A new P,S-coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with Pd^II and Pt^II

In our ongoing development of ferrocene ligands, 1-di­methyl­amino-2-(diphenyl­phosphino­thio­yl)ferrocene is being used as a convenient building block to obtain racemic or enantio­merically pure ligands. Using this building block in large excess allowed the formation of several by-products, two of which have already been reported; the structure of a third by-product, namely 1-(diphenyl­phosphino­thio­yl)-2-{[(diphenyl­phos­phino­thio­yl)sulfanyl]methyl}ferrocene, [Fe(C₅H₅)(C₃₀H₂₅P₂S₃)], is presented here. The crystal structure is built up from a ferrocene unit, with one of the cyclo­penta­dienyl (Cp) rings substituted in the 1- and 2-positions by a protected diphenyl­phosphino­thioyl group and a [(diphenyl­phosphino­thio­yl)sulfanyl]methyl fragment, –CH₂SP(=S)Ph₂. There are C—H...S inter­actions which result in the formation of chains parallel to the c axis. After desulfurization, the crude material was then reacted with Pd and Pt (M) precursors [MCl₂(CH₃CN)₂] to yield two isostructural dinuclear complexes arranged around twofold axes, namely (R,R/S,S)-bis­{μ-[2-(di­­phenylphosphan­yl)ferrocen-1-yl]methane­thiol­ato-κ³P,S:S}bis[chlorido­palladium(II)] pentane disolvate, [Pd₂{Fe(C₅H₅)(C₁₈H₁₅PS)}₂Cl₂]·2C₅H₁₂, and the platinum(II) ana­logue, (R,R/S,S)-bis­{μ-[2-(di­phenyl­phosphan­yl)ferrocen-1-yl]methanethiol­ato-κ³P,S:S}bis­[chlorido­platinum(II)] toluene mono­sol­vate, [Pt₂{Fe(C₅H₅)(C₁₈H₁₅PS)}₂Cl₂]·C₇H₈, in which the two metal atoms present a slightly distorted square-planar geometry formed by two bridging S atoms and P and Cl atoms. The P,S-chelating ligand results from the rupture of one of the P—S bonds in the starting ligand. These dinuclear complexes display a butterfly geometry. Surprisingly, only the (R,R/S,S) diastereo­isomer has been isolated.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012) for (2), (4); APEX2 (Bruker, 2013) for (3). Cell refinement: CrysAlis PRO (Agilent, 2012) for (2), (4); SAINT (Bruker, 2013) for (3). Data reduction: CrysAlis PRO (Agilent, 2012) for (2), (4); SAINT (Bruker, 2013) for (3). For all structures, program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012) for (2), (4); ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008) for (3). For all structures, software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

1-(diphenylphosphinothioyl)-2-{[(diphenylphosphinothioyl)sulfanyl]methyl}ferrocene (2)

Crystal data

[Fe(C5H5)(C30H25P2S3)]	F(000) = 1376
Mr = 664.56	Dx = 1.432 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19578 reflections
a = 10.7284 (4) Å	θ = 3.1–28.4°
b = 23.9422 (11) Å	µ = 0.82 mm^−1
c = 12.0949 (6) Å	T = 180 K
β = 97.311 (4)°	Block, orange
V = 3081.5 (2) Å^3	0.75 × 0.62 × 0.50 mm
Z = 4

Data collection

Oxford Xcalibur diffractometer with Sapphire1 detector and long-nozzle cooler	6763 independent reflections
Radiation source: fine-focus sealed tube	5819 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 8.2632 pixels mm^-1	θmax = 27.1°, θmin = 3.1°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −30→30
Tmin = 0.686, Tmax = 1.0	l = −15→15
32489 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 1.6561P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6763 reflections	Δρmax = 0.35 e Å^−3
370 parameters	Δρmin = −0.40 e Å^−3

Special details

Experimental. Absorption correction: Multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Oxford Diffraction, 2010)

