catena-Poly[[[penta­aqua­thulium(III)]-μ-5-sulfonatobenzene-1,3-dicarbox­ylato] 4,4′-bipyridyl 1.5-solvate hemihydrate]

The crystal structure of the title compound, {[Tm(C₈H₃O₇S)(H₂O)₅]·1.5C₁₀H₈N₂·0.5H₂O}_n, is built up from two [Tm(SIP)(H₂O)₅] mol­ecules (SIP³⁻ is 5-sulfonatobenzene-1,3-dicarboxylate), three 4,4′-bipyridyl (bpy) mol­ecules and one solvent water mol­ecule. One of the bpy mol­ecules and the solvent water mol­ecule are located on an inversion centre and a twofold rotation axis, respectively. The Tm^III ion coordination is composed of four carboxyl­ate O atoms from two trianionic SIP³⁻ ligands and five coordinated water mol­ecules. The Tm³⁺ ions are linked by the SIP³⁻ ligands to form a one-dimensional zigzag chain propagating along the c axis. The chains are linked by inter­chain O—H...O hydrogen bonds to generate a two-dimensional layered structure. The bpy mol­ecules are not involved in coordination but are linked by O—H...N hydrogen bonds to form two-dimensional layers. The two-dimensional layers are further bridged by the bpy mol­ecules as pillars and the solvent water mol­ecules through hydrogen bonds, giving a three-dimensional supra­molecular structure. π–π stacking inter­actions between the parallel aromatic rings, arranged in an offset fashion with a face-to-face distance of 3.566 (1) Å, are observed in the crystal packing.

S1. Comment

Crystal engineering and supramolecular chemistry have been the most active areas of materials research in recent years owing to the intriguing structural topologies examined and potential applications in host–guest chemistry, catalysis and electrical conductivity (Biradha & Zaworotko, 1998; Yaghi et al., 1995; Conn & Rebek, 1997). The key to successful construction of supramolecular architectures is the control and manipulation of coordination bonds and noncovalent interactions by carefully selecting the coordination geometry of the metal centers and organic ligands containing appropriate functional groups (such as carboxylic acid and pyridine; Tong et al., 1999; Dong et al., 2000). Among the linker molecules, carboxylic acids such as acetic acid, succinic acid and benzene-1,3,5-tricarboxylic acid have been studied extensively because of their versatile coordination modes (Saalfrank et al., 2001 or 1997???; Bowden et al., 2003; Yaghi et al., 1997). Using benzene-1,3,5-tricarboxylic acid, we recently investigated the influence of changing of one of the carboxylate groups for a sulfonate group by using 5-sulfoisophthalic acid with the goal of obtaining materials with desirable properties. The sulfonate group has one more O atom than the carboxylate group and thus can provide three potential hydrogen-bond acceptors (Evans et al., 1999). The combination of 5-sulfoisophthalic acid ligand with metal ions produced several complexes with diverse structural topologies (Liu & Xu, 2005a, 2006). The hydrothermal reaction of Tm₂O₃, 5-sulfoisophthalic acid monosodium salt (NaH₂SIP) and

4,4'-bipyridine (bpy) yields the title complex, (I). We present its structure here.

The asymmetric unit of (I) consists of a [Tm(SIP)(H₂O)₅] molecule, one and a half bpy molecules, and one-half of a solvent water molecule. One of the bpy molecules and the solvent water molecule are located on an inversion centre and a twofold rotation axis, respectively. As depicted in Fig. 1, the Tm atom is nine-coordinated by four carboxylate O atoms from two SIP^3- ligands and five O atoms from coordinated water molecules. The Tm—O bond lengths range from 2.292 (2) to 2.507 (2) Å with an average value of 2.393 Å, and the O—Tm—O bond angles range from 53.03 (6) to 146.00 (7)° (Table 1). The bond dimensions involving Tm are normal and are comparable to the values in related thulium(III) complexes (Liu & Xu, 2005b). Each SIP^3- anion bridges two neighboring Tm³⁺ ions through its two chelating carboxylate groups (Fig. 1). The sulfonate group is uncoordinated and engaged in hydrogen bonding with the coordinated water molecules. The three identical S—O bond distances (Table 1) suggest that strong conjugation of the sulfonate group is predominant in this structure. The Tm ions are linked by the SIP^3- ligands to produce a one-dimensional zigzag chain propagating along the crystallographic c axis as shown in Fig. 2. The chain is repeated by translation about every 17.4 Å along the c direction, comparable with the length of the c axis. The chains are linked by interchain hydrogen bonds between (a) coordinated water molecules and carboxylate O atoms and (b) coordinated water molecules and sulfonate O atoms, with O···O distances of 2.695 (2)–3.038 (3) Å (Table 2), to generate a two-dimensional layered structure (Figs. 3 and 4). π–π stacking interactions between the parallel phenyl rings, arranged in an off-set fashion with a face-to-face distance of 3.566 (1) Å and a centroid-to-centroid distance of 3.677 (2) Å, are observed within the two-dimensional layer.

