Conformational and structural diversity of iridium di­methyl sulfoxide complexes

Transition metal complexes containing dimethyl sulfoxide (DMSO) are important precursors in catalysis and metallodrugs. Understanding the solid-state supramolecular structure is crucial for predicting the properties and biological activity of the material. Several crystalline phases of DMSO-coordinated iridium anions with different cations, potassium (1a) and n-butyl­ammonium (1b), were obtained and their structures determined by X-ray crystallography. Compound (1a) is present in two solvatomorphic forms: α and β; the β form contains disordered solvent water. In addition, the structures exhibit different rotamers of the trans-[IrCl₄(DMSO)₂]⁻ anion with the trans-DMSO ligands being oriented in anti and gauche conformations. In consideration of these various conformers, the effects of the crystallized solvent and intermolecular interactions on the conformational preferences of the anion are discussed. In addition, density functional theory calculations were used to investigate the energies of the anions in the different conformations. It was found that hydrogen bonds between water and the DMSO complex stabilize the gauche conformation which is the least stable form of the trans-DMSO complex. Consequently, by controlling the number of hydrogen-bond donors and acceptors and the amount of water, it may be possible to obtain different solvatomorphs of clinically significant metallodrugs.

Computing details

For all structures, data collection: COLLECT (Enraf-Nonius, 1997-2004). Cell refinement: SCALEPACK (Otwinowski & Minor 1997) for 1a_alpha, 1a_beta, (1b); 'SCALEPACK (Otwinowski & Minor 1997)' for (2). For all structures, data reduction: 'DENZO and SCALEPACK (Otwinowski & Minor 1997)'. Program(s) used to solve structure: SHELXS86 (Sheldrick, 1986) for 1a_alpha, 1a_beta, (2); SIR2004 (Giacovazzo et al., 2004) for (1b). For all structures, program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016); molecular graphics: C.B. Hubschle, G.M. Scheldrick, and B. Dittrich Shelxle: a Qt graphical user interface for SHELXL J. Appl. Cryst., 44 (2011) 1281–1284; software used to prepare material for publication: The pyMOL Molecular Graphics System, Version #, Schrodinger, LLC. Version 1.7.2.1.

'Potassium tetrachlorobis(dimethyl sulfoxide)iridate(III) monohydrate' (1a_alpha)

Crystal data

K·C4H12Cl4IrO2S2·H2O	F(000) = 1032
Mr = 547.37	Dx = 2.437 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1963 (2) Å	Cell parameters from 17784 reflections
b = 7.4652 (2) Å	θ = 2.9–26.0°
c = 16.4793 (4) Å	µ = 10.21 mm^−1
β = 96.055 (1)°	T = 293 K
V = 1492.03 (6) Å^3	Prism, orange
Z = 4	0.38 × 0.20 × 0.12 mm

Data collection

KappaCCD diffractometer	2614 independent reflections
Radiation source: Enraf Nonius FR590	2582 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.061
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −14→14
Absorption correction: gaussian P. Coppens, L. Leiserowitz, D Rabinovich, Acta Cryst. (1965), 18, 1035-1038	k = −8→8
Tmin = 0.064, Tmax = 0.292	l = −19→19
8722 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + 0.9117P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
2614 reflections	Δρmax = 0.70 e Å^−3
141 parameters	Δρmin = −1.70 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ir1	0.24218 (2)	0.46664 (2)	0.13709 (2)	0.02112 (10)
K1	0.51889 (10)	0.43327 (17)	0.31396 (8)	0.0416 (3)
Cl1	0.42630 (9)	0.3868 (2)	0.12178 (8)	0.0418 (3)
Cl2	0.30679 (10)	0.66104 (15)	0.24523 (7)	0.0342 (3)
Cl3	0.05972 (11)	0.54715 (18)	0.15351 (9)	0.0412 (3)
Cl4	0.17749 (11)	0.27387 (17)	0.02982 (8)	0.0369 (3)
S1	0.23376 (9)	0.24668 (15)	0.23463 (7)	0.0268 (3)
S2	0.25551 (9)	0.68862 (16)	0.04040 (8)	0.0298 (3)
O1	0.3396 (3)	0.1670 (5)	0.2671 (2)	0.0413 (9)
O2	0.3124 (3)	0.8528 (5)	0.0699 (2)	0.0439 (9)
O1W	0.4085 (4)	0.4049 (7)	0.4513 (3)	0.0643 (13)
H2W	0.382 (2)	0.466 (4)	0.484 (3)	0.096*
H1W	0.3887 (16)	0.304 (8)	0.4571 (6)	0.096*
C1	0.1427 (5)	0.0713 (7)	0.1990 (4)	0.0399 (13)
H1A	0.170046	0.013903	0.153035	0.060*
H1B	0.070872	0.119972	0.182890	0.060*
H1C	0.138103	−0.014688	0.241807	0.060*
C2	0.1677 (5)	0.3264 (8)	0.3182 (3)	0.0400 (12)
H2A	0.212205	0.417797	0.346272	0.060*
H2B	0.158000	0.229295	0.354937	0.060*
H2C	0.097021	0.375364	0.298629	0.060*
C3	0.3208 (6)	0.6107 (9)	−0.0441 (4)	0.0586 (17)
H3A	0.397328	0.588101	−0.027180	0.088*
H3B	0.314536	0.699899	−0.086294	0.088*
H3C	0.286014	0.502066	−0.064491	0.088*
C4	0.1246 (5)	0.7504 (9)	−0.0079 (4)	0.0537 (16)
H4A	0.133750	0.833159	−0.051299	0.080*
H4B	0.082410	0.805944	0.031122	0.080*
H4C	0.086714	0.645569	−0.029873	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.01871 (14)	0.02648 (15)	0.01827 (14)	0.00006 (6)	0.00244 (8)	−0.00115 (6)
K1	0.0327 (6)	0.0560 (7)	0.0351 (7)	0.0073 (5)	−0.0006 (5)	0.0012 (5)
Cl1	0.0224 (6)	0.0666 (9)	0.0377 (8)	0.0076 (6)	0.0091 (5)	0.0020 (6)
Cl2	0.0435 (7)	0.0319 (6)	0.0261 (7)	−0.0057 (5)	−0.0014 (5)	−0.0051 (5)
Cl3	0.0252 (7)	0.0580 (9)	0.0416 (9)	0.0131 (5)	0.0088 (6)	0.0037 (6)
Cl4	0.0431 (7)	0.0409 (7)	0.0256 (7)	−0.0049 (5)	−0.0016 (5)	−0.0097 (5)
S1	0.0272 (6)	0.0300 (6)	0.0235 (6)	−0.0011 (5)	0.0039 (5)	0.0027 (5)
S2	0.0305 (6)	0.0350 (6)	0.0232 (7)	−0.0059 (5)	−0.0007 (5)	0.0052 (5)
O1	0.0303 (18)	0.045 (2)	0.047 (2)	0.0052 (15)	−0.0019 (16)	0.0167 (17)
O2	0.046 (2)	0.040 (2)	0.044 (2)	−0.0151 (16)	−0.0049 (17)	0.0073 (17)
O1W	0.073 (3)	0.066 (3)	0.057 (3)	−0.014 (2)	0.023 (2)	−0.010 (2)
C1	0.041 (3)	0.034 (3)	0.045 (4)	−0.007 (2)	0.007 (3)	−0.001 (2)
C2	0.048 (3)	0.047 (3)	0.027 (3)	−0.006 (2)	0.013 (2)	0.003 (2)
C3	0.080 (5)	0.065 (4)	0.036 (4)	−0.003 (3)	0.028 (3)	0.007 (3)
C4	0.041 (3)	0.065 (4)	0.051 (4)	−0.003 (3)	−0.016 (3)	0.029 (3)