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
Fe1	0.67877 (2)	0.01569 (2)	0.34245 (2)	0.02225 (7)
S1	0.55818 (5)	0.10535 (2)	0.05226 (4)	0.03312 (11)
S2	0.81884 (4)	0.20326 (2)	0.30072 (3)	0.02181 (9)
S3	1.07687 (4)	0.15148 (2)	0.45763 (4)	0.03104 (11)
P1	0.48494 (4)	0.10853 (2)	0.19230 (4)	0.02038 (9)
P2	0.93866 (4)	0.20425 (2)	0.45098 (3)	0.01853 (9)
C1	0.58641 (15)	0.08910 (6)	0.31561 (13)	0.0188 (3)
C2	0.71983 (15)	0.09855 (6)	0.34139 (13)	0.0194 (3)
C3	0.75804 (17)	0.07563 (7)	0.44893 (14)	0.0238 (3)
H3	0.8414	0.0755	0.4865	0.029*
C4	0.65162 (18)	0.05301 (7)	0.49053 (15)	0.0266 (4)
H4	0.6511	0.0356	0.5610	0.032*
C5	0.54625 (16)	0.06073 (7)	0.40962 (14)	0.0240 (3)
H5	0.4628	0.0491	0.4162	0.029*
C6	0.7805 (2)	−0.02143 (9)	0.2317 (2)	0.0430 (5)
H6	0.8353	−0.0027	0.1881	0.052*
C7	0.6517 (2)	−0.03169 (9)	0.20042 (19)	0.0453 (6)
H7	0.6043	−0.0214	0.1317	0.054*
C8	0.6055 (2)	−0.05970 (8)	0.2883 (2)	0.0485 (6)
H8	0.5212	−0.0716	0.2896	0.058*
C9	0.7056 (2)	−0.06729 (8)	0.3743 (2)	0.0468 (6)
H9	0.7008	−0.0851	0.4438	0.056*
C10	0.8138 (2)	−0.04379 (9)	0.3390 (2)	0.0427 (5)
H10	0.8953	−0.0431	0.3803	0.051*
C21	0.80586 (15)	0.12796 (7)	0.27354 (14)	0.0220 (3)
H21A	0.7756	0.1221	0.1936	0.026*
H21B	0.8905	0.1110	0.2888	0.026*
C111	0.34836 (16)	0.06368 (7)	0.19242 (15)	0.0245 (4)
C112	0.33480 (17)	0.01742 (8)	0.12312 (16)	0.0297 (4)
H112	0.3956	0.0098	0.0745	0.036*
C113	0.23261 (19)	−0.01771 (8)	0.12476 (19)	0.0384 (5)
H113	0.2234	−0.0494	0.0772	0.046*
C114	0.14420 (19)	−0.00686 (8)	0.1951 (2)	0.0401 (5)
H114	0.0746	−0.0313	0.1963	0.048*
C115	0.15629 (18)	0.03941 (8)	0.26390 (19)	0.0371 (5)
H115	0.0951	0.0468	0.3122	0.044*
C116	0.25799 (17)	0.07497 (8)	0.26221 (17)	0.0304 (4)
H116	0.2660	0.1071	0.3087	0.036*
C121	0.42835 (15)	0.17753 (7)	0.21989 (16)	0.0251 (4)
C122	0.34943 (19)	0.20409 (9)	0.1359 (2)	0.0406 (5)
H122	0.3236	0.1853	0.0676	0.049*
C123	0.3088 (2)	0.25792 (10)	0.1519 (3)	0.0562 (7)
H123	0.2537	0.2760	0.0953	0.067*
C124	0.3483 (2)	0.28520 (9)	0.2501 (3)	0.0568 (8)
H124	0.3227	0.3227	0.2597	0.068*
C125	0.4238 (2)	0.25923 (9)	0.3341 (2)	0.0481 (6)
H125	0.4488	0.2783	0.4023	0.058*
C126	0.46399 (18)	0.20472 (8)	0.31954 (18)	0.0331 (4)
H126	0.5158	0.1863	0.3780	0.040*
C211	0.83973 (16)	0.19367 (7)	0.55963 (14)	0.0209 (3)
C212	0.88425 (19)	0.16251 (7)	0.65311 (15)	0.0292 (4)
H212	0.9679	0.1487	0.6621	0.035*
C213	0.8057 (2)	0.15166 (8)	0.73336 (16)	0.0377 (5)
H213	0.8364	0.1308	0.7979	0.045*
C214	0.6847 (2)	0.17062 (9)	0.72043 (17)	0.0403 (5)
H214	0.6309	0.1618	0.7745	0.048*
C215	0.64057 (19)	0.20267 (9)	0.62876 (17)	0.0370 (5)
H215	0.5570	0.2166	0.6208	0.044*
C216	0.71777 (16)	0.21445 (8)	0.54851 (15)	0.0268 (4)
H216	0.6875	0.2367	0.4858	0.032*
C221	0.98860 (15)	0.27645 (7)	0.45827 (14)	0.0218 (3)
C222	1.07424 (19)	0.29455 (8)	0.38968 (18)	0.0355 (4)
H222	1.1041	0.2695	0.3381	0.043*
C223	1.1164 (2)	0.34916 (9)	0.3964 (2)	0.0405 (5)
H223	1.1738	0.3617	0.3480	0.049*
C224	1.07633 (19)	0.38538 (8)	0.47180 (18)	0.0352 (4)
H224	1.1075	0.4226	0.4772	0.042*
C225	0.9913 (3)	0.36781 (9)	0.5393 (2)	0.0513 (6)
H225	0.9624	0.3930	0.5911	0.062*
C226	0.9471 (2)	0.31333 (9)	0.53275 (18)	0.0438 (6)