The bpy molecules are not involved in coordination but link the chains through hydrogen bonds between coordinated water molecules and pyridyl N atoms, as depicted in Fig. 5. It is interesting that the bpy molecules exhibit two types of conformations with the two pyridyl rings coplanar and twisted with the dihedral angle of 26.2 (2)°. The two-dimensional layers are further linked by the bpy molecules as pillars through O—H···N hydrogen bonds (Table 2) to produce a three-dimensional supramolecular framework structure as illustrated in Fig. 5. The solvent water molecule is located in the space between the two-dimensional layers and stabilized by hydrogen bonding with the sulfonate group with a O···O distance of 2.785 (3) Å. The extensive hydrogen bonds and π–π stacking interactions are responsible for the three-dimensional supramolecular framework structure.

Related literature

For related literature, see: Biradha & Zaworotko (1998); Bowden et al. (2003); Conn & Rebek (1997); Dong et al. (2000); Evans et al. (1999); Liu & Xu (2005a, 2005b, 2006); Saalfrank et al. (2001); Sheldrick (1997a); Tong et al. (1999); Yaghi et al. (1995, 1997).

S2. Experimental

The title compound was synthesized by a hydrothermal method under autogenous pressure. A mixture of Tm₂O₃ (38.6 mg, 0.1 mmol), (NaH₂SIP) (28.6 mg, 0.1 mmol), bpy (23.4 mg, 1.5 mmol), and distilled water (15 ml) was stirred under ambient conditions. The final mixture was sealed in a 25 ml Teflon-lined steel autoclave, heated at 438 K for five days and then cooled to room temperature. Colorless prism-like crystals of (I) were obtained, recovered by filtration, washed with distilled water and dried in air (yield 56%). Analysis calculated for C₄₆H₅₂N₆O₂₅S₂Tm₂: C 37.04, H 3.52, N 5.64%; found: C 36.99, H 3.50, N 5.61%.

S3. Refinement

Aromatic H atoms were placed in calculated positions and treated using a riding-model approximation [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. H atoms bonded to O atoms were visible in a difference map and were refined with a DFIX (SHELXL97; Sheldrick, 1997a) restraint [O—H = 0.90 (1) Å] and with U_iso(H) values set at 1.5U_eq(O). Atom O5 of the sulfonate group was found to be disordered and was modelled over two sets of positions using restraints on their anisotropic displacement parameters. The major and minor disorder components have refined occupancies of 78.6 (7) and 21.4 (7)%, respectively. The atoms of the terminal pyridyl ring and the sulfonate group have larger displacement parameters because of their freedom of libration.

Computing details

Data collection: CrystalClear (Rigaku Corporation & Molecular Structure Corporation, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, -y, z + 1/2; (ii) -x - 1, -y + 1, -z; (iii) x, -y, z - 1/2.] No match with codes in Table 2.
	Fig. 2. A view of the [Tm(SIP)(H2O)5]2 zigzag chain. [Symmetry code: (i) x, -y, z + 1/2.]
	Fig. 3. A perspective view of the hydrogen bonds between the chains. Dashed lines indicate hydrogen bonds. [Symmetry codes: (iv) -x - 1/2, -y + 1/2, -z; (v) -x - 1/2, y - 1/2, -z + 1/2; (vi) -x - 1/2, y + 1/2, -z + 1/2; (vii) x, -y + 1, z + 1/2.] iv differs from Table 2.
	Fig. 4. A perspective view of the two-dimensional layered structure. Dashed lines between the O atoms indicate hydrogen bonds.
	Fig. 5. A view of the packing for (I) (viewed down the c axis) showing the bpy pillars between the layers. Some atoms have been omitted for clarity.

catena-Poly[[pentaaquathulium(III)]-µ-5-sulfonatobenzene-1,3-dicarboxylato]- 4,4'-bipyridyl 1.5-solvate hemihydrate]

Crystal data

[Tm(C8H3O7S)(H2O)5]·1.5C10H8N2·0.5H2O	F(000) = 2960
Mr = 745.46	Dx = 1.863 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8423 reflections
a = 30.516 (5) Å	θ = 2.0–27.5°
b = 10.8142 (16) Å	µ = 3.49 mm^−1
c = 17.350 (3) Å	T = 130 K
β = 111.795 (2)°	Prism, colorless
V = 5316.4 (15) Å^3	0.33 × 0.30 × 0.08 mm
Z = 8

Data collection

Rigaku Mercury70 (2x2 bin mode) diffractometer	6071 independent reflections
Radiation source: fine-focus sealed tube	5742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan CrystalClear (Rigaku Corporation & Molecular Structure Corporation, 2000)	h = −31→39
Tmin = 0.328, Tmax = 0.762	k = −13→14
20149 measured reflections	l = −22→22