Geometric parameters (Å, º)

Ir1—S1	2.3077 (12)	S2—O2	1.466 (4)
Ir1—S2	2.3165 (12)	S2—C4	1.768 (5)
Ir1—Cl3	2.3481 (12)	S2—C3	1.773 (6)
Ir1—Cl4	2.3503 (12)	O1W—H2W	0.80 (6)
Ir1—Cl1	2.3625 (11)	O1W—H1W	0.80 (6)
Ir1—Cl2	2.3678 (12)	C1—H1A	0.9600
K1—O2^i	2.725 (4)	C1—H1B	0.9600
K1—O1W	2.762 (5)	C1—H1C	0.9600
K1—O1^ii	2.880 (4)	C2—H2A	0.9600
K1—O1	2.995 (4)	C2—H2B	0.9600
K1—Cl2^i	3.1684 (17)	C2—H2C	0.9600
K1—Cl2	3.2012 (17)	C3—H3A	0.9600
K1—Cl1	3.2665 (19)	C3—H3B	0.9600
K1—Cl1^ii	3.5891 (19)	C3—H3C	0.9600
S1—O1	1.470 (4)	C4—H4A	0.9600
S1—C2	1.770 (5)	C4—H4B	0.9600
S1—C1	1.776 (5)	C4—H4C	0.9600
S1—Ir1—S2	178.48 (4)	Cl2^i—K1—K1^i	48.01 (3)
S1—Ir1—Cl3	89.40 (4)	Cl2—K1—K1^i	104.33 (5)
S2—Ir1—Cl3	91.85 (5)	Cl1—K1—K1^i	54.74 (4)
S1—Ir1—Cl4	92.99 (4)	Cl1^ii—K1—K1^i	166.73 (6)
S2—Ir1—Cl4	87.88 (4)	K1^ii—K1—K1^i	121.05 (6)
Cl3—Ir1—Cl4	89.79 (5)	Ir1—Cl1—K1	96.03 (5)
S1—Ir1—Cl1	90.43 (4)	Ir1—Cl1—K1^i	110.86 (5)
S2—Ir1—Cl1	88.31 (5)	K1—Cl1—K1^i	77.27 (4)
Cl3—Ir1—Cl1	179.46 (5)	Ir1—Cl2—K1^ii	110.02 (5)
Cl4—Ir1—Cl1	90.73 (5)	Ir1—Cl2—K1	97.65 (4)
S1—Ir1—Cl2	86.99 (4)	K1^ii—Cl2—K1	84.62 (3)
S2—Ir1—Cl2	92.14 (4)	O1—S1—C2	107.9 (3)
Cl3—Ir1—Cl2	90.04 (5)	O1—S1—C1	108.5 (2)
Cl4—Ir1—Cl2	179.83 (4)	C2—S1—C1	100.7 (3)
Cl1—Ir1—Cl2	89.45 (5)	O1—S1—Ir1	116.07 (15)
O2^i—K1—O1W	78.73 (14)	C2—S1—Ir1	111.09 (19)
O2^i—K1—O1^ii	90.82 (12)	C1—S1—Ir1	111.5 (2)
O1W—K1—O1^ii	142.61 (13)	O2—S2—C4	107.7 (3)
O2^i—K1—O1	120.75 (11)	O2—S2—C3	107.3 (3)
O1W—K1—O1	75.79 (13)	C4—S2—C3	101.0 (4)
O1^ii—K1—O1	137.68 (6)	O2—S2—Ir1	115.80 (16)
O2^i—K1—Cl2^i	66.01 (8)	C4—S2—Ir1	111.8 (2)
O1W—K1—Cl2^i	127.17 (12)	C3—S2—Ir1	112.0 (2)
O1^ii—K1—Cl2^i	77.97 (8)	S1—O1—K1^i	128.5 (2)
O1—K1—Cl2^i	89.45 (8)	S1—O1—K1	114.50 (19)
O2^i—K1—Cl2	152.57 (9)	K1^i—O1—K1	93.71 (10)
O1W—K1—Cl2	83.40 (12)	S2—O2—K1^ii	135.5 (2)
O1^ii—K1—Cl2	90.89 (8)	K1—O1W—H2W	140.8
O1—K1—Cl2	73.77 (7)	K1—O1W—H1W	110.5
Cl2^i—K1—Cl2	140.82 (5)	H2W—O1W—H1W	108.0
O2^i—K1—Cl1	144.66 (9)	S1—C1—H1A	109.5
O1W—K1—Cl1	129.64 (11)	S1—C1—H1B	109.5
O1^ii—K1—Cl1	77.15 (8)	H1A—C1—H1B	109.5
O1—K1—Cl1	60.74 (8)	S1—C1—H1C	109.5
Cl2^i—K1—Cl1	78.93 (4)	H1A—C1—H1C	109.5
Cl2—K1—Cl1	61.94 (4)	H1B—C1—H1C	109.5
O2^i—K1—Cl1^ii	84.11 (8)	S1—C2—H2A	109.5
O1W—K1—Cl1^ii	85.54 (11)	S1—C2—H2B	109.5
O1^ii—K1—Cl1^ii	57.53 (8)	H2A—C2—H2B	109.5
O1—K1—Cl1^ii	144.11 (8)	S1—C2—H2C	109.5
Cl2^i—K1—Cl1^ii	125.86 (5)	H2A—C2—H2C	109.5
Cl2—K1—Cl1^ii	73.84 (4)	H2B—C2—H2C	109.5
Cl1—K1—Cl1^ii	114.88 (5)	S2—C3—H3A	109.5
O2^i—K1—K1^ii	124.84 (9)	S2—C3—H3B	109.5
O1W—K1—K1^ii	115.68 (11)	H3A—C3—H3B	109.5
O1^ii—K1—K1^ii	44.20 (8)	S2—C3—H3C	109.5
O1—K1—K1^ii	114.40 (8)	H3A—C3—H3C	109.5
Cl2^i—K1—K1^ii	116.61 (6)	H3B—C3—H3C	109.5
Cl2—K1—K1^ii	47.37 (3)	S2—C4—H4A	109.5
Cl1—K1—K1^ii	66.90 (5)	S2—C4—H4B	109.5
Cl1^ii—K1—K1^ii	48.00 (3)	H4A—C4—H4B	109.5
O2^i—K1—K1^i	100.80 (8)	S2—C4—H4C	109.5
O1W—K1—K1^i	107.44 (11)	H4A—C4—H4C	109.5
O1^ii—K1—K1^i	109.76 (9)	H4B—C4—H4C	109.5
O1—K1—K1^i	42.09 (7)
C2—S1—O1—K1^i	164.4 (2)	Ir1—S1—O1—K1	46.8 (2)
C1—S1—O1—K1^i	56.2 (3)	C4—S2—O2—K1^ii	158.3 (3)
Ir1—S1—O1—K1^i	−70.2 (2)	C3—S2—O2—K1^ii	−93.7 (4)
C2—S1—O1—K1	−78.6 (3)	Ir1—S2—O2—K1^ii	32.3 (4)
C1—S1—O1—K1	173.2 (2)

