3,6,9,16,19,22-Hexaazatricyclo-[22.2.2.2]triaconta-1(27),11 (30),-12,14(29),24(28),25-hexaene hexakis(p-toluenesulfonate) dihydrate.

In the title compound, C(24)H(44)N(6) (6+).6C(7)H(7)O(3)S(-).2H(2)O, the macrocycle crystallizes in its hexaprotonated form, accompanied by six p-toluenesulfonate ions and two water molecules, and lies on an inversion center. The three independent p-toluenesulfonate anions and their inversion equivalents at (1 - x, 1 - y, 1 - z) are linked to the macrocyclic cation through N-Hcdots, three dots, centeredO hydrogen bonds. Of these, two p-toluenesulfonate ions are located on opposite sides of the macrocyclic plane and are linked to bridgehead N atoms via N-Hcdots, three dots, centeredO hydrogen bonds. The remaining four p-toluenesulfonate ions bridge two adjacent macrocyclic cationic units through N-Hcdots, three dots, centeredO hydrogen bonding involving other N atoms, forming a chain along the a axis. The water molecules, which could not be located and may be disordered, do not interact with the macrocycle; however, they form hydrogen bonds with anions.

Related literature

For general background, see: Bianchi et al. (1997 ▶); Chen & Martell (1991 ▶); Hossain (2008 ▶); Llobet et al. (1994 ▶); Nagarajan & Ganem (1987 ▶); Ragunathan & Schneider (1996 ▶). For related structures, see: Bazzicalupi et al. (1995 ▶); Clifford et al. (2001 ▶); He et al. (2000 ▶); Li et al. (2009 ▶); Liu et al. (2008 ▶); Lu et al. (1995 ▶, 1998 ▶); Zhu et al. (2002 ▶).

Experimental

Crystal data

C24H44N6 6+·6C7H7O3S−·2H2O

M = 1479.80

Triclinic,

a = 11.513 (3) Å

b = 12.639 (5) Å

c = 13.556 (6) Å

α = 78.578 (16)°

β = 71.88 (2)°

γ = 89.30 (2)°

V = 1835.0 (12) Å3

Z = 1

Mo Kα radiation

μ = 0.26 mm−1

T = 90 K

0.17 × 0.10 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.947, T max = 0.992

27691 measured reflections

7213 independent reflections

2920 reflections with I > 2σ(I)

R int = 0.145

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.156

S = 0.97

7213 reflections

446 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.33 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035648/ci2898sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035648/ci2898Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C24H44N66+·6C7H7O3S−·2H2O	Z = 1
Mr = 1479.80	F(000) = 784
Triclinic, P1	Dx = 1.339 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.513 (3) Å	Cell parameters from 6760 reflections
b = 12.639 (5) Å	θ = 2.5–26.0°
c = 13.556 (6) Å	µ = 0.26 mm−1
α = 78.578 (16)°	T = 90 K
β = 71.88 (2)°	Plate, colorless
γ = 89.30 (2)°	0.17 × 0.10 × 0.03 mm
V = 1835.0 (12) Å3

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	7213 independent reflections
Radiation source: fine-focus sealed tube	2920 reflections with I > 2σ(I)
graphite	Rint = 0.145
ω and φ scans	θmax = 26.3°, θmin = 2.7°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −13→14
Tmin = 0.947, Tmax = 0.992	k = −15→15
27691 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072	H-atom parameters constrained
wR(F2) = 0.156	w = 1/[σ2(Fo2) + (0.0515P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
7213 reflections	Δρmax = 0.39 e Å−3
446 parameters	Δρmin = −0.33 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (7)

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.

