Sildenafil citrate monohydrate

Sildenafil citrate is well known as Viagra for the treatment of erectile dysfuncion. In the title compound (systematic name: 1-{[3-(6,7-Di­hydro-1-methyl-7-oxo-3-propyl-1H-pyrazolo­[4,3-d]­pyrimidin-5-yl)-4-ethoxy­phenyl]­sulfonyl}-4-methyl­piper­az­in­ium citrate monohydrate), C₂₂H₃₁N₆O₄S⁺·C₆H₇O₇^-·H₂O, the pyrazolopyrimidone ring system and the benzene ring are almost coplanar, enabling an intramolecular hydrogen bond between the pyrazolopyrimidone NH group and the O atom of the ethoxy group. One of the N atoms of the piperazine ring is protonated and the citrate mol­ecule exists as an anion. The crystal packing is stabilized by several hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.079
• wR factor = 0.154
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         34 Perc.

Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.782
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.03
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.65 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.70 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.24 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C41
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

1-{[3-(6,7-Dihydro-1-methyl-7-oxo-3-propyl-1H-pyrazolo[4,3-d]pyrimidin-5-yl)- 4-ethoxyphenyl]sulfonyl}-4-methylpiperazinium citrate monohydrate

Crystal data

C22H31N6O4S^+·C6H7O7^−·H2O	F(000) = 2896
Mr = 684.72	Dx = 1.416 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8732 reflections
a = 24.002 (4) Å	θ = 2.0–23.1°
b = 10.9833 (17) Å	µ = 0.17 mm^−1
c = 24.364 (3) Å	T = 173 K
V = 6422.9 (17) Å^3	Needle, colourless
Z = 8	0.26 × 0.12 × 0.11 mm

Data collection

Stoe IPDS-II two-circle diffractometer	5856 independent reflections
Radiation source: fine-focus sealed tube	1970 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.098
ω scans	θmax = 25.4°, θmin = 1.9°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −28→28
Tmin = 0.937, Tmax = 0.951	k = −13→13
44385 measured reflections	l = −29→27

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 0.78	w = 1/[σ^2(Fo^2) + (0.0407P)^2] where P = (Fo^2 + 2Fc^2)/3
5856 reflections	(Δ/σ)max < 0.001
428 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.42 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. 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
