Crystal structure of S,N-dibenzyl-d-penicillamine monohydrate.

In the asymmetric unit of the title compound, C19H23NO2S·H2O, there are two independent organic mol-ecules and two water mol-ecules. Both organic mol-ecules exist as the zwitterionic form. The dihedral angles between the planes of the rings in the organic mol-ecules are 86.84 (10) and 88.77 (11)°. An intramolecular N-H⋯S hydrogen bond occurs. In the crystal, organic and water mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds, generating a tape structure running along the b-axis direction.

Related literature

For the synthesis of the title compound, see: Crooks (1949 ▶). For the coordination behavior of d-penicillamine and its derivatives, see: Igashira-Kamiyama & Konno (2011 ▶); Oji et al. (2014 ▶).

Experimental

Crystal data

C19H23NO2S·H2O

M = 347.46

Monoclinic,

a = 19.930 (2) Å

b = 6.2500 (7) Å

c = 30.645 (4) Å

β = 98.715 (7)°

V = 3773.2 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 200 K

0.15 × 0.10 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.778, T max = 0.994

15147 measured reflections

7694 independent reflections

7006 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.093

S = 1.06

7694 reflections

461 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack x determined using 2566 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: 0.03 (2)

Data collection: PROCESS-AUTO (Rigaku, 2000 ▶); cell refinement: PROCESS-AUTO (Rigaku, 2000 ▶); data reduction: PROCESS-AUTO (Rigaku, 2000 ▶); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Yadokari-XG (Kabuto et al., 2009 ▶); software used to prepare material for publication: Yadokari-XG (Kabuto et al., 2009 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814023459/is5378sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023459/is5378Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S1600536814023459/is5378fig1.tif

The asymmetric unit of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b x y z x y z . DOI: 10.1107/S1600536814023459/is5378fig2.tif

A view of the tape structure running along the b axis in (I). Blue dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, y + 1, z; (ii) x, y–1, z.]

CCDC reference: 1030824

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H23NO2S·H2O	F(000) = 1488
Mr = 347.46	Dx = 1.223 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71075 Å
a = 19.930 (2) Å	Cell parameters from 786 reflections
b = 6.2500 (7) Å	θ = 3.4–27.5°
c = 30.645 (4) Å	µ = 0.19 mm−1
β = 98.715 (7)°	T = 200 K
V = 3773.2 (8) Å3	Platelet, colorless
Z = 8	0.15 × 0.10 × 0.03 mm

Rigaku R-AXIS RAPID diffractometer	7694 independent reflections
Radiation source: fine-focus sealed tube	7006 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.027
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −25→25
Tmin = 0.778, Tmax = 0.994	k = −8→8
15147 measured reflections	l = −39→39

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.041	w = 1/[σ2(Fo2) + (0.0482P)2 + 1.222P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.44 e Å−3
7694 reflections	Δρmin = −0.25 e Å−3
461 parameters	Absolute structure: Flack x determined using 2566 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.03 (2)

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.