	x	y	z	Uiso*/Ueq
N1	0.7392 (3)	0.5311 (3)	0.4777 (3)	0.0292 (10)
H11N	0.7039	0.5968	0.4705	0.035*
H12N	0.6798	0.4779	0.4892	0.035*
N2	0.8843 (3)	0.5451 (3)	0.1864 (3)	0.0242 (10)
H21N	0.8920	0.4720	0.1907	0.029*
H22N	0.9589	0.5751	0.1815	0.029*
N3	0.7276 (3)	0.5161 (3)	0.7591 (3)	0.0222 (9)
H31N	0.8044	0.5469	0.7455	0.027*
H32N	0.7331	0.4423	0.7725	0.027*
C1	0.8391 (4)	0.5271 (4)	0.3779 (3)	0.0331 (13)
H1A	0.8667	0.4525	0.3792	0.040*
H1B	0.9097	0.5751	0.3710	0.040*
C2	0.7921 (4)	0.5632 (4)	0.2853 (3)	0.0263 (12)
H2A	0.7146	0.5220	0.2974	0.032*
H2B	0.7753	0.6409	0.2782	0.032*
C3	0.8538 (4)	0.5918 (4)	0.0876 (4)	0.0281 (12)
H3A	0.8608	0.6717	0.0750	0.034*
H3B	0.9132	0.5688	0.0264	0.034*
C4	0.7271 (4)	0.5565 (4)	0.0956 (3)	0.0219 (11)
C5	0.6934 (4)	0.4486 (4)	0.1162 (3)	0.0276 (12)
H5	0.7526	0.3962	0.1200	0.033*
C6	0.5747 (4)	0.4155 (4)	0.1315 (4)	0.0286 (12)
H6	0.5525	0.3404	0.1469	0.034*
C7	0.4869 (4)	0.4901 (4)	0.1246 (3)	0.0245 (12)
C8	0.5205 (4)	0.5989 (4)	0.1009 (3)	0.0253 (12)
H8	0.4624	0.6513	0.0933	0.030*
C9	0.6402 (4)	0.6312 (4)	0.0885 (3)	0.0247 (12)
H9	0.6625	0.7060	0.0748	0.030*
C10	0.6439 (3)	0.5474 (4)	0.8560 (3)	0.0239 (12)
H10A	0.6493	0.6270	0.8477	0.029*
H10B	0.6698	0.5149	0.9180	0.029*
C11	0.6896 (4)	0.5483 (4)	0.6635 (3)	0.0246 (12)
H11A	0.6815	0.6275	0.6486	0.030*
H11B	0.6092	0.5124	0.6751	0.030*
C12	0.7840 (4)	0.5161 (5)	0.5708 (4)	0.0389 (15)
H12A	0.8608	0.5607	0.5523	0.047*
H12B	0.8019	0.4394	0.5905	0.047*
S1	0.86065 (10)	0.27995 (10)	0.83408 (10)	0.0307 (4)
O1	0.8820 (2)	0.3732 (2)	0.8763 (3)	0.0301 (9)
O2	0.7479 (2)	0.2887 (2)	0.8063 (2)	0.0321 (9)
O3	0.9661 (3)	0.2628 (3)	0.7468 (3)	0.0405 (10)
C13	0.8414 (4)	0.1649 (4)	0.9368 (4)	0.0239 (12)
C14	0.8237 (4)	0.0639 (4)	0.9169 (4)	0.0368 (14)
H14	0.8200	0.0575	0.8493	0.044*
C15	0.8115 (4)	−0.0272 (4)	0.9950 (4)	0.0385 (14)
H15	0.7995	−0.0961	0.9805	0.046*
C16	0.8164 (4)	−0.0201 (4)	1.0952 (4)	0.0298 (13)
