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• The investigation on the metal-acyl complexes continues to be an active research area in organometa-llic chemistry since these complexes show excellent catalytic activity in many organic transformations^[1-4], and this category of complexes are proposed as the key active intermediates in numerous catalytic processes^[5-8]. Recent studies have proven the practicability that the metal-acyl moiety was introduced into the main chain of polymers to form potential functional organometallic materials^[9], and the organometallic aqueous colloids were formed through the self-assembly of the metal-acyl complexes^[10], which markedly broaden their application fields. Among the metal-acyl complexes, the acyl iron complexes have drawn more and more attention in recent years because of the successful elucidation of the structure of [Fe]-hydrogenase^[11-13], which suggests that an acyl-iron ligates to the active site of [Fe]-hydrogenase^[14]. Since then a number of acyl iron complexes have been synthesized and character-ized^[15-20], which promotes the rapid development of acyl iron complexes. To match the electronic and steric properties of biomimetic models for the active site of [Fe]-hydrogenase, several kinds of donor-functionalized acyl ligands, such as acylphosphine^[21], carbamoylpyri-dine^[19], acylmethylpyridine^[16], and acylmethylpyra-zole^[22-23], have been used to synthesize acyl iron comp-lexes. Because of the introduction of the chelation-assisted donor atoms bearing different electron-donating ability, the corresponding acyl iron complexes exhibit versatile reactivity. In addition, the incorporation of the sulfur-containing ligand to the metal center of model complexes for [Fe]-hydrogenase is also important, since the sulfur atom possibly plays a role in the catalytic cycle of hydrogen activation by [Fe]-hydro-genase^[24-25]. However, iron complexes with sulfur-functionalized acyl ligand^[26-27] are rare in known synth-etic model complexes of [Fe]-hydrogenase, in which phenylthiolate or 2-pyridinethiolate ligand is usually used to occupy the cysteine sulfur position. Other structural models with sulfur-functionalized acyl ligand should be conducive to gaining a deeper understanding of the structure and catalytic function of [Fe]-hydrogenase owing to the strong influence of the stereo-electronic environment of the iron center on the ability of the biomimic to bind hydrogen molecule. Our previous investigations showed that the different chelation-assisted donor atoms significantly affected the structure and reactivity of the corresponding acyl iron complexes^[22-23]. As an extension of our investiga-tions on this subject, herein we describe the synthesis and reactivity of thioether-based iron complexes.

  1   Experimental

  Solvents were dried and freshly distilled prior to use according to standard procedures. All reactions were carried out under an atmosphere of argon. NMR spectra were recorded on a Bruker 400 spectrometer using CDCl₃ as solvent unless otherwise noted, and the chemical shifts were reported with respect to the reference (internal SiMe₄ for ¹H and ¹³C NMR spectra, external 85% H₃PO₄ aqueous solution for ³¹P NMR spectra). IR spectra were recorded as KBr pellets on a Tensor 27 spectrometer. Elemental analyses were carried out on an Elementar Vario EL analyzer.

  1.1   Synthesis of [(o-ⁱPrS)C₆H₄COFe(CO)₂I]₂ (1)

  A hexane solution of n-BuLi (1.6 mol·L^-1, 1.3 mL, 2 mmol) was added to the solution of N, N, N′, N′-tetramethylethylenediamine (TMEDA) (0.2 mL, 2 mmol) in hexane (10 mL) at room temperature. After 30 min, isopropylthiobenzene (0.32 mL, 2 mmol) was added to the above-mentioned solution. The resulting mixture was stirred for 4 h at room temperature, during which time a solid was precipitated out. Then, the reaction mixture was cooled to -78 ℃, and THF (20 mL) was added, After the solid was completely dissolved, Fe(CO)₅ (0.26 mL, 2 mmol) was added. The reaction mixture was continuously stirred at -78 ℃ for 30 min, and allowed to reach room temperature slowly and stirred for 2 h. A solution of I₂ (0.51 g, 2 mmol) in THF (10 mL) was added dropwise. After completion of addition, the reaction mixture was stirred overnight. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica with CH₂Cl₂ as the eluent. The red eluate was concentrated to dryness to give 1 as a red solid. Yield: 0.33 g (38%). ¹H NMR: δ 1.43 (d, J=5.3 Hz, 6H, CH₃), 1.49 (d, J=5.0 Hz, 6H, CH₃), 3.20~3.35 (m, 2H, CH), 7.55~7.65 (m, 4H, C₆H₄), 7.74~7.80 (m, 4H, C₆H₄). ¹³C NMR: δ 22.1 (CH₃), 22.4 (CH₃), 48.7 (CH), 125.2, 130.8, 131.7, 132.1, 136.4, 150.5 (C₆H₄), 195.8, 205.0 (C≡O), 246.9 (C＝O). IR(cm^-1): ν(C≡O) 2 090, 2 030, 2 004, 1 975; ν(C＝O) 1 628. Anal. Calcd. for C₂₄H₂₂Fe₂I₂O₆S₂(%): C 34.48, H 2.65; Found(%): C 34.35, H 3.10.