H226	0.8879	0.3014	0.5799	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.02593 (13)	0.01308 (11)	0.02655 (14)	0.00217 (9)	−0.00119 (9)	−0.00136 (9)
S1	0.0376 (3)	0.0404 (3)	0.0220 (2)	−0.0030 (2)	0.00619 (18)	−0.00167 (19)
S2	0.0275 (2)	0.01965 (19)	0.0178 (2)	−0.00249 (16)	0.00097 (15)	0.00310 (15)
S3	0.0225 (2)	0.0270 (2)	0.0428 (3)	0.00562 (17)	0.00124 (18)	−0.00381 (19)
P1	0.0208 (2)	0.0180 (2)	0.0220 (2)	0.00031 (16)	0.00122 (15)	−0.00052 (16)
P2	0.01922 (19)	0.01693 (19)	0.0195 (2)	−0.00074 (15)	0.00259 (15)	0.00007 (15)
C1	0.0212 (8)	0.0135 (7)	0.0219 (8)	0.0013 (6)	0.0036 (6)	−0.0016 (6)
C2	0.0231 (8)	0.0135 (7)	0.0215 (8)	0.0008 (6)	0.0019 (6)	−0.0017 (6)
C3	0.0299 (9)	0.0170 (8)	0.0233 (9)	−0.0022 (7)	−0.0019 (7)	−0.0016 (6)
C4	0.0396 (10)	0.0187 (8)	0.0213 (9)	−0.0037 (7)	0.0033 (7)	0.0023 (7)
C5	0.0279 (9)	0.0184 (8)	0.0266 (9)	−0.0018 (7)	0.0073 (7)	0.0003 (7)
C6	0.0533 (13)	0.0292 (10)	0.0487 (13)	0.0134 (9)	0.0156 (10)	−0.0090 (9)
C7	0.0600 (14)	0.0299 (10)	0.0419 (12)	0.0166 (10)	−0.0101 (10)	−0.0191 (9)
C8	0.0465 (12)	0.0188 (9)	0.0782 (18)	−0.0017 (9)	0.0009 (12)	−0.0181 (10)
C9	0.0690 (16)	0.0155 (9)	0.0556 (14)	0.0110 (9)	0.0061 (12)	0.0031 (9)
C10	0.0416 (12)	0.0280 (10)	0.0555 (14)	0.0174 (9)	−0.0049 (10)	−0.0085 (9)
C21	0.0228 (8)	0.0209 (8)	0.0226 (8)	−0.0022 (6)	0.0038 (6)	−0.0043 (6)
C111	0.0216 (8)	0.0201 (8)	0.0306 (9)	0.0014 (6)	−0.0006 (7)	−0.0004 (7)
C112	0.0289 (9)	0.0243 (9)	0.0358 (10)	0.0005 (7)	0.0033 (7)	−0.0040 (7)
C113	0.0353 (10)	0.0237 (9)	0.0552 (14)	−0.0033 (8)	0.0016 (9)	−0.0084 (9)
C114	0.0279 (10)	0.0234 (9)	0.0684 (15)	−0.0052 (8)	0.0045 (9)	−0.0005 (9)
C115	0.0262 (9)	0.0301 (10)	0.0564 (13)	0.0003 (8)	0.0113 (9)	0.0001 (9)
C116	0.0264 (9)	0.0239 (9)	0.0412 (11)	0.0007 (7)	0.0057 (8)	−0.0053 (8)
C121	0.0200 (8)	0.0177 (8)	0.0380 (10)	0.0015 (6)	0.0053 (7)	0.0041 (7)
C122	0.0288 (10)	0.0350 (11)	0.0562 (14)	0.0007 (8)	−0.0016 (9)	0.0155 (10)
C123	0.0307 (11)	0.0378 (13)	0.101 (2)	0.0130 (10)	0.0131 (12)	0.0341 (14)
C124	0.0461 (13)	0.0235 (10)	0.110 (2)	0.0139 (10)	0.0451 (15)	0.0138 (13)
C125	0.0551 (14)	0.0252 (10)	0.0703 (16)	0.0027 (10)	0.0322 (12)	−0.0081 (10)
C126	0.0352 (10)	0.0229 (9)	0.0426 (11)	0.0047 (8)	0.0104 (8)	−0.0035 (8)
C211	0.0273 (8)	0.0163 (7)	0.0195 (8)	−0.0042 (6)	0.0048 (6)	−0.0020 (6)
C212	0.0435 (11)	0.0212 (8)	0.0226 (9)	0.0015 (8)	0.0029 (8)	0.0006 (7)
C213	0.0694 (15)	0.0220 (9)	0.0235 (10)	−0.0057 (9)	0.0125 (9)	0.0032 (7)
C214	0.0580 (14)	0.0340 (11)	0.0337 (11)	−0.0193 (10)	0.0251 (10)	−0.0089 (9)
C215	0.0308 (10)	0.0439 (12)	0.0384 (11)	−0.0077 (9)	0.0127 (8)	−0.0121 (9)
C216	0.0271 (9)	0.0291 (9)	0.0240 (9)	−0.0018 (7)	0.0034 (7)	−0.0030 (7)
C221	0.0234 (8)	0.0192 (8)	0.0225 (8)	−0.0033 (6)	0.0024 (6)	0.0006 (6)
C222	0.0372 (10)	0.0250 (9)	0.0486 (12)	−0.0021 (8)	0.0219 (9)	−0.0018 (8)
C223	0.0373 (11)	0.0303 (10)	0.0581 (14)	−0.0070 (9)	0.0221 (10)	0.0055 (10)
C224	0.0395 (11)	0.0229 (9)	0.0423 (12)	−0.0111 (8)	0.0022 (9)	0.0010 (8)
C225	0.0856 (18)	0.0306 (11)	0.0438 (13)	−0.0223 (11)	0.0315 (12)	−0.0164 (10)
C226	0.0705 (15)	0.0307 (10)	0.0364 (12)	−0.0217 (10)	0.0311 (11)	−0.0113 (9)

Geometric parameters (Å, º)