C17	0.8351 (4)	0.0810 (4)	1.1128 (4)	0.0349 (13)
H17	0.8388	0.0876	1.1803	0.042*
C18	0.8485 (4)	0.1730 (4)	1.0349 (4)	0.0370 (14)
H18	0.8625	0.2417	1.0488	0.044*
C19	0.8042 (4)	−0.1200 (4)	1.1794 (4)	0.0389 (14)
H19A	0.8052	−0.0996	1.2452	0.058*
H19B	0.8725	−0.1659	1.1561	0.058*
H19C	0.7267	−0.1599	1.1919	0.058*
S2	1.03881 (10)	0.29487 (10)	0.21857 (10)	0.0261 (4)
O4	1.0570 (2)	0.3649 (2)	0.2876 (2)	0.0265 (8)
O5	0.9472 (2)	0.3379 (2)	0.1689 (2)	0.0310 (9)
O6	1.1516 (2)	0.2716 (2)	0.1447 (2)	0.0318 (9)
C20	0.9732 (4)	0.1722 (4)	0.3034 (4)	0.0243 (12)
C21	1.0362 (4)	0.0795 (4)	0.3002 (4)	0.0413 (14)
H21	1.1164	0.0814	0.2517	0.050*
C22	0.9831 (5)	−0.0177 (4)	0.3677 (5)	0.0515 (16)
H22	1.0270	−0.0817	0.3641	0.062*
C23	0.8652 (5)	−0.0217 (5)	0.4410 (4)	0.0444 (15)
C24	0.8042 (4)	0.0714 (5)	0.4437 (4)	0.0429 (15)
H24	0.7245	0.0699	0.4930	0.052*
C25	0.8559 (4)	0.1684 (4)	0.3760 (4)	0.0344 (13)
H25	0.8113	0.2321	0.3791	0.041*
C26	0.8091 (5)	−0.1286 (4)	0.5137 (5)	0.0640 (19)
H26A	0.7470	−0.1148	0.5774	0.096*
H26B	0.8731	−0.1706	0.5340	0.096*
H26C	0.7709	−0.1694	0.4765	0.096*
S3	0.51388 (11)	0.31199 (11)	0.53979 (12)	0.0374 (4)
O7	0.4106 (3)	0.2991 (3)	0.5021 (3)	0.0422 (10)
O8	0.6303 (3)	0.3321 (3)	0.4573 (3)	0.0696 (14)
O9	0.4946 (3)	0.3943 (3)	0.6041 (3)	0.0540 (11)
C27	0.5184 (4)	0.1876 (4)	0.6248 (4)	0.0338 (13)
C28	0.4736 (4)	0.0918 (4)	0.6118 (5)	0.0427 (15)
H28	0.4402	0.0912	0.5560	0.051*
C29	0.4784 (5)	−0.0029 (5)	0.6816 (6)	0.061 (2)
H29	0.4467	−0.0685	0.6733	0.073*
C30	0.5274 (5)	−0.0056 (5)	0.7628 (6)	0.070 (2)
C31	0.5708 (5)	0.0922 (5)	0.7738 (5)	0.075 (2)
H31	0.6030	0.0934	0.8302	0.089*
C32	0.5681 (4)	0.1871 (5)	0.7050 (5)	0.0520 (17)
H32	0.6006	0.2526	0.7127	0.062*
C33	0.5288 (6)	−0.1102 (5)	0.8403 (7)	0.118 (4)
H33A	0.5662	−0.1657	0.8009	0.177*
H33B	0.4448	−0.1346	0.8840	0.177*
H33C	0.5764	−0.0978	0.8860	0.177*
O10	1.0391 (4)	0.6764 (4)	0.4660 (4)	0.0990 (16)