S1	0.51081 (6)	0.50964 (15)	0.29812 (6)	0.0445 (4)
O1	0.46362 (14)	0.5885 (4)	0.29471 (17)	0.0515 (11)
O2	0.50684 (18)	0.3861 (4)	0.27829 (17)	0.0606 (13)
N11	0.56093 (17)	0.5749 (4)	0.26385 (18)	0.0330 (11)
C12	0.6124 (2)	0.5013 (5)	0.2576 (2)	0.0376 (14)
H12A	0.6028	0.4164	0.2478	0.045*
H12B	0.6334	0.5002	0.2926	0.045*
C13	0.6476 (2)	0.5571 (5)	0.2131 (2)	0.0430 (15)
H13A	0.6276	0.5512	0.1776	0.052*
H13B	0.6828	0.5109	0.2097	0.052*
N14	0.66068 (18)	0.6888 (4)	0.22483 (19)	0.0372 (12)
H14	0.6816	0.6920	0.2569	0.045*
C15	0.6074 (2)	0.7577 (5)	0.2344 (2)	0.0391 (15)
H15A	0.6162	0.8430	0.2443	0.047*
H15B	0.5852	0.7586	0.2002	0.047*
C16	0.5742 (2)	0.7012 (5)	0.2790 (2)	0.0389 (15)
H16A	0.5957	0.7024	0.3137	0.047*
H16B	0.5393	0.7478	0.2847	0.047*
C17	0.6948 (3)	0.7416 (6)	0.1798 (3)	0.0536 (18)
H17A	0.7290	0.6938	0.1754	0.080*
H17B	0.7044	0.8259	0.1889	0.080*
H17C	0.6734	0.7398	0.1456	0.080*
C21	0.5329 (2)	0.5069 (5)	0.3659 (2)	0.0393 (14)
C22	0.5178 (2)	0.5976 (5)	0.4018 (2)	0.0394 (15)
H22	0.4926	0.6585	0.3896	0.047*
C23	0.5382 (2)	0.6037 (5)	0.4554 (2)	0.0385 (15)
C24	0.5757 (2)	0.5122 (6)	0.4726 (2)	0.0379 (14)
C25	0.5904 (2)	0.4195 (6)	0.4369 (3)	0.0431 (15)
H25	0.6148	0.3570	0.4491	0.052*
C26	0.5705 (2)	0.4163 (6)	0.3842 (3)	0.0460 (16)
H26	0.5820	0.3533	0.3600	0.055*
O27	0.59346 (15)	0.5167 (4)	0.52518 (17)	0.0434 (11)
C28	0.6344 (2)	0.4316 (6)	0.5457 (3)	0.0497 (17)
H28A	0.6694	0.4386	0.5244	0.060*
H28B	0.6204	0.3472	0.5423	0.060*
C29	0.6448 (3)	0.4610 (7)	0.6038 (3)	0.063 (2)
H29A	0.6724	0.4044	0.6188	0.094*
H29B	0.6099	0.4537	0.6245	0.094*
H29C	0.6588	0.5445	0.6067	0.094*
C31	0.5178 (2)	0.7057 (5)	0.4897 (2)	0.0371 (14)
N32	0.54446 (19)	0.7278 (5)	0.53903 (19)	0.0427 (13)
H32	0.5729	0.6802	0.5468	0.051*
C33	0.5318 (3)	0.8150 (6)	0.5771 (2)	0.0452 (16)
O33	0.55788 (19)	0.8276 (4)	0.61949 (18)	0.0551 (12)
C34	0.4839 (2)	0.8840 (5)	0.5588 (2)	0.0399 (14)
C35	0.4605 (2)	0.8619 (5)	0.5079 (2)	0.0384 (15)
N36	0.47678 (18)	0.7724 (4)	0.47275 (19)	0.0393 (12)
N37	0.4565 (2)	0.9798 (5)	0.5815 (2)	0.0480 (13)
C37	0.4657 (3)	1.0358 (6)	0.6346 (2)	0.062 (2)
H37A	0.4863	1.1121	0.6298	0.093*
H37B	0.4873	0.9804	0.6579	0.093*
H37C	0.4298	1.0529	0.6521	0.093*
N38	0.4156 (2)	1.0183 (5)	0.5475 (2)	0.0509 (14)
C39	0.4177 (3)	0.9500 (6)	0.5026 (3)	0.0438 (16)
