mer-Tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III): preparation and comparison with other mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)metal complexes

The crystal structure of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) is reported and compared with a different form of the complex previously reported. It is also compared with other mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)metal(III) complexes of molybdenum, ruthenium and rhodium.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.063
• Data-to-parameter ratio = 33.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min)           9 Note
PLAT971_ALERT_2_C Check Calcd Residual Density  0.89A From     Ir1       1.66 eA-3
PLAT971_ALERT_2_C Check Calcd Residual Density  0.75A From     Ir1       1.57 eA-3
PLAT971_ALERT_2_C Check Calcd Residual Density  0.82A From     Ir1       1.55 eA-3

Alert level G
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ir1    --  S3      ..        7.5 s.u.
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        392 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

mer-Trichloridotris(tetrahydrothiophene-κS)iridium(III)

Crystal data

[IrCl3(C4H8S)3]	F(000) = 1088
Mr = 563.04	Dx = 2.144 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.9160 (3) Å	Cell parameters from 9679 reflections
b = 10.2528 (2) Å	θ = 4.1–32.2°
c = 14.9434 (4) Å	µ = 8.46 mm^−1
β = 107.202 (3)°	T = 100 K
V = 1744.00 (7) Å^3	Cube, yellow
Z = 4	0.51 × 0.43 × 0.32 mm

Data collection

Rigaku OD Xcalibur Eos Gemini ultra diffractometer	5773 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5062 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.0061 pixels mm^-1	θmax = 32.2°, θmin = 3.6°
ω scans	h = −13→17
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015) based on expressions derived by Clark & Reid (1995)]	k = −13→15
Tmin = 0.064, Tmax = 0.155	l = −22→21
19537 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0223P)^2 + 0.8135P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
5773 reflections	Δρmax = 1.54 e Å^−3
172 parameters	Δρmin = −1.46 e Å^−3
0 restraints

