H21	0.0570	0.7758	0.0493	0.0326*
H22	−0.1673	0.9299	0.0822	0.0324*
H23	−0.0951	1.1043	0.0479	0.0324*
H24	−0.1975	0.6068	0.0224	0.0314*
H25	−0.1267	0.7840	−0.0119	0.0314*
H26	−0.3529	0.9196	0.0211	0.0294*
H27	−0.2818	1.1002	−0.0126	0.0294*
H28	−0.3813	0.6038	−0.0393	0.0294*
H29	−0.3103	0.7848	−0.0730	0.0294*
H30	−0.5379	0.9176	−0.0404	0.0323*
H31	−0.4670	1.0973	−0.0743	0.0323*
H32	−0.5671	0.5990	−0.1000	0.0363*
H33	−0.4926	0.7711	−0.1339	0.0363*
H34	−0.7216	0.9199	−0.1041	0.0468*
H35	−0.7005	0.8160	−0.1552	0.0468*
H36	−0.6471	1.0909	−0.1382	0.0468*
H37	0.460 (4)	0.773 (10)	0.6014 (15)	0.0248*
H38	0.480 (4)	1.085 (9)	0.6111 (14)	0.0248*
H39	0.428 (4)	0.995 (9)	0.5688 (16)	0.0248*
H40	0.2842	1.1307	0.6187	0.0255*
H41	0.0712	0.9779	0.6195	0.0302*
H42	−0.0850	0.7296	0.5805	0.0326*
H43	−0.0366	0.3821	0.5296	0.0320*
H44	0.1672	0.2956	0.5144	0.0308*
H45	0.3250	0.5465	0.5542	0.0275*
H46	0.3529	0.6821	0.6740	0.0393*
H47	0.3885	0.9738	0.6883	0.0393*
H48	0.2523	0.8840	0.6869	0.0393*
H49	0.537 (4)	0.754 (10)	0.4968 (15)	0.0274*
H50	0.617 (4)	0.593 (9)	0.5315 (15)	0.0274*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0234 (14)	0.0554 (18)	0.0283 (14)	0.0092 (14)	−0.0032 (11)	−0.0166 (14)
O2	0.0143 (11)	0.0232 (12)	0.0274 (13)	0.0005 (10)	−0.0012 (9)	−0.0011 (11)
O3	0.0258 (14)	0.0190 (12)	0.0375 (15)	−0.0016 (11)	0.0002 (11)	0.0018 (12)
O4	0.0272 (14)	0.0278 (14)	0.0260 (14)	0.0017 (12)	0.0009 (11)	−0.0013 (12)
N1	0.0195 (14)	0.0170 (14)	0.0221 (14)	−0.0019 (12)	−0.0000 (11)	−0.0020 (12)
N2	0.0189 (15)	0.0211 (15)	0.0227 (15)	−0.0024 (14)	−0.0004 (12)	0.0031 (14)
C1	0.0169 (16)	0.0198 (17)	0.0260 (18)	0.0018 (14)	−0.0019 (13)	−0.0023 (15)
C2	0.0144 (15)	0.0170 (16)	0.0245 (17)	0.0025 (14)	0.0008 (13)	−0.0007 (15)
C3	0.0217 (18)	0.0229 (17)	0.0205 (17)	−0.0008 (15)	−0.0024 (14)	−0.0015 (15)
C4	0.0195 (17)	0.0258 (17)	0.0252 (18)	−0.0056 (16)	−0.0001 (14)	0.0026 (16)
C5	0.0231 (18)	0.035 (2)	0.033 (2)	−0.0006 (17)	−0.0015 (16)	−0.0057 (18)
C6	0.027 (2)	0.040 (2)	0.041 (2)	0.0028 (19)	−0.0073 (17)	−0.002 (2)
C7	0.029 (2)	0.041 (2)	0.034 (2)	−0.012 (2)	−0.0093 (17)	0.002 (2)
C8	0.039 (2)	0.032 (2)	0.031 (2)	−0.0079 (19)	−0.0016 (17)	−0.0095 (17)
C9	0.028 (2)	0.027 (2)	0.034 (2)	−0.0008 (17)	−0.0043 (16)	−0.0024 (17)
C10	0.0170 (17)	0.0206 (18)	0.0262 (18)	0.0008 (15)	−0.0067 (14)	0.0030 (15)
C11	0.0183 (17)	0.0267 (18)	0.0303 (19)	−0.0029 (16)	0.0015 (14)	0.0054 (17)
C12	0.0280 (19)	0.0252 (18)	0.0231 (17)	0.0021 (17)	0.0070 (14)	0.0027 (16)