C40	0.3769 (2)	0.9660 (6)	0.4569 (3)	0.0509 (18)
H40A	0.3926	0.9301	0.4230	0.061*
H40B	0.3714	1.0542	0.4503	0.061*
C41	0.3207 (3)	0.9077 (6)	0.4684 (3)	0.0580 (19)
H41A	0.3266	0.8219	0.4793	0.070*
H41B	0.3030	0.9503	0.4997	0.070*
C42	0.2820 (3)	0.9114 (9)	0.4202 (3)	0.098 (3)
H42A	0.2467	0.8725	0.4301	0.146*
H42B	0.2989	0.8678	0.3893	0.146*
H42C	0.2752	0.9963	0.4097	0.146*
C1	0.6952 (3)	0.7525 (6)	0.4388 (3)	0.0519 (18)
O11	0.6764 (2)	0.7142 (6)	0.4812 (2)	0.100 (2)
O12	0.6703 (2)	0.8386 (5)	0.41230 (19)	0.0703 (15)
H12	0.6446	0.8674	0.4318	0.084*
C2	0.7480 (3)	0.7061 (5)	0.4127 (2)	0.0430 (16)
H2A	0.7797	0.7518	0.4286	0.052*
H2B	0.7526	0.6197	0.4233	0.052*
C3	0.7523 (2)	0.7140 (4)	0.3512 (3)	0.0350 (14)
O3	0.70777 (15)	0.6480 (3)	0.32673 (16)	0.0367 (10)
H3	0.7090	0.5751	0.3371	0.044*
C4	0.8086 (2)	0.6625 (5)	0.3308 (3)	0.0468 (17)
H4A	0.8395	0.7114	0.3463	0.056*
H4B	0.8129	0.5776	0.3439	0.056*
C5	0.8118 (2)	0.6649 (7)	0.2691 (3)	0.0549 (19)
O51	0.82320 (19)	0.7579 (4)	0.2438 (2)	0.0765 (16)
O52	0.79846 (19)	0.5650 (4)	0.24213 (19)	0.0582 (13)
H52	0.7845	0.5143	0.2640	0.070*
C6	0.7474 (3)	0.8472 (5)	0.3322 (3)	0.0417 (15)
O61	0.78086 (16)	0.9203 (4)	0.35450 (18)	0.0492 (11)
O62	0.71438 (16)	0.8711 (3)	0.29353 (16)	0.0420 (10)
O1W	0.8948 (6)	0.7871 (11)	0.1605 (6)	0.311 (7)
H1WA	0.9145	0.7301	0.1728	0.374*
H1WB	0.8721	0.7777	0.1864	0.374*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0363 (7)	0.0502 (10)	0.0471 (9)	−0.0069 (8)	0.0012 (8)	−0.0099 (9)
O1	0.028 (2)	0.068 (3)	0.058 (3)	0.007 (2)	−0.003 (2)	−0.014 (3)
O2	0.057 (3)	0.058 (3)	0.066 (3)	−0.026 (2)	0.011 (2)	−0.023 (3)
N11	0.029 (2)	0.027 (3)	0.044 (3)	0.001 (2)	−0.002 (2)	0.000 (2)
C12	0.037 (3)	0.027 (3)	0.050 (4)	0.009 (3)	0.002 (3)	0.003 (3)
C13	0.044 (3)	0.040 (4)	0.045 (4)	0.003 (3)	0.002 (3)	−0.002 (3)
N14	0.034 (3)	0.037 (3)	0.041 (3)	−0.001 (2)	0.001 (2)	0.000 (2)
C15	0.033 (3)	0.034 (3)	0.050 (4)	0.006 (3)	−0.005 (3)	0.001 (3)
C16	0.045 (3)	0.035 (3)	0.037 (4)	0.009 (3)	−0.003 (3)	−0.006 (3)
C17	0.064 (4)	0.049 (4)	0.048 (4)	0.002 (4)	0.013 (3)	0.006 (3)
C21	0.038 (3)	0.034 (3)	0.046 (4)	−0.006 (3)	0.015 (3)	−0.003 (3)
C22	0.040 (3)	0.036 (4)	0.042 (4)	0.004 (3)	0.005 (3)	0.006 (3)
C23	0.037 (3)	0.040 (4)	0.038 (4)	−0.001 (3)	0.004 (3)	0.001 (3)
C24	0.037 (3)	0.037 (4)	0.039 (4)	0.000 (3)	0.009 (3)	−0.002 (3)