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

'Potassium tetrachlorobis(dimethyl sulfoxide)iridate(III) 0.25-hydrate' (1a_beta)

Crystal data

K·C4H23Cl4IrO2S2·0.25(H2O)	F(000) = 1002
Mr = 533.90	Dx = 2.490 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.7530 (4) Å	Cell parameters from 41415 reflections
b = 7.8356 (2) Å	θ = 2.9–26.4°
c = 15.3277 (5) Å	µ = 10.69 mm^−1
β = 111.581 (2)°	T = 293 K
V = 1424.29 (8) Å^3	Prism, yellow
Z = 4	0.16 × 0.11 × 0.09 mm

Data collection

KappaCCD diffractometer	1781 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.104
Detector resolution: 9 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
Absorption correction: gaussian P. Coppens, L. Leiserowitz, D Rabinovich, Acta Cryst. (1965), 18, 1035-1038	h = −15→15
Tmin = 0.134, Tmax = 0.517	k = −9→9
8611 measured reflections	l = −17→18
2490 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0507P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
2490 reflections	Δρmax = 1.73 e Å^−3
143 parameters	Δρmin = −2.90 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ir1	0.000000	0.000000	0.000000	0.02889 (18)
Ir2	0.500000	0.500000	0.000000	0.03579 (19)
Cl1	0.19291 (12)	0.0688 (2)	0.06398 (12)	0.0445 (4)
Cl2	0.03468 (13)	−0.24915 (19)	0.09313 (11)	0.0416 (4)
Cl3	0.38743 (16)	0.7121 (2)	0.03150 (16)	0.0609 (5)
Cl4	0.33565 (15)	0.3439 (3)	−0.08381 (13)	0.0566 (5)
S1	−0.02358 (14)	0.1465 (2)	0.12207 (11)	0.0390 (4)
S2	0.50000 (15)	0.3508 (3)	0.13000 (12)	0.0494 (5)
O1	−0.0338 (5)	0.3332 (6)	0.1116 (4)	0.0624 (15)
O2	0.4076 (4)	0.3911 (8)	0.1619 (4)	0.0687 (16)
O1W	0.2819 (17)	0.427 (3)	0.2499 (14)	0.060 (5)	0.25
H1W	0.326887	0.347353	0.263737	0.090*	0.25
H2W	0.323776	0.499701	0.282487	0.090*	0.25
C1	0.0881 (6)	0.1045 (10)	0.2297 (4)	0.0496 (18)
H1A	0.071538	0.155506	0.280152	0.074*
H1B	0.156812	0.151869	0.228120	0.074*
H1C	0.096591	−0.016528	0.239337	0.074*
C2	−0.1399 (6)	0.0696 (11)	0.1459 (6)	0.058 (2)
H2A	−0.208335	0.098740	0.094995	0.087*
H2B	−0.140293	0.120272	0.202813	0.087*
H2C	−0.134577	−0.052205	0.152920	0.087*
C3	0.4973 (8)	0.1264 (10)	0.1132 (6)	0.074 (3)
H3A	0.426492	0.094079	0.066037	0.111*
H3B	0.506309	0.069880	0.171049	0.111*
H3C	0.557636	0.093968	0.093311	0.111*
C4	0.6276 (6)	0.3763 (13)	0.2269 (5)	0.072 (3)
H4A	0.627235	0.303574	0.277158	0.108*
H4B	0.635210	0.493001	0.247267	0.108*
H4C	0.689735	0.346076	0.208819	0.108*
K1	0.18504 (14)	0.4720 (2)	0.03656 (13)	0.0543 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0255 (3)	0.0293 (3)	0.0299 (3)	0.00003 (12)	0.0079 (2)	0.00262 (12)
Ir2	0.0273 (3)	0.0432 (3)	0.0336 (3)	−0.00532 (13)	0.0073 (2)	−0.00232 (13)
Cl1	0.0274 (8)	0.0547 (11)	0.0458 (10)	−0.0042 (7)	0.0067 (7)	0.0018 (8)
Cl2	0.0491 (9)	0.0344 (9)	0.0407 (9)	0.0044 (7)	0.0159 (7)	0.0109 (7)
Cl3	0.0573 (11)	0.0508 (11)	0.0836 (14)	0.0024 (9)	0.0366 (11)	−0.0036 (9)
Cl4	0.0410 (10)	0.0721 (13)	0.0461 (10)	−0.0231 (9)	0.0037 (8)	−0.0064 (9)
S1	0.0429 (10)	0.0385 (9)	0.0335 (9)	0.0047 (7)	0.0116 (7)	−0.0011 (7)
S2	0.0408 (10)	0.0642 (13)	0.0382 (10)	−0.0098 (8)	0.0086 (8)	0.0062 (8)
O1	0.098 (4)	0.030 (3)	0.051 (3)	0.018 (3)	0.018 (3)	−0.001 (2)
O2	0.054 (3)	0.102 (5)	0.056 (3)	−0.004 (3)	0.027 (3)	0.013 (3)
O1W	0.056 (12)	0.058 (13)	0.074 (15)	0.011 (11)	0.033 (11)	−0.007 (10)
C1	0.051 (4)	0.066 (5)	0.027 (4)	0.002 (4)	0.010 (3)	−0.005 (3)
C2	0.048 (4)	0.081 (6)	0.054 (5)	0.011 (4)	0.028 (4)	−0.004 (4)
C3	0.092 (7)	0.048 (5)	0.073 (6)	−0.017 (4)	0.019 (5)	0.015 (4)
C4	0.048 (5)	0.107 (7)	0.042 (4)	−0.013 (4)	−0.006 (4)	0.020 (4)
K1	0.0426 (10)	0.0475 (9)	0.0659 (12)	0.0024 (7)	0.0120 (9)	−0.0004 (7)