	x	y	z	Uiso*/Ueq
S1	0.54021 (3)	0.37960 (9)	0.07484 (2)	0.02754 (16)
O1	0.53088 (10)	−0.0974 (3)	0.19789 (6)	0.0392 (5)
O2	0.60252 (10)	−0.2717 (3)	0.16081 (6)	0.0349 (5)
N1	0.58790 (11)	0.2829 (3)	0.17415 (7)	0.0240 (4)
H1	0.5905 (13)	0.407 (5)	0.1604 (9)	0.029*
H2	0.5508 (14)	0.309 (5)	0.1889 (9)	0.029*
C1	0.52331 (12)	0.1335 (4)	0.10419 (8)	0.0244 (5)
C2	0.58099 (12)	0.0945 (4)	0.14360 (8)	0.0234 (5)
H3	0.6245	0.0792	0.1314	0.028*
C3	0.57073 (12)	−0.1113 (4)	0.16993 (8)	0.0260 (5)
C4	0.51755 (14)	−0.0596 (4)	0.07331 (9)	0.0347 (6)
H4	0.5008	−0.1831	0.0882	0.052*
H5	0.5623	−0.0930	0.0655	0.052*
H6	0.4859	−0.0268	0.0464	0.052*
C5	0.45430 (13)	0.1776 (5)	0.11894 (10)	0.0356 (6)
H7	0.4435	0.0616	0.1382	0.053*
H8	0.4191	0.1858	0.0930	0.053*
H9	0.4563	0.3135	0.1350	0.053*
C6	0.6145 (2)	0.3154 (6)	0.04975 (14)	0.0591 (10)
H10	0.6489	0.2435	0.0716	0.071*
H11	0.6019	0.2172	0.0245	0.071*
C7	0.64320 (14)	0.5184 (5)	0.03420 (10)	0.0335 (6)
C8	0.62917 (15)	0.5776 (6)	−0.00969 (10)	0.0458 (8)
H12	0.6005	0.4913	−0.0302	0.055*
C9	0.65753 (18)	0.7659 (6)	−0.02381 (12)	0.0578 (10)
H13	0.6477	0.8079	−0.0539	0.069*
C10	0.69916 (16)	0.8889 (6)	0.00542 (15)	0.0574 (10)
H14	0.7189	1.0148	−0.0045	0.069*
C11	0.71268 (18)	0.8333 (6)	0.04855 (15)	0.0601 (10)
H15	0.7414	0.9205	0.0688	0.072*
C12	0.68468 (17)	0.6499 (6)	0.06289 (11)	0.0501 (8)
H16	0.6941	0.6127	0.0933	0.060*
C13	0.64745 (13)	0.2701 (4)	0.21067 (8)	0.0318 (6)
H17	0.6487	0.4014	0.2289	0.038*
H18	0.6410	0.1468	0.2299	0.038*
C14	0.71428 (14)	0.2462 (5)	0.19426 (9)	0.0308 (6)
C15	0.74302 (14)	0.4186 (5)	0.17595 (9)	0.0387 (6)
H19	0.7200	0.5520	0.1730	0.046*
C16	0.80556 (15)	0.3974 (6)	0.16177 (12)	0.0529 (9)
H20	0.8247	0.5154	0.1484	0.063*
C17	0.84014 (16)	0.2054 (7)	0.16701 (12)	0.0557 (9)
H21	0.8835	0.1928	0.1580	0.067*
C18	0.81217 (16)	0.0333 (6)	0.18518 (12)	0.0545 (9)
H22	0.8359	−0.0990	0.1884	0.065*
C19	0.74940 (15)	0.0521 (5)	0.19883 (10)	0.0425 (7)
H23	0.7300	−0.0677	0.2114	0.051*
S2	0.46646 (3)	0.93252 (9)	0.42752 (2)	0.03026 (17)
O3	0.50246 (10)	0.4534 (3)	0.30958 (6)	0.0380 (5)
O4	0.42108 (11)	0.2829 (3)	0.33859 (7)	0.0391 (5)