C25	0.040 (3)	0.041 (4)	0.048 (4)	0.004 (3)	0.003 (3)	0.006 (3)
C26	0.043 (4)	0.039 (4)	0.055 (4)	0.008 (3)	0.016 (3)	0.000 (3)
O27	0.048 (2)	0.038 (3)	0.044 (3)	0.014 (2)	−0.004 (2)	0.003 (2)
C28	0.038 (4)	0.036 (4)	0.075 (5)	0.009 (3)	−0.003 (3)	0.010 (4)
C29	0.049 (4)	0.082 (6)	0.057 (5)	0.009 (4)	−0.011 (3)	0.002 (4)
C31	0.043 (4)	0.037 (3)	0.031 (3)	−0.005 (3)	0.002 (3)	0.001 (3)
N32	0.042 (3)	0.047 (3)	0.038 (3)	0.011 (3)	−0.007 (2)	−0.002 (3)
C33	0.071 (5)	0.039 (4)	0.026 (4)	−0.003 (3)	−0.002 (3)	0.003 (3)
O33	0.072 (3)	0.050 (3)	0.043 (3)	0.001 (2)	−0.016 (2)	−0.002 (2)
C34	0.051 (4)	0.034 (3)	0.035 (3)	0.004 (3)	0.000 (3)	−0.002 (3)
C35	0.043 (4)	0.036 (3)	0.036 (4)	0.005 (3)	0.006 (3)	−0.001 (3)
N36	0.039 (3)	0.036 (3)	0.043 (3)	0.008 (2)	−0.002 (2)	−0.001 (2)
N37	0.053 (3)	0.047 (3)	0.044 (3)	0.006 (3)	0.000 (3)	−0.004 (3)
C37	0.100 (6)	0.045 (4)	0.040 (4)	0.006 (4)	0.002 (4)	−0.009 (3)
N38	0.058 (3)	0.048 (3)	0.047 (3)	0.010 (3)	0.005 (3)	0.008 (3)
C39	0.052 (4)	0.044 (4)	0.036 (4)	0.002 (3)	0.012 (3)	−0.001 (3)
C40	0.048 (4)	0.054 (4)	0.050 (4)	0.012 (3)	0.010 (3)	0.011 (3)
C41	0.050 (4)	0.053 (4)	0.071 (5)	−0.006 (4)	0.005 (4)	0.014 (4)
C42	0.071 (5)	0.120 (8)	0.102 (7)	−0.009 (6)	−0.023 (5)	0.032 (6)
C1	0.068 (5)	0.045 (4)	0.042 (4)	0.002 (4)	−0.014 (4)	0.010 (4)
O11	0.093 (4)	0.113 (5)	0.095 (5)	0.016 (4)	0.018 (4)	0.052 (4)
O12	0.078 (4)	0.072 (4)	0.060 (3)	0.034 (3)	0.021 (3)	0.008 (3)
C2	0.047 (4)	0.021 (3)	0.061 (4)	0.002 (3)	−0.019 (3)	0.005 (3)
C3	0.027 (3)	0.016 (3)	0.062 (4)	0.008 (2)	−0.011 (3)	−0.005 (3)
O3	0.031 (2)	0.026 (2)	0.054 (3)	0.0013 (18)	−0.0065 (19)	0.003 (2)
C4	0.030 (3)	0.024 (3)	0.087 (5)	0.004 (3)	−0.005 (3)	−0.006 (4)
C5	0.027 (3)	0.040 (4)	0.099 (6)	0.006 (3)	0.016 (4)	0.003 (4)
O51	0.067 (3)	0.043 (3)	0.120 (4)	−0.013 (3)	0.039 (3)	0.008 (3)
O52	0.067 (3)	0.036 (3)	0.072 (3)	0.000 (2)	0.021 (3)	0.008 (3)
C6	0.045 (4)	0.026 (3)	0.054 (4)	−0.003 (3)	−0.004 (3)	−0.002 (3)
O61	0.043 (2)	0.028 (2)	0.077 (3)	−0.004 (2)	−0.009 (2)	−0.005 (2)
O62	0.047 (2)	0.029 (2)	0.050 (3)	−0.0028 (18)	−0.007 (2)	0.003 (2)
O1W	0.42 (2)	0.199 (12)	0.311 (16)	0.052 (13)	−0.035 (14)	−0.013 (12)

Geometric parameters (Å, º)

S1—O1	1.428 (4)	N32—H32	0.8800
S1—O2	1.443 (4)	C33—O33	1.216 (7)
S1—N11	1.630 (5)	C33—C34	1.447 (8)
S1—C21	1.734 (6)	C34—N37	1.359 (7)
N11—C16	1.470 (7)	C34—C35	1.385 (8)
