Fe^III in a low-spin state in caesium bis­[3-ethoxysalicylaldehyde 4-methyl­thiosemicarbazonato(2-)-[kappa]³O²,N¹,S]ferrate(III) methanol monosolvate

The synthesis and crystal structure (at 100 K) of the title compound, Cs[Fe(C₁₁H₁₃N₃O₂S₂)₂]·CH₃OH, is reported. The asymmetric unit consists of an octa­hedral [Fe^III(L)₂]^- fragment, where L^2- is 3-eth­oxysalicyl­aldehyde 4-methyl­thio­semi­carbazonate(2-) {systematic name: [2-(3-ethoxy-2-oxido­benzyli­dene)hy­dra­zin-1-ylidene](methyl­amino)methane­thiol­ate}, a caesium cation and a methanol solvent mol­ecule. Each L^2- ligand binds through the thiol­ate S, the imine N and the phenolate O atoms as donors, resulting in an Fe^IIIS₂N₂O₂ chromophore. The O,N,S-coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The Fe^III cation is in the low-spin state at 100 K.

S1. Introduction

Transition metal fragments displaying switching behaviour are appealing materials, which may be used in a functional way in research and technology (Létard et al., 2004; Gütlich et al., 2004; Gütlich & Goodwin, 2004; van Koningsbruggen et al., 2004). It is now established that some molecular species containing transition metal ions may exhibit a crossover between states having different magnetic moments. Among these, iron(III) occupies a unique position in the development of the spin crossover area since it was with iron(III) tris­(di­thio­carbamates) that the temperature-induced phenomenon was first discovered (Cambi & Szegö, 1931, 1933). The magnetic inter­conversion between the low-spin (S = 1/2) and high-spin (S = 5/2) states in Fe^III systems has now been found to be triggered by a change in temperature or pressure or by light irradiation (Hayami et al., 2000, 2009; van Koningsbruggen et al., 2004).

The generation of Fe^III spin crossover behaviour has been demonstrated for a variety of ligand systems (van Koningsbruggen et al., 2004). Among these, particular inter­est has been focused on Fe^III entities containing two tridentate O,N,S-thio­semicarbazonate ligands, which exhibit a thermal spin transition (Zelentsov et al., 1973; Ryabova et al., 1978, 1982; Ryabova, Ponomarev, Zelentsov & Atovmyan, 1981; Ryabova, Ponomarev, Zelentsov, Shipilov, & Atovmyan, 1981; Floquet et al., 2003, 2006, 2009; Li et al., 2013). In our research we first focused on using derivatives of pyridoxal-4-R-thio­semicarbazone for generating Fe^III spin crossover, resulting in the o­cta­hedral Fe^IIIS₂N₂O₂ entity [Fe^III(HL)(L)].2H₂O, where HL^- and L^2- are the mono- and dianionic forms of pyridoxal-4-methyl-thio­semicarbazone, respectively (Yemeli Tido et al., 2008). The crystal structure of this compound has been determined at 100 K and, from the values of the geometric parameters, it could be inferred that the Fe^III cation is in the low-spin state. Temperature-dependent magnetic susceptibility measurements (5–300 K) showed that this spin state is retained over this temperature range. Complete dehydration of the compound results in an Fe^III high-spin material (Yemeli Tido et al., 2008). Furthermore, it appeared that varying the pH during the synthesis of the Fe^III entities leads to the formation of Fe^III compounds differing in the degree of deprotonation of the ligand (Yemeli Tido, 2010). In addition, we have identified a photo-induced spin transition through light-induced excited spin-state trapping (LIESST) of Fe^III in [Fe^III(HL)(L)].xH₂O, where HL^- = 5-chloro-salicyl­aldehyde-thio­semicarbazone(-1) and L^2- = 5-chloro-salicyl­aldehyde-thio­semicarbazonato(-2) (x = 1), or HL^- = 5-bromo-salicyl­aldehyde-thio­semicarbazone(-1) and L^2- = 5-bromo-salicyl­aldehyde-thio­semicarbazonato(-2) (x = 1/2) (Yemeli Tido, 2010). Here, we report the title novel Fe^III compound, Cs[Fe(C₁₁H₁₃N₃O₂S₂)₂].CH₃OH, (I), containing two dianionic tridentate 3-eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazonate(-2) ligands, and the determination of its structure at 100 K. [Please provide a proper scheme showing the full structure of the compound, including the Cs⁺ cation and solvent molecule.]

S2. Experimental

S2.1. Synthesis and crystallization

FeCl₃.6H₂O (1.0 mmol, 0.27 g) was dissolved in methanol (5 ml). 3-Eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazone (1.0 mmol, 0.25 g) was dissolved in methanol (30 ml) with the addition of CsOH.H₂O (4.0 mmol, 0.67 g). To this mixture, the methano­lic Fe^III salt solution was added with constant stirring. The resulting dark-green solution was stirred and heated to 353 K for approximately 10 min. The solution was then allowed to stand at room temperature until crystals were formed. The dark-green microcrystals of (I) were isolated by filtration and dried.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms on the secondary amine atoms N13 and N23 were located in difference Fourier maps and refined with restrained N—H distances and with U_iso(H) = 1.2U_eq(N). The H atom attached to atom O3 of the methanol molecule was located in a difference Fourier map and refined freely, with U_iso(H) = 1.5U_eq(O). The remaining H atoms were included in the refinement in calculated positions and treated as riding on their parent atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C), C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C), and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methine (-CH═), methyl­ene (–CH₂–) and methyl (–CH₃) H atoms, respectively.

The eth­oxy group of one of the ligands shows positional disorder. Two different sets of positions for the methyl and methyl­ene C atoms were identified in the difference Fourier synthesis, i.e. C111 and C110, and C113 and C112, respectively, which were refined with inversely proportional occupancy factors (0.55 and 0.45). The residual density on a difference Fourier map included a quadrilateral of peaks near Cs of height 1.21–1.84 e Å^-3. Unreasonably close contacts to some ligand atoms, which persisted after refinement, ruled out an attribution of these peaks to disorder of the Cs site. Twinning was also considered and rejected: three possible twin laws were provided by ROTAX (Cooper et al., 2002), but refinement in SHELXL97 (Sheldrick, 2008) led to a negligible scale factor for each such twin component. Therefore the peaks, which represent a small fraction of the 54 electrons in the Cs⁺ cation, are assumed to arise from limitations of the data.