Fe1—C1	2.0236 (15)	C112—C113	1.384 (3)
Fe1—C2	2.0327 (16)	C112—H112	0.9500
Fe1—C5	2.0343 (17)	C113—C114	1.377 (3)
Fe1—C10	2.0357 (19)	C113—H113	0.9500
Fe1—C6	2.037 (2)	C114—C115	1.382 (3)
Fe1—C9	2.037 (2)	C114—H114	0.9500
Fe1—C3	2.0403 (16)	C115—C116	1.386 (3)
Fe1—C8	2.043 (2)	C115—H115	0.9500
Fe1—C7	2.048 (2)	C116—H116	0.9500
Fe1—C4	2.0553 (18)	C121—C126	1.380 (3)
S1—P1	1.9572 (6)	C121—C122	1.391 (3)
S2—C21	1.8348 (17)	C122—C123	1.382 (3)
S2—P2	2.0884 (6)	C122—H122	0.9500
S3—P2	1.9419 (6)	C123—C124	1.374 (4)
P1—C1	1.7923 (17)	C123—H123	0.9500
P1—C121	1.8059 (17)	C124—C125	1.366 (4)
P1—C111	1.8168 (18)	C124—H124	0.9500
P2—C221	1.8086 (17)	C125—C126	1.393 (3)
P2—C211	1.8091 (17)	C125—H125	0.9500
C1—C5	1.437 (2)	C126—H126	0.9500
C1—C2	1.444 (2)	C211—C212	1.388 (2)
C2—C3	1.423 (2)	C211—C216	1.390 (2)
C2—C21	1.488 (2)	C212—C213	1.389 (3)
C3—C4	1.413 (3)	C212—H212	0.9500
C3—H3	0.9500	C213—C214	1.365 (3)
C4—C5	1.410 (2)	C213—H213	0.9500
C4—H4	0.9500	C214—C215	1.382 (3)
C5—H5	0.9500	C214—H214	0.9500
C6—C10	1.407 (3)	C215—C216	1.383 (3)
C6—C7	1.407 (3)	C215—H215	0.9500
C6—H6	0.9500	C216—H216	0.9500
C7—C8	1.399 (4)	C221—C226	1.375 (3)
C7—H7	0.9500	C221—C222	1.384 (3)
C8—C9	1.410 (3)	C222—C223	1.383 (3)
C8—H8	0.9500	C222—H222	0.9500
C9—C10	1.404 (3)	C223—C224	1.367 (3)
C9—H9	0.9500	C223—H223	0.9500
C10—H10	0.9500	C224—C225	1.366 (3)
C21—H21A	0.9900	C224—H224	0.9500
C21—H21B	0.9900	C225—C226	1.387 (3)
C111—C112	1.385 (2)	C225—H225	0.9500
C111—C116	1.391 (3)	C226—H226	0.9500
C1—Fe1—C2	41.69 (6)	C6—C7—H7	126.0
C1—Fe1—C5	41.48 (7)	Fe1—C7—H7	126.4
C2—Fe1—C5	69.40 (7)	C7—C8—C9	108.2 (2)
C1—Fe1—C10	159.98 (9)	C7—C8—Fe1	70.19 (12)
C2—Fe1—C10	121.82 (8)	C9—C8—Fe1	69.56 (12)
C5—Fe1—C10	156.13 (9)	C7—C8—H8	125.9
C1—Fe1—C6	124.47 (8)	C9—C8—H8	125.9
C2—Fe1—C6	106.68 (8)	Fe1—C8—H8	125.9
C5—Fe1—C6	162.61 (8)	C10—C9—C8	107.8 (2)
C10—Fe1—C6	40.44 (9)	C10—C9—Fe1	69.77 (11)
C1—Fe1—C9	158.75 (9)	C8—C9—Fe1	70.02 (12)
C2—Fe1—C9	158.04 (9)	C10—C9—H9	126.1
C5—Fe1—C9	122.05 (9)	C8—C9—H9	126.1
C10—Fe1—C9	40.34 (10)	Fe1—C9—H9	125.7
C6—Fe1—C9	67.93 (10)	C9—C10—C6	108.1 (2)
C1—Fe1—C3	69.30 (7)	C9—C10—Fe1	69.89 (12)
C2—Fe1—C3	40.90 (6)	C6—C10—Fe1	69.82 (11)
C5—Fe1—C3	68.37 (7)	C9—C10—H10	126.0
C10—Fe1—C3	105.33 (8)	C6—C10—H10	126.0
C6—Fe1—C3	120.46 (9)	Fe1—C10—H10	125.9
C9—Fe1—C3	121.93 (9)	C2—C21—S2	113.86 (11)
C1—Fe1—C8	123.73 (8)	C2—C21—H21A	108.8
C2—Fe1—C8	159.24 (9)	S2—C21—H21A	108.8
C5—Fe1—C8	109.66 (8)	C2—C21—H21B	108.8
C10—Fe1—C8	67.75 (9)	S2—C21—H21B	108.8
C6—Fe1—C8	67.68 (10)	H21A—C21—H21B	107.7
C9—Fe1—C8	40.42 (10)	C112—C111—C116	119.67 (17)
C3—Fe1—C8	159.45 (9)	C112—C111—P1	119.64 (14)
C1—Fe1—C7	109.40 (8)	C116—C111—P1	120.68 (13)
C2—Fe1—C7	122.89 (9)	C113—C112—C111	119.98 (18)
C5—Fe1—C7	126.64 (8)	C113—C112—H112	120.0
C10—Fe1—C7	67.72 (9)	C111—C112—H112	120.0
C6—Fe1—C7	40.31 (9)	C114—C113—C112	120.22 (19)
C9—Fe1—C7	67.68 (10)	C114—C113—H113	119.9
C3—Fe1—C7	157.26 (9)	C112—C113—H113	119.9
C8—Fe1—C7	40.00 (10)	C113—C114—C115	120.27 (18)
C1—Fe1—C4	68.98 (7)	C113—C114—H114	119.9
C2—Fe1—C4	68.65 (7)	C115—C114—H114	119.9
C5—Fe1—C4	40.33 (7)	C114—C115—C116	119.83 (19)
C10—Fe1—C4	120.15 (8)	C114—C115—H115	120.1
C6—Fe1—C4	155.53 (9)	C116—C115—H115	120.1
C9—Fe1—C4	106.94 (9)	C115—C116—C111	120.02 (18)
C3—Fe1—C4	40.36 (7)	C115—C116—H116	120.0
C8—Fe1—C4	124.91 (9)	C111—C116—H116	120.0
C7—Fe1—C4	161.99 (9)	C126—C121—C122	119.84 (18)
C21—S2—P2	101.03 (6)	C126—C121—P1	122.04 (14)
C1—P1—C121	105.46 (8)	C122—C121—P1	118.09 (16)
C1—P1—C111	104.51 (8)	C123—C122—C121	119.8 (2)
C121—P1—C111	104.50 (8)	C123—C122—H122	120.1
C1—P1—S1	116.22 (6)	C121—C122—H122	120.1
C121—P1—S1	112.14 (6)	C124—C123—C122	119.8 (2)
C111—P1—S1	112.98 (6)	C124—C123—H123	120.1
C221—P2—C211	107.21 (8)	C122—C123—H123	120.1
C221—P2—S3	113.57 (6)	C125—C124—C123	121.0 (2)
C211—P2—S3	113.22 (6)	C125—C124—H124	119.5
C221—P2—S2	101.47 (6)	C123—C124—H124	119.5
C211—P2—S2	106.11 (6)	C124—C125—C126	119.7 (2)
S3—P2—S2	114.26 (3)	C124—C125—H125	120.1
C5—C1—C2	106.98 (14)	C126—C125—H125	120.1
C5—C1—P1	124.73 (12)	C121—C126—C125	119.8 (2)
C2—C1—P1	128.29 (12)	C121—C126—H126	120.1
C5—C1—Fe1	69.66 (9)	C125—C126—H126	120.1
C2—C1—Fe1	69.49 (9)	C212—C211—C216	119.56 (16)
P1—C1—Fe1	126.30 (8)	C212—C211—P2	119.62 (14)
C3—C2—C1	107.42 (14)	C216—C211—P2	120.77 (13)
C3—C2—C21	124.05 (15)	C211—C212—C213	119.57 (18)
C1—C2—C21	128.51 (15)	C211—C212—H212	120.2
C3—C2—Fe1	69.83 (9)	C213—C212—H212	120.2
C1—C2—Fe1	68.81 (9)	C214—C213—C212	120.70 (19)
C21—C2—Fe1	127.99 (11)	C214—C213—H213	119.6
C4—C3—C2	108.76 (15)	C212—C213—H213	119.6
C4—C3—Fe1	70.39 (10)	C213—C214—C215	120.04 (18)
C2—C3—Fe1	69.26 (9)	C213—C214—H214	120.0
C4—C3—H3	125.6	C215—C214—H214	120.0
C2—C3—H3	125.6	C214—C215—C216	120.12 (19)
Fe1—C3—H3	126.3	C214—C215—H215	119.9
C5—C4—C3	108.39 (15)	C216—C215—H215	119.9
C5—C4—Fe1	69.03 (10)	C215—C216—C211	119.96 (18)
C3—C4—Fe1	69.25 (10)	C215—C216—H216	120.0
C5—C4—H4	125.8	C211—C216—H216	120.0
C3—C4—H4	125.8	C226—C221—C222	119.13 (17)
Fe1—C4—H4	127.5	C226—C221—P2	121.80 (14)
C4—C5—C1	108.46 (15)	C222—C221—P2	119.03 (14)
C4—C5—Fe1	70.64 (10)	C223—C222—C221	119.87 (18)
C1—C5—Fe1	68.86 (9)	C223—C222—H222	120.1
C4—C5—H5	125.8	C221—C222—H222	120.1
C1—C5—H5	125.8	C224—C223—C222	120.74 (19)
Fe1—C5—H5	126.3	C224—C223—H223	119.6
C10—C6—C7	107.9 (2)	C222—C223—H223	119.6
C10—C6—Fe1	69.74 (12)	C225—C224—C223	119.62 (18)
C7—C6—Fe1	70.28 (12)	C225—C224—H224	120.2
C10—C6—H6	126.1	C223—C224—H224	120.2
C7—C6—H6	126.1	C224—C225—C226	120.3 (2)
Fe1—C6—H6	125.5	C224—C225—H225	119.8
C8—C7—C6	108.1 (2)	C226—C225—H225	119.8
C8—C7—Fe1	69.81 (12)	C221—C226—C225	120.29 (19)
C6—C7—Fe1	69.41 (12)	C221—C226—H226	119.9
C8—C7—H7	126.0	C225—C226—H226	119.9