N2	0.43753 (12)	0.8345 (3)	0.32686 (7)	0.0254 (5)
H24	0.4737 (15)	0.852 (5)	0.3142 (9)	0.030*
H25	0.4328 (14)	0.955 (5)	0.3400 (9)	0.030*
C20	0.49179 (13)	0.6890 (4)	0.40019 (8)	0.0276 (6)
C21	0.44067 (13)	0.6488 (4)	0.35761 (8)	0.0249 (5)
H26	0.3947	0.6325	0.3665	0.030*
C22	0.45587 (13)	0.4405 (4)	0.33312 (8)	0.0275 (5)
C23	0.49265 (17)	0.4945 (5)	0.43061 (9)	0.0402 (7)
H27	0.5127	0.3722	0.4173	0.060*
H28	0.4461	0.4594	0.4348	0.060*
H29	0.5197	0.5273	0.4593	0.060*
C24	0.56361 (14)	0.7409 (5)	0.39158 (10)	0.0398 (7)
H30	0.5930	0.7668	0.4197	0.060*
H31	0.5625	0.8690	0.3730	0.060*
H32	0.5814	0.6201	0.3764	0.060*
C25	0.3886 (2)	0.8563 (6)	0.44760 (15)	0.0630 (11)
H33	0.3596	0.7698	0.4251	0.076*
H34	0.3991	0.7703	0.4749	0.076*
C26	0.35257 (14)	1.0599 (5)	0.45678 (10)	0.0365 (7)
C27	0.3042 (2)	1.1515 (10)	0.42613 (13)	0.0805 (15)
H35	0.2931	1.0879	0.3978	0.097*
C28	0.2713 (3)	1.3345 (13)	0.4359 (3)	0.124 (3)
H36	0.2370	1.3944	0.4145	0.149*
C29	0.2872 (3)	1.4297 (8)	0.4754 (3)	0.110 (3)
H37	0.2646	1.5575	0.4817	0.133*
C30	0.3356 (2)	1.3424 (7)	0.50638 (17)	0.0781 (15)
H38	0.3468	1.4092	0.5344	0.094*
C31	0.36859 (16)	1.1567 (6)	0.49720 (10)	0.0447 (8)
H39	0.4023	1.0961	0.5189	0.054*
C32	0.38062 (14)	0.8229 (5)	0.28808 (9)	0.0334 (6)
H40	0.3883	0.9333	0.2662	0.040*
H41	0.3819	0.6813	0.2737	0.040*
C33	0.31154 (14)	0.8556 (5)	0.30101 (9)	0.0339 (6)
C34	0.28147 (16)	1.0576 (6)	0.29587 (10)	0.0444 (8)
H42	0.3056	1.1741	0.2857	0.053*
C35	0.21634 (18)	1.0884 (7)	0.30561 (12)	0.0605 (11)
H43	0.1958	1.2257	0.3021	0.073*
C36	0.18146 (16)	0.9183 (8)	0.32053 (11)	0.0605 (11)
H44	0.1369	0.9394	0.3271	0.073*
C37	0.21099 (17)	0.7187 (7)	0.32586 (11)	0.0544 (9)
H45	0.1869	0.6031	0.3363	0.065*
C38	0.27558 (15)	0.6868 (6)	0.31597 (10)	0.0413 (7)
H46	0.2956	0.5487	0.3194	0.050*
O5	0.49439 (11)	0.4819 (3)	0.21838 (8)	0.0391 (5)
H47	0.4939 (16)	0.483 (6)	0.2448 (11)	0.047*
H48	0.5069 (17)	0.601 (6)	0.2145 (11)	0.047*
O6	0.54027 (12)	0.0182 (4)	0.28774 (8)	0.0425 (5)
H49	0.5289 (18)	0.141 (6)	0.2907 (11)	0.051*
H50	0.5348 (17)	0.001 (6)	0.2613 (12)	0.051*