S3. Results and discussion

In solution the free ligand, 3-eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazone (H₂L), exists in two tautomeric forms, i.e. the thione and the thiol forms, as illustrated in Scheme 2. Consequently, in Fe^III compounds the ligand may be present in either of the possible tautomers, and may be neutral, anionic or dianionic. Referring to the thiol tautomer, neutral 3-eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazone (H₂L) has H atoms located on the phenol O atom and the thiol S atom. The first deprotonation step involving the phenol group results in the formation of 3-eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazone(-1) (abbreviated as HL^-). Subsequent deprotonation yields 3-eth­oxy-salicyl­aldehyde-methyl­thio­semicarbazonato(-2) (abbreviated as L^2-).

The structure of (I) (Fig. 1) was determined at 100 K. It crystallizes in the triclinic system in space group P1. The asymmetric unit consists of one formula unit, Cs[Fe(L)₂].CH₃OH, with no atom on a special position. The Fe^III cation is coordinated by two dianionic tridentate O,N,S-thio­semicarbazonate ligands, displaying a distorted o­cta­hedral Fe^IIIS₂N₂O₂ geometry. Selected geometric parameters are listed in Table 2.

The donor atoms of the ligands are situated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. These features are corroborated by the bond angles involving the Fe1 atom and the donor atoms (Table 2).

The bond distances involving the Fe1 atom and the donor atoms (Table 2) suggest that (I) contains low-spin Fe^III at 100 K. Typical distances for Fe—S, Fe—O and Fe—N bonds are 2.23–2.31, 1.93–1.95 and 1.88–1.96 Å, respectively, for low-spin Fe^III compounds of this family, and 2.40–2.44, 1.96–1.99 and 2.05–2.15 Å, respectively, for the corresponding high-spin Fe^III compounds (van Koningsbruggen et al., 2004). It is noteworthy that the Fe—O distances are both shorter than the typical values quoted for low-spin Fe^III. Two reasons may be invoked for this occurrence. Firstly, the low-spin Fe—O reference values are mainly taken from X-ray crystal structures determined at temperatures higher than that at which the structure of (I) was determined (100 K), hence it may be anti­cipated that the range of actual low-spin Fe—O distances at 100 K will be slightly shorter than the cited values. Secondly, it is significant to note in this respect that the Fe—O distances seem to be less sensitive to a change in Fe^III spin state than the Fe—N and Fe—S distances, which may be related to the π-acceptor capability of the N and S donor atoms opposed to the π-donor capability of the O donor atoms. This is of particular significance when Fe^III is in the low-spin state, as increased back-bonding will lead to comparatively more pronounced shortening of the Fe—N and Fe—S bonds than of the Fe—O bonds.

The tridentate ligands in (I) are coordinated to the Fe^III cation by the thiol­ate S, phenolate O and imine N atoms, forming six- and five-membered chelate rings. As might be expected, the five-membered chelate ring involves a significantly less restricted bite angle [O11—Fe1—N11 = 94.37 (19)° and O21—Fe1—N21 = 93.7 (2)°] than the six-membered chelate ring [S11—Fe1—N11 = 85.55 (15)° and S21—Fe1—N21 = 84.71 (16)°]. Further stabilisation arises from the near alternation of single and double bonds in the different electronic forms, allowing a high degree of π-electron delocalisation throughout both of the chelate rings. H atoms could not be located on the phenolate O and thiol­ate S atoms, which implies that both ligands are in the dianionic form. This is concomitant with the presence of a trivalent iron ion together with a monovalent caesium ion. Ryabova, Ponomarev, Zelentsov & Atovmyan (1981) reported the related compound Cs[Fe(L)₂] [where L^2- = salicyl­aldehyde-thio­semicarbazonato(-2)], although this contains high-spin Fe^III.

The binding of the twofold deprotonated ligand of (I) to the Fe^III cation involves electron delocalisation within the chelate ring, which is evident from the geometric parameters. The C18—S11 bond distance of 1.742 (7) Å and C28—S21 bond distance of 1.759 (6) Å suggest partial electron delocalisation of these bonds. This corresponds well with the C—S bond distance of 1.750 (6) Å for the low-spin Fe^III compound NH₄[Fe(L)₂] [where L^2- = 5-chloro-salicyl­aldehyde-thio­semicarbazonato(-2)] at 135 K (Ryabova et al., 1978). Similarly, a bond order larger than 1 can be inferred for the C—N bond involving the deprotonated hydrazinic N atom. The bond distances for the C17—N11 and C27—N21 separations in (I) are 1.302 (7) and 1.291 (8) Å, respectively, which correlates with the value reported by Ryabova et al. (1978), i.e. a C—N bond distance of 1.265 (8) Å for NH₄[Fe(L)₂] at 135 K. Moreover, for (I) the N—N bond distances for N11—N12 and N21—N22 are 1.398 (7) and 1.406 (7) Å, respectively, indicating some electron delocalisation.

The hydrogen-bonding inter­actions of (I) are listed in Table 3 and displayed in Fig. 2. N13—H13···S11(-x + 1, -y + 1, -z + 1) inter­actions paired about the inversion centre at (1/2, 1/2, 1/2) create R₂²(8) rings (Bernstein et al., 1995), as do N23—H23···S21(-x, -y + 1, -z + 1) contacts about (0, 1/2, 1/2). In this manner, successive Fe^III entities are linked in the x direction. Atom O3 of the CH₃OH solvate forms an O3—H3···N12 contact with hydrazinic atom N12. In turn, hydrazinic atom N12 is bonded to imine atom N11, which is coordinated to the Fe^III cation centre. However, the Fe1—N11 bond length [1.933 (5) Å] is virtually identical to the Fe1—N21 bond length [1.939 (5) Å] involving the other ligand, which is devoid of hydrogen-bonding inter­actions.

This study has focused on the synthesis and characterisation of (I) and it has shown that the Fe^III cation is in the low-spin state in this compound at 100 K. We are currently in the process of further investigating new members of this Fe^III bis­(ligand) system, while tuning the spin state of Fe^III by varying the degree of deprotonation of the ligand, as well as varying the R- and R'-substituents of the R-salicyl­aldehyde-R'-thio­semicarbazone ligand.