C13	0.0259 (18)	0.0240 (17)	0.0208 (17)	0.0030 (16)	0.0004 (14)	−0.0004 (16)
C14	0.0294 (19)	0.0237 (18)	0.0259 (18)	0.0035 (16)	−0.0015 (15)	−0.0003 (16)
C15	0.0252 (17)	0.0232 (17)	0.0237 (17)	0.0018 (16)	−0.0024 (14)	−0.0002 (16)
C16	0.031 (2)	0.0233 (18)	0.0276 (18)	−0.0002 (17)	−0.0039 (15)	−0.0041 (17)
C17	0.0311 (19)	0.0219 (17)	0.0281 (19)	0.0004 (17)	−0.0024 (15)	−0.0029 (17)
C18	0.0293 (19)	0.0219 (17)	0.0265 (18)	−0.0005 (16)	−0.0032 (15)	−0.0016 (16)
C19	0.0268 (18)	0.0209 (17)	0.0269 (18)	0.0004 (16)	−0.0006 (14)	−0.0008 (16)
C20	0.0256 (18)	0.0251 (18)	0.0228 (17)	0.0009 (16)	0.0003 (14)	−0.0011 (16)
C21	0.0270 (18)	0.0248 (18)	0.0290 (19)	0.0007 (17)	0.0017 (15)	−0.0006 (17)
C22	0.035 (2)	0.031 (2)	0.0260 (19)	0.0031 (19)	−0.0003 (16)	−0.0012 (18)
C23	0.030 (2)	0.036 (2)	0.050 (3)	0.000 (2)	−0.0110 (18)	0.003 (2)
C24	0.0149 (15)	0.0212 (16)	0.0276 (17)	0.0001 (15)	0.0009 (13)	0.0001 (16)
C25	0.0218 (17)	0.0200 (16)	0.0211 (16)	−0.0010 (15)	0.0011 (13)	0.0073 (15)
C26	0.0172 (17)	0.030 (2)	0.0276 (18)	0.0019 (16)	0.0045 (14)	0.0008 (16)
C27	0.0182 (17)	0.0319 (19)	0.032 (2)	−0.0010 (16)	0.0019 (14)	0.0064 (18)
C28	0.0217 (18)	0.0242 (18)	0.033 (2)	−0.0081 (16)	−0.0064 (15)	0.0070 (16)
C29	0.0233 (18)	0.0207 (16)	0.0332 (19)	−0.0016 (16)	−0.0005 (15)	−0.0036 (17)
C30	0.0162 (17)	0.0261 (18)	0.0278 (18)	0.0051 (15)	−0.0008 (14)	0.0007 (16)
C31	0.0257 (19)	0.049 (3)	0.0229 (18)	−0.0050 (19)	0.0026 (15)	−0.0016 (18)

Geometric parameters (Å, º)

O1—C1	1.245 (5)	C15—H18	0.95
O2—C1	1.268 (4)	C15—H19	0.93
O3—C10	1.236 (4)	C16—C17	1.521 (5)
O4—H49	0.88 (5)	C16—H20	0.97
O4—H50	1.05 (4)	C16—H21	0.95
N1—C2	1.448 (4)	C17—C18	1.533 (5)
N1—C10	1.329 (5)	C17—H22	0.95
N1—H1	0.94 (4)	C17—H23	0.93
N2—C24	1.499 (5)	C18—C19	1.520 (5)
N2—H37	0.88 (5)	C18—H24	0.97
N2—H38	0.96 (4)	C18—H25	0.95
N2—H39	0.86 (4)	C19—C20	1.523 (5)
C1—C2	1.549 (5)	C19—H26	0.95
C2—C3	1.528 (5)	C19—H27	0.93
C2—H2	0.93	C20—C21	1.520 (5)
C3—C4	1.514 (5)	C20—H28	0.97
C3—H3	0.97	C20—H29	0.95
C3—H4	0.95	C21—C22	1.529 (5)
C4—C5	1.404 (5)	C21—H30	0.95
C4—C9	1.398 (6)	C21—H31	0.93
C5—C6	1.396 (6)	C22—C23	1.518 (6)
C5—H5	0.94	C22—H32	0.97
C6—C7	1.383 (6)	C22—H33	0.95
C6—H6	0.95	C23—H34	0.95
C7—C8	1.376 (6)	C23—H35	0.96
C7—H7	0.95	C23—H36	0.93
C8—C9	1.394 (6)	C24—C25	1.495 (5)
C8—H8	0.97	C24—C31	1.527 (5)
C9—H9	0.96	C24—H40	0.93
C10—C11	1.516 (5)	C25—C26	1.400 (5)
C11—C12	1.527 (5)	C25—C30	1.386 (5)
C11—H10	0.96	C26—C27	1.384 (5)
C11—H11	0.93	C26—H41	0.94
C12—C13	1.521 (5)	C27—C28	1.378 (6)