	U11	U22	U33	U12	U13	U23
S1	0.0323 (3)	0.0171 (3)	0.0342 (3)	0.0018 (2)	0.0084 (3)	0.0037 (3)
O1	0.0554 (12)	0.0240 (10)	0.0426 (11)	−0.0015 (9)	0.0219 (10)	0.0062 (9)
O2	0.0442 (11)	0.0158 (9)	0.0455 (11)	0.0028 (8)	0.0091 (9)	0.0017 (8)
N1	0.0281 (11)	0.0137 (10)	0.0321 (12)	−0.0022 (8)	0.0101 (10)	−0.0005 (8)
C1	0.0250 (12)	0.0157 (12)	0.0327 (13)	−0.0031 (9)	0.0048 (11)	0.0039 (10)
C2	0.0238 (12)	0.0150 (11)	0.0327 (13)	−0.0013 (9)	0.0082 (11)	−0.0002 (10)
C3	0.0311 (12)	0.0175 (12)	0.0284 (12)	−0.0029 (10)	0.0010 (11)	−0.0017 (10)
C4	0.0395 (14)	0.0210 (13)	0.0411 (15)	−0.0051 (12)	−0.0018 (12)	−0.0023 (12)
C5	0.0238 (13)	0.0365 (16)	0.0477 (16)	−0.0011 (11)	0.0088 (12)	0.0100 (13)
C6	0.071 (2)	0.0302 (17)	0.089 (3)	0.0130 (16)	0.053 (2)	0.0130 (17)
C7	0.0304 (14)	0.0277 (14)	0.0463 (16)	0.0041 (11)	0.0179 (13)	0.0057 (12)
C8	0.0330 (15)	0.056 (2)	0.0477 (18)	−0.0005 (14)	0.0025 (14)	0.0030 (16)
C9	0.050 (2)	0.069 (3)	0.057 (2)	0.0199 (19)	0.0183 (18)	0.033 (2)
C10	0.0424 (17)	0.0333 (18)	0.106 (3)	0.0004 (15)	0.040 (2)	0.008 (2)
C11	0.0464 (19)	0.052 (2)	0.086 (3)	−0.0097 (16)	0.022 (2)	−0.025 (2)
C12	0.0473 (19)	0.062 (2)	0.0436 (17)	0.0082 (17)	0.0142 (15)	−0.0038 (16)
C13	0.0409 (15)	0.0250 (14)	0.0288 (13)	−0.0049 (12)	0.0036 (12)	−0.0022 (11)
C14	0.0304 (14)	0.0285 (15)	0.0307 (13)	−0.0023 (11)	−0.0043 (11)	−0.0033 (11)
C15	0.0338 (13)	0.0333 (16)	0.0486 (16)	0.0028 (13)	0.0049 (12)	0.0040 (14)
C16	0.0364 (15)	0.057 (2)	0.067 (2)	−0.0038 (16)	0.0131 (15)	0.0060 (19)
C17	0.0285 (15)	0.069 (3)	0.069 (2)	0.0056 (16)	0.0063 (16)	−0.006 (2)
C18	0.0399 (17)	0.045 (2)	0.075 (2)	0.0126 (15)	−0.0035 (17)	−0.0053 (18)
C19	0.0408 (16)	0.0302 (16)	0.0532 (18)	−0.0008 (13)	−0.0035 (14)	−0.0016 (13)
S2	0.0398 (4)	0.0192 (4)	0.0337 (3)	−0.0036 (3)	0.0115 (3)	−0.0060 (3)