Related literature

For related literature, see: Bernstein et al. (1995); Cambi & Szegö (1931, 1933); Cooper et al. (2002); Floquet et al. (2003, 2006, 2009); Gütlich & Goodwin (2004); Gütlich, van Koningsbruggen & Renz (2004); Hayami et al. (2000, 2009); Koningsbruggen, Maeda & Oshio (2004); Létard et al. (2004); Li et al. (2013); Ryabova et al. (1978, 1982); Ryabova, Ponomarev, Zelentsov & Atovmyan (1981); Ryabova, Ponomarev, Zelentsov, Shipilov & Atovmyan (1981); Sheldrick (2008); Yemeli (2010); Yemeli Tido, Alberda van Ekenstein, Meetsma & van Koningsbruggen (2008); Zelentsov et al. (1973).

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2013); cell refinement: CrystalClear-SM Expert (Rigaku, 2013); data reduction: CrystalClear-SM Expert (Rigaku, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

Fig. 1. The molecular structure and atom-numbering scheme for (I). The Cs+ cation, CH₃OH molecule and an alternative orientation for C110–C111 have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. A projection showing the unit cell of (I). An alternative orientation for C110–C111 has been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds [OK?] [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y + 1, -z + 1; (iii) 1 - x, 1 - y, 1 - z; (iv) -x, 1 - y, 1 - z.]

Caesium bis{[2-(3-ethoxy-2-oxidobenzylidene)hydrazin-1-ylidene](methylamino)methanethiolato-κ²O²,N¹,S}ferrate(III) methanol monosolvate

Crystal data

Cs[Fe(C11H13N3O2S)2]·CH4O	Z = 2
Mr = 723.40	F(000) = 726
Triclinic, P1	Dx = 1.754 Mg m^−3
a = 8.486 (3) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.078 (3) Å	Cell parameters from 2733 reflections
c = 19.875 (7) Å	θ = 2.5–25.0°
α = 100.629 (5)°	µ = 2.06 mm^−1
β = 91.549 (5)°	T = 100 K
γ = 113.674 (5)°	Plate, green
V = 1369.5 (8) Å^3	0.04 × 0.02 × 0.01 mm