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0208P)^2 + 19.846P] where P = (Fo^2 + 2Fc^2)/3
6071 reflections	(Δ/σ)max = 0.002
403 parameters	Δρmax = 0.91 e Å^−3
12 restraints	Δρmin = −0.87 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	Occ. (<1)
Tm1	−0.257837 (4)	0.193024 (9)	0.319545 (6)	0.00838 (4)
S1	−0.36602 (2)	0.44786 (6)	−0.13949 (4)	0.01302 (13)
O1	−0.27147 (7)	0.11168 (16)	0.18392 (10)	0.0134 (4)
O1W	−0.5000	0.3321 (4)	−0.2500	0.0578 (13)
H1W	−0.4740 (13)	0.381 (4)	−0.225 (3)	0.087*
O2	−0.29363 (7)	0.30459 (15)	0.18378 (11)	0.0113 (4)
O3	−0.27794 (7)	−0.09440 (16)	−0.07165 (10)	0.0137 (4)
O4	−0.28662 (7)	0.01635 (16)	−0.18215 (11)	0.0148 (4)
O5	−0.34050 (12)	0.5570 (2)	−0.09374 (17)	0.0180 (7)	0.786 (7)
O5A	−0.3584 (5)	0.5489 (7)	−0.0789 (5)	0.0180 (7)	0.214 (7)
O6	−0.41449 (8)	0.4359 (2)	−0.14853 (14)	0.0331 (6)
O7	−0.35848 (8)	0.4398 (2)	−0.21710 (13)	0.0287 (5)
O8	−0.19994 (7)	0.30252 (16)	0.29530 (11)	0.0121 (4)
H8A	−0.2043 (11)	0.359 (2)	0.2558 (14)	0.018*
H8B	−0.1701 (5)	0.315 (3)	0.3288 (17)	0.018*
O9	−0.33836 (7)	0.21186 (18)	0.28583 (12)	0.0167 (4)
H9A	−0.3590 (10)	0.260 (3)	0.2480 (16)	0.025*
H9B	−0.3543 (11)	0.182 (3)	0.3159 (19)	0.025*
O10	−0.19349 (7)	0.05411 (16)	0.33629 (12)	0.0150 (4)
H10B	−0.1761 (10)	0.068 (3)	0.3059 (17)	0.022*
H10C	−0.2007 (12)	−0.0258 (12)	0.327 (2)	0.022*
O11	−0.19749 (7)	0.23648 (18)	0.45654 (11)	0.0161 (4)
H11C	−0.2045 (12)	0.295 (2)	0.4860 (18)	0.024*
H11B	−0.1871 (12)	0.177 (2)	0.4948 (16)	0.024*
O12	−0.26790 (7)	0.39398 (17)	0.35546 (12)	0.0147 (4)
H12B	−0.2945 (7)	0.417 (3)	0.361 (2)	0.022*
H12C	−0.2576 (11)	0.453 (2)	0.3316 (18)	0.022*
N1	0.10200 (9)	0.6135 (3)	0.35702 (17)	0.0299 (6)
N2	−0.10723 (10)	0.3564 (3)	0.37579 (18)	0.0335 (7)
N3	−0.41372 (9)	0.3367 (2)	0.16550 (17)	0.0260 (6)
C1	−0.30190 (9)	0.2150 (2)	0.05261 (15)	0.0104 (5)
C2	−0.29256 (9)	0.1130 (2)	0.01235 (15)	0.0109 (5)
H2	−0.2794	0.0423	0.0426	0.013*
C3	−0.30259 (9)	0.1155 (2)	−0.07229 (15)	0.0101 (5)
C4	−0.32458 (9)	0.2189 (2)	−0.11896 (15)	0.0107 (5)
H4	−0.3317	0.2207	−0.1759	0.013*
C5	−0.33561 (9)	0.3189 (2)	−0.07944 (15)	0.0098 (5)
C6	−0.32340 (9)	0.3192 (2)	0.00652 (15)	0.0108 (5)
H6	−0.3296	0.3882	0.0329	0.013*