O3	0.0476 (11)	0.0289 (11)	0.0412 (10)	0.0018 (9)	0.0189 (9)	−0.0071 (9)
O4	0.0501 (12)	0.0178 (10)	0.0506 (12)	−0.0071 (9)	0.0119 (10)	−0.0058 (9)
N2	0.0319 (11)	0.0157 (10)	0.0300 (12)	−0.0018 (9)	0.0093 (10)	−0.0017 (9)
C20	0.0355 (14)	0.0175 (12)	0.0303 (13)	0.0024 (10)	0.0061 (12)	−0.0050 (10)
C21	0.0302 (13)	0.0159 (12)	0.0305 (13)	−0.0019 (10)	0.0108 (11)	−0.0024 (10)
C22	0.0346 (13)	0.0183 (12)	0.0291 (12)	0.0014 (11)	0.0031 (11)	−0.0005 (11)
C23	0.0590 (19)	0.0256 (15)	0.0337 (15)	0.0034 (13)	−0.0004 (14)	0.0007 (12)
C24	0.0330 (15)	0.0426 (18)	0.0437 (16)	−0.0013 (13)	0.0052 (13)	−0.0122 (14)
C25	0.071 (2)	0.039 (2)	0.091 (3)	−0.0139 (17)	0.054 (2)	−0.0174 (19)
C26	0.0333 (15)	0.0376 (17)	0.0424 (16)	−0.0056 (13)	0.0177 (13)	−0.0084 (13)
C27	0.050 (2)	0.143 (5)	0.047 (2)	−0.001 (3)	0.0041 (19)	0.017 (3)
C28	0.061 (3)	0.149 (7)	0.169 (6)	0.050 (4)	0.038 (4)	0.107 (5)
C29	0.070 (3)	0.042 (3)	0.243 (8)	0.014 (2)	0.096 (5)	0.020 (4)
C30	0.072 (3)	0.065 (3)	0.111 (3)	−0.033 (2)	0.057 (3)	−0.052 (3)
C31	0.0386 (16)	0.052 (2)	0.0454 (17)	−0.0048 (14)	0.0122 (14)	−0.0092 (15)
C32	0.0427 (15)	0.0287 (14)	0.0281 (13)	0.0011 (12)	0.0029 (12)	−0.0006 (11)
C33	0.0357 (14)	0.0324 (15)	0.0311 (14)	−0.0018 (12)	−0.0032 (12)	−0.0081 (11)
C34	0.0443 (17)	0.0398 (19)	0.0446 (17)	0.0038 (14)	−0.0076 (14)	−0.0110 (14)
C35	0.049 (2)	0.060 (2)	0.065 (2)	0.0200 (18)	−0.0163 (18)	−0.026 (2)
C36	0.0316 (15)	0.093 (3)	0.055 (2)	0.006 (2)	−0.0012 (15)	−0.033 (2)
C37	0.0389 (18)	0.074 (3)	0.0501 (19)	−0.0087 (18)	0.0062 (16)	−0.0110 (19)
C38	0.0381 (16)	0.0424 (17)	0.0420 (16)	−0.0028 (13)	0.0021 (14)	−0.0072 (14)
O5	0.0536 (13)	0.0256 (11)	0.0425 (11)	0.0005 (9)	0.0214 (10)	0.0005 (9)
O6	0.0581 (14)	0.0281 (11)	0.0461 (12)	−0.0041 (10)	0.0236 (11)	−0.0020 (10)