  1.2   Synthesis of (o-ⁱPrS)C₆H₄COFe(CO)₂(SPy) (2)

  Sodium hydride (12 mg, 0.5 mmol) was added to a solution of 2-mercaptopyridine (56 mg, 0.5 mmol) in CH₂Cl₂ (20 mL). The reaction mixture was stirred for 1 h at room temperature, followed by the addition of a solution of 1 (0.21 g, 0.25 mmol) in CH₂Cl₂ (10 mL). The reaction mixture was continuously stirred for 6 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica with CH₂Cl₂ as the eluent. The red eluate was concentrated to dryness to afford 0.16 g (72%) of 2. This complex consisted of two isomers (2A/2B) in solution. The relative ratio of isomers was ca. 1: 1 in CDCl₃ and 2: 1 in acetone-d₆, respectively, according to the integral of the corresponding protons of the methine and methyl groups. 2A: ¹H NMR: δ 1.38 (d, J=6.6 Hz, CH₃), 1.49 (d, J=6.6 Hz, CH₃), 3.35~3.46 (m, CH), 3.50~3.66 (m, CH), 6.55~6.61 (m), 6.82~6.90 (m), 7.00~7.16 (m), 7.29 ~7.35 (m), 7.36~7.41 (m), 7.61~7.70 (m), 7.88~7.95 (m) (phenyl and pyridyl protons). ¹³C NMR: δ 21.5, 22.0, 22.1, 22.6 (CH₃), 46.3, 46.9 (CH), 117.5, 117.9, 122.2, 122.5, 125.4, 127.4, 130.3, 130.5, 130.8, 131.4, 131.7, 131.8, 135.5, 136.1, 138.1, 138.6, 148.5, 148.7, 149.7, 151.0, 177.3, 180.8 (phenyl and pyridyl carbons), 208.8, 210.2, 210.7, 211.6 (C≡O), 260.3, 262.2 (C＝O). 2B: ¹H NMR (acetone-d₆): δ 1.39 (d, J=6.8 Hz), 1.41 (d, J=6.7 Hz), 1.53 (d, J=6.7 Hz), 3.55~3.65 (m), 3.68~3.83 (m), 6.77 (t, J=6.2 Hz), 6.89 (dd, J₁=2.8 Hz, J₂=8.3 Hz), 7.00~7.03 (m), 7.09~7.24 (m), 7.42 (dd, J₁=1.0 Hz, J₂=7.6 Hz), 7.89 (t, J=8.1 Hz), 8.20 (d, J=5.3 Hz). The other signals in the range of 7.48~7.70 overlapped seriously. IR(cm^-1): ν(C≡O) 2 023, 1 967, 1 957; ν(C＝O) 1 615. Anal. Calcd. for C₁₇H₁₅FeNO₃S₂(%): C 50.88, H 3.77, N 3.49; Found(%): C 50.66, H 4.23, N 3.46.

  1.3   Synthesis of C₆H₅SCH₂Fe(CO)₃I (3)

  This complex was similarly obtained using thioanisole instead of isopropylthiobenzene as above-mentioned synthesis of 1. Yield: 39%. ¹H NMR: δ 3.95 ~4.00 (m, 2H, CH₂), 7.39 (s, br, 3H, C₆H₅), 7.53 (s, br, 2H, C₆H₅). ¹³C NMR: δ 38.7 (CH₂), 129.8, 130.0, 130.1, 135.8 (C₆H₅), 203.8, 209.4, 210.2 (C≡O). IR: ν(C≡O) 2 077, 2 019, 1 996 cm^-1. Anal. Calcd. for C₁₀H₇FeIO₃S(%): C 30.80, H 1.81; Found(%): C 30.92, H 2.14.