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	0.45092 (2)	0.70407 (2)	0.73222 (2)	0.01133 (4)
Cl1	0.59718 (7)	0.70422 (8)	0.65431 (6)	0.01922 (17)
Cl2	0.59716 (8)	0.73216 (8)	0.87865 (6)	0.01887 (16)
Cl3	0.30344 (7)	0.71455 (8)	0.80946 (6)	0.01688 (16)
S1	0.46678 (7)	0.47667 (8)	0.74921 (6)	0.01509 (16)
S2	0.30373 (7)	0.68096 (8)	0.59053 (6)	0.01540 (16)
S3	0.44035 (7)	0.93361 (9)	0.72529 (6)	0.01636 (16)
C1	0.6230 (3)	0.4314 (4)	0.7907 (3)	0.0236 (8)
H1A	0.6388	0.3570	0.7540	0.028*
H1B	0.6727	0.5059	0.7837	0.028*
C2	0.6496 (3)	0.3940 (4)	0.8934 (3)	0.0281 (9)
H2A	0.7157	0.3314	0.9114	0.034*
H2B	0.6710	0.4722	0.9337	0.034*
C3	0.5384 (4)	0.3321 (4)	0.9044 (3)	0.0257 (8)
H3A	0.5449	0.3203	0.9715	0.031*
H3B	0.5246	0.2459	0.8732	0.031*
C4	0.4380 (3)	0.4262 (4)	0.8582 (3)	0.0216 (7)
H4A	0.4387	0.5024	0.8991	0.026*
H4B	0.3610	0.3820	0.8448	0.026*
C5	0.3455 (3)	0.5674 (4)	0.5104 (3)	0.0277 (9)
H5A	0.3271	0.6057	0.4469	0.033*
H5B	0.4308	0.5488	0.5331	0.033*
C6	0.2749 (3)	0.4419 (4)	0.5082 (3)	0.0261 (8)
H6A	0.2620	0.3969	0.4474	0.031*
H6B	0.3179	0.3822	0.5588	0.031*
C7	0.1582 (3)	0.4802 (4)	0.5219 (3)	0.0225 (8)
H7A	0.1078	0.5244	0.4654	0.027*
H7B	0.1163	0.4024	0.5348	0.027*
C8	0.1883 (3)	0.5720 (4)	0.6051 (3)	0.0192 (7)
H8A	0.2167	0.5224	0.6643	0.023*
H8B	0.1182	0.6229	0.6065	0.023*
C9	0.3843 (3)	0.9968 (4)	0.6060 (2)	0.0188 (7)
H9A	0.3912	0.9305	0.5597	0.023*
H9B	0.3010	1.0232	0.5920	0.023*
C10	0.4624 (3)	1.1147 (4)	0.6047 (3)	0.0213 (7)
H10A	0.4527	1.1433	0.5396	0.026*
H10B	0.4424	1.1883	0.6400	0.026*
C11	0.5875 (3)	1.0686 (4)	0.6510 (3)	0.0228 (8)
H11A	0.6424	1.1434	0.6631	0.027*
H11B	0.6119	1.0058	0.6099	0.027*
C12	0.5882 (3)	1.0027 (4)	0.7436 (3)	0.0209 (7)
H12A	0.6061	1.0674	0.7951	0.025*
H12B	0.6483	0.9330	0.7598	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.01159 (6)	0.01222 (7)	0.01049 (6)	0.00034 (4)	0.00376 (5)	−0.00076 (4)
Cl1	0.0165 (4)	0.0225 (4)	0.0222 (4)	−0.0003 (3)	0.0112 (3)	−0.0008 (3)
Cl2	0.0199 (4)	0.0171 (4)	0.0157 (4)	−0.0013 (3)	−0.0007 (3)	−0.0021 (3)
Cl3	0.0183 (4)	0.0179 (4)	0.0177 (4)	0.0004 (3)	0.0102 (3)	−0.0020 (3)
S1	0.0158 (4)	0.0132 (4)	0.0156 (4)	0.0007 (3)	0.0035 (3)	−0.0012 (3)
S2	0.0151 (4)	0.0170 (4)	0.0130 (4)	0.0001 (3)	0.0024 (3)	0.0001 (3)
S3	0.0202 (4)	0.0152 (4)	0.0157 (4)	0.0008 (3)	0.0084 (3)	−0.0004 (3)
C1	0.0173 (17)	0.0225 (18)	0.032 (2)	0.0057 (14)	0.0092 (16)	0.0040 (16)
C2	0.0209 (18)	0.025 (2)	0.030 (2)	0.0032 (15)	−0.0046 (17)	0.0039 (17)
C3	0.031 (2)	0.0182 (18)	0.026 (2)	0.0064 (15)	0.0056 (17)	0.0081 (16)
C4	0.0242 (18)	0.0193 (18)	0.0240 (18)	0.0017 (14)	0.0113 (16)	0.0053 (15)
C5	0.0195 (18)	0.046 (3)	0.0179 (18)	0.0012 (17)	0.0059 (15)	−0.0126 (17)
C6	0.032 (2)	0.0249 (19)	0.0184 (18)	0.0067 (16)	0.0027 (16)	−0.0076 (16)
C7	0.0290 (19)	0.0168 (17)	0.0180 (17)	−0.0032 (14)	0.0015 (16)	−0.0019 (14)
C8	0.0143 (15)	0.0214 (17)	0.0238 (18)	−0.0031 (13)	0.0082 (14)	−0.0051 (15)
C9	0.0191 (17)	0.0207 (17)	0.0149 (16)	0.0011 (13)	0.0023 (14)	0.0031 (13)
C10	0.0262 (18)	0.0181 (17)	0.0212 (18)	0.0021 (14)	0.0097 (16)	0.0024 (15)
C11	0.0222 (18)	0.0221 (18)	0.0260 (19)	−0.0030 (14)	0.0100 (16)	0.0021 (15)
C12	0.0189 (17)	0.0199 (18)	0.0209 (18)	−0.0037 (13)	0.0013 (15)	−0.0008 (14)

Geometric parameters (Å, º)