Data collection

Rigaku AFC12 four-circle κ diffractometer	4844 independent reflections
Radiation source: Rotating anode, Rotating anode	3414 reflections with I > 2σ(I)
Confocal mirrors, VHF Varimax monochromator	Rint = 0.082
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.1°, θmin = 2.5°
profile data from ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2013)	k = −10→10
Tmin = 0.711, Tmax = 1.000	l = −23→22
15188 measured reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.0635P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max < 0.001
4844 reflections	Δρmax = 1.84 e Å^−3
377 parameters	Δρmin = −0.62 e Å^−3
5 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs1	0.57891 (5)	0.28483 (5)	0.26270 (2)	0.03559 (16)
Fe1	0.08110 (11)	0.30324 (9)	0.31166 (5)	0.0266 (2)
S11	0.3264 (2)	0.44993 (18)	0.38549 (9)	0.0319 (4)
O11	−0.1195 (5)	0.1797 (4)	0.2469 (2)	0.0282 (10)
O12	−0.3529 (7)	0.0646 (6)	0.1372 (3)	0.0448 (13)
N11	0.1004 (6)	0.1112 (6)	0.3326 (3)	0.0268 (12)
N12	0.2322 (6)	0.1243 (6)	0.3803 (3)	0.0272 (12)
N13	0.4747 (7)	0.3043 (6)	0.4520 (3)	0.0317 (13)
H13	0.556 (6)	0.403 (4)	0.466 (3)	0.038*
C11	−0.1382 (8)	−0.0921 (7)	0.2500 (3)	0.0281 (14)
C12	−0.1862 (8)	0.0187 (7)	0.2223 (3)	0.0293 (15)
C13	−0.3131 (8)	−0.0478 (7)	0.1652 (4)	0.0372 (17)
C14	−0.3949 (8)	−0.2141 (8)	0.1380 (4)	0.0393 (17)
H14	−0.4804	−0.2547	0.0994	0.047*
C15	−0.3516 (9)	−0.3233 (8)	0.1675 (4)	0.0402 (18)
H15	−0.4101	−0.4386	0.1500	0.048*
C16	−0.2252 (8)	−0.2630 (7)	0.2213 (4)	0.0349 (16)
H16	−0.1942	−0.3376	0.2403	0.042*
C17	0.0002 (8)	−0.0410 (7)	0.3039 (3)	0.0290 (15)
H17	0.0204	−0.1248	0.3200	0.035*
C18	0.3411 (8)	0.2772 (7)	0.4062 (3)	0.0302 (15)
C19	0.5001 (9)	0.1727 (8)	0.4766 (4)	0.0415 (18)
H19A	0.5236	0.1023	0.4382	0.062*
H19B	0.3954	0.1068	0.4954	0.062*
H19C	0.5984	0.2206	0.5127	0.062*
C110	−0.3870 (19)	0.0423 (14)	0.0647 (6)	0.047 (5)	0.552 (17)
H11A	−0.5119	−0.0267	0.0506	0.056*	0.552 (17)
H11B	−0.3219	−0.0177	0.0413	0.056*	0.552 (17)
C111	−0.338 (2)	0.2021 (19)	0.0411 (10)	0.043 (4)	0.552 (17)
H11C	−0.3722	0.1788	−0.0086	0.065*	0.552 (17)
H11D	−0.2126	0.2665	0.0508	0.065*	0.552 (17)
H11E	−0.3977	0.2648	0.0657	0.065*	0.552 (17)
C112	−0.2503 (16)	0.1287 (14)	0.0901 (7)	0.023 (4)	0.448 (17)
H11F	−0.2773	0.0453	0.0466	0.027*	0.448 (17)
H11G	−0.1270	0.1659	0.1072	0.027*	0.448 (17)
C113	−0.286 (2)	0.2708 (18)	0.0784 (10)	0.029 (4)	0.448 (17)
H11H	−0.2307	0.3088	0.0385	0.043*	0.448 (17)
H11I	−0.2388	0.3606	0.1193	0.043*	0.448 (17)
H11J	−0.4110	0.2364	0.0699	0.043*	0.448 (17)
S21	−0.0784 (2)	0.32882 (18)	0.39898 (9)	0.0316 (4)
O21	0.2202 (5)	0.2897 (5)	0.2382 (2)	0.0290 (10)
O22	0.3242 (5)	0.1540 (5)	0.1222 (2)	0.0336 (11)
N21	0.0586 (6)	0.4957 (5)	0.2920 (3)	0.0265 (12)
N22	0.0018 (7)	0.5926 (6)	0.3401 (3)	0.0306 (13)
N23	−0.1254 (7)	0.6013 (6)	0.4403 (3)	0.0352 (13)
H23	−0.128 (9)	0.582 (8)	0.4817 (17)	0.042*
C21	0.1506 (8)	0.4674 (7)	0.1771 (3)	0.0306 (15)
C22	0.2078 (7)	0.3420 (7)	0.1814 (3)	0.0291 (15)
C23	0.2581 (8)	0.2713 (7)	0.1211 (3)	0.0299 (15)
C24	0.2536 (8)	0.3237 (8)	0.0606 (4)	0.0385 (17)
H24	0.2869	0.2734	0.0205	0.046*
C25	0.2016 (9)	0.4479 (7)	0.0573 (4)	0.0381 (17)
H25	0.2020	0.4852	0.0157	0.046*
C26	0.1487 (8)	0.5181 (7)	0.1152 (4)	0.0365 (17)
H26	0.1106	0.6022	0.1126	0.044*
C27	0.0929 (8)	0.5449 (7)	0.2350 (4)	0.0317 (16)
H27	0.0786	0.6416	0.2310	0.038*