  1.4   Synthesis of C₆H₅SCH₂Fe(CO)₂(PPh₃)I (4)

  PPh₃ (26 mg, 0.1 mmol) was added to a solution of 3 (39 mg, 0.1 mmol) in THF (20 mL). The reaction mixture was stirred overnight at room temperature. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica with CH₂Cl₂/hexane (1: 2, V/V) as the eluent to give a red eluate, which was concentrated to dryness to afford 20 mg (32%) of 4 as a red solid. ¹H NMR: δ 3.92~4.11 (m, 2H, CH₂), 7.03~7.60 (m, 20H, C₆H₅). ¹³C NMR: δ 36.0 (d, J_P-C=20.2 Hz, CH₂), 128.4 (d, J_P-C=9.5 Hz), 128.1, 129.0, 129.3, 130.2, 133.6, 133.9 (d, J_P-C =10.1 Hz), 135.0, 135.4, 136.0 (C₆H₅), 214.9 (d, J_P-C=17.5 Hz), 218.1 (C≡O). ³¹P NMR: δ 40.1. IR: ν(C≡O) 2 004, 1 950 cm^-1. Anal. Calcd. for C₂₇H₂₂FeIO₂PS(%): C 51.95, H 3.55; Found(%): C 51.80, H 3.89.

  1.5   Reaction of 1 with PPh₃

  Reaction of 1 with PPh₃, like that of 3 with PPh₃, resulted in the decomposition of the starting material. No characterizable product was obtained.

  1.6   Crystal structure determination

  Crystals of 1, 2A, 3 and 4 suitable for X-ray analyses were obtained by slow diffusion of hexane into their CH₂Cl₂ solutions at -18 ℃. All intensity data were collected on a Rigaku Saturn CCD detector using Mo Kα radiation (λ=0.071 073 nm). Semi-empirical absorption corrections were applied using the Crystal-clear program^[28]. The structures were solved by direct methods and difference Fourier map using SHELXS of the SHELXTL package and refined with SHELXL^[29] by full-matrix least-squares on F². All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were added geometrically and refined with riding model position parameters. A summary of the fundamental crystal data for 1, 2A, 3 and 4 is listed in Table 1.

  Table 1.  Crystal data and refinement parameters for complexes 1, 2A, 3 and 4

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  Complex	1	2A	3	4
  Formula	C24H22Fe2l2O6S2	C17H15FeNO3S2	C10H7FeIO3S	C27H22FeIO2PS
  Formula weight	836.03	401.27	389.97	624.23
  Crystal size/mm	0.20×0.18×0.12	0.20×0.18×0.12	0.24×0.22×0.16	0.20×0.18×0.12
  Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	C2/c	P21/n	P21/n	P21/c
  a/nm	2.267 3(5)	1.166 2(2)	1.229 12(13)	1.273 57(18)
  b/nm	0.961 08(19)	1.250 4(3)	0.710 29(7)	1.049 13(15)
  c/nm	1.649 6(3)	1.188 6(2)	1.433 60(14)	1.871 3(2)
  β/(°)	127.86(3)	95.379(2)	97.984(2)	92.063(3)
  T/K	113(2)	113(2)	113(2)	113(2)
  V/nm3	2.837 8(13)	1.725 5(6)	1.239 4(2)	2.498 7(6)
  Z	4	4	4	4
  Dc/(g·cm-3)	1.957	1.545	2.090	1.659
  F(000)	1 616	824	744	1 240
  μ/mm-1	3.381	1.130	3.863	2.009
  θ range/(°)	2.40~25.02	2.34~36.37	2.05~28.71	3.20~27.52
  Measured reflection	14 131	30 684	16 369	31 228
  Unique reflection (Rint)	2 513 (0.076 8)	8 160 (0.019 9)	3 210 (0.019 9)	5 749 (0.046 5)
  Observed reflection with [I > 2σ(I)]	2 004	7 136	3 082	5 039
  Parameter	165	219	145	298
  GOF	1.219	1.014	1.056	0.998
  Residuals R, wR2	0.076 9, 0.160 5	0.024 7, 0.063 5	0.011 5, 0.028 1	0.023 7, 0.060 0

  CCDC: 1545834, 1; 1545835, 2A; 1545836, 3; 1545837, 4.