(R,R/S,S)-Bis{µ-[2-(diphenylphosphanyl)ferrocen-1-yl]methanethiolato-κ³P,S:S}bis[chloridopalladium(II)] pentane disolvate (3)

Crystal data

[Fe2Pd2(C5H5)2(C18H15PS)2Cl2]·2C5H12	F(000) = 2560
Mr = 1258.53	Dx = 1.644 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.5734 (4) Å	Cell parameters from 9010 reflections
b = 11.0824 (2) Å	θ = 2.4–36.3°
c = 21.1091 (4) Å	µ = 1.54 mm^−1
β = 105.653 (1)°	T = 180 K
V = 5084.96 (16) Å^3	Block, orange
Z = 4	0.34 × 0.19 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5210 independent reflections
Radiation source: fine-focus sealed tube	4742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −28→28
Tmin = 0.596, Tmax = 0.747	k = −13→13
78869 measured reflections	l = −26→26

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.0132P)^2 + 14.9112P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.002
5210 reflections	Δρmax = 0.60 e Å^−3
253 parameters	Δρmin = −0.32 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
Pd1	0.92541 (2)	0.09502 (2)	0.73265 (2)	0.01769 (5)
Fe1	0.88116 (2)	−0.04219 (3)	0.52425 (2)	0.01968 (7)
Cl1	0.86299 (2)	0.15245 (6)	0.79979 (3)	0.03189 (13)
S1	0.99385 (2)	0.02674 (5)	0.67910 (2)	0.01897 (10)
P1	0.85153 (2)	0.14917 (5)	0.64028 (2)	0.01744 (10)
C1	0.87006 (9)	0.12045 (19)	0.56396 (10)	0.0200 (4)
C2	0.93170 (9)	0.11053 (18)	0.55651 (10)	0.0198 (4)
C3	0.92626 (10)	0.09225 (19)	0.48813 (10)	0.0229 (4)
H3	0.9595	0.0831	0.4689	0.027*
C4	0.86290 (10)	0.0900 (2)	0.45367 (10)	0.0263 (5)
H4	0.8466	0.0791	0.4076	0.032*
C5	0.82813 (10)	0.1068 (2)	0.49980 (10)	0.0236 (4)
H5	0.7845	0.1087	0.4899	0.028*
C6	0.87618 (11)	−0.1753 (2)	0.58992 (11)	0.0297 (5)
H6	0.8779	−0.1636	0.6350	0.036*
C7	0.92688 (11)	−0.1970 (2)	0.56451 (12)	0.0308 (5)
H7	0.9687	−0.2026	0.5895	0.037*
C8	0.90476 (12)	−0.2090 (2)	0.49527 (12)	0.0328 (5)
H8	0.9290	−0.2242	0.4657	0.039*
C9	0.84006 (12)	−0.1943 (2)	0.47806 (12)	0.0340 (5)
H9	0.8133	−0.1975	0.4348	0.041*
C10	0.82223 (11)	−0.1738 (2)	0.53666 (13)	0.0323 (5)
H10	0.7814	−0.1614	0.5397	0.039*
C21	0.99066 (9)	0.1246 (2)	0.60896 (10)	0.0230 (4)
H21A	0.9951	0.2096	0.6239	0.028*
H21B	1.0255	0.1052	0.5905	0.028*
C111	0.77901 (9)	0.07201 (19)	0.63370 (10)	0.0217 (4)
C112	0.77877 (11)	−0.0334 (2)	0.66927 (11)	0.0264 (5)
H112	0.8159	−0.0616	0.6985	0.032*
C113	0.72484 (12)	−0.0975 (2)	0.66250 (12)	0.0356 (6)
H113	0.7251	−0.1702	0.6864	0.043*
C114	0.67068 (12)	−0.0556 (3)	0.62088 (13)	0.0423 (7)
H114	0.6336	−0.0994	0.6164	0.051*
C115	0.67004 (12)	0.0494 (3)	0.58571 (13)	0.0417 (6)
H115	0.6325	0.0780	0.5573	0.050*
C116	0.72424 (10)	0.1136 (2)	0.59182 (11)	0.0304 (5)
H116	0.7238	0.1858	0.5674	0.036*
C121	0.83252 (9)	0.30930 (19)	0.63502 (10)	0.0205 (4)
C122	0.85682 (11)	0.3865 (2)	0.59653 (12)	0.0293 (5)
H122	0.8826	0.3553	0.5716	0.035*
C123	0.84346 (12)	0.5090 (2)	0.59445 (13)	0.0362 (6)
H123	0.8599	0.5613	0.5678	0.043*
C124	0.80635 (12)	0.5549 (2)	0.63092 (12)	0.0343 (5)
H124	0.7977	0.6389	0.6297	0.041*
C125	0.78166 (11)	0.4791 (2)	0.66928 (12)	0.0326 (5)
H125	0.7557	0.5108	0.6940	0.039*
C126	0.79494 (10)	0.3563 (2)	0.67160 (11)	0.0280 (5)
H126	0.7783	0.3043	0.6982	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01777 (8)	0.01998 (8)	0.01567 (8)	0.00106 (6)	0.00511 (6)	0.00112 (6)
Fe1	0.02284 (14)	0.01817 (15)	0.01825 (14)	−0.00331 (12)	0.00593 (11)	−0.00204 (11)
Cl1	0.0253 (3)	0.0480 (4)	0.0237 (3)	0.0110 (2)	0.0089 (2)	−0.0016 (2)
S1	0.0183 (2)	0.0214 (3)	0.0174 (2)	−0.00077 (19)	0.00517 (18)	−0.00184 (19)
P1	0.0187 (2)	0.0161 (2)	0.0177 (2)	0.00008 (19)	0.00521 (19)	0.00143 (19)
C1	0.0238 (10)	0.0180 (10)	0.0176 (9)	−0.0004 (8)	0.0047 (8)	0.0014 (8)
C2	0.0250 (10)	0.0160 (10)	0.0194 (10)	−0.0021 (8)	0.0079 (8)	0.0005 (8)
C3	0.0279 (11)	0.0220 (11)	0.0206 (10)	−0.0043 (9)	0.0096 (8)	0.0007 (8)
C4	0.0331 (12)	0.0263 (12)	0.0185 (10)	−0.0012 (9)	0.0052 (9)	0.0017 (9)
C5	0.0255 (10)	0.0235 (11)	0.0203 (10)	0.0002 (9)	0.0036 (8)	0.0024 (8)
C6	0.0455 (13)	0.0175 (11)	0.0284 (11)	−0.0066 (10)	0.0138 (10)	−0.0001 (9)
C7	0.0338 (12)	0.0187 (11)	0.0394 (13)	−0.0017 (9)	0.0088 (10)	0.0022 (10)
C8	0.0446 (14)	0.0201 (11)	0.0401 (13)	−0.0013 (10)	0.0223 (11)	−0.0056 (10)
C9	0.0408 (13)	0.0265 (12)	0.0320 (12)	−0.0105 (10)	0.0053 (10)	−0.0110 (10)
C10	0.0313 (12)	0.0226 (12)	0.0466 (14)	−0.0100 (10)	0.0166 (11)	−0.0071 (10)
C21	0.0236 (10)	0.0272 (12)	0.0197 (10)	−0.0060 (9)	0.0085 (8)	−0.0013 (8)
C111	0.0226 (10)	0.0233 (11)	0.0210 (10)	−0.0051 (8)	0.0087 (8)	−0.0031 (8)
C112	0.0344 (12)	0.0252 (12)	0.0233 (10)	−0.0030 (9)	0.0140 (9)	−0.0010 (9)
C113	0.0516 (15)	0.0292 (13)	0.0327 (12)	−0.0147 (11)	0.0229 (11)	−0.0067 (10)
C114	0.0386 (14)	0.0518 (17)	0.0410 (14)	−0.0256 (13)	0.0184 (12)	−0.0186 (13)
C115	0.0259 (12)	0.0559 (18)	0.0404 (14)	−0.0090 (12)	0.0038 (10)	−0.0050 (13)
C116	0.0251 (11)	0.0348 (13)	0.0291 (12)	−0.0045 (10)	0.0038 (9)	0.0025 (10)
C121	0.0206 (9)	0.0168 (10)	0.0221 (10)	0.0003 (8)	0.0026 (8)	−0.0004 (8)
C122	0.0345 (12)	0.0237 (12)	0.0332 (12)	−0.0024 (9)	0.0150 (10)	0.0016 (9)
C123	0.0468 (15)	0.0226 (12)	0.0417 (14)	−0.0037 (11)	0.0162 (12)	0.0039 (10)
C124	0.0425 (14)	0.0174 (11)	0.0402 (13)	0.0025 (10)	0.0061 (11)	−0.0005 (10)
C125	0.0369 (13)	0.0270 (12)	0.0348 (13)	0.0059 (10)	0.0112 (10)	−0.0030 (10)
C126	0.0327 (12)	0.0255 (12)	0.0278 (11)	0.0035 (9)	0.0115 (9)	0.0028 (9)

Geometric parameters (Å, º)