	U11	U22	U33	U12	U13	U23
N1	0.024 (2)	0.042 (3)	0.019 (2)	0.0028 (19)	−0.0035 (19)	−0.009 (2)
N2	0.0124 (19)	0.037 (3)	0.022 (2)	0.0006 (17)	−0.0023 (17)	−0.007 (2)
N3	0.0195 (19)	0.028 (2)	0.018 (2)	−0.0020 (17)	−0.0027 (17)	−0.0059 (19)
C1	0.023 (3)	0.056 (4)	0.021 (3)	0.007 (2)	−0.005 (2)	−0.013 (3)
C2	0.021 (2)	0.033 (3)	0.024 (3)	0.000 (2)	−0.003 (2)	−0.011 (3)
C3	0.018 (2)	0.048 (3)	0.018 (3)	−0.001 (2)	−0.005 (2)	−0.006 (3)
C4	0.014 (2)	0.036 (3)	0.015 (3)	0.001 (2)	−0.001 (2)	−0.011 (2)
C5	0.019 (3)	0.039 (4)	0.027 (3)	0.006 (2)	−0.006 (2)	−0.013 (3)
C6	0.028 (3)	0.027 (3)	0.031 (3)	−0.007 (2)	−0.009 (2)	−0.005 (3)
C7	0.020 (3)	0.035 (3)	0.022 (3)	0.004 (2)	−0.008 (2)	−0.010 (3)
C8	0.021 (3)	0.034 (3)	0.021 (3)	0.005 (2)	−0.006 (2)	−0.007 (2)
C9	0.022 (3)	0.030 (3)	0.019 (3)	−0.007 (2)	0.000 (2)	−0.006 (2)
C10	0.021 (3)	0.034 (3)	0.016 (3)	0.000 (2)	−0.004 (2)	−0.006 (2)
C11	0.023 (2)	0.033 (3)	0.022 (3)	0.002 (2)	−0.013 (2)	−0.005 (2)
C12	0.025 (3)	0.075 (4)	0.015 (3)	0.009 (3)	−0.005 (2)	−0.010 (3)
S1	0.0238 (7)	0.0303 (9)	0.0379 (9)	0.0036 (6)	−0.0102 (6)	−0.0060 (7)
O1	0.0245 (17)	0.022 (2)	0.047 (2)	−0.0024 (14)	−0.0159 (16)	−0.0081 (17)
O2	0.0287 (18)	0.029 (2)	0.042 (2)	0.0011 (15)	−0.0177 (16)	−0.0050 (17)
O3	0.0298 (19)	0.044 (2)	0.038 (2)	0.0123 (16)	−0.0013 (17)	−0.0027 (18)
C13	0.016 (2)	0.024 (3)	0.033 (3)	0.004 (2)	−0.006 (2)	−0.009 (3)
C14	0.052 (3)	0.033 (4)	0.035 (4)	−0.003 (3)	−0.020 (3)	−0.017 (3)
C15	0.047 (3)	0.026 (4)	0.044 (4)	0.000 (3)	−0.014 (3)	−0.013 (3)
C16	0.025 (3)	0.028 (4)	0.036 (4)	0.003 (2)	−0.010 (2)	−0.007 (3)
C17	0.045 (3)	0.029 (4)	0.030 (3)	0.002 (3)	−0.014 (3)	−0.003 (3)