C7	−0.28834 (9)	0.2107 (2)	0.14486 (15)	0.0105 (5)
C8	−0.28867 (9)	0.0064 (2)	−0.11084 (15)	0.0113 (5)
C9	−0.02016 (10)	0.4533 (3)	0.38463 (17)	0.0219 (6)
C10	−0.02900 (11)	0.3265 (3)	0.3773 (2)	0.0272 (7)
H10A	−0.0059	0.2715	0.3759	0.033*
C11	−0.07279 (12)	0.2836 (3)	0.3723 (2)	0.0330 (8)
H11A	−0.0785	0.1990	0.3661	0.040*
C12	−0.09794 (12)	0.4774 (4)	0.3856 (2)	0.0355 (8)
H12A	−0.1212	0.5299	0.3894	0.043*
C13	−0.05533 (12)	0.5286 (3)	0.3903 (2)	0.0310 (7)
H13	−0.0505	0.6135	0.3972	0.037*
C14	0.02386 (10)	0.5063 (3)	0.37958 (18)	0.0209 (6)
C15	0.03996 (11)	0.6243 (3)	0.4102 (2)	0.0270 (7)
H15	0.0247	0.6694	0.4385	0.032*
C16	0.07879 (12)	0.6732 (3)	0.3979 (2)	0.0319 (8)
H16	0.0893	0.7513	0.4192	0.038*
C17	0.08679 (11)	0.5008 (3)	0.32900 (19)	0.0271 (7)
H17	0.1027	0.4580	0.3009	0.033*
C18	0.04876 (11)	0.4432 (3)	0.33906 (19)	0.0250 (6)
H18	0.0400	0.3635	0.3190	0.030*
C19	−0.41004 (13)	0.3527 (4)	0.0926 (3)	0.0434 (10)
H19	−0.3837	0.3194	0.0854	0.052*
C20	−0.44238 (13)	0.4150 (4)	0.0263 (2)	0.0447 (10)
H20	−0.4375	0.4230	−0.0233	0.054*
C21	−0.48207 (10)	0.4656 (3)	0.03454 (18)	0.0202 (6)
C22	−0.48636 (12)	0.4484 (3)	0.11064 (19)	0.0298 (7)
H22	−0.5125	0.4795	0.1195	0.036*
C23	−0.45174 (12)	0.3851 (3)	0.1734 (2)	0.0314 (7)
H23	−0.4554	0.3759	0.2240	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tm1	0.01177 (6)	0.00666 (6)	0.00715 (6)	−0.00174 (4)	0.00402 (4)	−0.00005 (4)
S1	0.0152 (3)	0.0097 (3)	0.0125 (3)	0.0029 (2)	0.0032 (3)	0.0024 (2)
O1	0.0225 (10)	0.0086 (8)	0.0097 (8)	0.0019 (7)	0.0068 (8)	0.0010 (6)
O1W	0.052 (3)	0.039 (3)	0.074 (3)	0.000	0.013 (3)	0.000
O2	0.0150 (9)	0.0089 (8)	0.0096 (8)	0.0004 (7)	0.0042 (7)	−0.0020 (6)
O3	0.0209 (10)	0.0109 (9)	0.0101 (8)	0.0057 (7)	0.0066 (8)	0.0017 (7)
O4	0.0256 (11)	0.0096 (8)	0.0137 (9)	0.0032 (7)	0.0125 (8)	0.0015 (7)
O5	0.0254 (18)	0.0087 (10)	0.0195 (12)	−0.0022 (10)	0.0078 (12)	0.0017 (9)
O5A	0.0254 (18)	0.0087 (10)	0.0195 (12)	−0.0022 (10)	0.0078 (12)	0.0017 (9)
O6	0.0160 (11)	0.0489 (15)	0.0367 (13)	0.0119 (10)	0.0124 (10)	0.0240 (11)
O7	0.0336 (13)	0.0349 (12)	0.0250 (11)	0.0184 (10)	0.0196 (10)	0.0206 (9)
O8	0.0122 (9)	0.0132 (9)	0.0107 (8)	−0.0006 (7)	0.0040 (7)	0.0052 (7)
O9	0.0119 (10)	0.0198 (10)	0.0188 (9)	−0.0011 (8)	0.0059 (8)	0.0069 (8)