  2   Results and discussion

  2.1   Synthesis and reactivity of ortho-isopropyl-thiobenzoyl iron complex

  It is known that isopropylthiobenzene is deproto-nated with n-BuLi in the presence of TMEDA to give the ortho-lithiation product^[30]. Herein, we find that reaction of this ortho-lithiation product with iron carbonyl followed by iodine yields a dimeric ortho-isopropylthiobenzoyl iron complex 1 (Scheme 1). This result is significantly different from the similar reac-tions of (pyrazol-1-yl)methyllithium^[23] and (2-pyridyl)methyllithium^[31], which only give mononuclear acyl iron complexes, revealing that different chelation-assisted donors strongly affect the fundamental structures of metal-acyl complexes. The substitution of iodide in 1 by 2-pyridinethiolate is successful, which gives mono-nuclear complex 2. However, reaction of 1 with PPh₃ leads to the decomposition of the starting material. Complexes 1 and 2 are air-stable solids and their solution could be manipulated in air for a short time without notable decomposition. They have been characterized by spectroscopic methods.

  图Scheme 1 Synthesis and reactivity of thiobenzoyl and thiomethyl iron complexes Scheme1. Synthesis and reactivity of thiobenzoyl and thiomethyl iron complexes

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  The IR spectra of 1 and 2 show that the acyl carbonyl peak occurrs at 1 628 and 1 615 cm^-1, respe-ctively, lower than those in polydentate acyl ligated iron complexes^[22-23], but comparable to those in mono-dentate acyl ligated iron complexes^[23]. The correspon-ding acyl carbon resonates at 246.9 in the ¹³C NMR spectrum of 1. The ¹H and ¹³C NMR spectra of 2 contain two sets of proton and carbon signals, indica-ting that this complex possibly exists in solution as mixture of two geometric isomers (Scheme 1). The main structural difference of two isomers arises from the relative position of ortho-isopropylthiobenzoyl with 2-pyridinethiolate. Furthermore, the relative ratio of two isomers is variable in the CDCl₃ and acetone-d₆ solutions, showing that the interconversion between two isomers is possible in solution with the help of solvent, through partial dissociation of the ligands and succedent association process. Similar isomerism and interconversion have been observed in (pyrazol-1-yl)acyl iron complexes^[23].

  The structures of 1 and 2A were confirmed by X-ray crystallography, and are shown in Fig. 1 and 2, respectively. The selected bond distances and angles are listed in Table 2. Fig. 1 shows that complex 1 consists of two unequal iodide bridges between two benzoyl iron fragments. The Fe-I(1) bond distance (0.266 8(2) nm) is slightly shorter than the Fe-I(1A) bond distance (0.273 4(2) nm). These values are similar to those in bidentate acyl ligated iron complexes, but shorter than those in monodentate acyl ligated iron complexes^[23]. Fig. 2 shows that the pyridyl nitrogen atom in 2A occupies the cis-position to the acyl group with the C(8)-Fe(1)-N(1) angle of 94.54(3)°. Complexes 1 and 2A possess analogous Fe-C_acyl and CC_acyl bond distances, which are also comparable to the correspon-ding values reported for monodentate acyl iron complexes^[23].

  图1 Molecular structure of 1 with 30% probability displacement ellipsoids Figure1. Molecular structure of 1 with 30% probability displacement ellipsoids

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  图2 Molecular structure of 2A with 30% probability displacement ellipsoids Figure2. Molecular structure of 2A with 30% probability displacement ellipsoids

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  Table 2.  Selected bond distances (nm) and angles (°) for complexes 1, 2A, 3 and 4