C18	0.036 (3)	0.032 (4)	0.052 (4)	−0.003 (2)	−0.018 (3)	−0.022 (3)
C19	0.039 (3)	0.039 (4)	0.039 (4)	0.002 (3)	−0.012 (3)	−0.006 (3)
S2	0.0209 (7)	0.0306 (8)	0.0250 (8)	−0.0015 (6)	−0.0034 (6)	−0.0079 (7)
O4	0.0207 (16)	0.031 (2)	0.030 (2)	−0.0027 (14)	−0.0065 (14)	−0.0141 (17)
O5	0.0295 (18)	0.035 (2)	0.034 (2)	0.0029 (15)	−0.0168 (16)	−0.0073 (17)
O6	0.0240 (17)	0.039 (2)	0.024 (2)	0.0006 (15)	0.0047 (15)	−0.0082 (17)
C20	0.024 (3)	0.027 (3)	0.026 (3)	0.001 (2)	−0.011 (2)	−0.010 (2)
C21	0.031 (3)	0.035 (4)	0.049 (4)	−0.001 (3)	0.001 (3)	−0.011 (3)
C22	0.056 (4)	0.025 (4)	0.068 (5)	0.004 (3)	−0.017 (3)	−0.001 (3)
C23	0.039 (3)	0.041 (4)	0.052 (4)	−0.016 (3)	−0.021 (3)	0.006 (3)
C24	0.031 (3)	0.047 (4)	0.043 (4)	−0.011 (3)	−0.008 (3)	0.002 (3)
C25	0.024 (3)	0.035 (4)	0.041 (4)	0.002 (2)	−0.009 (3)	−0.004 (3)
C26	0.061 (4)	0.046 (4)	0.080 (5)	−0.022 (3)	−0.030 (3)	0.014 (4)
S3	0.0244 (7)	0.0398 (10)	0.0454 (10)	0.0028 (6)	−0.0109 (7)	−0.0034 (8)
O7	0.040 (2)	0.046 (2)	0.051 (3)	0.0073 (17)	−0.0270 (18)	−0.0139 (19)
O8	0.032 (2)	0.066 (3)	0.075 (3)	0.0132 (19)	0.012 (2)	0.021 (2)
O9	0.075 (3)	0.033 (2)	0.072 (3)	0.0047 (19)	−0.045 (2)	−0.017 (2)
C27	0.022 (3)	0.035 (4)	0.046 (4)	−0.002 (2)	−0.014 (3)	−0.008 (3)
C28	0.031 (3)	0.033 (4)	0.063 (4)	−0.009 (3)	−0.010 (3)	−0.016 (3)
C29	0.039 (3)	0.021 (4)	0.114 (6)	−0.004 (3)	−0.014 (4)	−0.008 (4)
C30	0.051 (4)	0.036 (4)	0.120 (6)	−0.011 (3)	−0.047 (4)	0.023 (4)
C31	0.071 (5)	0.057 (5)	0.102 (6)	−0.025 (4)	−0.059 (4)	0.022 (4)
C32	0.052 (4)	0.034 (4)	0.070 (5)	−0.018 (3)	−0.032 (3)	0.012 (3)
C33	0.106 (6)	0.049 (5)	0.193 (9)	−0.030 (4)	−0.087 (6)	0.058 (6)
O10	0.116 (4)	0.111 (4)	0.087 (4)	0.044 (3)	−0.047 (3)	−0.039 (3)