Ir1—Cl1	2.3648 (8)	C5—H5A	0.9900
Ir1—Cl2	2.3774 (9)	C5—H5B	0.9900
Ir1—Cl3	2.3732 (8)	C5—C6	1.533 (6)
Ir1—S1	2.3469 (9)	C6—H6A	0.9900
Ir1—S2	2.3279 (9)	C6—H6B	0.9900
Ir1—S3	2.3575 (9)	C6—C7	1.516 (5)
S1—C1	1.839 (4)	C7—H7A	0.9900
S1—C4	1.835 (4)	C7—H7B	0.9900
S2—C5	1.841 (4)	C7—C8	1.515 (5)
S2—C8	1.834 (3)	C8—H8A	0.9900
S3—C9	1.827 (4)	C8—H8B	0.9900
S3—C12	1.843 (4)	C9—H9A	0.9900
C1—H1A	0.9900	C9—H9B	0.9900
C1—H1B	0.9900	C9—C10	1.529 (5)
C1—C2	1.522 (6)	C10—H10A	0.9900
C2—H2A	0.9900	C10—H10B	0.9900
C2—H2B	0.9900	C10—C11	1.521 (5)
C2—C3	1.521 (6)	C11—H11A	0.9900
C3—H3A	0.9900	C11—H11B	0.9900
C3—H3B	0.9900	C11—C12	1.537 (5)
C3—C4	1.533 (5)	C12—H12A	0.9900
C4—H4A	0.9900	C12—H12B	0.9900
C4—H4B	0.9900
Cl1—Ir1—Cl2	90.39 (3)	S2—C5—H5A	110.3
Cl1—Ir1—Cl3	177.35 (3)	S2—C5—H5B	110.3
Cl3—Ir1—Cl2	89.63 (3)	H5A—C5—H5B	108.6
S1—Ir1—Cl1	90.37 (3)	C6—C5—S2	107.0 (2)
S1—Ir1—Cl2	90.41 (3)	C6—C5—H5A	110.3
S1—Ir1—Cl3	92.28 (3)	C6—C5—H5B	110.3
S1—Ir1—S3	176.44 (3)	C5—C6—H6A	110.2
S2—Ir1—Cl1	91.09 (3)	C5—C6—H6B	110.2
S2—Ir1—Cl2	178.15 (3)	H6A—C6—H6B	108.5
S2—Ir1—Cl3	88.85 (3)	C7—C6—C5	107.4 (3)
S2—Ir1—S1	90.70 (3)	C7—C6—H6A	110.2
S2—Ir1—S3	92.61 (3)	C7—C6—H6B	110.2
S3—Ir1—Cl1	90.88 (3)	C6—C7—H7A	110.6
S3—Ir1—Cl2	86.25 (3)	C6—C7—H7B	110.6
S3—Ir1—Cl3	86.47 (3)	H7A—C7—H7B	108.8
C1—S1—Ir1	109.15 (13)	C8—C7—C6	105.5 (3)
C4—S1—Ir1	110.23 (12)	C8—C7—H7A	110.6
C4—S1—C1	93.79 (17)	C8—C7—H7B	110.6
C5—S2—Ir1	112.32 (13)	S2—C8—H8A	110.4
C8—S2—Ir1	110.12 (13)	S2—C8—H8B	110.4
C8—S2—C5	92.79 (17)	C7—C8—S2	106.6 (2)
C9—S3—Ir1	113.33 (12)	C7—C8—H8A	110.4
C9—S3—C12	93.79 (16)	C7—C8—H8B	110.4
C12—S3—Ir1	109.93 (12)	H8A—C8—H8B	108.6
S1—C1—H1A	110.3	S3—C9—H9A	110.9
S1—C1—H1B	110.3	S3—C9—H9B	110.9
H1A—C1—H1B	108.6	H9A—C9—H9B	108.9
C2—C1—S1	106.9 (3)	C10—C9—S3	104.2 (2)
C2—C1—H1A	110.3	C10—C9—H9A	110.9
C2—C1—H1B	110.3	C10—C9—H9B	110.9
C1—C2—H2A	110.4	C9—C10—H10A	110.7
C1—C2—H2B	110.4	C9—C10—H10B	110.7
H2A—C2—H2B	108.6	H10A—C10—H10B	108.8
C3—C2—C1	106.7 (3)	C11—C10—C9	105.5 (3)
C3—C2—H2A	110.4	C11—C10—H10A	110.7
C3—C2—H2B	110.4	C11—C10—H10B	110.7
C2—C3—H3A	110.5	C10—C11—H11A	110.4
C2—C3—H3B	110.5	C10—C11—H11B	110.4
C2—C3—C4	106.1 (3)	C10—C11—C12	106.8 (3)
H3A—C3—H3B	108.7	H11A—C11—H11B	108.6
C4—C3—H3A	110.5	C12—C11—H11A	110.4
C4—C3—H3B	110.5	C12—C11—H11B	110.4
S1—C4—H4A	110.8	S3—C12—H12A	110.4
S1—C4—H4B	110.8	S3—C12—H12B	110.4
C3—C4—S1	104.6 (2)	C11—C12—S3	106.5 (2)
C3—C4—H4A	110.8	C11—C12—H12A	110.4
C3—C4—H4B	110.8	C11—C12—H12B	110.4
H4A—C4—H4B	108.9	H12A—C12—H12B	108.6
Ir1—S1—C1—C2	106.1 (3)	C2—C3—C4—S1	43.0 (4)
Ir1—S1—C4—C3	−132.6 (2)	C4—S1—C1—C2	−6.9 (3)
Ir1—S2—C5—C6	106.8 (2)	C5—S2—C8—C7	−20.6 (3)
Ir1—S2—C8—C7	−135.6 (2)	C5—C6—C7—C8	−48.0 (4)
Ir1—S3—C9—C10	−138.6 (2)	C6—C7—C8—S2	42.1 (3)
Ir1—S3—C12—C11	114.0 (2)	C8—S2—C5—C6	−6.3 (3)
S1—C1—C2—C3	33.0 (4)	C9—S3—C12—C11	−2.5 (3)
S2—C5—C6—C7	31.9 (4)	C9—C10—C11—C12	−49.9 (4)
S3—C9—C10—C11	46.4 (3)	C10—C11—C12—S3	29.9 (4)
C1—S1—C4—C3	−20.5 (3)	C12—S3—C9—C10	−25.0 (3)
C1—C2—C3—C4	−49.8 (4)