C28	−0.0599 (8)	0.5248 (7)	0.3910 (4)	0.0313 (15)
C29	−0.1007 (10)	0.7715 (7)	0.4438 (4)	0.0411 (18)
H29A	−0.1756	0.7753	0.4064	0.062*
H29B	0.0206	0.8386	0.4391	0.062*
H29C	−0.1303	0.8148	0.4882	0.062*
C210	0.2056 (9)	−0.0007 (7)	0.1370 (4)	0.0395 (17)
H21A	0.1604	0.0214	0.1814	0.047*
H21B	0.2691	−0.0696	0.1418	0.047*
C211	0.0565 (9)	−0.0936 (8)	0.0815 (4)	0.047 (2)
H21C	−0.0028	−0.0235	0.0747	0.071*
H21D	−0.0249	−0.1927	0.0951	0.071*
H21E	0.0997	−0.1252	0.0384	0.071*
O3	0.3902 (7)	−0.0555 (6)	0.2962 (3)	0.0464 (13)
H3	0.337 (10)	−0.021 (10)	0.326 (3)	0.070*
C31	0.4608 (10)	−0.1567 (8)	0.3210 (4)	0.0467 (19)
H31A	0.4769	−0.2306	0.2819	0.070*
H31B	0.3813	−0.2219	0.3499	0.070*
H31C	0.5728	−0.0869	0.3483	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0301 (2)	0.0342 (2)	0.0458 (3)	0.01752 (17)	0.00371 (19)	0.00666 (17)
Fe1	0.0238 (5)	0.0223 (4)	0.0343 (6)	0.0105 (4)	0.0035 (4)	0.0056 (4)
S11	0.0298 (9)	0.0232 (7)	0.0413 (11)	0.0104 (6)	0.0003 (8)	0.0057 (7)
O11	0.022 (2)	0.023 (2)	0.039 (3)	0.0092 (17)	−0.0014 (19)	0.0060 (18)
O12	0.056 (3)	0.047 (3)	0.040 (3)	0.036 (3)	−0.007 (3)	−0.002 (2)
N11	0.021 (3)	0.026 (3)	0.034 (3)	0.011 (2)	0.002 (2)	0.006 (2)
N12	0.025 (3)	0.029 (3)	0.027 (3)	0.012 (2)	−0.001 (2)	0.004 (2)
N13	0.027 (3)	0.027 (3)	0.039 (4)	0.010 (2)	−0.004 (3)	0.006 (2)
C11	0.026 (3)	0.031 (3)	0.028 (4)	0.013 (3)	0.006 (3)	0.004 (3)
C12	0.019 (3)	0.027 (3)	0.041 (4)	0.007 (3)	0.008 (3)	0.009 (3)
C13	0.031 (4)	0.030 (3)	0.054 (5)	0.017 (3)	0.010 (3)	0.006 (3)
C14	0.026 (4)	0.035 (4)	0.053 (5)	0.013 (3)	−0.003 (3)	0.001 (3)
C15	0.033 (4)	0.025 (3)	0.058 (5)	0.010 (3)	0.004 (4)	0.003 (3)
C16	0.031 (4)	0.023 (3)	0.055 (5)	0.015 (3)	0.011 (3)	0.010 (3)
C17	0.031 (4)	0.027 (3)	0.035 (4)	0.016 (3)	0.008 (3)	0.011 (3)
C18	0.029 (4)	0.032 (3)	0.031 (4)	0.015 (3)	0.009 (3)	0.003 (3)
C19	0.044 (4)	0.037 (4)	0.046 (5)	0.022 (3)	−0.001 (4)	0.006 (3)
C110	0.044 (10)	0.032 (7)	0.064 (11)	0.019 (7)	0.002 (8)	0.002 (6)
C111	0.046 (10)	0.045 (9)	0.045 (11)	0.020 (8)	0.017 (8)	0.017 (7)
C112	0.009 (8)	0.018 (6)	0.034 (9)	0.000 (6)	0.000 (6)	0.004 (6)
C113	0.030 (9)	0.026 (8)	0.032 (11)	0.013 (7)	0.002 (8)	0.007 (7)
S21	0.0303 (9)	0.0273 (8)	0.0402 (11)	0.0139 (7)	0.0072 (8)	0.0094 (7)
O21	0.023 (2)	0.031 (2)	0.034 (3)	0.0133 (18)	0.002 (2)	0.0055 (19)
O22	0.025 (2)	0.037 (2)	0.039 (3)	0.0149 (19)	0.007 (2)	0.004 (2)
N21	0.025 (3)	0.022 (2)	0.029 (3)	0.009 (2)	0.001 (2)	0.002 (2)
N22	0.030 (3)	0.026 (3)	0.038 (3)	0.013 (2)	0.007 (3)	0.008 (2)
N23	0.039 (3)	0.031 (3)	0.045 (4)	0.021 (2)	0.013 (3)	0.012 (3)
C21	0.026 (3)	0.022 (3)	0.037 (4)	0.002 (3)	0.006 (3)	0.008 (3)
C22	0.017 (3)	0.027 (3)	0.035 (4)	0.001 (2)	0.004 (3)	0.006 (3)
C23	0.021 (3)	0.028 (3)	0.032 (4)	0.004 (3)	0.000 (3)	0.002 (3)
C24	0.027 (4)	0.035 (4)	0.043 (5)	0.006 (3)	0.005 (3)	0.001 (3)
C25	0.042 (4)	0.031 (3)	0.032 (4)	0.004 (3)	0.010 (3)	0.010 (3)
C26	0.035 (4)	0.021 (3)	0.047 (5)	0.003 (3)	0.007 (3)	0.010 (3)
C27	0.029 (4)	0.024 (3)	0.044 (5)	0.012 (3)	0.001 (3)	0.011 (3)
C28	0.031 (4)	0.028 (3)	0.035 (4)	0.012 (3)	0.002 (3)	0.007 (3)
C29	0.055 (5)	0.029 (3)	0.048 (5)	0.024 (3)	0.015 (4)	0.011 (3)
C210	0.036 (4)	0.028 (3)	0.051 (5)	0.012 (3)	0.004 (3)	0.003 (3)
C211	0.035 (4)	0.041 (4)	0.061 (6)	0.010 (3)	0.010 (4)	0.012 (3)
O3	0.048 (3)	0.043 (3)	0.057 (4)	0.025 (2)	0.014 (3)	0.016 (2)
C31	0.042 (4)	0.037 (4)	0.067 (6)	0.021 (3)	0.011 (4)	0.012 (4)