S1—C6	1.814 (3)	O3—C22	1.262 (3)
S1—C1	1.839 (2)	O4—C22	1.230 (3)
O1—C3	1.256 (3)	N2—C21	1.490 (3)
O2—C3	1.240 (3)	N2—C32	1.515 (4)
N1—C2	1.497 (3)	N2—H24	0.88 (3)
N1—C13	1.505 (3)	N2—H25	0.87 (3)
N1—H1	0.89 (3)	C20—C24	1.529 (4)
N1—H2	0.94 (3)	C20—C23	1.531 (4)
C1—C4	1.527 (4)	C20—C21	1.549 (4)
C1—C5	1.536 (3)	C21—C22	1.556 (3)
C1—C2	1.555 (3)	C21—H26	1.0000
C2—C3	1.549 (3)	C23—H27	0.9800
C2—H3	1.0000	C23—H28	0.9800
C4—H4	0.9800	C23—H29	0.9800
C4—H5	0.9800	C24—H30	0.9800
C4—H6	0.9800	C24—H31	0.9800
C5—H7	0.9800	C24—H32	0.9800
C5—H8	0.9800	C25—C26	1.508 (5)
C5—H9	0.9800	C25—H33	0.9900
C6—C7	1.498 (4)	C25—H34	0.9900
C6—H10	0.9900	C26—C27	1.366 (5)
C6—H11	0.9900	C26—C31	1.372 (4)
C7—C8	1.382 (4)	C27—C28	1.373 (9)
C7—C12	1.383 (5)	C27—H35	0.9500
C8—C9	1.402 (5)	C28—C29	1.343 (9)
C8—H12	0.9500	C28—H36	0.9500
C9—C10	1.363 (5)	C29—C30	1.362 (8)
C9—H13	0.9500	C29—H37	0.9500
C10—C11	1.354 (6)	C30—C31	1.384 (6)
C10—H14	0.9500	C30—H38	0.9500
C11—C12	1.376 (5)	C31—H39	0.9500
C11—H15	0.9500	C32—C33	1.503 (4)
C12—H16	0.9500	C32—H40	0.9900
C13—C14	1.501 (4)	C32—H41	0.9900
C13—H17	0.9900	C33—C38	1.392 (4)
C13—H18	0.9900	C33—C34	1.396 (4)
C14—C15	1.379 (4)	C34—C35	1.389 (5)
C14—C19	1.397 (4)	C34—H42	0.9500
C15—C16	1.387 (4)	C35—C36	1.385 (6)
C15—H19	0.9500	C35—H43	0.9500
C16—C17	1.381 (5)	C36—C37	1.378 (6)
C16—H20	0.9500	C36—H44	0.9500
C17—C18	1.368 (5)	C37—C38	1.381 (4)
C17—H21	0.9500	C37—H45	0.9500
C18—C19	1.383 (4)	C38—H46	0.9500
C18—H22	0.9500	O5—H47	0.81 (3)
C19—H23	0.9500	O5—H48	0.80 (4)
S2—C25	1.817 (3)	O6—H49	0.81 (4)
S2—C20	1.844 (3)	O6—H50	0.81 (3)
C6—S1—C1	104.14 (14)	C21—N2—C32	114.4 (2)
C2—N1—C13	114.3 (2)	C21—N2—H24	114.7 (19)
C2—N1—H1	113.4 (18)	C32—N2—H24	103.1 (18)
C13—N1—H1	107.6 (18)	C21—N2—H25	112.5 (19)
C2—N1—H2	115.6 (18)	C32—N2—H25	106.5 (19)
C13—N1—H2	104.0 (17)	H24—N2—H25	105 (3)
H1—N1—H2	101 (2)	C24—C20—C23	110.4 (2)
C4—C1—C5	109.7 (2)	C24—C20—C21	113.7 (2)
C4—C1—C2	109.6 (2)	C23—C20—C21	109.2 (2)
C5—C1—C2	112.9 (2)	C24—C20—S2	103.38 (18)
C4—C1—S1	111.12 (17)	C23—C20—S2	110.94 (17)
C5—C1—S1	103.44 (17)	C21—C20—S2	109.02 (17)
C2—C1—S1	110.01 (16)	N2—C21—C20	111.4 (2)
N1—C2—C3	109.52 (19)	N2—C21—C22	109.84 (18)
N1—C2—C1	110.5 (2)	C20—C21—C22	113.0 (2)
C3—C2—C1	113.22 (19)	N2—C21—H26	107.4
N1—C2—H3	107.8	C20—C21—H26	107.4
C3—C2—H3	107.8	C22—C21—H26	107.4
C1—C2—H3	107.8	O4—C22—O3	127.4 (2)
O2—C3—O1	127.4 (2)	O4—C22—C21	116.7 (2)
O2—C3—C2	116.2 (2)	O3—C22—C21	115.9 (2)
O1—C3—C2	116.4 (2)	C20—C23—H27	109.5
C1—C4—H4	109.5	C20—C23—H28	109.5