Geometric parameters (Å, º)

Ir1—S1^i	2.3071 (17)	S2—O2	1.466 (6)
Ir1—S1	2.3072 (17)	S2—C4	1.765 (7)
Ir1—Cl1	2.3517 (15)	S2—C3	1.776 (8)
Ir1—Cl1^i	2.3517 (15)	O1—K1^iv	2.826 (5)
Ir1—Cl2	2.3622 (14)	O2—K1	2.853 (5)
Ir1—Cl2^i	2.3622 (14)	O1W—K1	3.06 (2)
Ir2—S2^ii	2.3101 (18)	O1W—H1W	0.8200
Ir2—S2	2.3101 (18)	O1W—H2W	0.8156
Ir2—Cl4^ii	2.3577 (16)	C1—H1A	0.9600
Ir2—Cl4	2.3577 (16)	C1—H1B	0.9600
Ir2—Cl3^ii	2.3593 (18)	C1—H1C	0.9600
Ir2—Cl3	2.3593 (18)	C2—H2A	0.9600
Cl1—K1	3.184 (2)	C2—H2B	0.9600
Cl2—K1^iii	3.229 (2)	C2—H2C	0.9600
Cl2—K1^i	3.279 (2)	C3—H3A	0.9600
Cl3—K1	3.218 (3)	C3—H3B	0.9600
Cl4—K1	3.272 (3)	C3—H3C	0.9600
S1—O1	1.472 (5)	C4—H4A	0.9600
S1—C2	1.760 (7)	C4—H4B	0.9600
S1—C1	1.770 (6)	C4—H4C	0.9600
S1^i—Ir1—S1	180.0	H1A—C1—H1C	109.5
S1^i—Ir1—Cl1	91.37 (6)	H1B—C1—H1C	109.5
S1—Ir1—Cl1	88.63 (6)	S1—C2—H2A	109.5
S1^i—Ir1—Cl1^i	88.63 (6)	S1—C2—H2B	109.5
S1—Ir1—Cl1^i	91.37 (6)	H2A—C2—H2B	109.5
Cl1—Ir1—Cl1^i	180.0	S1—C2—H2C	109.5
S1^i—Ir1—Cl2	91.58 (6)	H2A—C2—H2C	109.5
S1—Ir1—Cl2	88.42 (6)	H2B—C2—H2C	109.5
Cl1—Ir1—Cl2	90.17 (6)	S2—C3—H3A	109.5
Cl1^i—Ir1—Cl2	89.83 (6)	S2—C3—H3B	109.5
S1^i—Ir1—Cl2^i	88.42 (6)	H3A—C3—H3B	109.5
S1—Ir1—Cl2^i	91.58 (6)	S2—C3—H3C	109.5
Cl1—Ir1—Cl2^i	89.83 (6)	H3A—C3—H3C	109.5
Cl1^i—Ir1—Cl2^i	90.17 (6)	H3B—C3—H3C	109.5
Cl2—Ir1—Cl2^i	180.0	S2—C4—H4A	109.5
S2^ii—Ir2—S2	180.0	S2—C4—H4B	109.5
S2^ii—Ir2—Cl4^ii	85.72 (6)	H4A—C4—H4B	109.5
S2—Ir2—Cl4^ii	94.28 (6)	S2—C4—H4C	109.5
S2^ii—Ir2—Cl4	94.28 (6)	H4A—C4—H4C	109.5
S2—Ir2—Cl4	85.73 (6)	H4B—C4—H4C	109.5
Cl4^ii—Ir2—Cl4	180.0	O1^iv—K1—O2	151.27 (17)
S2^ii—Ir2—Cl3^ii	89.25 (7)	O1^iv—K1—O1W	144.0 (4)
S2—Ir2—Cl3^ii	90.75 (7)	O2—K1—O1W	49.0 (4)
Cl4^ii—Ir2—Cl3^ii	89.49 (7)	O1^iv—K1—Cl1	128.41 (12)
Cl4—Ir2—Cl3^ii	90.51 (7)	O2—K1—Cl1	73.47 (13)
S2^ii—Ir2—Cl3	90.75 (7)	O1W—K1—Cl1	76.3 (4)
S2—Ir2—Cl3	89.25 (7)	O1^iv—K1—Cl3	88.91 (13)
Cl4^ii—Ir2—Cl3	90.51 (7)	O2—K1—Cl3	62.47 (12)
Cl4—Ir2—Cl3	89.49 (7)	O1W—K1—Cl3	94.7 (4)
Cl3^ii—Ir2—Cl3	180.0	Cl1—K1—Cl3	126.64 (7)
Ir1—Cl1—K1	101.25 (6)	O1^iv—K1—Cl2^v	63.46 (11)
Ir1—Cl2—K1^iii	113.25 (7)	O2—K1—Cl2^v	120.77 (14)
Ir1—Cl2—K1^i	98.36 (6)	O1W—K1—Cl2^v	80.7 (4)
Ir2—Cl3—K1	98.44 (7)	Cl1—K1—Cl2^v	128.98 (7)
Ir2—Cl4—K1	97.02 (7)	Cl3—K1—Cl2^v	99.88 (6)
O1—S1—C2	108.4 (4)	O1^iv—K1—Cl4	94.64 (13)
O1—S1—C1	107.2 (3)	O2—K1—Cl4	70.51 (12)
C2—S1—C1	101.2 (4)	O1W—K1—Cl4	118.5 (4)
O1—S1—Ir1	116.1 (2)	Cl1—K1—Cl4	76.91 (6)
C2—S1—Ir1	111.7 (3)	Cl3—K1—Cl4	61.53 (6)
C1—S1—Ir1	111.3 (2)	Cl2^v—K1—Cl4	152.70 (7)
O2—S2—C4	107.5 (4)	O1^iv—K1—Cl2^i	67.80 (12)
O2—S2—C3	106.7 (4)	O2—K1—Cl2^i	134.97 (14)
C4—S2—C3	101.3 (4)	O1W—K1—Cl2^i	120.3 (4)
O2—S2—Ir2	115.7 (2)	Cl1—K1—Cl2^i	61.98 (5)
C4—S2—Ir2	112.1 (3)	Cl3—K1—Cl2^i	144.17 (8)
C3—S2—Ir2	112.5 (3)	Cl2^v—K1—Cl2^i	93.65 (6)
S1—O1—K1^iv	129.2 (3)	Cl4—K1—Cl2^i	92.45 (6)
S2—O2—K1	123.1 (3)	O1^iv—K1—K1^iv	52.97 (13)
K1—O1W—H1W	109.5	O2—K1—K1^iv	153.05 (13)
K1—O1W—H2W	119.3	O1W—K1—K1^iv	104.7 (4)
H1W—O1W—H2W	97.7	Cl1—K1—K1^iv	96.32 (6)
S1—C1—H1A	109.5	Cl3—K1—K1^iv	136.17 (7)
S1—C1—H1B	109.5	Cl2^v—K1—K1^iv	47.30 (4)
H1A—C1—H1B	109.5	Cl4—K1—K1^iv	132.52 (8)
S1—C1—H1C	109.5	Cl2^i—K1—K1^iv	46.35 (4)
C2—S1—O1—K1^iv	−72.2 (5)	C4—S2—O2—K1	161.7 (4)
C1—S1—O1—K1^iv	179.4 (4)	C3—S2—O2—K1	−90.3 (4)
Ir1—S1—O1—K1^iv	54.3 (4)	Ir2—S2—O2—K1	35.6 (4)