Pd1—S1	2.2758 (5)	C7—C8	1.418 (3)
Pd1—P1	2.2779 (5)	C7—H7	0.9500
Pd1—Cl1	2.3402 (5)	C8—C9	1.416 (4)
Pd1—S1^i	2.3522 (5)	C8—H8	0.9500
Pd1—Pd1^i	3.2473 (3)	C9—C10	1.419 (3)
Fe1—C5	2.023 (2)	C9—H9	0.9500
Fe1—C1	2.032 (2)	C10—H10	0.9500
Fe1—C10	2.038 (2)	C21—H21A	0.9900
Fe1—C9	2.040 (2)	C21—H21B	0.9900
Fe1—C6	2.048 (2)	C111—C112	1.389 (3)
Fe1—C4	2.051 (2)	C111—C116	1.390 (3)
Fe1—C2	2.052 (2)	C112—C113	1.383 (3)
Fe1—C8	2.062 (2)	C112—H112	0.9500
Fe1—C7	2.063 (2)	C113—C114	1.379 (4)
Fe1—C3	2.063 (2)	C113—H113	0.9500
S1—C21	1.821 (2)	C114—C115	1.379 (4)
S1—Pd1^i	2.3522 (5)	C114—H114	0.9500
P1—C1	1.799 (2)	C115—C116	1.391 (3)
P1—C111	1.819 (2)	C115—H115	0.9500
P1—C121	1.822 (2)	C116—H116	0.9500
C1—C5	1.436 (3)	C121—C122	1.391 (3)
C1—C2	1.446 (3)	C121—C126	1.393 (3)
C2—C3	1.430 (3)	C122—C123	1.389 (3)
C2—C21	1.492 (3)	C122—H122	0.9500
C3—C4	1.419 (3)	C123—C124	1.379 (4)
C3—H3	0.9500	C123—H123	0.9500
C4—C5	1.418 (3)	C124—C125	1.385 (4)
C4—H4	0.9500	C124—H124	0.9500
C5—H5	0.9500	C125—C126	1.391 (3)
C6—C7	1.409 (3)	C125—H125	0.9500
C6—C10	1.417 (3)	C126—H126	0.9500
C6—H6	0.9500
S1—Pd1—P1	95.780 (18)	C5—C4—Fe1	68.59 (12)
S1—Pd1—Cl1	172.55 (2)	C3—C4—Fe1	70.30 (12)
P1—Pd1—Cl1	91.457 (19)	C5—C4—H4	125.9
S1—Pd1—S1^i	78.56 (2)	C3—C4—H4	125.9
P1—Pd1—S1^i	174.044 (19)	Fe1—C4—H4	126.8
Cl1—Pd1—S1^i	94.147 (18)	C4—C5—C1	108.38 (19)
S1—Pd1—Pd1^i	46.406 (13)	C4—C5—Fe1	70.66 (13)
P1—Pd1—Pd1^i	131.930 (15)	C1—C5—Fe1	69.58 (12)
Cl1—Pd1—Pd1^i	128.356 (16)	C4—C5—H5	125.8
S1^i—Pd1—Pd1^i	44.486 (12)	C1—C5—H5	125.8
C5—Fe1—C1	41.47 (8)	Fe1—C5—H5	125.5
C5—Fe1—C10	104.79 (9)	C7—C6—C10	108.2 (2)
C1—Fe1—C10	115.13 (9)	C7—C6—Fe1	70.54 (13)
C5—Fe1—C9	113.01 (10)	C10—C6—Fe1	69.35 (13)
C1—Fe1—C9	147.05 (9)	C7—C6—H6	125.9
C10—Fe1—C9	40.70 (10)	C10—C6—H6	125.9
C5—Fe1—C6	128.59 (9)	Fe1—C6—H6	125.8
C1—Fe1—C6	108.92 (9)	C6—C7—C8	108.2 (2)
C10—Fe1—C6	40.59 (10)	C6—C7—Fe1	69.36 (13)
C9—Fe1—C6	68.15 (10)	C8—C7—Fe1	69.85 (14)
C5—Fe1—C4	40.74 (9)	C6—C7—H7	125.9
C1—Fe1—C4	69.08 (8)	C8—C7—H7	125.9
C10—Fe1—C4	126.49 (10)	Fe1—C7—H7	126.5
C9—Fe1—C4	105.47 (10)	C9—C8—C7	107.8 (2)
C6—Fe1—C4	165.80 (10)	C9—C8—Fe1	68.99 (13)
C5—Fe1—C2	69.45 (8)	C7—C8—Fe1	69.94 (13)
C1—Fe1—C2	41.47 (8)	C9—C8—H8	126.1
C10—Fe1—C2	150.62 (9)	C7—C8—H8	126.1
C9—Fe1—C2	168.58 (9)	Fe1—C8—H8	126.5
C6—Fe1—C2	119.77 (9)	C8—C9—C10	108.1 (2)
C4—Fe1—C2	68.68 (8)	C8—C9—Fe1	70.63 (13)
C5—Fe1—C8	146.99 (10)	C10—C9—Fe1	69.57 (13)
C1—Fe1—C8	171.24 (9)	C8—C9—H9	126.0
C10—Fe1—C8	68.05 (10)	C10—C9—H9	126.0
C9—Fe1—C8	40.38 (10)	Fe1—C9—H9	125.4
C6—Fe1—C8	67.73 (9)	C6—C10—C9	107.7 (2)
C4—Fe1—C8	116.26 (9)	C6—C10—Fe1	70.06 (13)
C2—Fe1—C8	132.29 (9)	C9—C10—Fe1	69.72 (13)
C5—Fe1—C7	168.39 (9)	C6—C10—H10	126.1
C1—Fe1—C7	132.17 (9)	C9—C10—H10	126.1
C10—Fe1—C7	67.87 (10)	Fe1—C10—H10	125.7
C9—Fe1—C7	67.82 (10)	C2—C21—S1	111.91 (14)
C6—Fe1—C7	40.10 (9)	C2—C21—H21A	109.2
C4—Fe1—C7	150.87 (9)	S1—C21—H21A	109.2
C2—Fe1—C7	112.18 (9)	C2—C21—H21B	109.2
C8—Fe1—C7	40.20 (10)	S1—C21—H21B	109.2
C5—Fe1—C3	68.48 (9)	H21A—C21—H21B	107.9
C1—Fe1—C3	68.89 (8)	C112—C111—C116	119.3 (2)
C10—Fe1—C3	165.61 (9)	C112—C111—P1	119.26 (17)
C9—Fe1—C3	128.75 (9)	C116—C111—P1	121.35 (17)
C6—Fe1—C3	153.24 (9)	C113—C112—C111	120.5 (2)
C4—Fe1—C3	40.36 (9)	C113—C112—H112	119.7
C2—Fe1—C3	40.65 (8)	C111—C112—H112	119.7
C8—Fe1—C3	110.18 (9)	C114—C113—C112	119.8 (2)
C7—Fe1—C3	120.72 (9)	C114—C113—H113	120.1
C21—S1—Pd1	108.83 (7)	C112—C113—H113	120.1
C21—S1—Pd1^i	107.74 (7)	C115—C114—C113	120.4 (2)
Pd1—S1—Pd1^i	89.107 (18)	C115—C114—H114	119.8
C1—P1—C111	105.69 (9)	C113—C114—H114	119.8
C1—P1—C121	103.04 (10)	C114—C115—C116	120.1 (2)
C111—P1—C121	105.13 (10)	C114—C115—H115	120.0
C1—P1—Pd1	115.25 (7)	C116—C115—H115	120.0
C111—P1—Pd1	112.18 (7)	C111—C116—C115	119.9 (2)
C121—P1—Pd1	114.50 (7)	C111—C116—H116	120.1
C5—C1—C2	107.35 (17)	C115—C116—H116	120.1
C5—C1—P1	127.59 (16)	C122—C121—C126	119.3 (2)
C2—C1—P1	125.04 (15)	C122—C121—P1	120.76 (16)
C5—C1—Fe1	68.95 (12)	C126—C121—P1	119.93 (16)
C2—C1—Fe1	70.02 (12)	C123—C122—C121	120.2 (2)
P1—C1—Fe1	127.65 (11)	C123—C122—H122	119.9
C3—C2—C1	107.32 (18)	C121—C122—H122	119.9
C3—C2—C21	125.48 (18)	C124—C123—C122	120.2 (2)
C1—C2—C21	127.10 (18)	C124—C123—H123	119.9
C3—C2—Fe1	70.09 (12)	C122—C123—H123	119.9
C1—C2—Fe1	68.51 (11)	C123—C124—C125	120.2 (2)
C21—C2—Fe1	129.56 (15)	C123—C124—H124	119.9
C4—C3—C2	108.67 (18)	C125—C124—H124	119.9
C4—C3—Fe1	69.34 (12)	C124—C125—C126	119.8 (2)
C2—C3—Fe1	69.25 (11)	C124—C125—H125	120.1
C4—C3—H3	125.7	C126—C125—H125	120.1
C2—C3—H3	125.7	C125—C126—C121	120.3 (2)
Fe1—C3—H3	127.3	C125—C126—H126	119.9
C5—C4—C3	108.28 (18)	C121—C126—H126	119.9

Symmetry code: (i) −x+2, y, −z+3/2.

(R,R/S,S)-Bis{µ-[2-(diphenylphosphanyl)ferrocen-1-yl]methanethiolato-κ³P,S:S}bis[chloridoplatinum(II)] toluene monosolvate (4)

Crystal data

[Fe2Pt2(C5H5)2(C18H15PS)2Cl2]·C7H8	F(000) = 2680
Mr = 1383.75	Dx = 1.765 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7900 reflections
a = 23.5510 (13) Å	θ = 3.1–32.7°
b = 11.0936 (3) Å	µ = 6.18 mm^−1
c = 20.7693 (8) Å	T = 180 K
β = 106.285 (5)°	Plate, orange
V = 5208.6 (4) Å^3	0.24 × 0.15 × 0.04 mm
Z = 4

Data collection

Agilent Xcalibur Gemini Ultra diffractometer with Eos detector	5966 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4810 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 16.1978 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −30→30
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −14→14
Tmin = 0.652, Tmax = 1.0	l = −26→26
33461 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 34.125P] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.002
5966 reflections	Δρmax = 2.05 e Å^−3
253 parameters	Δρmin = −0.66 e Å^−3

Special details

Experimental. Multi-scan absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent Technologies, 2012)