Geometric parameters (Å, º)

Cs1—O11^i	3.075 (4)	C110—C111	1.508 (15)
Cs1—O12^i	3.117 (5)	C111—H11C	0.9800
Cs1—C12^i	3.701 (6)	C111—H11D	0.9800
Cs1—C13^i	3.725 (6)	C111—H11E	0.9800
Cs1—C18	3.533 (6)	C112—H11F	0.9900
Cs1—O21	3.089 (4)	C112—H11G	0.9900
Cs1—O22	3.205 (5)	C112—C113	1.492 (15)
Cs1—N21^i	3.712 (5)	C113—Cs1^ii	3.862 (19)
Cs1—N22^i	3.622 (5)	C113—H11H	0.9800
Cs1—C28^i	3.578 (6)	C113—H11I	0.9800
Cs1—C210	3.686 (7)	C113—H11J	0.9800
Cs1—O3	3.065 (5)	S21—Cs1^ii	3.767 (2)
Cs1—H3	3.22 (8)	S21—C28	1.759 (6)
Fe1—Cs1^ii	4.2755 (18)	O21—C22	1.320 (8)
Fe1—S11	2.2686 (19)	O22—C23	1.391 (8)
Fe1—O11	1.904 (4)	O22—C210	1.451 (7)
Fe1—N11	1.933 (5)	N21—Cs1^ii	3.712 (5)
Fe1—S21	2.265 (2)	N21—N22	1.406 (7)
Fe1—O21	1.918 (4)	N21—C27	1.291 (8)
Fe1—N21	1.939 (5)	N22—Cs1^ii	3.622 (5)
S11—C18	1.742 (7)	N22—C28	1.293 (8)
O11—Cs1^ii	3.075 (4)	N23—H23	0.87 (2)
O11—C12	1.324 (7)	N23—C28	1.357 (8)
O12—Cs1^ii	3.117 (5)	N23—C29	1.462 (8)
O12—C13	1.393 (8)	C21—C22	1.420 (9)
O12—C110	1.423 (13)	C21—C26	1.392 (9)
O12—C112	1.346 (12)	C21—C27	1.439 (9)
N11—N12	1.398 (7)	C22—C23	1.412 (9)
N11—C17	1.302 (7)	C23—C24	1.378 (10)
N12—C18	1.314 (7)	C24—H24	0.9500
N13—H13	0.87 (2)	C24—C25	1.377 (10)
N13—C18	1.347 (8)	C25—H25	0.9500
N13—C19	1.459 (8)	C25—C26	1.385 (9)
C11—C12	1.414 (9)	C26—H26	0.9500
C11—C16	1.417 (8)	C27—H27	0.9500
C11—C17	1.433 (9)	C28—Cs1^ii	3.578 (6)
C12—Cs1^ii	3.701 (6)	C29—H29A	0.9800
C12—C13	1.405 (9)	C29—H29B	0.9800
C13—Cs1^ii	3.725 (6)	C29—H29C	0.9800
C13—C14	1.374 (9)	C210—H21A	0.9900
C14—H14	0.9500	C210—H21B	0.9900
C14—C15	1.398 (10)	C210—C211	1.501 (10)
C15—H15	0.9500	C211—H21C	0.9800
C15—C16	1.358 (10)	C211—H21D	0.9800
C16—H16	0.9500	C211—H21E	0.9800
C17—H17	0.9500	O3—H3	0.85 (2)
C19—H19A	0.9800	O3—C31	1.428 (9)
C19—H19B	0.9800	C31—H31A	0.9800
C19—H19C	0.9800	C31—H31B	0.9800
C110—H11A	0.9900	C31—H31C	0.9800
C110—H11B	0.9900
O11^i—Cs1—O12^i	50.71 (12)	C15—C14—H14	120.1
O11^i—Cs1—C12^i	19.92 (11)	C14—C15—H15	120.3
O11^i—Cs1—C13^i	38.88 (13)	C16—C15—C14	119.4 (6)
O11^i—Cs1—C18	126.17 (14)	C16—C15—H15	120.3
O11^i—Cs1—O21	160.79 (10)	C11—C16—H16	119.0
O11^i—Cs1—O22	110.91 (11)	C15—C16—C11	122.0 (6)
O11^i—Cs1—N21^i	44.01 (10)	C15—C16—H16	119.0
O11^i—Cs1—N22^i	63.92 (11)	N11—C17—C11	125.3 (6)
O11^i—Cs1—C28^i	66.84 (13)	N11—C17—H17	117.3
O11^i—Cs1—C210	109.83 (13)	C11—C17—H17	117.3
O11^i—Cs1—H3	95.6 (11)	S11—C18—Cs1	84.4 (2)
O12^i—Cs1—C12^i	39.63 (14)	N12—C18—Cs1	91.4 (4)
O12^i—Cs1—C13^i	21.20 (15)	N12—C18—S11	124.8 (5)
O12^i—Cs1—C18	143.96 (14)	N12—C18—N13	118.3 (6)
O12^i—Cs1—O22	60.30 (12)	N13—C18—Cs1	94.4 (4)
O12^i—Cs1—N21^i	83.74 (12)	N13—C18—S11	116.9 (4)
O12^i—Cs1—N22^i	105.65 (13)	N13—C19—H19A	109.5
O12^i—Cs1—C28^i	115.91 (14)	N13—C19—H19B	109.5
O12^i—Cs1—C210	62.24 (15)	N13—C19—H19C	109.5
O12^i—Cs1—H3	94.3 (7)	H19A—C19—H19B	109.5
C12^i—Cs1—C13^i	21.81 (15)	H19A—C19—H19C	109.5
C12^i—Cs1—N21^i	63.92 (12)	H19B—C19—H19C	109.5
C12^i—Cs1—H3	80.9 (9)	O12—C110—H11A	108.9
C13^i—Cs1—H3	79.6 (6)	O12—C110—H11B	108.9
C18—Cs1—C12^i	122.28 (15)	O12—C110—C111	113.2 (10)
C18—Cs1—C13^i	128.55 (15)	H11A—C110—H11B	107.8
C18—Cs1—N21^i	118.74 (13)	C111—C110—H11A	108.9
C18—Cs1—N22^i	100.47 (13)	C111—C110—H11B	108.9
C18—Cs1—C28^i	82.85 (15)	C110—C111—H11C	109.5
C18—Cs1—C210	95.74 (16)	C110—C111—H11D	109.5
C18—Cs1—H3	49.9 (6)	C110—C111—H11E	109.5
O21—Cs1—O12^i	110.99 (12)	H11C—C111—H11D	109.5
O21—Cs1—C12^i	142.14 (12)	H11C—C111—H11E	109.5
O21—Cs1—C13^i	121.97 (13)	H11D—C111—H11E	109.5
O21—Cs1—C18	63.41 (14)	O12—C112—H11F	110.4
O21—Cs1—O22	51.74 (11)	O12—C112—H11G	110.4
O21—Cs1—N21^i	151.27 (10)	O12—C112—C113	106.5 (11)
O21—Cs1—N22^i	134.09 (11)	H11F—C112—H11G	108.6
O21—Cs1—C28^i	132.31 (13)	C113—C112—H11F	110.4
O21—Cs1—C210	50.96 (13)	C113—C112—H11G	110.4
O21—Cs1—H3	78.6 (14)	Cs1^ii—C113—H11H	159.8
O22—Cs1—C12^i	98.06 (13)	Cs1^ii—C113—H11I	50.8
O22—Cs1—C13^i	76.39 (14)	Cs1^ii—C113—H11J	78.0