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

'N-Butylammonium tetrachlorobis(dimethyl sulfoxide)iridate(III) hemihydrate' (1b)

Crystal data

(C4H12Cl4IrO2S2)·(C4H12N)·0.5H2O	F(000) = 2216
Mr = 573.44	Dx = 2.055 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.8210 (4) Å	Cell parameters from 32346 reflections
b = 10.0830 (2) Å	θ = 2.9–26.7°
c = 19.5720 (5) Å	µ = 8.01 mm^−1
β = 108.657 (2)°	T = 293 K
V = 3706.01 (15) Å^3	Prism, yellow
Z = 8	0.21 × 0.12 × 0.11 mm

Data collection

KappaCCD diffractometer	3050 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	Rint = 0.099
CCD rotation images, thick slices scans	θmax = 25.5°, θmin = 2.9°
Absorption correction: gaussian P. Coppens, L. Leiserowitz, D Rabinovich, Acta Cryst. (1965), 18, 1035-1038	h = −23→24
Tmin = 0.263, Tmax = 0.659	k = −12→12
18983 measured reflections	l = −23→23
3424 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.074P)^2 + 31.6594P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3424 reflections	Δρmax = 3.53 e Å^−3
176 parameters	Δρmin = −1.96 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ir1	0.500000	0.72595 (4)	0.250000	0.03584 (17)
Ir2	0.250000	0.750000	0.500000	0.03713 (17)
Cl1	0.41409 (11)	0.5629 (2)	0.24985 (12)	0.0499 (5)
Cl2	0.41675 (10)	0.8949 (2)	0.24664 (11)	0.0483 (5)
Cl3	0.33783 (11)	0.6704 (2)	0.60413 (12)	0.0527 (5)
Cl4	0.31152 (11)	0.9528 (2)	0.50844 (12)	0.0526 (5)
S1	0.54364 (11)	0.7253 (2)	0.37442 (11)	0.0407 (5)
S2	0.30821 (11)	0.6623 (2)	0.42474 (12)	0.0491 (5)
O1	0.5205 (3)	0.8386 (6)	0.4091 (3)	0.0526 (15)
O2	0.3722 (4)	0.5843 (9)	0.4585 (4)	0.080 (2)
N1	0.5292 (4)	0.1119 (8)	0.3728 (4)	0.0525 (18)
H1D	0.512298	0.157483	0.331886	0.079*
H1E	0.516268	0.027337	0.364862	0.079*
H1F	0.576549	0.117368	0.388569	0.079*
C1	0.5221 (5)	0.5778 (9)	0.4114 (5)	0.056 (2)
H1A	0.471398	0.571561	0.400076	0.084*
H1B	0.544087	0.578831	0.462833	0.084*
H1C	0.539205	0.502934	0.391503	0.084*
C2	0.6381 (4)	0.7143 (10)	0.4069 (5)	0.053 (2)
H2A	0.654081	0.712163	0.458606	0.080*
H2B	0.658158	0.790003	0.390701	0.080*
H2C	0.652954	0.634829	0.388763	0.080*
C3	0.2509 (6)	0.5662 (12)	0.3549 (6)	0.073 (3)
H3A	0.237839	0.487005	0.374794	0.110*
H3B	0.274837	0.542808	0.320986	0.110*
H3C	0.208887	0.616436	0.330807	0.110*
C4	0.3303 (6)	0.7883 (11)	0.3718 (6)	0.067 (3)
H4A	0.346831	0.748130	0.335655	0.101*
H4B	0.367081	0.843760	0.402306	0.101*
H4C	0.288873	0.841052	0.348994	0.101*
C5	0.5007 (5)	0.1672 (13)	0.4271 (5)	0.067 (3)
H5A	0.510586	0.261565	0.432056	0.081*
H5B	0.523954	0.125606	0.473311	0.081*
C6	0.4220 (8)	0.1452 (18)	0.4063 (8)	0.106 (5)
H6A	0.413609	0.052357	0.393469	0.127*
H6B	0.408793	0.158553	0.449444	0.127*
C7	0.3758 (8)	0.216 (2)	0.3533 (12)	0.149 (9)
H7A	0.385754	0.194966	0.309095	0.178*
H7B	0.387361	0.308458	0.363547	0.178*
C8	0.2956 (7)	0.2015 (17)	0.3374 (9)	0.111 (5)
H8A	0.283422	0.225326	0.379447	0.166*
H8B	0.281763	0.111390	0.324432	0.166*
H8C	0.271243	0.259126	0.298197	0.166*
O1W	0.500000	0.2891 (9)	0.250000	0.059 (2)
H1W	0.533787	0.336685	0.271020	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0358 (3)	0.0377 (3)	0.0346 (3)	0.000	0.01210 (18)	0.000
Ir2	0.0322 (3)	0.0383 (3)	0.0397 (3)	−0.00194 (15)	0.00987 (19)	0.00591 (16)
Cl1	0.0486 (11)	0.0480 (12)	0.0542 (12)	−0.0130 (9)	0.0178 (9)	−0.0001 (9)
Cl2	0.0463 (11)	0.0498 (12)	0.0508 (12)	0.0102 (9)	0.0182 (9)	−0.0033 (9)
Cl3	0.0447 (11)	0.0582 (13)	0.0484 (12)	0.0040 (9)	0.0053 (9)	0.0114 (10)
Cl4	0.0524 (12)	0.0447 (11)	0.0598 (13)	−0.0146 (9)	0.0168 (10)	0.0051 (10)
S1	0.0420 (11)	0.0426 (11)	0.0371 (11)	0.0012 (8)	0.0120 (8)	0.0005 (8)
S2	0.0443 (11)	0.0552 (13)	0.0510 (12)	0.0041 (9)	0.0199 (9)	0.0054 (10)
O1	0.075 (4)	0.046 (3)	0.044 (3)	0.012 (3)	0.029 (3)	−0.004 (3)
O2	0.064 (4)	0.111 (7)	0.071 (5)	0.039 (4)	0.027 (4)	0.018 (4)
N1	0.050 (4)	0.055 (4)	0.051 (4)	−0.001 (3)	0.013 (3)	0.005 (3)
C1	0.066 (6)	0.054 (5)	0.049 (5)	0.002 (4)	0.020 (4)	0.012 (4)
C2	0.036 (4)	0.073 (6)	0.046 (5)	0.001 (4)	0.006 (4)	0.002 (4)
C3	0.084 (7)	0.071 (7)	0.073 (7)	−0.019 (6)	0.038 (6)	−0.018 (6)
C4	0.078 (7)	0.074 (7)	0.063 (6)	−0.014 (6)	0.040 (5)	0.003 (5)
C5	0.050 (5)	0.100 (9)	0.056 (6)	−0.003 (5)	0.022 (4)	−0.010 (6)
C6	0.119 (12)	0.120 (13)	0.084 (10)	0.015 (10)	0.040 (9)	−0.008 (9)
C7	0.091 (13)	0.23 (3)	0.120 (14)	0.063 (13)	0.023 (10)	0.009 (15)
C8	0.054 (7)	0.139 (14)	0.129 (13)	−0.013 (8)	0.018 (8)	−0.034 (11)
O1W	0.070 (6)	0.055 (5)	0.051 (5)	0.000	0.018 (4)	0.000