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
Pt1	0.92769 (2)	0.09459 (2)	0.73357 (2)	0.02925 (7)
Fe1	0.87814 (4)	−0.04224 (6)	0.52205 (3)	0.03114 (17)
Cl1	0.87080 (7)	0.15249 (16)	0.80463 (7)	0.0486 (4)
S1	0.99233 (6)	0.02752 (11)	0.67768 (6)	0.0308 (3)
P1	0.85447 (6)	0.14840 (11)	0.64253 (6)	0.0291 (3)
C1	0.8695 (2)	0.1199 (4)	0.5635 (2)	0.0309 (11)
C2	0.9277 (3)	0.1094 (4)	0.5539 (2)	0.0315 (11)
C3	0.9198 (3)	0.0910 (5)	0.4833 (2)	0.0368 (12)
H3	0.9506	0.0809	0.4624	0.044*
C4	0.8586 (3)	0.0907 (5)	0.4504 (3)	0.0389 (13)
H4	0.8413	0.0811	0.4035	0.047*
C5	0.8273 (3)	0.1072 (4)	0.4988 (3)	0.0357 (12)
H5	0.7855	0.1095	0.4900	0.043*
C6	0.8771 (3)	−0.1774 (5)	0.5892 (3)	0.0425 (14)
H6	0.8813	−0.1679	0.6357	0.051*
C7	0.9235 (3)	−0.1969 (5)	0.5598 (3)	0.0407 (13)
H7	0.9644	−0.2022	0.5830	0.049*
C8	0.8982 (3)	−0.2073 (5)	0.4897 (3)	0.0404 (13)
H8	0.9193	−0.2208	0.4575	0.048*
C9	0.8369 (3)	−0.1944 (5)	0.4759 (3)	0.0423 (13)
H9	0.8092	−0.1983	0.4327	0.051*
C10	0.8232 (3)	−0.1744 (5)	0.5374 (3)	0.0442 (14)
H10	0.7849	−0.1614	0.5427	0.053*
C21	0.9862 (3)	0.1245 (5)	0.6053 (3)	0.0358 (12)
H21A	0.9911	0.2096	0.6201	0.043*
H21B	1.0184	0.1047	0.5848	0.043*
C111	0.7854 (3)	0.0703 (5)	0.6377 (3)	0.0362 (12)
C112	0.7322 (3)	0.1112 (6)	0.5967 (3)	0.0504 (16)
H112	0.7308	0.1843	0.5726	0.060*
C113	0.6803 (3)	0.0456 (8)	0.5906 (4)	0.064 (2)
H113	0.6439	0.0731	0.5614	0.077*
C114	0.6819 (4)	−0.0584 (8)	0.6267 (4)	0.067 (2)
H114	0.6465	−0.1020	0.6233	0.081*
C115	0.7344 (4)	−0.0994 (6)	0.6674 (3)	0.0562 (19)
H115	0.7352	−0.1722	0.6918	0.067*
C116	0.7863 (3)	−0.0363 (5)	0.6736 (3)	0.0443 (14)
H116	0.8225	−0.0655	0.7023	0.053*
C121	0.8351 (2)	0.3081 (4)	0.6371 (2)	0.0308 (11)
C122	0.8553 (3)	0.3843 (5)	0.5956 (3)	0.0401 (13)
H122	0.8784	0.3528	0.5686	0.048*
C123	0.8419 (3)	0.5068 (5)	0.5931 (3)	0.0460 (14)
H123	0.8562	0.5586	0.5647	0.055*
C124	0.8086 (3)	0.5525 (5)	0.6313 (3)	0.0483 (15)
H124	0.7997	0.6362	0.6297	0.058*
C125	0.7876 (3)	0.4766 (5)	0.6725 (3)	0.0518 (16)
H125	0.7642	0.5084	0.6991	0.062*
C126	0.8006 (3)	0.3550 (5)	0.6751 (3)	0.0488 (15)
H126	0.7857	0.3033	0.7030	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.04125 (13)	0.02486 (10)	0.02359 (10)	0.00224 (8)	0.01229 (8)	0.00190 (7)
Fe1	0.0452 (4)	0.0243 (3)	0.0256 (3)	−0.0053 (3)	0.0127 (3)	−0.0033 (3)
Cl1	0.0522 (9)	0.0658 (9)	0.0310 (6)	0.0172 (8)	0.0169 (6)	0.0008 (7)
S1	0.0393 (7)	0.0272 (6)	0.0276 (6)	−0.0028 (5)	0.0124 (5)	−0.0032 (5)
P1	0.0409 (7)	0.0226 (6)	0.0252 (6)	−0.0008 (5)	0.0117 (5)	0.0013 (5)
C1	0.044 (3)	0.022 (2)	0.028 (2)	−0.001 (2)	0.013 (2)	−0.0006 (19)
C2	0.048 (3)	0.024 (2)	0.025 (2)	−0.005 (2)	0.015 (2)	0.0003 (19)
C3	0.057 (4)	0.031 (3)	0.026 (2)	−0.009 (3)	0.018 (2)	−0.001 (2)
C4	0.056 (4)	0.037 (3)	0.026 (2)	−0.006 (3)	0.015 (2)	0.003 (2)
C5	0.051 (3)	0.026 (2)	0.029 (2)	0.001 (2)	0.008 (2)	0.001 (2)
C6	0.074 (4)	0.026 (2)	0.033 (3)	−0.012 (3)	0.022 (3)	−0.002 (2)
C7	0.051 (3)	0.026 (2)	0.044 (3)	−0.002 (2)	0.011 (3)	−0.001 (2)
C8	0.055 (4)	0.028 (3)	0.043 (3)	−0.003 (3)	0.022 (3)	−0.009 (2)
C9	0.053 (4)	0.031 (3)	0.042 (3)	−0.010 (3)	0.012 (3)	−0.013 (2)
C10	0.058 (4)	0.026 (2)	0.056 (3)	−0.008 (3)	0.027 (3)	−0.004 (2)
C21	0.044 (3)	0.036 (3)	0.029 (2)	−0.012 (2)	0.013 (2)	−0.003 (2)
C111	0.047 (3)	0.031 (3)	0.033 (3)	−0.009 (2)	0.015 (2)	−0.005 (2)
C112	0.051 (4)	0.059 (4)	0.040 (3)	−0.012 (3)	0.012 (3)	0.000 (3)
C113	0.051 (4)	0.089 (6)	0.050 (4)	−0.022 (4)	0.011 (3)	−0.008 (4)
C114	0.071 (5)	0.080 (5)	0.064 (4)	−0.045 (4)	0.041 (4)	−0.030 (4)
C115	0.089 (6)	0.043 (3)	0.052 (4)	−0.029 (4)	0.046 (4)	−0.018 (3)
C116	0.071 (4)	0.030 (3)	0.041 (3)	−0.008 (3)	0.031 (3)	−0.005 (2)
C121	0.040 (3)	0.025 (2)	0.026 (2)	0.000 (2)	0.006 (2)	−0.0019 (19)
C122	0.055 (4)	0.028 (3)	0.042 (3)	−0.003 (2)	0.021 (3)	0.002 (2)
C123	0.065 (4)	0.024 (2)	0.054 (3)	−0.005 (3)	0.025 (3)	0.003 (2)
C124	0.071 (4)	0.024 (2)	0.049 (3)	0.003 (3)	0.015 (3)	−0.001 (2)
C125	0.083 (5)	0.033 (3)	0.047 (3)	0.010 (3)	0.031 (3)	0.000 (3)
C126	0.074 (4)	0.033 (3)	0.044 (3)	0.012 (3)	0.024 (3)	0.007 (3)

Geometric parameters (Å, º)