O22—Cs1—C18	110.36 (13)	C112—C113—Cs1^ii	84.3 (9)
O22—Cs1—N21^i	129.96 (11)	C112—C113—H11H	109.5
O22—Cs1—N22^i	141.63 (12)	C112—C113—H11I	109.5
O22—Cs1—C28^i	162.18 (13)	C112—C113—H11J	109.5
O22—Cs1—C210	22.98 (13)	H11H—C113—H11I	109.5
O22—Cs1—H3	92.3 (16)	H11H—C113—H11J	109.5
N21^i—Cs1—C13^i	80.59 (13)	H11I—C113—H11J	109.5
N21^i—Cs1—H3	126.2 (16)	Fe1—S21—Cs1^ii	86.49 (6)
N22^i—Cs1—C12^i	83.55 (12)	C28—S21—Cs1^ii	70.2 (2)
N22^i—Cs1—C13^i	102.00 (13)	C28—S21—Fe1	94.3 (2)
N22^i—Cs1—N21^i	22.07 (11)	Fe1—O21—Cs1	122.27 (19)
N22^i—Cs1—C210	163.06 (15)	C22—O21—Cs1	110.5 (3)
N22^i—Cs1—H3	125.5 (16)	C22—O21—Fe1	122.8 (4)
C28^i—Cs1—C12^i	83.85 (14)	C23—O22—Cs1	105.1 (3)
C28^i—Cs1—C13^i	105.22 (15)	C23—O22—C210	115.9 (5)
C28^i—Cs1—N21^i	35.96 (13)	C210—O22—Cs1	97.5 (4)
C28^i—Cs1—N22^i	20.68 (13)	Fe1—N21—Cs1^ii	92.97 (16)
C28^i—Cs1—C210	173.95 (15)	N22—N21—Cs1^ii	75.4 (3)
C28^i—Cs1—H3	105.4 (16)	N22—N21—Fe1	121.3 (4)
C210—Cs1—C12^i	92.00 (15)	C27—N21—Cs1^ii	100.8 (4)
C210—Cs1—C13^i	71.05 (16)	C27—N21—Fe1	123.8 (4)
C210—Cs1—N21^i	144.62 (14)	C27—N21—N22	114.9 (5)
C210—Cs1—H3	69.5 (15)	N21—N22—Cs1^ii	82.6 (3)
O3—Cs1—O11^i	83.41 (12)	C28—N22—Cs1^ii	77.8 (4)
O3—Cs1—O12^i	79.58 (14)	C28—N22—N21	113.1 (5)
O3—Cs1—C12^i	67.03 (13)	C28—N23—H23	121 (5)
O3—Cs1—C13^i	64.40 (14)	C28—N23—C29	120.9 (6)
O3—Cs1—C18	64.93 (14)	C29—N23—H23	110 (5)
O3—Cs1—O21	87.47 (13)	C22—C21—C27	122.1 (6)
O3—Cs1—O22	88.26 (13)	C26—C21—C22	119.8 (6)
O3—Cs1—N21^i	120.17 (13)	C26—C21—C27	118.1 (6)
O3—Cs1—N22^i	126.29 (13)	O21—C22—Cs1	50.3 (3)
O3—Cs1—C28^i	108.60 (15)	O21—C22—C21	124.3 (6)
O3—Cs1—C210	65.61 (15)	O21—C22—C23	118.1 (6)
O3—Cs1—H3	15.2 (6)	C21—C22—Cs1	140.5 (4)
S11—Fe1—Cs1^ii	141.53 (5)	C23—C22—Cs1	81.3 (4)
O11—Fe1—Cs1^ii	40.12 (12)	C23—C22—C21	117.5 (6)
O11—Fe1—S11	177.83 (14)	O22—C23—Cs1	54.3 (3)
O11—Fe1—N11	94.37 (19)	O22—C23—C22	120.9 (6)
O11—Fe1—S21	92.56 (14)	C22—C23—Cs1	77.2 (4)
O11—Fe1—O21	88.49 (18)	C24—C23—Cs1	140.9 (4)
O11—Fe1—N21	85.55 (18)	C24—C23—O22	117.9 (6)
N11—Fe1—Cs1^ii	119.22 (14)	C24—C23—C22	121.1 (6)
N11—Fe1—S11	85.55 (15)	C23—C24—H24	119.6
N11—Fe1—S21	94.17 (16)	C25—C24—C23	120.9 (7)
N11—Fe1—N21	178.9 (2)	C25—C24—H24	119.6
S21—Fe1—Cs1^ii	61.59 (5)	C24—C25—H25	120.2
S21—Fe1—S11	89.61 (7)	C24—C25—C26	119.5 (7)
O21—Fe1—Cs1^ii	118.58 (13)	C26—C25—H25	120.2
O21—Fe1—S11	89.34 (13)	C21—C26—H26	119.5
O21—Fe1—N11	87.4 (2)	C25—C26—C21	121.1 (7)
O21—Fe1—S21	178.01 (13)	C25—C26—H26	119.5
O21—Fe1—N21	93.7 (2)	N21—C27—C21	126.2 (6)
N21—Fe1—Cs1^ii	60.11 (14)	N21—C27—H27	116.9
N21—Fe1—S11	94.57 (15)	C21—C27—H27	116.9
N21—Fe1—S21	84.71 (16)	S21—C28—Cs1^ii	82.2 (2)
Fe1—S11—Cs1	90.32 (6)	N22—C28—Cs1^ii	81.5 (4)
C18—S11—Cs1	68.4 (2)	N22—C28—S21	124.3 (5)
C18—S11—Fe1	94.6 (2)	N22—C28—N23	119.8 (6)
Fe1—O11—Cs1^ii	116.35 (16)	N23—C28—Cs1^ii	104.0 (4)
C12—O11—Cs1^ii	107.8 (3)	N23—C28—S21	115.8 (5)
C12—O11—Fe1	126.1 (4)	N23—C29—H29A	109.5
C13—O12—Cs1^ii	104.8 (4)	N23—C29—H29B	109.5
C13—O12—C110	120.8 (6)	N23—C29—H29C	109.5
C110—O12—Cs1^ii	133.0 (6)	H29A—C29—H29B	109.5
C112—O12—Cs1^ii	122.2 (6)	H29A—C29—H29C	109.5
C112—O12—C13	114.7 (7)	H29B—C29—H29C	109.5
N12—N11—Fe1	121.8 (3)	Cs1—C210—H21A	72.6
C17—N11—Fe1	125.4 (4)	Cs1—C210—H21B	78.0
C17—N11—N12	112.7 (5)	O22—C210—Cs1	59.6 (3)
N11—N12—Cs1	92.7 (3)	O22—C210—H21A	109.2
C18—N12—Cs1	68.4 (3)	O22—C210—H21B	109.2
C18—N12—N11	113.3 (5)	O22—C210—C211	112.1 (6)
C18—N13—H13	120 (5)	H21A—C210—H21B	107.9
C18—N13—C19	123.2 (5)	C211—C210—Cs1	171.0 (5)
C19—N13—H13	116 (5)	C211—C210—H21A	109.2
C12—C11—C16	119.0 (6)	C211—C210—H21B	109.2
C12—C11—C17	123.6 (5)	C210—C211—H21C	109.5
C16—C11—C17	117.4 (6)	C210—C211—H21D	109.5
O11—C12—Cs1^ii	52.3 (3)	C210—C211—H21E	109.5
O11—C12—C11	124.2 (6)	H21C—C211—H21D	109.5
O11—C12—C13	118.4 (6)	H21C—C211—H21E	109.5
C11—C12—Cs1^ii	141.1 (4)	H21D—C211—H21E	109.5
C13—C12—Cs1^ii	80.1 (4)	Cs1—O3—H3	93 (6)