N11—C12	1.485 (6)	C35—N36	1.361 (7)
C12—C13	1.506 (7)	C35—C39	1.417 (8)
C12—H12A	0.9900	N37—N38	1.352 (6)
C12—H12B	0.9900	N37—C37	1.450 (7)
C13—N14	1.507 (7)	C37—H37A	0.9800
C13—H13A	0.9900	C37—H37B	0.9800
C13—H13B	0.9900	C37—H37C	0.9800
N14—C17	1.486 (7)	N38—C39	1.328 (8)
N14—C15	1.504 (7)	C39—C40	1.493 (8)
N14—H14	0.9300	C40—C41	1.519 (8)
C15—C16	1.484 (8)	C40—H40A	0.9900
C15—H15A	0.9900	C40—H40B	0.9900
C15—H15B	0.9900	C41—C42	1.497 (9)
C16—H16A	0.9900	C41—H41A	0.9900
C16—H16B	0.9900	C41—H41B	0.9900
C17—H17A	0.9800	C42—H42A	0.9800
C17—H17B	0.9800	C42—H42B	0.9800
C17—H17C	0.9800	C42—H42C	0.9800
C21—C22	1.373 (7)	C1—O11	1.204 (7)
C21—C26	1.417 (8)	C1—O12	1.293 (7)
C22—C23	1.398 (8)	C1—C2	1.506 (9)
C22—H22	0.9500	O12—H12	0.8400
C23—C24	1.413 (8)	C2—C3	1.505 (8)
C23—C31	1.481 (8)	C2—H2A	0.9900
C24—O27	1.350 (6)	C2—H2B	0.9900
C24—C25	1.385 (8)	C3—O3	1.423 (6)
C25—C26	1.370 (8)	C3—C6	1.540 (8)
C25—H25	0.9500	C3—C4	1.546 (7)
C26—H26	0.9500	O3—H3	0.8400
O27—C28	1.446 (6)	C4—C5	1.506 (9)
C28—C29	1.472 (8)	C4—H4A	0.9900
C28—H28A	0.9900	C4—H4B	0.9900
C28—H28B	0.9900	C5—O51	1.224 (8)
C29—H29A	0.9800	C5—O52	1.318 (8)
C29—H29B	0.9800	O52—H52	0.8400
C29—H29C	0.9800	C6—O61	1.258 (7)
C31—N36	1.295 (7)	C6—O62	1.259 (7)
C31—N32	1.383 (7)	O1W—H1WA	0.8401
N32—C33	1.367 (7)	O1W—H1WB	0.8401
O1—S1—O2	119.9 (3)	N36—C31—C23	120.0 (5)
O1—S1—N11	106.8 (3)	N32—C31—C23	118.0 (5)
O2—S1—N11	106.9 (2)	C33—N32—C31	127.6 (5)
O1—S1—C21	107.9 (3)	C33—N32—H32	116.2
O2—S1—C21	108.8 (3)	C31—N32—H32	116.2
N11—S1—C21	105.7 (2)	O33—C33—N32	122.8 (6)
C16—N11—C12	111.0 (4)	O33—C33—C34	127.6 (6)
C16—N11—S1	116.5 (4)	N32—C33—C34	109.6 (5)
C12—N11—S1	115.3 (4)	N37—C34—C35	107.7 (5)
N11—C12—C13	108.6 (4)	N37—C34—C33	131.8 (6)
N11—C12—H12A	110.0	C35—C34—C33	120.4 (5)
C13—C12—H12A	110.0	N36—C35—C34	125.0 (5)
N11—C12—H12B	110.0	N36—C35—C39	130.1 (6)
C13—C12—H12B	110.0	C34—C35—C39	104.9 (5)
H12A—C12—H12B	108.4	C31—N36—C35	115.2 (5)
C12—C13—N14	111.7 (5)	N38—N37—C34	110.2 (5)
C12—C13—H13A	109.3	N38—N37—C37	121.7 (5)
N14—C13—H13A	109.3	C34—N37—C37	128.1 (5)
C12—C13—H13B	109.3	N37—C37—H37A	109.5
N14—C13—H13B	109.3	N37—C37—H37B	109.5
H13A—C13—H13B	107.9	H37A—C37—H37B	109.5
C17—N14—C15	112.8 (5)	N37—C37—H37C	109.5
C17—N14—C13	110.4 (5)	H37A—C37—H37C	109.5
C15—N14—C13	109.6 (4)	H37B—C37—H37C	109.5
C17—N14—H14	108.0	C39—N38—N37	107.5 (5)