Pt1—P1	2.2531 (13)	C7—C8	1.416 (8)
Pt1—S1	2.2823 (13)	C7—H7	0.9500
Pt1—Cl1	2.3441 (13)	C8—C9	1.398 (8)
Pt1—S1^i	2.3563 (13)	C8—H8	0.9500
Fe1—C5	2.022 (5)	C9—C10	1.420 (8)
Fe1—C1	2.028 (5)	C9—H9	0.9500
Fe1—C10	2.039 (6)	C10—H10	0.9500
Fe1—C9	2.047 (5)	C21—H21A	0.9900
Fe1—C2	2.049 (5)	C21—H21B	0.9900
Fe1—C8	2.052 (5)	C111—C112	1.379 (9)
Fe1—C6	2.052 (5)	C111—C116	1.395 (7)
Fe1—C7	2.057 (6)	C112—C113	1.396 (9)
Fe1—C4	2.054 (5)	C112—H112	0.9500
Fe1—C3	2.060 (5)	C113—C114	1.371 (11)
S1—C21	1.821 (5)	C113—H113	0.9500
S1—Pt1^i	2.3563 (13)	C114—C115	1.364 (11)
P1—C1	1.803 (5)	C114—H114	0.9500
P1—C111	1.821 (6)	C115—C116	1.384 (9)
P1—C121	1.825 (5)	C115—H115	0.9500
C1—C2	1.443 (8)	C116—H116	0.9500
C1—C5	1.436 (7)	C121—C126	1.383 (8)
C2—C3	1.441 (7)	C121—C122	1.383 (7)
C2—C21	1.498 (8)	C122—C123	1.393 (7)
C3—C4	1.411 (9)	C122—H122	0.9500
C3—H3	0.9500	C123—C124	1.361 (9)
C4—C5	1.415 (8)	C123—H123	0.9500
C4—H4	0.9500	C124—C125	1.388 (9)
C5—H5	0.9500	C124—H124	0.9500
C6—C7	1.409 (8)	C125—C126	1.381 (8)
C6—C10	1.416 (9)	C125—H125	0.9500
C6—H6	0.9500	C126—H126	0.9500
P1—Pt1—S1	97.02 (5)	C3—C4—H4	125.6
P1—Pt1—Cl1	91.01 (5)	C5—C4—H4	125.6
S1—Pt1—Cl1	171.90 (5)	Fe1—C4—H4	127.3
P1—Pt1—S1^i	174.85 (4)	C4—C5—C1	108.4 (5)
S1—Pt1—S1^i	78.12 (5)	C4—C5—Fe1	70.9 (3)
Cl1—Pt1—S1^i	93.82 (5)	C1—C5—Fe1	69.4 (3)
C5—Fe1—C1	41.5 (2)	C4—C5—H5	125.8
C5—Fe1—C10	105.5 (2)	C1—C5—H5	125.8
C1—Fe1—C10	115.4 (2)	Fe1—C5—H5	125.4
C5—Fe1—C9	113.2 (2)	C7—C6—C10	108.3 (5)
C1—Fe1—C9	147.1 (2)	C7—C6—Fe1	70.1 (3)
C10—Fe1—C9	40.7 (2)	C10—C6—Fe1	69.3 (3)
C5—Fe1—C2	69.5 (2)	C7—C6—H6	125.8
C1—Fe1—C2	41.4 (2)	C10—C6—H6	125.8
C10—Fe1—C2	150.4 (2)	Fe1—C6—H6	126.3
C9—Fe1—C2	168.8 (2)	C6—C7—C8	107.7 (5)
C5—Fe1—C8	146.0 (2)	C6—C7—Fe1	69.8 (3)
C1—Fe1—C8	172.0 (2)	C8—C7—Fe1	69.6 (3)
C10—Fe1—C8	67.9 (2)	C6—C7—H7	126.1
C9—Fe1—C8	39.9 (2)	C8—C7—H7	126.1
C2—Fe1—C8	132.6 (2)	Fe1—C7—H7	126.0
C5—Fe1—C6	130.0 (2)	C9—C8—C7	108.4 (5)
C1—Fe1—C6	109.8 (2)	C9—C8—Fe1	69.9 (3)
C10—Fe1—C6	40.5 (2)	C7—C8—Fe1	70.1 (3)
C9—Fe1—C6	67.7 (2)	C9—C8—H8	125.8
C2—Fe1—C6	119.7 (2)	C7—C8—H8	125.8
C8—Fe1—C6	67.5 (2)	Fe1—C8—H8	125.8
C5—Fe1—C7	169.8 (2)	C8—C9—C10	108.3 (5)
C1—Fe1—C7	132.9 (2)	C8—C9—Fe1	70.2 (3)
C10—Fe1—C7	68.0 (3)	C10—C9—Fe1	69.4 (3)
C9—Fe1—C7	67.5 (2)	C8—C9—H9	125.8
C2—Fe1—C7	112.0 (2)	C10—C9—H9	125.8
C8—Fe1—C7	40.3 (2)	Fe1—C9—H9	126.1
C6—Fe1—C7	40.1 (2)	C6—C10—C9	107.3 (5)
C5—Fe1—C4	40.6 (2)	C6—C10—Fe1	70.3 (3)
C1—Fe1—C4	69.0 (2)	C9—C10—Fe1	70.0 (3)
C10—Fe1—C4	127.4 (3)	C6—C10—H10	126.3
C9—Fe1—C4	105.8 (2)	C9—C10—H10	126.3
C2—Fe1—C4	68.6 (2)	Fe1—C10—H10	125.0
C8—Fe1—C4	115.4 (2)	C2—C21—S1	111.5 (4)
C6—Fe1—C4	166.9 (3)	C2—C21—H21A	109.3
C7—Fe1—C4	149.6 (2)	S1—C21—H21A	109.3
C5—Fe1—C3	68.5 (2)	C2—C21—H21B	109.3
C1—Fe1—C3	69.2 (2)	S1—C21—H21B	109.3
C10—Fe1—C3	166.0 (2)	H21A—C21—H21B	108.0
C9—Fe1—C3	128.6 (2)	C112—C111—C116	118.9 (6)
C2—Fe1—C3	41.07 (19)	C112—C111—P1	121.4 (4)
C8—Fe1—C3	109.5 (2)	C116—C111—P1	119.7 (5)
C6—Fe1—C3	152.6 (3)	C111—C112—C113	120.4 (7)
C7—Fe1—C3	119.6 (2)	C111—C112—H112	119.8
C4—Fe1—C3	40.1 (2)	C113—C112—H112	119.8
C21—S1—Pt1	108.55 (19)	C114—C113—C112	119.9 (7)
C21—S1—Pt1^i	108.66 (18)	C114—C113—H113	120.0
Pt1—S1—Pt1^i	90.00 (4)	C112—C113—H113	120.0
C1—P1—C111	105.5 (2)	C115—C114—C113	120.1 (6)
C1—P1—C121	102.9 (2)	C115—C114—H114	120.0
C111—P1—C121	104.8 (3)	C113—C114—H114	120.0
C1—P1—Pt1	114.72 (19)	C114—C115—C116	120.8 (6)
C111—P1—Pt1	112.45 (19)	C114—C115—H115	119.6
C121—P1—Pt1	115.34 (16)	C116—C115—H115	119.6
C2—C1—C5	107.3 (4)	C115—C116—C111	119.9 (7)
C2—C1—P1	125.2 (4)	C115—C116—H116	120.0
C5—C1—P1	127.4 (4)	C111—C116—H116	120.0
C2—C1—Fe1	70.0 (3)	C126—C121—C122	119.0 (5)
C5—C1—Fe1	69.0 (3)	C126—C121—P1	120.5 (4)
P1—C1—Fe1	127.6 (3)	C122—C121—P1	120.5 (4)
C1—C2—C3	107.2 (5)	C121—C122—C123	120.4 (5)
C1—C2—C21	127.8 (4)	C121—C122—H122	119.8
C3—C2—C21	124.8 (5)	C123—C122—H122	119.8
C1—C2—Fe1	68.5 (3)	C124—C123—C122	120.2 (5)
C3—C2—Fe1	69.9 (3)	C124—C123—H123	119.9
C21—C2—Fe1	130.5 (4)	C122—C123—H123	119.9
C4—C3—C2	108.4 (5)	C123—C124—C125	119.8 (5)
C4—C3—Fe1	69.7 (3)	C123—C124—H124	120.1
C2—C3—Fe1	69.1 (3)	C125—C124—H124	120.1
C4—C3—H3	125.8	C126—C125—C124	120.2 (6)
C2—C3—H3	125.8	C126—C125—H125	119.9
Fe1—C3—H3	127.0	C124—C125—H125	119.9
C3—C4—C5	108.7 (5)	C121—C126—C125	120.4 (6)
C3—C4—Fe1	70.2 (3)	C121—C126—H126	119.8
C5—C4—Fe1	68.5 (3)	C125—C126—H126	119.8

Symmetry code: (i) −x+2, y, −z+3/2.