Geometric parameters (Å, º)

Ir1—S1^i	2.309 (2)	C1—H1C	0.9600
Ir1—S1	2.309 (2)	C2—H2A	0.9600
Ir1—Cl2^i	2.358 (2)	C2—H2B	0.9600
Ir1—Cl2	2.358 (2)	C2—H2C	0.9600
Ir1—Cl1^i	2.367 (2)	C3—H3A	0.9600
Ir1—Cl1	2.367 (2)	C3—H3B	0.9600
Ir2—S2^ii	2.317 (2)	C3—H3C	0.9600
Ir2—S2	2.317 (2)	C4—H4A	0.9600
Ir2—Cl3	2.3576 (19)	C4—H4B	0.9600
Ir2—Cl3^ii	2.3576 (19)	C4—H4C	0.9600
Ir2—Cl4	2.360 (2)	C5—C6	1.496 (17)
Ir2—Cl4^ii	2.360 (2)	C5—H5A	0.9700
S1—O1	1.475 (6)	C5—H5B	0.9700
S1—C1	1.765 (9)	C6—C7	1.34 (2)
S1—C2	1.777 (8)	C6—H6A	0.9700
S2—O2	1.459 (7)	C6—H6B	0.9700
S2—C3	1.762 (10)	C7—C8	1.525 (19)
S2—C4	1.780 (10)	C7—H7A	0.9700
N1—C5	1.465 (12)	C7—H7B	0.9700
N1—H1D	0.8900	C8—H8A	0.9600
N1—H1E	0.8900	C8—H8B	0.9600
N1—H1F	0.8900	C8—H8C	0.9600
C1—H1A	0.9600	O1W—H1W	0.8197
C1—H1B	0.9600	O1W—H1W^i	0.8196
S1^i—Ir1—S1	179.68 (10)	S1—C1—H1B	109.5
S1^i—Ir1—Cl2^i	93.11 (7)	H1A—C1—H1B	109.5
S1—Ir1—Cl2^i	87.13 (7)	S1—C1—H1C	109.5
S1^i—Ir1—Cl2	87.13 (7)	H1A—C1—H1C	109.5
S1—Ir1—Cl2	93.10 (7)	H1B—C1—H1C	109.5
Cl2^i—Ir1—Cl2	87.47 (11)	S1—C2—H2A	109.5
S1^i—Ir1—Cl1^i	91.49 (7)	S1—C2—H2B	109.5
S1—Ir1—Cl1^i	88.29 (7)	H2A—C2—H2B	109.5
Cl2^i—Ir1—Cl1^i	90.30 (8)	S1—C2—H2C	109.5
Cl2—Ir1—Cl1^i	177.31 (8)	H2A—C2—H2C	109.5
S1^i—Ir1—Cl1	88.29 (7)	H2B—C2—H2C	109.5
S1—Ir1—Cl1	91.49 (7)	S2—C3—H3A	109.5
Cl2^i—Ir1—Cl1	177.31 (7)	S2—C3—H3B	109.5
Cl2—Ir1—Cl1	90.30 (8)	H3A—C3—H3B	109.5
Cl1^i—Ir1—Cl1	91.96 (11)	S2—C3—H3C	109.5
S2^ii—Ir2—S2	180.0	H3A—C3—H3C	109.5
S2^ii—Ir2—Cl3	87.74 (8)	H3B—C3—H3C	109.5
S2—Ir2—Cl3	92.26 (8)	S2—C4—H4A	109.5
S2^ii—Ir2—Cl3^ii	92.26 (8)	S2—C4—H4B	109.5
S2—Ir2—Cl3^ii	87.74 (8)	H4A—C4—H4B	109.5
Cl3—Ir2—Cl3^ii	180.0	S2—C4—H4C	109.5
S2^ii—Ir2—Cl4	88.63 (8)	H4A—C4—H4C	109.5
S2—Ir2—Cl4	91.37 (8)	H4B—C4—H4C	109.5
Cl3—Ir2—Cl4	90.71 (8)	N1—C5—C6	111.0 (9)
Cl3^ii—Ir2—Cl4	89.29 (8)	N1—C5—H5A	109.4
S2^ii—Ir2—Cl4^ii	91.37 (8)	C6—C5—H5A	109.4
S2—Ir2—Cl4^ii	88.63 (8)	N1—C5—H5B	109.4
Cl3—Ir2—Cl4^ii	89.29 (8)	C6—C5—H5B	109.4
Cl3^ii—Ir2—Cl4^ii	90.71 (8)	H5A—C5—H5B	108.0
Cl4—Ir2—Cl4^ii	180.0	C7—C6—C5	121.6 (16)
O1—S1—C1	108.2 (4)	C7—C6—H6A	106.9
O1—S1—C2	109.3 (4)	C5—C6—H6A	106.9
C1—S1—C2	99.6 (5)	C7—C6—H6B	106.9
O1—S1—Ir1	114.6 (3)	C5—C6—H6B	106.9
C1—S1—Ir1	112.1 (3)	H6A—C6—H6B	106.7
C2—S1—Ir1	111.9 (3)	C6—C7—C8	121.1 (19)
O2—S2—C3	107.8 (6)	C6—C7—H7A	107.0
O2—S2—C4	108.0 (5)	C8—C7—H7A	107.0
C3—S2—C4	99.1 (5)	C6—C7—H7B	107.0
O2—S2—Ir2	117.1 (3)	C8—C7—H7B	107.0
C3—S2—Ir2	112.0 (4)	H7A—C7—H7B	106.8
C4—S2—Ir2	111.3 (4)	C7—C8—H8A	109.5
C5—N1—H1D	109.5	C7—C8—H8B	109.5
C5—N1—H1E	109.5	H8A—C8—H8B	109.5
H1D—N1—H1E	109.5	C7—C8—H8C	109.5
C5—N1—H1F	109.5	H8A—C8—H8C	109.5
H1D—N1—H1F	109.5	H8B—C8—H8C	109.5
H1E—N1—H1F	109.5	H1W—O1W—H1W^i	108.3
S1—C1—H1A	109.5
N1—C5—C6—C7	−74 (2)	C5—C6—C7—C8	−174.2 (16)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y+3/2, −z+1.