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  Complex 1
  Fe(1)-I(1)	0.266 8(2)	Fe(1)-I(1A)	0.273 4(2)	Fe(1)-S(1)	0.229 8(3)
  Fe(1)-C(1)	0.178 1(13)	Fe(1)-C(2)	0.172 6(15)	Fe(1)-C(3)	0.194 8(15)
  C(1)-O(1)	0.113 7(16)	C(3)-O(3)	0.126 3(16)	C(3)-C(4)	0.151 9(19)
  Fe(1)-I(1)-Fe(1A)	91.82(6)	I(1)-Fe(1)-I(1A)	88.18(6)	C(2)-Fe(1)-I(1)	176.4(5)
  C(3)-Fe(1)-I(1A)	174.8(4)	C(3)-Fe(1)-S(1)	87.6(4)	Fe(1)-C(3)-O(3)	124.6(11)
  Fe(1)-S(1)-C(9)	99.1(4)	C(4)-C(3)-O(3)	118.5(13)	C(11)-C(10)-S(1)	113.9(9)
  Complex 2A
  Fe(1)-S⑴	0.241 60(5)	Fe(1)-S(2)	0.227 92(4)	Fe(1)-N(1)	0.200 22(8)
  Fe(1)-C(1)	0.178 97(9)	Fe(1)-C(2)	0.177 37(9)	Fe(1)-C(8)	0.194 77(9)
  C(1)-O(1)	0.114 1(1)	C(8)-O(3)	0.122 4(1)	C(8)-C(9)	0.151 6(1)
  C(8)-Fe(1)-S(1)	164.20(2)	C(8)-Fe(1)-S(2)	88.00(3)	C(8)-Fe(1)-N(1)	94.54(3)
  Fe(1)-C(3)-N(1)	101.95(5)	Fe(1)-C(8)-O(3)	125.67(7)	Fe(1)-S(1)-C(3)	77.19(3)
  Fe(1)-S(2)-C(14)	99.47(3)	S(1)-Fe(1)-S(2)	87.75(1)	N(1)-Fe(1)-S(1)	69.78(2)
  N(1)-Fe(1)-S(2)	81.67(2)	C(17)-C(15)-S(2)	114.68(6)
  Complex 3
  Fe(1)-I(1)	0.265 17(3)	Fe(1)-S(1)	0.226 51(4)	Fe(1)-C(1)	0.178 6(1)
  Fe(1)-C(4)	0.201 9(1)	C(4)-S(1)	0.176 1(1)
  S(1)-C(4)-Fe(1)	73.28(4)	C(1)-Fe(1)-C(4)	99.60(5)	C(2)-Fe(1)-S(1)	96.58(4)
  C(2)-Fe(1)-I(1)	176.90(4)	C(4)-Fe(1)-I(1)	89.43(4)	C(4)-Fe(1)-S(1)	48.11(3)
  Fe(1)-S(1)-C(4)	58.61(4)	Fe(1)-S(1)-C(5)	111.75(4)
  Complex 4
  Fe(1)-P(1)	0.229 44(6)	Fe(1)-S(1)	0.226 54(6)	Fe(1)-I(1)	0.268 21(4)
  Fe(1)-C(1)	0.175 6(2)	Fe(1)-C(3)	0.201 7(2)	C(3)-S(1)	0.176 7(2)
  C(1)-Fe(1)-C(3)	87.94(9)	C(1)-Fe(1)-I(1)	171.26(6)	C(2)-Fe(1)-S(1)	148.87(7)
  C(3)-Fe(1)-S(1)	48.30(6)	C(3)-Fe(1)-P(1)	154.97(6)	C(3)-S(1)-Fe(1)	58.47(7)
  C(16)-P(1)-C(22)	103.62(8)	C(16)-P(1)-Fe(1)	113.49(6)	S(1)-C(3)-Fe(1)	73.22(7)
  S(1)-Fe(1)-P(1)	106.88(2)	S(1)-Fe(1)-I(1)	85.15(2)	P(1)-Fe(1)-I(1)	92.87(2)
  Symmetry codes: A: -x+2, -y+1, -z+1 for 1.

  2.2   Synthesis and reactivity of phenylthiomethyl iron complex

  The lithiation process of thioanisole with n-BuLi is different from that of isopropylthiobenzene^{[30, 32]}. Thioan-isole was deprotonated with n-BuLi to give the methyl metalation product instead of the ortho lithiation product of phenyl group^[32]. Reactions of α-thiocarban-ions with iron carbonyl have been investigated, which generated acyl iron intermediates and subsequently transferred to various organic and organometallic derivatives^[33-34]. However, we find that reaction of phenylthiomethyllithium with iron carbonyl followed by iodine only affords phenylthiomethyl iron complex 3 (Scheme 1). No acyl iron derivatives are obtained. Reactivity of 3 is significantly different from that of 1. For example, similar treatment of 3 with 2-pyridinethiolate results in the decomposition of 3, rather than the substitution of iodide. In addition, reaction of alkylmetal carbonyl compounds with nucleophilic ligands, such as phosphine (PR₃), has been extensively used to form acyl metal derivatives through alkyl/carbonyl migratory insertion reaction^[9], but reaction of 3 with PPh₃ only give the carbonyl substitution product 4. No induced carbonyl insertion reaction took place, though such reaction should be able to reduce the ring strain in 3. Complexes 3 and 4 also are air-stable solids. Their IR and NMR spectra are highly consistent with the alkyl iron structure. These two complexes only exhibit three (for 3) or two (for 4) absorption bands in the range of 2 077~1 950 cm^-1 for terminal carbonyl ligands, and no acyl carbonyl absorption band is observed in their IR spectra.