C15—N14—H14	108.0	N38—C39—C35	109.7 (6)
C13—N14—H14	108.0	N38—C39—C40	121.6 (6)
C16—C15—N14	111.1 (5)	C35—C39—C40	128.6 (6)
C16—C15—H15A	109.4	C39—C40—C41	113.2 (5)
N14—C15—H15A	109.4	C39—C40—H40A	108.9
C16—C15—H15B	109.4	C41—C40—H40A	108.9
N14—C15—H15B	109.4	C39—C40—H40B	108.9
H15A—C15—H15B	108.0	C41—C40—H40B	108.9
N11—C16—C15	109.0 (5)	H40A—C40—H40B	107.7
N11—C16—H16A	109.9	C42—C41—C40	113.2 (6)
C15—C16—H16A	109.9	C42—C41—H41A	108.9
N11—C16—H16B	109.9	C40—C41—H41A	108.9
C15—C16—H16B	109.9	C42—C41—H41B	108.9
H16A—C16—H16B	108.3	C40—C41—H41B	108.9
N14—C17—H17A	109.5	H41A—C41—H41B	107.7
N14—C17—H17B	109.5	C41—C42—H42A	109.5
H17A—C17—H17B	109.5	C41—C42—H42B	109.5
N14—C17—H17C	109.5	H42A—C42—H42B	109.5
H17A—C17—H17C	109.5	C41—C42—H42C	109.5
H17B—C17—H17C	109.5	H42A—C42—H42C	109.5
C22—C21—C26	118.5 (5)	H42B—C42—H42C	109.5
C22—C21—S1	120.9 (5)	O11—C1—O12	120.6 (7)
C26—C21—S1	120.5 (5)	O11—C1—C2	124.1 (6)
C21—C22—C23	122.6 (6)	O12—C1—C2	115.3 (6)
C21—C22—H22	118.7	C1—O12—H12	109.5
C23—C22—H22	118.7	C3—C2—C1	117.3 (5)
C22—C23—C24	117.8 (5)	C3—C2—H2A	108.0
C22—C23—C31	116.6 (5)	C1—C2—H2A	108.0
C24—C23—C31	125.6 (5)	C3—C2—H2B	108.0
O27—C24—C25	122.9 (6)	C1—C2—H2B	108.0
O27—C24—C23	117.2 (5)	H2A—C2—H2B	107.2
C25—C24—C23	119.9 (5)	O3—C3—C2	109.6 (5)
C26—C25—C24	121.3 (6)	O3—C3—C6	107.5 (4)
C26—C25—H25	119.4	C2—C3—C6	110.4 (5)
C24—C25—H25	119.4	O3—C3—C4	109.6 (4)
C25—C26—C21	119.9 (6)	C2—C3—C4	111.1 (5)
C25—C26—H26	120.0	C6—C3—C4	108.5 (5)
C21—C26—H26	120.0	C3—O3—H3	109.5
C24—O27—C28	121.3 (5)	C5—C4—C3	111.0 (5)
O27—C28—C29	107.8 (5)	C5—C4—H4A	109.4
O27—C28—H28A	110.1	C3—C4—H4A	109.4
C29—C28—H28A	110.1	C5—C4—H4B	109.4
O27—C28—H28B	110.1	C3—C4—H4B	109.4
C29—C28—H28B	110.1	H4A—C4—H4B	108.0
H28A—C28—H28B	108.5	O51—C5—O52	119.9 (7)
C28—C29—H29A	109.5	O51—C5—C4	122.0 (7)
C28—C29—H29B	109.5	O52—C5—C4	118.0 (6)
H29A—C29—H29B	109.5	C5—O52—H52	109.5
C28—C29—H29C	109.5	O61—C6—O62	126.3 (6)
H29A—C29—H29C	109.5	O61—C6—C3	115.3 (5)
H29B—C29—H29C	109.5	O62—C6—C3	118.1 (5)
N36—C31—N32	122.0 (5)	H1WA—O1W—H1WB	90.4
O1—S1—N11—C16	53.1 (4)	C31—N32—C33—C34	0.9 (8)
O2—S1—N11—C16	−177.4 (4)	O33—C33—C34—N37	2.0 (11)
C21—S1—N11—C16	−61.6 (4)	N32—C33—C34—N37	−178.9 (6)
O1—S1—N11—C12	−174.1 (4)	O33—C33—C34—C35	176.9 (6)
O2—S1—N11—C12	−44.7 (5)	N32—C33—C34—C35	−4.0 (8)
C21—S1—N11—C12	71.1 (5)	N37—C34—C35—N36	−179.7 (5)
C16—N11—C12—C13	−60.3 (6)	C33—C34—C35—N36	4.3 (9)