Potassium tetrachlorobis(dimethylsulfoxide)iridate(III) (2)

Crystal data

C4H12Cl4IrKO2S2	F(000) = 992
Mr = 529.36	Dx = 2.393 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9902 (7) Å	Cell parameters from 2542 reflections
b = 15.1990 (14) Å	θ = 3.5–28.9°
c = 10.7569 (9) Å	µ = 10.36 mm^−1
β = 91.425 (7)°	T = 293 K
V = 1469.4 (2) Å^3	Needle, yellow
Z = 4	0.14 × 0.05 × 0.05 mm

Data collection

Gemini diffractometer	2582 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1704 reflections with I > 2σ(I)
Detector resolution: 16.1158 pixels mm^-1	Rint = 0.133
ω scans	θmax = 25.0°, θmin = 3.5°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→10
Tmin = 0.271, Tmax = 1.000	k = −18→16
8941 measured reflections	l = −12→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.072	H-atom parameters constrained
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.0647P)^2 + 13.5359P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2582 reflections	Δρmax = 2.94 e Å^−3
131 parameters	Δρmin = −2.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ir1	0.28570 (8)	0.61353 (5)	0.26792 (7)	0.0329 (3)
K1	0.5409 (6)	0.6218 (3)	0.5981 (5)	0.0606 (14)
Cl1	0.2611 (7)	0.4819 (4)	0.1571 (6)	0.0665 (18)
Cl2	0.5394 (6)	0.5752 (4)	0.3036 (6)	0.0607 (16)
Cl3	0.3126 (7)	0.7372 (4)	0.3968 (6)	0.0730 (19)
Cl4	0.2362 (7)	0.5342 (5)	0.4528 (5)	0.0664 (18)
S1	0.3560 (7)	0.6945 (4)	0.1060 (6)	0.0652 (18)
S2	0.0420 (5)	0.6467 (3)	0.2359 (5)	0.0411 (12)
O1	0.2424 (19)	0.7464 (11)	0.0400 (14)	0.074 (5)
O2	−0.0024 (16)	0.7381 (9)	0.2477 (13)	0.056 (4)
C1	0.446 (5)	0.6300 (19)	−0.005 (3)	0.138 (18)
H1A	0.469098	0.665600	−0.075464	0.207*
H1B	0.382727	0.582332	−0.030471	0.207*
H1C	0.537007	0.606749	0.031330	0.207*
C2	0.502 (3)	0.7701 (18)	0.146 (3)	0.119 (13)
H2A	0.551910	0.787383	0.071852	0.179*
H2B	0.571533	0.742491	0.202441	0.179*
H2C	0.460364	0.821192	0.184435	0.179*
C3	−0.027 (3)	0.6111 (14)	0.088 (2)	0.068 (7)
H3A	−0.133272	0.608586	0.087888	0.102*
H3B	0.012380	0.553819	0.069897	0.102*
H3C	0.004140	0.651872	0.025037	0.102*
C4	−0.067 (3)	0.5856 (18)	0.340 (3)	0.093 (11)
H4A	−0.162880	0.613232	0.346780	0.140*
H4B	−0.018358	0.583620	0.419844	0.140*
H4C	−0.080478	0.526839	0.308512	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0275 (4)	0.0398 (5)	0.0317 (5)	0.0001 (3)	0.0074 (3)	0.0031 (3)
K1	0.065 (3)	0.051 (3)	0.066 (3)	−0.004 (3)	0.004 (3)	−0.002 (3)
Cl1	0.075 (4)	0.051 (4)	0.073 (4)	0.014 (3)	−0.003 (3)	−0.023 (3)
Cl2	0.035 (3)	0.073 (4)	0.073 (4)	0.008 (3)	0.003 (3)	0.022 (3)
Cl3	0.063 (4)	0.076 (4)	0.079 (5)	−0.001 (3)	−0.012 (4)	−0.031 (4)
Cl4	0.057 (4)	0.097 (5)	0.046 (3)	0.003 (3)	0.009 (3)	0.030 (3)
S1	0.057 (4)	0.070 (4)	0.071 (4)	0.015 (3)	0.041 (3)	0.028 (3)
S2	0.030 (2)	0.051 (3)	0.041 (3)	0.004 (2)	0.000 (2)	0.003 (2)
O1	0.089 (13)	0.087 (13)	0.047 (10)	0.029 (10)	0.028 (9)	0.025 (9)
O2	0.050 (9)	0.064 (10)	0.054 (9)	0.036 (8)	0.010 (7)	0.004 (8)
C1	0.21 (4)	0.11 (3)	0.11 (3)	0.08 (3)	0.12 (3)	0.07 (2)
C2	0.08 (2)	0.08 (2)	0.19 (4)	−0.046 (18)	0.00 (2)	0.07 (2)
C3	0.071 (18)	0.060 (15)	0.072 (17)	0.018 (13)	−0.020 (14)	0.003 (13)
C4	0.036 (14)	0.10 (2)	0.15 (3)	0.008 (14)	0.016 (16)	0.06 (2)