  Complexes 3 and 4 were also characterized by single crystal X-ray structural determination. Fig. 3 and 4 reveal that the fundamental frameworks in complexes 3 and 4 are similar to each other, except that PPh₃ locates on the trans-position of the methyl carbon in 4 instead of one carbonyl group like in 3. The phenylthiomethyl group bonds to the iron atom in a bidentate κ²-[C, S] chelating fashion in these two complexes, yielding a three-membered metallocyclic structure. Complexes 3 and 4 possess analogous Fe-S, Fe-I and Fe-C_methyl bond distances (Table 2). The Fe-S and Fe-I bond distances are also comparable to the corresponding values in 1 and 2.

  图3 Molecular structure of 3 with 30% probability displacement ellipsoids Figure3. Molecular structure of 3 with 30% probability displacement ellipsoids

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  图4 Molecular structure of 4 with 30% probability displacement ellipsoids Figure4. Molecular structure of 4 with 30% probability displacement ellipsoids

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  3   Conclusions

  In summary, ortho-isopropylthiobenzoyl and phenylthiomethyl iron derivatives have been obtained by the reaction of ortho-isopropylthiophenyllithium or phenylthiomethyllithium with iron carbonyl followed by treatment with iodine. These complexes also show markedly different reactivities upon treatment with nucleophilic ligands.

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  Scheme 1  Synthesis and reactivity of thiobenzoyl and thiomethyl iron complexes

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  Figure 1  Molecular structure of 1 with 30% probability displacement ellipsoids

  Symmetry codes: A:-x+2, -y+1, -z+1 for 1.

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  Figure 2  Molecular structure of 2A with 30% probability displacement ellipsoids

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  Figure 3  Molecular structure of 3 with 30% probability displacement ellipsoids

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  Figure 4  Molecular structure of 4 with 30% probability displacement ellipsoids

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  Table 1.  Crystal data and refinement parameters for complexes 1, 2A, 3 and 4

  Complex	1	2A	3	4
  Formula	C24H22Fe2l2O6S2	C17H15FeNO3S2	C10H7FeIO3S	C27H22FeIO2PS
  Formula weight	836.03	401.27	389.97	624.23
  Crystal size/mm	0.20×0.18×0.12	0.20×0.18×0.12	0.24×0.22×0.16	0.20×0.18×0.12
  Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	C2/c	P21/n	P21/n	P21/c
  a/nm	2.267 3(5)	1.166 2(2)	1.229 12(13)	1.273 57(18)
  b/nm	0.961 08(19)	1.250 4(3)	0.710 29(7)	1.049 13(15)
  c/nm	1.649 6(3)	1.188 6(2)	1.433 60(14)	1.871 3(2)
  β/(°)	127.86(3)	95.379(2)	97.984(2)	92.063(3)
  T/K	113(2)	113(2)	113(2)	113(2)
  V/nm3	2.837 8(13)	1.725 5(6)	1.239 4(2)	2.498 7(6)
  Z	4	4	4	4
  Dc/(g·cm-3)	1.957	1.545	2.090	1.659
  F(000)	1 616	824	744	1 240
  μ/mm-1	3.381	1.130	3.863	2.009
  θ range/(°)	2.40~25.02	2.34~36.37	2.05~28.71	3.20~27.52
  Measured reflection	14 131	30 684	16 369	31 228
  Unique reflection (Rint)	2 513 (0.076 8)	8 160 (0.019 9)	3 210 (0.019 9)	5 749 (0.046 5)
  Observed reflection with [I > 2σ(I)]	2 004	7 136	3 082	5 039
  Parameter	165	219	145	298
  GOF	1.219	1.014	1.056	0.998
  Residuals R, wR2	0.076 9, 0.160 5	0.024 7, 0.063 5	0.011 5, 0.028 1	0.023 7, 0.060 0