O10	0.0182 (10)	0.0082 (8)	0.0190 (9)	−0.0006 (7)	0.0075 (8)	0.0013 (7)
O11	0.0215 (11)	0.0149 (9)	0.0105 (8)	−0.0018 (8)	0.0043 (8)	−0.0001 (7)
O12	0.0163 (10)	0.0126 (9)	0.0174 (9)	−0.0008 (7)	0.0086 (8)	−0.0038 (7)
N1	0.0164 (13)	0.0438 (17)	0.0294 (14)	−0.0067 (12)	0.0084 (11)	0.0110 (12)
N2	0.0158 (14)	0.0467 (18)	0.0335 (15)	−0.0049 (12)	0.0040 (12)	0.0193 (13)
N3	0.0192 (14)	0.0219 (13)	0.0286 (13)	−0.0009 (10)	−0.0006 (11)	0.0038 (11)
C1	0.0118 (12)	0.0110 (11)	0.0091 (11)	0.0005 (9)	0.0046 (10)	0.0000 (9)
C2	0.0115 (12)	0.0089 (11)	0.0117 (11)	0.0016 (9)	0.0037 (10)	0.0014 (9)
C3	0.0112 (12)	0.0080 (11)	0.0121 (11)	0.0011 (9)	0.0054 (10)	0.0004 (9)
C4	0.0112 (12)	0.0128 (12)	0.0082 (10)	−0.0005 (9)	0.0039 (10)	−0.0005 (9)
C5	0.0097 (12)	0.0090 (11)	0.0101 (11)	−0.0003 (9)	0.0031 (10)	0.0007 (9)
C6	0.0128 (13)	0.0087 (11)	0.0120 (11)	−0.0008 (9)	0.0059 (10)	−0.0030 (9)
C7	0.0099 (12)	0.0108 (11)	0.0101 (11)	−0.0010 (9)	0.0030 (10)	−0.0010 (9)
C8	0.0123 (12)	0.0104 (11)	0.0113 (11)	−0.0002 (9)	0.0043 (10)	−0.0007 (9)
C9	0.0143 (14)	0.0304 (16)	0.0185 (13)	−0.0020 (12)	0.0031 (12)	0.0070 (11)
C10	0.0185 (16)	0.0294 (16)	0.0319 (16)	−0.0039 (13)	0.0073 (14)	0.0053 (13)
C11	0.0254 (18)	0.0348 (18)	0.0345 (18)	−0.0102 (14)	0.0060 (15)	0.0078 (14)
C12	0.0197 (17)	0.045 (2)	0.044 (2)	0.0053 (15)	0.0143 (16)	0.0161 (16)
C13	0.0233 (17)	0.0302 (17)	0.0417 (19)	0.0004 (13)	0.0147 (15)	0.0097 (14)
C14	0.0136 (14)	0.0272 (15)	0.0197 (13)	−0.0030 (12)	0.0035 (11)	0.0065 (11)
C15	0.0247 (17)	0.0309 (17)	0.0296 (16)	−0.0053 (13)	0.0150 (14)	0.0016 (13)
C16	0.0286 (18)	0.0316 (18)	0.0355 (18)	−0.0104 (14)	0.0118 (15)	0.0031 (14)
C17	0.0153 (15)	0.0441 (19)	0.0227 (15)	0.0016 (14)	0.0080 (13)	0.0069 (13)
C18	0.0166 (15)	0.0307 (17)	0.0260 (15)	−0.0024 (12)	0.0058 (12)	0.0025 (13)
C19	0.0190 (18)	0.063 (3)	0.053 (2)	0.0178 (17)	0.0187 (17)	0.033 (2)
C20	0.0266 (19)	0.070 (3)	0.046 (2)	0.0217 (19)	0.0230 (17)	0.036 (2)
C21	0.0161 (14)	0.0168 (13)	0.0237 (14)	−0.0009 (11)	0.0027 (12)	0.0021 (11)
C22	0.0288 (18)	0.0346 (18)	0.0210 (15)	0.0134 (14)	0.0034 (14)	−0.0041 (13)
C23	0.0343 (19)	0.0344 (18)	0.0198 (14)	0.0104 (15)	0.0034 (14)	−0.0017 (13)