Geometric parameters (Å, º)

Ir1—S1	2.236 (6)	S1—C2	1.79 (3)
Ir1—S2	2.266 (5)	S2—O2	1.451 (14)
Ir1—Cl1	2.337 (6)	S2—C4	1.77 (2)
Ir1—Cl3	2.344 (6)	S2—C3	1.78 (2)
Ir1—Cl2	2.376 (5)	C1—H1A	0.9600
Ir1—Cl4	2.377 (5)	C1—H1B	0.9600
K1—O2^i	2.703 (15)	C1—H1C	0.9600
K1—O1^i	2.782 (17)	C2—H2A	0.9600
K1—Cl4^ii	3.161 (8)	C2—H2B	0.9600
K1—Cl2	3.246 (9)	C2—H2C	0.9600
K1—Cl2^ii	3.262 (8)	C3—H3A	0.9600
K1—Cl4	3.392 (8)	C3—H3B	0.9600
K1—Cl3	3.428 (8)	C3—H3C	0.9600
K1—Cl1^ii	3.515 (8)	C4—H4A	0.9600
S1—O1	1.461 (16)	C4—H4B	0.9600
S1—C1	1.76 (3)	C4—H4C	0.9600
S1—Ir1—S2	92.9 (2)	Cl3—K1—K1^ii	92.19 (19)
S1—Ir1—Cl1	95.7 (3)	Cl1^ii—K1—K1^ii	93.35 (18)
S2—Ir1—Cl1	91.9 (2)	Ir1—Cl1—K1^ii	87.82 (19)
S1—Ir1—Cl3	89.6 (3)	Ir1—Cl2—K1	94.8 (2)
S2—Ir1—Cl3	89.8 (2)	Ir1—Cl2—K1^ii	93.3 (2)
Cl1—Ir1—Cl3	174.4 (2)	K1—Cl2—K1^ii	83.08 (19)
S1—Ir1—Cl2	88.4 (2)	Ir1—Cl3—K1	90.8 (2)
S2—Ir1—Cl2	178.52 (19)	Ir1—Cl4—K1^ii	95.9 (2)
Cl1—Ir1—Cl2	87.2 (2)	Ir1—Cl4—K1	91.2 (2)
Cl3—Ir1—Cl2	91.0 (2)	K1^ii—Cl4—K1	82.29 (19)
S1—Ir1—Cl4	173.2 (2)	O1—S1—C1	107.6 (14)
S2—Ir1—Cl4	92.27 (19)	O1—S1—C2	105.6 (12)
Cl1—Ir1—Cl4	88.6 (2)	C1—S1—C2	99.9 (19)
Cl3—Ir1—Cl4	86.0 (3)	O1—S1—Ir1	117.9 (7)
Cl2—Ir1—Cl4	86.5 (2)	C1—S1—Ir1	111.4 (9)
O2^i—K1—O1^i	70.8 (4)	C2—S1—Ir1	112.8 (11)
O2^i—K1—Cl4^ii	142.7 (4)	O2—S2—C4	106.8 (12)
O1^i—K1—Cl4^ii	94.7 (4)	O2—S2—C3	106.2 (9)
O2^i—K1—Cl2	139.1 (4)	C4—S2—C3	102.7 (14)
O1^i—K1—Cl2	85.7 (3)	O2—S2—Ir1	117.8 (6)
Cl4^ii—K1—Cl2	69.79 (18)	C4—S2—Ir1	109.8 (8)
O2^i—K1—Cl2^ii	119.6 (4)	C3—S2—Ir1	112.4 (9)
O1^i—K1—Cl2^ii	152.1 (4)	S1—O1—K1^iii	137.0 (9)
Cl4^ii—K1—Cl2^ii	60.92 (17)	S2—O2—K1^iii	131.1 (8)
Cl2—K1—Cl2^ii	96.92 (19)	S1—C1—H1A	109.5
O2^i—K1—Cl4	117.2 (4)	S1—C1—H1B	109.5
O1^i—K1—Cl4	134.6 (4)	H1A—C1—H1B	109.5
Cl4^ii—K1—Cl4	97.71 (19)	S1—C1—H1C	109.5
Cl2—K1—Cl4	58.74 (17)	H1A—C1—H1C	109.5
Cl2^ii—K1—Cl4	66.83 (17)	H1B—C1—H1C	109.5
O2^i—K1—Cl3	83.1 (4)	S1—C2—H2A	109.5
O1^i—K1—Cl3	82.7 (4)	S1—C2—H2B	109.5
Cl4^ii—K1—Cl3	130.3 (2)	H2A—C2—H2B	109.5
Cl2—K1—Cl3	60.49 (17)	S1—C2—H2C	109.5
Cl2^ii—K1—Cl3	122.7 (2)	H2A—C2—H2C	109.5
Cl4—K1—Cl3	56.35 (17)	H2B—C2—H2C	109.5
O2^i—K1—Cl1^ii	89.1 (4)	S2—C3—H3A	109.5
O1^i—K1—Cl1^ii	99.8 (4)	S2—C3—H3B	109.5
Cl4^ii—K1—Cl1^ii	58.79 (16)	H3A—C3—H3B	109.5
Cl2—K1—Cl1^ii	128.5 (2)	S2—C3—H3C	109.5
Cl2^ii—K1—Cl1^ii	57.14 (16)	H3A—C3—H3C	109.5
Cl4—K1—Cl1^ii	123.9 (2)	H3B—C3—H3C	109.5
Cl3—K1—Cl1^ii	170.6 (2)	S2—C4—H4A	109.5
O2^i—K1—K1^ii	160.3 (4)	S2—C4—H4B	109.5
O1^i—K1—K1^ii	127.7 (4)	H4A—C4—H4B	109.5
Cl4^ii—K1—K1^ii	51.16 (16)	S2—C4—H4C	109.5
Cl2—K1—K1^ii	48.63 (15)	H4A—C4—H4C	109.5
Cl2^ii—K1—K1^ii	48.30 (15)	H4B—C4—H4C	109.5
Cl4—K1—K1^ii	46.55 (15)
C1—S1—O1—K1^iii	−175.0 (17)	C4—S2—O2—K1^iii	−163.0 (13)
C2—S1—O1—K1^iii	−69.0 (19)	C3—S2—O2—K1^iii	−53.9 (14)
Ir1—S1—O1—K1^iii	58.0 (17)	Ir1—S2—O2—K1^iii	73.1 (11)

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+3/2, z−1/2.