S1—N11—C12—C13	164.5 (4)	N37—C34—C35—C39	−0.4 (6)
N11—C12—C13—N14	56.5 (6)	C33—C34—C35—C39	−176.4 (5)
C12—C13—N14—C17	−179.3 (5)	N32—C31—N36—C35	−2.6 (8)
C12—C13—N14—C15	−54.6 (6)	C23—C31—N36—C35	178.6 (5)
C17—N14—C15—C16	179.2 (5)	C34—C35—N36—C31	−0.7 (8)
C13—N14—C15—C16	55.8 (6)	C39—C35—N36—C31	−179.9 (6)
C12—N11—C16—C15	62.2 (6)	C35—C34—N37—N38	1.2 (7)
S1—N11—C16—C15	−163.1 (4)	C33—C34—N37—N38	176.6 (6)
N14—C15—C16—N11	−59.6 (6)	C35—C34—N37—C37	179.5 (6)
O1—S1—C21—C22	−19.7 (5)	C33—C34—N37—C37	−5.1 (11)
O2—S1—C21—C22	−151.2 (4)	C34—N37—N38—C39	−1.6 (7)
N11—S1—C21—C22	94.3 (5)	C37—N37—N38—C39	179.9 (5)
O1—S1—C21—C26	165.6 (4)	N37—N38—C39—C35	1.4 (7)
O2—S1—C21—C26	34.0 (5)	N37—N38—C39—C40	178.2 (5)
N11—S1—C21—C26	−80.4 (5)	N36—C35—C39—N38	178.7 (6)
C26—C21—C22—C23	−0.1 (8)	C34—C35—C39—N38	−0.6 (7)
S1—C21—C22—C23	−174.9 (4)	N36—C35—C39—C40	2.2 (11)
C21—C22—C23—C24	0.1 (8)	C34—C35—C39—C40	−177.1 (6)
C21—C22—C23—C31	−179.2 (5)	N38—C39—C40—C41	−78.7 (8)
C22—C23—C24—O27	−177.6 (5)	C35—C39—C40—C41	97.5 (7)
C31—C23—C24—O27	1.6 (8)	C39—C40—C41—C42	−173.4 (6)
C22—C23—C24—C25	−1.0 (8)	O11—C1—C2—C3	151.0 (7)
C31—C23—C24—C25	178.2 (5)	O12—C1—C2—C3	−28.9 (8)
O27—C24—C25—C26	178.3 (5)	C1—C2—C3—O3	−58.5 (6)
C23—C24—C25—C26	1.9 (9)	C1—C2—C3—C6	59.8 (7)
C24—C25—C26—C21	−1.9 (9)	C1—C2—C3—C4	−179.8 (5)
C22—C21—C26—C25	1.0 (8)	O3—C3—C4—C5	56.0 (7)
S1—C21—C26—C25	175.8 (5)	C2—C3—C4—C5	177.3 (5)
C25—C24—O27—C28	7.3 (8)	C6—C3—C4—C5	−61.1 (7)
C23—C24—O27—C28	−176.2 (5)	C3—C4—C5—O51	80.0 (7)
C24—O27—C28—C29	179.8 (5)	C3—C4—C5—O52	−95.9 (6)
C22—C23—C31—N36	10.5 (8)	O3—C3—C6—O61	173.5 (5)
C24—C23—C31—N36	−168.7 (5)	C2—C3—C6—O61	53.9 (7)
C22—C23—C31—N32	−168.3 (5)	C4—C3—C6—O61	−68.0 (7)
C24—C23—C31—N32	12.5 (8)	O3—C3—C6—O62	−12.1 (7)
N36—C31—N32—C33	2.6 (9)	C2—C3—C6—O62	−131.6 (6)
C23—C31—N32—C33	−178.6 (5)	C4—C3—C6—O62	106.4 (6)
C31—N32—C33—O33	−179.9 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14···O3	0.93	1.88	2.764 (6)	159
N14—H14···O62	0.93	2.30	2.911 (6)	123
N32—H32···O27	0.88	1.94	2.622 (6)	134
O12—H12···N38^i	0.84	1.98	2.771 (7)	157
O3—H3···O61^ii	0.84	1.77	2.605 (5)	173
O52—H52···O62^ii	0.84	1.73	2.490 (6)	149
O1W—H1WA···O1^iii	0.84	2.11	2.946 (13)	179
O1W—H1WB···O51	0.84	1.84	2.678 (16)	179

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y−1/2, z; (iii) x+1/2, y, −z+1/2.