C1—C4—H5	109.5	H27—C23—H28	109.5
H4—C4—H5	109.5	C20—C23—H29	109.5
C1—C4—H6	109.5	H27—C23—H29	109.5
H4—C4—H6	109.5	H28—C23—H29	109.5
H5—C4—H6	109.5	C20—C24—H30	109.5
C1—C5—H7	109.5	C20—C24—H31	109.5
C1—C5—H8	109.5	H30—C24—H31	109.5
H7—C5—H8	109.5	C20—C24—H32	109.5
C1—C5—H9	109.5	H30—C24—H32	109.5
H7—C5—H9	109.5	H31—C24—H32	109.5
H8—C5—H9	109.5	C26—C25—S2	107.3 (2)
C7—C6—S1	108.8 (2)	C26—C25—H33	110.3
C7—C6—H10	109.9	S2—C25—H33	110.3
S1—C6—H10	109.9	C26—C25—H34	110.3
C7—C6—H11	109.9	S2—C25—H34	110.3
S1—C6—H11	109.9	H33—C25—H34	108.5
H10—C6—H11	108.3	C27—C26—C31	118.7 (4)
C8—C7—C12	118.2 (3)	C27—C26—C25	122.1 (4)
C8—C7—C6	120.4 (3)	C31—C26—C25	119.2 (3)
C12—C7—C6	121.4 (3)	C26—C27—C28	120.6 (5)
C7—C8—C9	119.6 (3)	C26—C27—H35	119.7
C7—C8—H12	120.2	C28—C27—H35	119.7
C9—C8—H12	120.2	C29—C28—C27	120.8 (5)
C10—C9—C8	120.3 (3)	C29—C28—H36	119.6
C10—C9—H13	119.9	C27—C28—H36	119.6
C8—C9—H13	119.9	C28—C29—C30	119.7 (5)
C11—C10—C9	120.5 (3)	C28—C29—H37	120.2
C11—C10—H14	119.7	C30—C29—H37	120.2
C9—C10—H14	119.7	C29—C30—C31	120.2 (4)
C10—C11—C12	119.7 (4)	C29—C30—H38	119.9
C10—C11—H15	120.1	C31—C30—H38	119.9
C12—C11—H15	120.1	C26—C31—C30	120.1 (4)
C11—C12—C7	121.6 (3)	C26—C31—H39	120.0
C11—C12—H16	119.2	C30—C31—H39	120.0
C7—C12—H16	119.2	C33—C32—N2	113.2 (2)
C14—C13—N1	113.3 (2)	C33—C32—H40	108.9
C14—C13—H17	108.9	N2—C32—H40	108.9
N1—C13—H17	108.9	C33—C32—H41	108.9
C14—C13—H18	108.9	N2—C32—H41	108.9
N1—C13—H18	108.9	H40—C32—H41	107.8
H17—C13—H18	107.7	C38—C33—C34	119.3 (3)
C15—C14—C19	119.1 (3)	C38—C33—C32	121.4 (3)
C15—C14—C13	120.2 (3)	C34—C33—C32	119.2 (3)
C19—C14—C13	120.6 (3)	C35—C34—C33	120.0 (3)
C14—C15—C16	120.1 (3)	C35—C34—H42	120.0
C14—C15—H19	119.9	C33—C34—H42	120.0
C16—C15—H19	119.9	C36—C35—C34	119.8 (3)
C17—C16—C15	120.2 (3)	C36—C35—H43	120.1
C17—C16—H20	119.9	C34—C35—H43	120.1
C15—C16—H20	119.9	C37—C36—C35	120.5 (3)
C18—C17—C16	120.3 (3)	C37—C36—H44	119.8
C18—C17—H21	119.9	C35—C36—H44	119.8
C16—C17—H21	119.9	C36—C37—C38	120.0 (4)
C17—C18—C19	119.9 (3)	C36—C37—H45	120.0
C17—C18—H22	120.0	C38—C37—H45	120.0
C19—C18—H22	120.0	C37—C38—C33	120.4 (3)
C18—C19—C14	120.4 (3)	C37—C38—H46	119.8
C18—C19—H23	119.8	C33—C38—H46	119.8
C14—C19—H23	119.8	H47—O5—H48	101 (4)
C25—S2—C20	104.13 (14)	H49—O6—H50	104 (4)
C6—S1—C1—C4	−53.7 (2)	C25—S2—C20—C24	−169.3 (2)
C6—S1—C1—C5	−171.4 (2)	C25—S2—C20—C23	−51.0 (3)
C6—S1—C1—C2	67.8 (2)	C25—S2—C20—C21	69.4 (2)
C13—N1—C2—C3	60.9 (3)	C32—N2—C21—C20	−170.4 (2)
C13—N1—C2—C1	−173.69 (19)	C32—N2—C21—C22	63.5 (3)
C4—C1—C2—N1	179.6 (2)	C24—C20—C21—N2	−56.5 (3)