Geometric parameters (Å, º)

Tm1—O8	2.2919 (18)	C1—C6	1.396 (3)
Tm1—O12	2.3124 (18)	C1—C7	1.498 (3)
Tm1—O9	2.314 (2)	C2—C3	1.385 (3)
Tm1—O1	2.3994 (17)	C2—H2	0.9300
Tm1—O10	2.4027 (19)	C3—C4	1.398 (3)
Tm1—O4^i	2.4249 (18)	C3—C8	1.494 (3)
Tm1—O3^i	2.4366 (17)	C4—C5	1.387 (3)
Tm1—O11	2.4517 (19)	C4—H4	0.9300
Tm1—O2	2.5073 (17)	C5—C6	1.397 (3)
S1—O6	1.434 (2)	C6—H6	0.9300
S1—O7	1.451 (2)	C8—Tm1^ii	2.800 (2)
S1—O5	1.473 (2)	C9—C13	1.379 (4)
S1—O5A	1.474 (2)	C9—C10	1.395 (4)
S1—C5	1.781 (2)	C9—C14	1.493 (4)
O1—C7	1.269 (3)	C10—C11	1.386 (5)
O1W—H1W	0.92 (5)	C10—H10A	0.9300
O2—C7	1.263 (3)	C11—H11A	0.9300
O3—C8	1.262 (3)	C12—C13	1.388 (5)
O3—Tm1^ii	2.4366 (17)	C12—H12A	0.9300
O4—C8	1.266 (3)	C13—H13	0.9300
O4—Tm1^ii	2.4249 (18)	C14—C18	1.391 (4)
O8—H8A	0.89 (1)	C14—C15	1.399 (4)
O8—H8B	0.89 (1)	C15—C16	1.384 (4)
O9—H9A	0.89 (3)	C15—H15	0.9300
O9—H9B	0.90 (3)	C16—H16	0.9300
O10—H10B	0.89 (3)	C17—C18	1.384 (4)
O10—H10C	0.89 (1)	C17—H17	0.9300
O11—H11C	0.89 (3)	C18—H18	0.9300
O11—H11B	0.89 (1)	C19—C20	1.382 (5)
O12—H12B	0.89 (3)	C19—H19	0.9300
O12—H12C	0.88 (3)	C20—C21	1.384 (5)
N1—C17	1.331 (4)	C20—H20	0.9300
N1—C16	1.340 (5)	C21—C22	1.387 (4)
N2—C11	1.332 (5)	C21—C21^iii	1.488 (6)
N2—C12	1.336 (5)	C22—C23	1.385 (4)
N3—C19	1.322 (5)	C22—H22	0.9300
N3—C23	1.325 (4)	C23—H23	0.9300
C1—C2	1.391 (3)
O8—Tm1—O12	75.67 (7)	Tm1—O12—H12C	117 (2)
O8—Tm1—O9	136.62 (6)	H12B—O12—H12C	110 (3)
O12—Tm1—O9	75.56 (7)	C17—N1—C16	117.0 (3)
O8—Tm1—O1	82.78 (6)	C11—N2—C12	116.8 (3)
O12—Tm1—O1	128.08 (6)	C19—N3—C23	115.8 (3)
O9—Tm1—O1	90.18 (7)	C2—C1—C6	119.5 (2)
O8—Tm1—O10	72.19 (6)	C2—C1—C7	119.0 (2)
O12—Tm1—O10	137.67 (7)	C6—C1—C7	121.5 (2)
O9—Tm1—O10	146.00 (7)	C3—C2—C1	120.7 (2)
O1—Tm1—O10	74.08 (6)	C3—C2—H2	119.6
O8—Tm1—O4^i	141.33 (6)	C1—C2—H2	119.6
O12—Tm1—O4^i	142.85 (6)	C2—C3—C4	120.0 (2)
O9—Tm1—O4^i	74.53 (7)	C2—C3—C8	118.2 (2)
O1—Tm1—O4^i	73.48 (6)	C4—C3—C8	121.9 (2)
O10—Tm1—O4^i	72.17 (6)	C5—C4—C3	119.3 (2)
O8—Tm1—O3^i	143.25 (6)	C5—C4—H4	120.3
O12—Tm1—O3^i	96.07 (6)	C3—C4—H4	120.3
O9—Tm1—O3^i	71.65 (7)	C4—C5—C6	120.8 (2)
O1—Tm1—O3^i	126.69 (6)	C4—C5—S1	119.38 (18)
O10—Tm1—O3^i	93.56 (6)	C6—C5—S1	119.85 (18)
O4^i—Tm1—O3^i	53.59 (6)	C1—C6—C5	119.5 (2)
O8—Tm1—O11	74.11 (6)	C1—C6—H6	120.2
O12—Tm1—O11	71.68 (7)	C5—C6—H6	120.2
O9—Tm1—O11	124.97 (7)	O2—C7—O1	120.0 (2)
O1—Tm1—O11	144.62 (7)	O2—C7—C1	120.4 (2)
O10—Tm1—O11	73.54 (7)	O1—C7—C1	119.6 (2)
O4^i—Tm1—O11	109.21 (6)	O2—C7—Tm1	62.45 (13)
O3^i—Tm1—O11	69.35 (6)	O1—C7—Tm1	57.58 (12)
O8—Tm1—O2	71.07 (6)	C1—C7—Tm1	176.39 (18)
O12—Tm1—O2	75.27 (6)	O3—C8—O4	120.2 (2)
O9—Tm1—O2	70.66 (6)	O3—C8—C3	120.1 (2)
O1—Tm1—O2	53.03 (6)	O4—C8—C3	119.7 (2)