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  Table 2.  Selected bond distances (nm) and angles (°) for complexes 1, 2A, 3 and 4

  Complex 1
  Fe(1)-I(1)	0.266 8(2)	Fe(1)-I(1A)	0.273 4(2)	Fe(1)-S(1)	0.229 8(3)
  Fe(1)-C(1)	0.178 1(13)	Fe(1)-C(2)	0.172 6(15)	Fe(1)-C(3)	0.194 8(15)
  C(1)-O(1)	0.113 7(16)	C(3)-O(3)	0.126 3(16)	C(3)-C(4)	0.151 9(19)
  Fe(1)-I(1)-Fe(1A)	91.82(6)	I(1)-Fe(1)-I(1A)	88.18(6)	C(2)-Fe(1)-I(1)	176.4(5)
  C(3)-Fe(1)-I(1A)	174.8(4)	C(3)-Fe(1)-S(1)	87.6(4)	Fe(1)-C(3)-O(3)	124.6(11)
  Fe(1)-S(1)-C(9)	99.1(4)	C(4)-C(3)-O(3)	118.5(13)	C(11)-C(10)-S(1)	113.9(9)
  Complex 2A
  Fe(1)-S⑴	0.241 60(5)	Fe(1)-S(2)	0.227 92(4)	Fe(1)-N(1)	0.200 22(8)
  Fe(1)-C(1)	0.178 97(9)	Fe(1)-C(2)	0.177 37(9)	Fe(1)-C(8)	0.194 77(9)
  C(1)-O(1)	0.114 1(1)	C(8)-O(3)	0.122 4(1)	C(8)-C(9)	0.151 6(1)
  C(8)-Fe(1)-S(1)	164.20(2)	C(8)-Fe(1)-S(2)	88.00(3)	C(8)-Fe(1)-N(1)	94.54(3)
  Fe(1)-C(3)-N(1)	101.95(5)	Fe(1)-C(8)-O(3)	125.67(7)	Fe(1)-S(1)-C(3)	77.19(3)
  Fe(1)-S(2)-C(14)	99.47(3)	S(1)-Fe(1)-S(2)	87.75(1)	N(1)-Fe(1)-S(1)	69.78(2)
  N(1)-Fe(1)-S(2)	81.67(2)	C(17)-C(15)-S(2)	114.68(6)
  Complex 3
  Fe(1)-I(1)	0.265 17(3)	Fe(1)-S(1)	0.226 51(4)	Fe(1)-C(1)	0.178 6(1)
  Fe(1)-C(4)	0.201 9(1)	C(4)-S(1)	0.176 1(1)
  S(1)-C(4)-Fe(1)	73.28(4)	C(1)-Fe(1)-C(4)	99.60(5)	C(2)-Fe(1)-S(1)	96.58(4)
  C(2)-Fe(1)-I(1)	176.90(4)	C(4)-Fe(1)-I(1)	89.43(4)	C(4)-Fe(1)-S(1)	48.11(3)
  Fe(1)-S(1)-C(4)	58.61(4)	Fe(1)-S(1)-C(5)	111.75(4)
  Complex 4
  Fe(1)-P(1)	0.229 44(6)	Fe(1)-S(1)	0.226 54(6)	Fe(1)-I(1)	0.268 21(4)
  Fe(1)-C(1)	0.175 6(2)	Fe(1)-C(3)	0.201 7(2)	C(3)-S(1)	0.176 7(2)
  C(1)-Fe(1)-C(3)	87.94(9)	C(1)-Fe(1)-I(1)	171.26(6)	C(2)-Fe(1)-S(1)	148.87(7)
  C(3)-Fe(1)-S(1)	48.30(6)	C(3)-Fe(1)-P(1)	154.97(6)	C(3)-S(1)-Fe(1)	58.47(7)
  C(16)-P(1)-C(22)	103.62(8)	C(16)-P(1)-Fe(1)	113.49(6)	S(1)-C(3)-Fe(1)	73.22(7)
  S(1)-Fe(1)-P(1)	106.88(2)	S(1)-Fe(1)-I(1)	85.15(2)	P(1)-Fe(1)-I(1)	92.87(2)
  Symmetry codes: A: -x+2, -y+1, -z+1 for 1.

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