C5—C1—C2—N1	−57.9 (3)	C23—C20—C21—N2	179.7 (2)
S1—C1—C2—N1	57.1 (2)	S2—C20—C21—N2	58.3 (2)
C4—C1—C2—C3	−57.2 (3)	C24—C20—C21—C22	67.8 (3)
C5—C1—C2—C3	65.4 (3)	C23—C20—C21—C22	−56.1 (3)
S1—C1—C2—C3	−179.64 (16)	S2—C20—C21—C22	−177.47 (17)
N1—C2—C3—O2	−137.9 (2)	N2—C21—C22—O4	−134.3 (2)
C1—C2—C3—O2	98.4 (3)	C20—C21—C22—O4	100.6 (3)
N1—C2—C3—O1	42.6 (3)	N2—C21—C22—O3	45.3 (3)
C1—C2—C3—O1	−81.2 (3)	C20—C21—C22—O3	−79.8 (3)
C1—S1—C6—C7	−166.4 (3)	C20—S2—C25—C26	−161.7 (2)
S1—C6—C7—C8	−99.3 (3)	S2—C25—C26—C27	93.5 (4)
S1—C6—C7—C12	81.4 (4)	S2—C25—C26—C31	−86.6 (3)
C12—C7—C8—C9	0.6 (4)	C31—C26—C27—C28	−1.2 (6)
C6—C7—C8—C9	−178.7 (3)	C25—C26—C27—C28	178.6 (4)
C7—C8—C9—C10	0.6 (5)	C26—C27—C28—C29	1.5 (8)
C8—C9—C10—C11	−1.2 (5)	C27—C28—C29—C30	−0.9 (9)
C9—C10—C11—C12	0.6 (5)	C28—C29—C30—C31	0.2 (7)
C10—C11—C12—C7	0.6 (5)	C27—C26—C31—C30	0.4 (5)
C8—C7—C12—C11	−1.2 (5)	C25—C26—C31—C30	−179.4 (3)
C6—C7—C12—C11	178.1 (3)	C29—C30—C31—C26	0.1 (5)
C2—N1—C13—C14	57.6 (3)	C21—N2—C32—C33	71.1 (3)
N1—C13—C14—C15	74.4 (3)	N2—C32—C33—C38	−85.2 (3)
N1—C13—C14—C19	−108.1 (3)	N2—C32—C33—C34	97.9 (3)
C19—C14—C15—C16	0.9 (4)	C38—C33—C34—C35	−0.1 (4)
C13—C14—C15—C16	178.5 (3)	C32—C33—C34—C35	176.9 (3)
C14—C15—C16—C17	−1.7 (5)	C33—C34—C35—C36	0.2 (5)
C15—C16—C17—C18	1.7 (5)	C34—C35—C36—C37	0.1 (5)
C16—C17—C18—C19	−0.7 (5)	C35—C36—C37—C38	−0.5 (5)
C17—C18—C19—C14	−0.1 (5)	C36—C37—C38—C33	0.6 (5)
C15—C14—C19—C18	0.0 (4)	C34—C33—C38—C37	−0.3 (4)
C13—C14—C19—C18	−177.5 (3)	C32—C33—C38—C37	−177.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.89 (3)	2.67 (3)	3.107 (2)	112 (2)
N1—H1···O2i	0.89 (3)	2.02 (3)	2.835 (3)	152 (2)
N1—H2···O5	0.94 (3)	1.89 (3)	2.761 (3)	154 (3)
N2—H24···O6i	0.88 (3)	1.96 (3)	2.774 (3)	155 (3)
N2—H25···S2	0.87 (3)	2.67 (3)	3.112 (2)	113 (2)
N2—H25···O4i	0.87 (3)	2.06 (3)	2.851 (3)	151 (3)
O5—H47···O3	0.81 (3)	1.97 (3)	2.781 (3)	172 (4)
O5—H48···O1i	0.80 (4)	2.03 (4)	2.824 (3)	173 (3)
O6—H49···O3	0.81 (4)	2.13 (4)	2.927 (3)	171 (3)
O6—H50···O1	0.81 (3)	2.03 (4)	2.825 (3)	169 (4)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1S1	0.89(3)	2.67(3)	3.107(2)	112(2)
N1H1O2i	0.89(3)	2.02(3)	2.835(3)	152(2)
N1H2O5	0.94(3)	1.89(3)	2.761(3)	154(3)
N2H24O6i	0.88(3)	1.96(3)	2.774(3)	155(3)
N2H25S2	0.87(3)	2.67(3)	3.112(2)	113(2)
N2H25O4i	0.87(3)	2.06(3)	2.851(3)	151(3)
O5H47O3	0.81(3)	1.97(3)	2.781(3)	172(4)
O5H48O1i	0.80(4)	2.03(4)	2.824(3)	173(3)
O6H49O3	0.81(4)	2.13(4)	2.927(3)	171(3)
O6H50O1	0.81(3)	2.03(4)	2.825(3)	169(4)

Symmetry code: (i) .