C12—H12	0.97	C27—H42	0.95
C12—H13	0.95	C28—C29	1.383 (5)
C13—C14	1.520 (5)	C28—H43	0.95
C13—H14	0.95	C29—C30	1.400 (5)
C13—H15	0.93	C29—H44	0.96
C14—C15	1.525 (5)	C30—H45	0.96
C14—H16	0.97	C31—H46	0.97
C14—H17	0.95	C31—H47	0.94
C15—C16	1.520 (5)	C31—H48	0.95
O1···O4^i	2.683 (4)	O3···C9^iv	3.448 (5)
O1···C27^ii	3.276 (5)	O4···N2^iii	2.810 (4)
O1···N2^i	3.532 (4)	O4···O4^i	2.857 (4)
O2···N2^iii	2.747 (4)	O4···O4^iii	2.857 (4)
O2···N2^i	2.845 (4)	O4···C1^iii	3.393 (4)
O2···O4^i	3.397 (4)	N2···C1^iii	3.360 (5)
O2···C24^iii	3.461 (4)	C26···C29^iv	3.514 (6)
O3···N1^iv	2.913 (4)	C28···C28^ii	3.555 (6)
O3···C31^i	3.351 (5)	C28···C28^v	3.555 (6)
H49—O4—H50	101 (4)	C15—C16—H20	108.6
C2—N1—C10	121.2 (3)	C15—C16—H21	109.1
C2—N1—H1	120 (3)	C17—C16—H20	108.7
C10—N1—H1	118 (3)	C17—C16—H21	109.0
C24—N2—H37	109 (3)	H20—C16—H21	107.6
C24—N2—H38	107 (2)	C16—C17—C18	113.7 (3)
C24—N2—H39	113 (3)	C16—C17—H22	107.8
H37—N2—H38	119 (4)	C16—C17—H23	108.3
H37—N2—H39	114 (4)	C18—C17—H22	107.8
H38—N2—H39	95 (4)	C18—C17—H23	108.3
O1—C1—O2	124.5 (3)	H22—C17—H23	111.0
O1—C1—C2	116.5 (3)	C17—C18—C19	113.7 (3)
O2—C1—C2	119.0 (3)	C17—C18—H24	108.7
N1—C2—C1	112.1 (3)	C17—C18—H25	109.1
N1—C2—C3	110.5 (3)	C19—C18—H24	108.5
N1—C2—H2	107.2	C19—C18—H25	108.9
C1—C2—C3	112.3 (3)	H24—C18—H25	107.9
C1—C2—H2	107.7	C18—C19—C20	113.7 (3)
C3—C2—H2	106.7	C18—C19—H26	107.8
C2—C3—C4	111.3 (3)	C18—C19—H27	108.2
C2—C3—H3	109.7	C20—C19—H26	107.8
C2—C3—H4	110.0	C20—C19—H27	108.2
C4—C3—H3	108.6	H26—C19—H27	111.1
C4—C3—H4	108.9	C19—C20—C21	113.9 (3)
H3—C3—H4	108.4	C19—C20—H28	108.5
C3—C4—C5	120.0 (3)	C19—C20—H29	109.0
C3—C4—C9	121.5 (3)	C21—C20—H28	108.5
C5—C4—C9	118.4 (3)	C21—C20—H29	109.1
C4—C5—C6	120.4 (4)	H28—C20—H29	107.7
C4—C5—H5	119.5	C20—C21—C22	113.1 (3)
C6—C5—H5	120.1	C20—C21—H30	108.2
C5—C6—C7	120.2 (4)	C20—C21—H31	108.5
C5—C6—H6	119.9	C22—C21—H30	107.8
C7—C6—H6	119.9	C22—C21—H31	108.2
C6—C7—C8	120.0 (4)	H30—C21—H31	111.1
C6—C7—H7	120.8	C21—C22—C23	113.7 (3)
C8—C7—H7	119.2	C21—C22—H32	108.6
C7—C8—C9	120.5 (4)	C21—C22—H33	108.9
C7—C8—H8	120.2	C23—C22—H32	108.8
C9—C8—H8	119.2	C23—C22—H33	109.1
C4—C9—C8	120.5 (4)	H32—C22—H33	107.8
C4—C9—H9	120.3	C22—C23—H34	108.9
C8—C9—H9	119.2	C22—C23—H35	108.6
O3—C10—N1	122.9 (3)	C22—C23—H36	109.4
O3—C10—C11	121.0 (3)	H34—C23—H35	108.4
N1—C10—C11	116.1 (3)	H34—C23—H36	111.2
C10—C11—C12	113.6 (3)	H35—C23—H36	110.2
C10—C11—H10	108.6	N2—C24—C25	111.1 (3)
C10—C11—H11	109.2	N2—C24—C31	108.7 (3)
C12—C11—H10	107.5	N2—C24—H40	108.2
C12—C11—H11	108.1	C25—C24—C31	113.3 (3)