O10—Tm1—O2	117.76 (6)	O3—C8—Tm1^ii	60.37 (12)
O4^i—Tm1—O2	114.11 (6)	O4—C8—Tm1^ii	59.85 (13)
O3^i—Tm1—O2	142.31 (6)	C3—C8—Tm1^ii	177.03 (18)
O11—Tm1—O2	136.63 (6)	C13—C9—C10	117.2 (3)
O8—Tm1—C8^i	151.96 (7)	C13—C9—C14	121.3 (3)
O12—Tm1—C8^i	120.54 (7)	C10—C9—C14	121.3 (3)
O9—Tm1—C8^i	71.42 (7)	C11—C10—C9	119.0 (3)
O1—Tm1—C8^i	100.20 (7)	C11—C10—H10A	120.5
O10—Tm1—C8^i	81.76 (7)	C9—C10—H10A	120.5
O4^i—Tm1—C8^i	26.84 (6)	N2—C11—C10	123.9 (3)
O3^i—Tm1—C8^i	26.75 (6)	N2—C11—H11A	118.0
O11—Tm1—C8^i	88.92 (7)	C10—C11—H11A	118.0
O2—Tm1—C8^i	132.61 (7)	N2—C12—C13	123.3 (3)
O8—Tm1—C7	74.80 (7)	N2—C12—H12A	118.4
O12—Tm1—C7	101.63 (7)	C13—C12—H12A	118.4
O9—Tm1—C7	80.04 (7)	C9—C13—C12	119.8 (3)
O1—Tm1—C7	26.52 (6)	C9—C13—H13	120.1
O10—Tm1—C7	95.79 (7)	C12—C13—H13	120.1
O4^i—Tm1—C7	94.39 (6)	C18—C14—C15	117.3 (3)
O3^i—Tm1—C7	141.51 (7)	C18—C14—C9	120.9 (3)
O11—Tm1—C7	148.88 (7)	C15—C14—C9	121.6 (3)
O2—Tm1—C7	26.52 (6)	C16—C15—C14	119.3 (3)
C8^i—Tm1—C7	119.00 (7)	C16—C15—H15	120.3
O6—S1—O7	113.93 (14)	C14—C15—H15	120.3
O6—S1—O5	116.66 (19)	N1—C16—C15	123.3 (3)
O7—S1—O5	108.31 (18)	N1—C16—H16	118.4
O6—S1—O5A	91.6 (6)	C15—C16—H16	118.4
O7—S1—O5A	132.0 (5)	N1—C17—C18	124.1 (3)
O6—S1—C5	106.59 (12)	N1—C17—H17	117.9
O7—S1—C5	105.54 (12)	C18—C17—H17	117.9
O5—S1—C5	104.81 (13)	C17—C18—C14	118.9 (3)
O5A—S1—C5	104.7 (4)	C17—C18—H18	120.5
C7—O1—Tm1	95.89 (14)	C14—C18—H18	120.5
C7—O2—Tm1	91.02 (14)	N3—C19—C20	124.9 (3)
C8—O3—Tm1^ii	92.88 (14)	N3—C19—H19	117.6
C8—O4—Tm1^ii	93.30 (15)	C20—C19—H19	117.6
Tm1—O8—H8A	126 (2)	C19—C20—C21	119.3 (3)
Tm1—O8—H8B	129 (2)	C19—C20—H20	120.4
H8A—O8—H8B	103 (3)	C21—C20—H20	120.4
Tm1—O9—H9A	129 (2)	C20—C21—C22	116.2 (3)
Tm1—O9—H9B	125 (2)	C20—C21—C21^iii	121.6 (3)
H9A—O9—H9B	105 (3)	C22—C21—C21^iii	122.2 (3)
Tm1—O10—H10B	118 (2)	C23—C22—C21	120.0 (3)
Tm1—O10—H10C	117 (2)	C23—C22—H22	120.0
H10B—O10—H10C	102 (3)	C21—C22—H22	120.0
Tm1—O11—H11C	116 (2)	N3—C23—C22	123.8 (3)
Tm1—O11—H11B	121 (2)	N3—C23—H23	118.1
H11C—O11—H11B	100 (3)	C22—C23—H23	118.1
Tm1—O12—H12B	121 (2)
O8—Tm1—O1—C7	−70.25 (15)	O10—Tm1—C7—O2	−147.72 (14)
O12—Tm1—O1—C7	−4.86 (18)	O4^i—Tm1—C7—O2	139.79 (15)
O9—Tm1—O1—C7	66.82 (16)	O3^i—Tm1—C7—O2	109.11 (15)
O10—Tm1—O1—C7	−143.72 (16)	O11—Tm1—C7—O2	−80.25 (19)
O4^i—Tm1—O1—C7	140.61 (16)	C8^i—Tm1—C7—O2	128.50 (14)
O3^i—Tm1—O1—C7	133.86 (15)	O8—Tm1—C7—O1	104.63 (16)
O11—Tm1—O1—C7	−119.30 (16)	O12—Tm1—C7—O1	176.10 (15)
O2—Tm1—O1—C7	1.46 (14)	O9—Tm1—C7—O1	−111.04 (16)
C8^i—Tm1—O1—C7	137.97 (15)	O10—Tm1—C7—O1	34.88 (16)
O8—Tm1—O2—C7	93.81 (15)	O4^i—Tm1—C7—O1	−37.60 (16)
O12—Tm1—O2—C7	173.41 (16)	O3^i—Tm1—C7—O1	−68.28 (19)
O9—Tm1—O2—C7	−107.02 (16)	O11—Tm1—C7—O1	102.35 (18)