N1—C12	1.484 (5)	C15—C16	1.397 (7)
N1—C1	1.488 (5)	C15—H15	0.95
N1—H11N	0.92	C16—C17	1.376 (6)
N1—H12N	0.92	C16—C19	1.501 (6)
N2—C2	1.486 (5)	C17—C18	1.381 (6)
N2—C3	1.496 (5)	C17—H17	0.95
N2—H21N	0.92	C18—H18	0.95
N2—H22N	0.92	C19—H19A	0.98
N3—C11	1.476 (5)	C19—H19B	0.98
N3—C10	1.490 (5)	C19—H19C	0.98
N3—H31N	0.92	S2—O6	1.440 (3)
N3—H32N	0.92	S2—O5	1.465 (3)
C1—C2	1.506 (6)	S2—O4	1.469 (3)
C1—H1A	0.99	S2—C20	1.754 (5)
C1—H1B	0.99	C20—C21	1.372 (6)
C2—H2A	0.99	C20—C25	1.397 (6)
C2—H2B	0.99	C21—C22	1.394 (7)
C3—C4	1.496 (5)	C21—H21	0.95
C3—H3A	0.99	C22—C23	1.406 (7)
C3—H3B	0.99	C22—H22	0.95
C4—C5	1.372 (6)	C23—C24	1.363 (7)
C4—C9	1.379 (6)	C23—C26	1.521 (7)
C5—C6	1.374 (5)	C24—C25	1.390 (6)
C5—H5	0.95	C24—H24	0.95
C6—C7	1.386 (6)	C25—H25	0.95
C6—H6	0.95	C26—H26A	0.98
C7—C8	1.380 (6)	C26—H26B	0.98
C7—C10i	1.511 (5)	C26—H26C	0.98
C8—C9	1.391 (5)	S3—O8	1.440 (4)
C8—H8	0.95	S3—O7	1.455 (3)
C9—H9	0.95	S3—O9	1.457 (4)
C10—C7i	1.511 (5)	S3—C27	1.766 (5)
C10—H10A	0.99	C27—C32	1.375 (7)
C10—H10B	0.99	C27—C28	1.386 (6)
C11—C12	1.506 (6)	C28—C29	1.383 (7)
C11—H11A	0.99	C28—H28	0.95
C11—H11B	0.99	C29—C30	1.380 (8)
C12—H12A	0.99	C29—H29	0.95
C12—H12B	0.99	C30—C31	1.391 (8)
S1—O2	1.457 (3)	C30—C33	1.521 (8)
S1—O3	1.457 (3)	C31—C32	1.373 (7)
S1—O1	1.463 (3)	C31—H31	0.95
S1—C13	1.765 (5)	C32—H32	0.95
C13—C18	1.381 (6)	C33—H33A	0.98
C13—C14	1.386 (6)	C33—H33B	0.98
C14—C15	1.376 (6)	C33—H33C	0.98
C14—H14	0.95
C12—N1—C1	112.2 (3)	C15—C14—C13	120.1 (5)
C12—N1—H11N	109.2	C15—C14—H14	119.9
C1—N1—H11N	109.2	C13—C14—H14	119.9
C12—N1—H12N	109.2	C14—C15—C16	121.1 (5)
C1—N1—H12N	109.2	C14—C15—H15	119.4
H11N—N1—H12N	107.9	C16—C15—H15	119.4
C2—N2—C3	113.9 (3)	C17—C16—C15	117.7 (5)
C2—N2—H21N	108.8	C17—C16—C19	121.6 (5)
C3—N2—H21N	108.8	C15—C16—C19	120.7 (5)
C2—N2—H22N	108.8	C16—C17—C18	121.8 (5)
C3—N2—H22N	108.8	C16—C17—H17	119.1
H21N—N2—H22N	107.7	C18—C17—H17	119.1
C11—N3—C10	114.6 (3)	C17—C18—C13	119.9 (5)
C11—N3—H31N	108.6	C17—C18—H18	120.1
C10—N3—H31N	108.6	C13—C18—H18	120.1
C11—N3—H32N	108.6	C16—C19—H19A	109.5
C10—N3—H32N	108.6	C16—C19—H19B	109.5
H31N—N3—H32N	107.6	H19A—C19—H19B	109.5
N1—C1—C2	109.0 (3)	C16—C19—H19C	109.5
N1—C1—H1A	109.9	H19A—C19—H19C	109.5
C2—C1—H1A	109.9	H19B—C19—H19C	109.5
N1—C1—H1B	109.9	O6—S2—O5	113.90 (19)
C2—C1—H1B	109.9	O6—S2—O4	113.11 (17)