H10—C11—H11	109.8	C25—C24—H40	107.6
C11—C12—C13	114.1 (3)	C31—C24—H40	107.9
C11—C12—H12	108.8	C24—C25—C26	117.8 (3)
C11—C12—H13	109.1	C24—C25—C30	124.1 (3)
C13—C12—H12	108.3	C26—C25—C30	118.1 (3)
C13—C12—H13	108.5	C25—C26—C27	121.3 (4)
H12—C12—H13	107.7	C25—C26—H41	119.6
C12—C13—C14	112.8 (3)	C27—C26—H41	119.0
C12—C13—H14	107.9	C26—C27—C28	119.6 (3)
C12—C13—H15	108.3	C26—C27—H42	120.2
C14—C13—H14	108.1	C28—C27—H42	120.2
C14—C13—H15	108.5	C27—C28—C29	120.5 (3)
H14—C13—H15	111.3	C27—C28—H43	119.7
C13—C14—C15	114.1 (3)	C29—C28—H43	119.8
C13—C14—H16	108.7	C28—C29—C30	119.5 (4)
C13—C14—H17	108.9	C28—C29—H44	120.0
C15—C14—H16	108.5	C30—C29—H44	120.5
C15—C14—H17	108.8	C25—C30—C29	120.9 (3)
H16—C14—H17	107.7	C25—C30—H45	120.6
C14—C15—C16	113.9 (3)	C29—C30—H45	118.5
C14—C15—H18	107.8	C24—C31—H46	109.4
C14—C15—H19	108.2	C24—C31—H47	110.0
C16—C15—H18	107.7	C24—C31—H48	110.0
C16—C15—H19	108.0	H46—C31—H47	108.6
H18—C15—H19	111.3	H46—C31—H48	108.1
C15—C16—C17	113.7 (3)	H47—C31—H48	110.7
O1—C1—C2—N1	167.1 (3)	C6—C7—C8—C9	0.5 (7)
O1—C1—C2—C3	−67.8 (4)	C10—C11—C12—C13	52.9 (4)
O2—C1—C2—N1	−10.0 (4)	C11—C12—C13—C14	175.5 (3)
O2—C1—C2—C3	115.1 (4)	C12—C13—C14—C15	178.7 (3)
O3—C10—N1—C2	−2.4 (5)	C13—C14—C15—C16	179.2 (3)
O3—C10—C11—C12	−121.3 (4)	C14—C15—C16—C17	179.8 (3)
N1—C2—C3—C4	−65.2 (4)	C15—C16—C17—C18	176.8 (3)
N1—C10—C11—C12	56.7 (4)	C16—C17—C18—C19	179.2 (3)
N2—C24—C25—C26	−162.9 (3)	C17—C18—C19—C20	179.1 (3)
N2—C24—C25—C30	19.9 (5)	C18—C19—C20—C21	179.8 (3)
C1—C2—N1—C10	−76.7 (4)	C19—C20—C21—C22	−179.6 (3)
C1—C2—C3—C4	168.8 (3)	C20—C21—C22—C23	−177.8 (3)
C2—N1—C10—C11	179.7 (3)	C24—C25—C26—C27	−176.7 (4)
C2—C3—C4—C5	−82.7 (4)	C24—C25—C30—C29	176.7 (3)
C2—C3—C4—C9	95.1 (4)	C25—C26—C27—C28	0.3 (6)
C3—C2—N1—C10	157.2 (3)	C25—C30—C29—C28	−0.7 (6)
C3—C4—C5—C6	176.8 (4)	C26—C25—C24—C31	74.5 (4)
C3—C4—C9—C8	−177.0 (4)	C26—C25—C30—C29	−0.5 (5)
C4—C5—C6—C7	1.1 (6)	C26—C27—C28—C29	−1.6 (6)
C4—C9—C8—C7	−0.5 (6)	C27—C26—C25—C30	0.7 (6)
C5—C4—C9—C8	0.8 (6)	C27—C28—C29—C30	1.8 (6)
C5—C6—C7—C8	−0.8 (7)	C30—C25—C24—C31	−102.7 (4)
C6—C5—C4—C9	−1.1 (6)	C30—C25—C24—C31	−102.7 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H49···O4^i	0.88 (5)	2.01 (5)	2.857 (4)	164 (4)
O4—H50···O1^iii	1.05 (4)	1.64 (4)	2.683 (4)	176 (4)
N1—H1···O3^vi	0.94 (4)	1.98 (4)	2.913 (4)	170 (4)
N2—H37···O2^iii	0.88 (5)	1.97 (5)	2.845 (4)	172 (3)
N2—H38···O2^i	0.96 (4)	1.83 (4)	2.747 (4)	158 (4)
N2—H39···O4^i	0.86 (4)	1.96 (4)	2.810 (4)	172 (4)

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