C13—C12—C11	117.4 (5)	C31—O3—Cs1	129.1 (4)
O12—C13—Cs1^ii	54.0 (3)	C31—O3—H3	111 (6)
O12—C13—C12	116.2 (5)	O3—C31—H31A	109.5
C12—C13—Cs1^ii	78.1 (3)	O3—C31—H31B	109.5
C14—C13—Cs1^ii	138.2 (5)	O3—C31—H31C	109.5
C14—C13—O12	121.3 (7)	H31A—C31—H31B	109.5
C14—C13—C12	122.5 (7)	H31A—C31—H31C	109.5
C13—C14—H14	120.1	H31B—C31—H31C	109.5
C13—C14—C15	119.7 (7)
Cs1—S11—C18—N12	−87.8 (5)	C13—O12—C110—C111	−150.5 (9)
Cs1—S11—C18—N13	92.1 (5)	C13—O12—C112—C113	−167.5 (9)
Cs1^ii—O11—C12—C11	−131.7 (5)	C13—C14—C15—C16	−2.1 (11)
Cs1^ii—O11—C12—C13	48.2 (6)	C14—C15—C16—C11	1.7 (10)
Cs1^ii—O12—C13—C12	−50.2 (6)	C16—C11—C12—Cs1^ii	106.4 (7)
Cs1^ii—O12—C13—C14	129.6 (6)	C16—C11—C12—O11	176.8 (6)
Cs1^ii—O12—C110—C111	45.2 (15)	C16—C11—C12—C13	−3.0 (9)
Cs1^ii—O12—C112—C113	−39.0 (12)	C16—C11—C17—N11	175.3 (6)
Cs1—N12—C18—S11	84.1 (5)	C17—N11—N12—Cs1	108.1 (5)
Cs1—N12—C18—N13	−95.8 (5)	C17—N11—N12—C18	175.6 (5)
Cs1^ii—C12—C13—O12	39.4 (5)	C17—C11—C12—Cs1^ii	−76.6 (8)
Cs1^ii—C12—C13—C14	−140.3 (7)	C17—C11—C12—O11	−6.2 (10)
Cs1^ii—C13—C14—C15	−110.5 (8)	C17—C11—C12—C13	174.0 (6)
Cs1^ii—S21—C28—N22	−74.2 (5)	C17—C11—C16—C15	−176.3 (6)
Cs1^ii—S21—C28—N23	101.9 (5)	C19—N13—C18—Cs1	−96.8 (6)
Cs1—O21—C22—C21	−130.3 (5)	C19—N13—C18—S11	177.3 (5)
Cs1—O21—C22—C23	48.3 (6)	C19—N13—C18—N12	−2.8 (9)
Cs1—O22—C23—C22	−41.5 (6)	C110—O12—C13—Cs1^ii	−168.2 (9)
Cs1—O22—C23—C24	134.5 (5)	C110—O12—C13—C12	141.6 (9)
Cs1—O22—C210—C211	176.2 (5)	C110—O12—C13—C14	−38.6 (11)
Cs1^ii—N21—N22—C28	73.3 (5)	C110—O12—C112—C113	82.2 (12)
Cs1^ii—N21—C27—C21	−100.4 (6)	C112—O12—C13—Cs1^ii	136.7 (8)
Cs1^ii—N22—C28—S21	74.5 (5)	C112—O12—C13—C12	86.5 (9)
Cs1^ii—N22—C28—N23	−101.4 (6)	C112—O12—C13—C14	−93.7 (9)
Cs1—C22—C23—O22	33.4 (5)	C112—O12—C110—C111	−53.4 (11)
Cs1—C22—C23—C24	−142.4 (5)	O21—C22—C23—Cs1	−35.6 (4)
Cs1—C23—C24—C25	−108.7 (8)	O21—C22—C23—O22	−2.1 (8)
Fe1—S11—C18—Cs1	88.53 (10)	O21—C22—C23—C24	−178.0 (5)
Fe1—S11—C18—N12	0.8 (6)	O22—C23—C24—C25	−175.3 (5)
Fe1—S11—C18—N13	−179.4 (5)	N21—N22—C28—Cs1^ii	−76.3 (4)
Fe1—O11—C12—Cs1^ii	144.3 (5)	N21—N22—C28—S21	−1.8 (8)
Fe1—O11—C12—C11	12.6 (9)	N21—N22—C28—N23	−177.7 (5)
Fe1—O11—C12—C13	−167.5 (4)	N22—N21—C27—C21	−179.1 (6)
Fe1—N11—N12—Cs1	−70.0 (4)	C21—C22—C23—Cs1	143.2 (5)
Fe1—N11—N12—C18	−2.4 (7)	C21—C22—C23—O22	176.6 (5)
Fe1—N11—C17—C11	2.3 (9)	C21—C22—C23—C24	0.8 (8)
Fe1—S21—C28—Cs1^ii	84.70 (10)	C22—C21—C26—C25	0.1 (9)
Fe1—S21—C28—N22	10.6 (6)	C22—C21—C27—N21	−12.1 (10)
Fe1—S21—C28—N23	−173.4 (5)	C22—C23—C24—C25	0.7 (9)
Fe1—O21—C22—Cs1	156.7 (5)	C23—O22—C210—Cs1	−110.9 (5)
Fe1—O21—C22—C21	26.4 (7)	C23—O22—C210—C211	65.4 (7)
Fe1—O21—C22—C23	−155.0 (4)	C23—C24—C25—C26	−1.7 (9)
Fe1—N21—N22—Cs1^ii	−84.5 (3)	C24—C25—C26—C21	1.3 (9)
Fe1—N21—N22—C28	−11.2 (7)	C26—C21—C22—Cs1	110.3 (7)
Fe1—N21—C27—C21	0.7 (9)	C26—C21—C22—O21	177.5 (5)
O11—C12—C13—Cs1^ii	−36.8 (5)	C26—C21—C22—C23	−1.1 (8)
O11—C12—C13—O12	2.6 (9)	C26—C21—C27—N21	167.6 (6)
O11—C12—C13—C14	−177.1 (6)	C27—N21—N22—Cs1^ii	95.3 (5)
O12—C13—C14—C15	−180.0 (6)	C27—N21—N22—C28	168.6 (5)
O12—C112—C113—Cs1^ii	25.6 (8)	C27—C21—C22—Cs1	−70.0 (8)
N11—N12—C18—Cs1	−83.3 (4)	C27—C21—C22—O21	−2.8 (9)
N11—N12—C18—S11	0.8 (8)	C27—C21—C22—C23	178.6 (5)
N11—N12—C18—N13	−179.1 (5)	C27—C21—C26—C25	−179.6 (6)
N12—N11—C17—C11	−175.7 (5)	C29—N23—C28—Cs1^ii	−98.9 (6)
C11—C12—C13—Cs1^ii	143.1 (5)	C29—N23—C28—S21	173.1 (5)
C11—C12—C13—O12	−177.5 (6)	C29—N23—C28—N22	−10.7 (10)
C11—C12—C13—C14	2.7 (10)	C210—O22—C23—Cs1	106.3 (5)
C12—C11—C16—C15	0.9 (10)	C210—O22—C23—C22	64.9 (7)
C12—C11—C17—N11	−1.8 (10)	C210—O22—C23—C24	−119.2 (6)
C12—C13—C14—C15	−0.2 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···S11^iii	0.87 (2)	2.97 (6)	3.505 (6)	122 (5)
N23—H23···S21^iv	0.87 (2)	2.70 (5)	3.416 (6)	141 (6)
O3—H3···N12	0.85 (2)	2.04 (4)	2.852 (7)	160 (8)

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1.