H1A—C1—H1B	108.3	O5—S2—O4	110.35 (19)
N2—C2—C1	109.8 (3)	O6—S2—C20	107.5 (2)
N2—C2—H2A	109.7	O5—S2—C20	105.69 (19)
C1—C2—H2A	109.7	O4—S2—C20	105.7 (2)
N2—C2—H2B	109.7	C21—C20—C25	119.2 (4)
C1—C2—H2B	109.7	C21—C20—S2	120.8 (4)
H2A—C2—H2B	108.2	C25—C20—S2	120.0 (4)
C4—C3—N2	111.6 (3)	C20—C21—C22	120.4 (5)
C4—C3—H3A	109.3	C20—C21—H21	119.8
N2—C3—H3A	109.3	C22—C21—H21	119.8
C4—C3—H3B	109.3	C21—C22—C23	120.5 (5)
N2—C3—H3B	109.3	C21—C22—H22	119.7
H3A—C3—H3B	108.0	C23—C22—H22	119.7
C5—C4—C9	118.8 (4)	C24—C23—C22	118.4 (5)
C5—C4—C3	120.4 (4)	C24—C23—C26	122.0 (5)
C9—C4—C3	120.7 (4)	C22—C23—C26	119.6 (5)
C4—C5—C6	120.6 (4)	C23—C24—C25	121.5 (5)
C4—C5—H5	119.7	C23—C24—H24	119.2
C6—C5—H5	119.7	C25—C24—H24	119.2
C5—C6—C7	120.9 (4)	C24—C25—C20	120.0 (5)
C5—C6—H6	119.6	C24—C25—H25	120.0
C7—C6—H6	119.6	C20—C25—H25	120.0
C8—C7—C6	119.0 (4)	C23—C26—H26A	109.5
C8—C7—C10i	120.6 (4)	C23—C26—H26B	109.5
C6—C7—C10i	120.3 (4)	H26A—C26—H26B	109.5
C7—C8—C9	119.4 (4)	C23—C26—H26C	109.5
C7—C8—H8	120.3	H26A—C26—H26C	109.5
C9—C8—H8	120.3	H26B—C26—H26C	109.5
C4—C9—C8	121.2 (4)	O8—S3—O7	114.2 (2)
C4—C9—H9	119.4	O8—S3—O9	110.6 (2)
C8—C9—H9	119.4	O7—S3—O9	111.7 (2)
N3—C10—C7i	111.1 (4)	O8—S3—C27	107.7 (2)
N3—C10—H10A	109.4	O7—S3—C27	105.5 (2)
C7i—C10—H10A	109.4	O9—S3—C27	106.6 (2)
N3—C10—H10B	109.4	C32—C27—C28	120.0 (5)
C7i—C10—H10B	109.4	C32—C27—S3	118.6 (4)
H10A—C10—H10B	108.0	C28—C27—S3	121.3 (4)
N3—C11—C12	109.2 (3)	C29—C28—C27	118.7 (5)
N3—C11—H11A	109.8	C29—C28—H28	120.7
C12—C11—H11A	109.8	C27—C28—H28	120.7
N3—C11—H11B	109.8	C30—C29—C28	122.4 (5)
C12—C11—H11B	109.8	C30—C29—H29	118.8
H11A—C11—H11B	108.3	C28—C29—H29	118.8
N1—C12—C11	110.5 (4)	C29—C30—C31	117.3 (5)
N1—C12—H12A	109.6	C29—C30—C33	121.5 (6)
C11—C12—H12A	109.6	C31—C30—C33	121.2 (6)
N1—C12—H12B	109.6	C32—C31—C30	121.4 (6)
C11—C12—H12B	109.6	C32—C31—H31	119.3
H12A—C12—H12B	108.1	C30—C31—H31	119.3
O2—S1—O3	112.8 (2)	C31—C32—C27	120.1 (5)
O2—S1—O1	110.85 (18)	C31—C32—H32	119.9
O3—S1—O1	111.88 (19)	C27—C32—H32	119.9
O2—S1—C13	107.44 (19)	C30—C33—H33A	109.5
O3—S1—C13	106.6 (2)	C30—C33—H33B	109.5
O1—S1—C13	106.9 (2)	H33A—C33—H33B	109.5
C18—C13—C14	119.4 (5)	C30—C33—H33C	109.5
C18—C13—S1	121.5 (4)	H33A—C33—H33C	109.5
C14—C13—S1	119.1 (4)	H33B—C33—H33C	109.5
C12—N1—C1—C2	−169.6 (4)	C14—C13—C18—C17	−1.5 (7)