O1—Tm1—O2—C7	−1.46 (14)	O2—Tm1—C7—O1	−177.4 (3)
O10—Tm1—O2—C7	36.90 (16)	C8^i—Tm1—C7—O1	−48.89 (17)
O4^i—Tm1—O2—C7	−44.85 (16)	Tm1^ii—O3—C8—O4	1.7 (3)
O3^i—Tm1—O2—C7	−105.87 (16)	Tm1^ii—O3—C8—C3	−176.6 (2)
O11—Tm1—O2—C7	132.12 (15)	Tm1^ii—O4—C8—O3	−1.7 (3)
C8^i—Tm1—O2—C7	−68.42 (17)	Tm1^ii—O4—C8—C3	176.6 (2)
C6—C1—C2—C3	2.6 (4)	C2—C3—C8—O3	15.4 (4)
C7—C1—C2—C3	−177.1 (2)	C4—C3—C8—O3	−165.5 (2)
C1—C2—C3—C4	−3.3 (4)	C2—C3—C8—O4	−163.0 (2)
C1—C2—C3—C8	175.8 (2)	C4—C3—C8—O4	16.1 (4)
C2—C3—C4—C5	0.8 (4)	C13—C9—C10—C11	2.9 (5)
C8—C3—C4—C5	−178.3 (2)	C14—C9—C10—C11	−172.2 (3)
C3—C4—C5—C6	2.4 (4)	C12—N2—C11—C10	−0.7 (5)
C3—C4—C5—S1	−177.18 (19)	C9—C10—C11—N2	−1.5 (5)
O6—S1—C5—C4	101.4 (2)	C11—N2—C12—C13	1.4 (5)
O7—S1—C5—C4	−20.1 (2)	C10—C9—C13—C12	−2.3 (5)
O5—S1—C5—C4	−134.3 (3)	C14—C9—C13—C12	172.9 (3)
O5A—S1—C5—C4	−162.4 (6)	N2—C12—C13—C9	0.1 (5)
O6—S1—C5—C6	−78.2 (2)	C13—C9—C14—C18	−151.5 (3)
O7—S1—C5—C6	160.3 (2)	C10—C9—C14—C18	23.4 (4)
O5—S1—C5—C6	46.0 (3)	C13—C9—C14—C15	24.1 (4)
O5A—S1—C5—C6	18.0 (6)	C10—C9—C14—C15	−161.0 (3)
C2—C1—C6—C5	0.6 (4)	C18—C14—C15—C16	1.0 (5)
C7—C1—C6—C5	−179.7 (2)	C9—C14—C15—C16	−174.7 (3)
C4—C5—C6—C1	−3.1 (4)	C17—N1—C16—C15	−1.5 (5)
S1—C5—C6—C1	176.50 (19)	C14—C15—C16—N1	0.7 (5)
Tm1—O2—C7—O1	2.5 (2)	C16—N1—C17—C18	0.5 (5)
Tm1—O2—C7—C1	−177.5 (2)	N1—C17—C18—C14	1.2 (5)
Tm1—O1—C7—O2	−2.7 (3)	C15—C14—C18—C17	−1.9 (4)
Tm1—O1—C7—C1	177.4 (2)	C9—C14—C18—C17	173.9 (3)
C2—C1—C7—O2	175.5 (2)	C23—N3—C19—C20	0.2 (6)
C6—C1—C7—O2	−4.2 (4)	N3—C19—C20—C21	−0.2 (7)
C2—C1—C7—O1	−4.6 (4)	C19—C20—C21—C22	−0.3 (6)
C6—C1—C7—O1	175.8 (2)	C19—C20—C21—C21^iii	179.6 (4)
O8—Tm1—C7—O2	−77.97 (15)	C20—C21—C22—C23	0.8 (5)
O12—Tm1—C7—O2	−6.51 (16)	C21^iii—C21—C22—C23	−179.2 (3)
O9—Tm1—C7—O2	66.36 (15)	C19—N3—C23—C22	0.3 (5)
O1—Tm1—C7—O2	177.4 (3)	C21—C22—C23—N3	−0.8 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O6	0.92 (5)	1.90 (5)	2.785 (3)	161 (5)
O8—H8A···O4^iv	0.89 (1)	1.80 (1)	2.695 (2)	175 (3)
O8—H8B···N2	0.89 (1)	1.84 (1)	2.713 (3)	166 (3)
O9—H9A···N3	0.89 (3)	1.94 (3)	2.811 (3)	167 (3)
O9—H9B···N1^v	0.90 (3)	1.88 (3)	2.764 (3)	168 (3)
O10—H10B···O7^iv	0.89 (3)	2.17 (3)	3.038 (3)	166 (3)
O10—H10C···O2^vi	0.89 (1)	1.85 (1)	2.730 (2)	172 (3)
O11—H11B···O5^vi	0.89 (1)	2.07 (1)	2.954 (3)	173 (3)
O11—H11B···O5A^vi	0.89 (1)	2.12 (2)	2.974 (7)	161 (3)
O11—H11C···O3^vii	0.89 (3)	2.13 (3)	3.001 (3)	169 (3)
O12—H12B···O5^viii	0.89 (3)	1.87 (2)	2.723 (4)	161 (3)
O12—H12C···O1^vii	0.88 (3)	1.99 (2)	2.839 (3)	161 (3)

Symmetry codes: (iv) −x−1/2, −y+1/2, −z; (v) x−1/2, y−1/2, z; (vi) −x−1/2, y−1/2, −z+1/2; (vii) −x−1/2, y+1/2, −z+1/2; (viii) x, −y+1, z+1/2.