C3—N2—C2—C1	−172.3 (4)	S1—C13—C18—C17	−178.9 (3)
N1—C1—C2—N2	−172.0 (4)	O6—S2—C20—C21	7.7 (4)
C2—N2—C3—C4	−51.8 (5)	O5—S2—C20—C21	129.6 (4)
N2—C3—C4—C5	−57.0 (6)	O4—S2—C20—C21	−113.4 (4)
N2—C3—C4—C9	119.2 (4)	O6—S2—C20—C25	−172.8 (4)
C9—C4—C5—C6	−1.2 (7)	O5—S2—C20—C25	−50.8 (4)
C3—C4—C5—C6	175.1 (4)	O4—S2—C20—C25	66.2 (4)
C4—C5—C6—C7	1.1 (7)	C25—C20—C21—C22	0.7 (8)
C5—C6—C7—C8	0.7 (7)	S2—C20—C21—C22	−179.7 (4)
C5—C6—C7—C10i	−178.6 (4)	C20—C21—C22—C23	−1.0 (8)
C6—C7—C8—C9	−2.4 (7)	C21—C22—C23—C24	0.5 (8)
C10i—C7—C8—C9	176.9 (4)	C21—C22—C23—C26	179.9 (5)
C5—C4—C9—C8	−0.5 (7)	C22—C23—C24—C25	0.2 (8)
C3—C4—C9—C8	−176.8 (4)	C26—C23—C24—C25	−179.2 (5)
C7—C8—C9—C4	2.3 (7)	C23—C24—C25—C20	−0.4 (8)
C11—N3—C10—C7i	51.9 (5)	C21—C20—C25—C24	−0.1 (7)
C10—N3—C11—C12	177.8 (4)	S2—C20—C25—C24	−179.6 (4)
C1—N1—C12—C11	165.6 (4)	O8—S3—C27—C32	84.8 (5)
N3—C11—C12—N1	170.9 (4)	O7—S3—C27—C32	−152.9 (4)
O2—S1—C13—C18	−119.5 (4)	O9—S3—C27—C32	−33.9 (5)
O3—S1—C13—C18	119.3 (4)	O8—S3—C27—C28	−95.0 (4)
O1—S1—C13—C18	−0.5 (4)	O7—S3—C27—C28	27.4 (5)
O2—S1—C13—C14	63.1 (4)	O9—S3—C27—C28	146.3 (4)
O3—S1—C13—C14	−58.1 (4)	C32—C27—C28—C29	1.0 (7)
O1—S1—C13—C14	−177.8 (3)	S3—C27—C28—C29	−179.3 (4)
C18—C13—C14—C15	1.0 (7)	C27—C28—C29—C30	−0.8 (8)
S1—C13—C14—C15	178.4 (3)	C28—C29—C30—C31	1.2 (9)
C13—C14—C15—C16	0.1 (7)	C28—C29—C30—C33	178.5 (6)
C14—C15—C16—C17	−0.6 (7)	C29—C30—C31—C32	−1.7 (10)
C14—C15—C16—C19	−179.4 (4)	C33—C30—C31—C32	−179.1 (6)
C15—C16—C17—C18	0.1 (7)	C30—C31—C32—C27	2.0 (9)
C19—C16—C17—C18	178.9 (4)	C28—C27—C32—C31	−1.5 (8)
C16—C17—C18—C13	1.0 (7)	S3—C27—C32—C31	178.7 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O7i	0.92	1.86	2.738 (5)	159
N1—H12N···O8	0.92	2.10	2.923 (6)	148
N1—H12N···O9	0.92	2.33	3.130 (5)	145
N2—H21N···O5	0.92	1.85	2.745 (5)	164
N2—H22N···O1ii	0.92	1.83	2.706 (4)	159
N3—H31N···O4ii	0.92	1.84	2.748 (4)	168
N3—H32N···O2	0.92	1.92	2.842 (5)	177
N3—H32N···O1	0.92	2.58	3.081 (4)	115

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O7i	0.92	1.86	2.738 (5)	159
N1—H12N⋯O8	0.92	2.10	2.923 (6)	148
N1—H12N⋯O9	0.92	2.33	3.130 (5)	145
N2—H21N⋯O5	0.92	1.85	2.745 (5)	164
N2—H22N⋯O1ii	0.92	1.83	2.706 (4)	159
N3—H31N⋯O4ii	0.92	1.84	2.748 (4)	168
N3—H32N⋯O2	0.92	1.92	2.842 (5)	177

Symmetry codes: (i) ; (ii) .