Crystal structure of chlorido­(η2-phenyl iso­thio­cyanate-κ2C,S)-mer-tris­(tri­methyl­phosphane-κP)iridium(I)

Merola, J.S.; Grieb, A.W.

doi:10.1107/S160053681402162X

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Volume 70| Part 11| November 2014| Pages 352-354

doi:10.1107/S160053681402162X

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Crystal structure of chlorido(η²-phenyl isothiocyanate-κ²C,S)-mer-tris(trimethylphosphane-κP)iridium(I)

Joseph S. Merola ^a ^* and Arthur W. Grieb ^a

^aDepartment of Chemistry 0212, Virginia Tech, Blacksburg, VA 24061, USA
^*Correspondence e-mail: jmerola@vt.edu

Edited by M. Zeller, Youngstown State University, USA (Received 14 January 2014; accepted 30 September 2014; online 18 October 2014)

The molecule of the title compound, [IrCl(C₇H₅NS)(C₃H₉P)₃], is a distorted octahedral iridium complex with three PMe₃ ligands arranged in a meridional geometry, a chloride ion cis to all three PMe₃ groups and the phenyl isothiocyanate ligand bonded in an η²-fashion through the C and S atoms. The C atom is trans to the chloride ion and the S atom is responsible for a significant deviation from an ideal octahedral geometry. The geometric parameters for the metal-complexing phenyl isothiocyanate group are compared with other metal-complexed phenyl isothiocyanates, as well as with examples of uncomplexed aryl isothiocyanates.

Keywords: crystal structure; iridium complex; phenyl isothiocyanate.

CCDC reference: 1027097

1. Chemical context

Various phenyl isothiocyanate complexes of metals have been characterized, all showing the effect of complexation of lengthening of N—C and C—S bonds and the bending of the N—C—S angle away from linearity. Complexation of an aryl isothiocyanate to a metal has a similar effect across a wide range of metal systems with the N—C bond length averaging about 1.26 Å, the C—S distance averaging about 1.74 Å and the N—C—S bond angle ranging from 137 to 142°.

2. Structural commentary

The molecule of the title iridium compound has a distorted octahedral coordination sphere with three PMe₃ ligands arranged in a meridional geometry, a chloride ion cis to all three PMe₃ groups and the phenyl isothiocyanate bonded in an η² fashion to the C and S atoms (Fig. 1). The C atom is trans to the chloride ion and the S atom is significantly off from an ideal octahedral geometry [the P2—Ir1—S1 angle is 144.51 (5)° instead of the expected angle near 180°].

Figure 1
Displacement ellipsoid drawing of the title compound. Ellipsoids are drawn at the 50% probability level and hydrogen atoms are omitted for clarity.

Upon complexation to the iridium cation in the title compound, the N—C bond in phenyl isothiocyanate lengthens to 1.256 (7) Å, the C—S bond lengthens to 1.757 (6) Å and the N—C—S bond angle bends to 137.2 (4)°. These significant changes in geometry reflect the normal consequences of π-bonding of the C–S π-electrons to the metal and π-back-bonding from the metal to the π*-orbitals of the ligand.

3. Database survey

A search of the Cambridge Crystallographic Database (Groom & Allen, 2014 ) on 28 January 2014 found 16 aryl isothiocyanates in which the SCN group is not disordered on coordinating to a metal. All of those structures display a nearly linear N—C—S geometry (ranging from 174–179° with an average of 176°). The multiply bonded nature of both the C—S and C—N bonds is seen in the bond lengths. For C—N, the distances range from 1.14 to 1.17 Å with an average of 1.16 Å and the C—S distances range from 1.54 to 1.59 Å with an average of 1.57 Å. Of those 16, four structures of good precision with no disorder, ionic interactions or other complex interactions that could affect the geometry of the N—C—S group were chosen for comparison to contrast `free' versus `complexed' isothiocyanates. The first entry in Table 1 shows the average values for all 16 structures, the next four entries are the specific non-complexed aryl isothiocyanates, the next six entries are other examples from the CCDC in which phenyl isothiocyanate is complexed to a metal and the last entry is the data from the title compound. For the structures of several uncomplexed aryl isothiocyanates, see: Majewska et al. (2007 , 2008 ); Laliberté et al. (2004 ); Biswas et al. (2007 ). For the structures of a cobalt and a nickel complex of phenyl isothiocyanate, see: Bianchini et al. (1984 ). For the structure of a vanadium complex of phenyl isothiocyanate see: Gambarotta et al. (1984 ). For a phenyl isothiocyanate complex of molybdenum, see: Ohnishi et al. (2005 ). For a phenyl isothiocyanate complex of osmium, see: Flügel et al. (1996 ). For a tris-trimethylphosphine nickel complex of phenyl isothiocyanate, see: Huang et al. (2013 ).

Table 1
Comparison of bond lengths and angles (Å, °) for the SCN moiety of isothiocyanate complexes

Compound	CCDC refcode	N—C	C—S	N—C—S	Reference
Not complexing to a metal
Average of 16 compounds		1.16	1.57	176	Groom & Allen (2014)
C₂₉H₁₆N₄S₄	221549	1.152 (5)	1.566 (4)	175.7 (3)	Laliberté et al. (2004)
C₂₁H₂₃N₁O₂S₁	673469	1.174 (3)	!.584 (3)	177.6 (3)	Majewska et al. (2008)
C₂₄H₃₇N₁S₁	637960	1.134 (7)	1.543 (6)	176.1 (5)	Biswas et al. (2007)
C₂₁H₂₁N₁O₁S₁	646594	1.167 (4)	1.587 (4)	178.8 (3)	Majewska et al. (2007)

Complexing to a metal
C₄₈H₄₄N₁Ni₁P₃S	555280	1.26 (3)	1.68 (3)	142 (2)	Bianchini et al. (1984)
C₄₉H₄₇Co₁N₂P₃S	555508	1.27 (2)	1.72 (1)	141 (1)	Bianchini et al. (1984)
C₂₇H₃₅N₁S₁V₁	557730	1.265 (9)	1.745 (7)	138.6 (6)	Gambarotta et al. (1984)
C₇₀H₆₃Mo₁N₃P₄S₂	257394	1.256 (7)	1.737 (5)	134.9 (4)	Ohnishi et al. (2005)
C₂₅H₄₇ClN₂O₁Os₁P₂S₁	661980	1.253 (7)	1.764 (6)	141.2 (4)	Flügel et al. (1996)
C₁₆H₃₂N₁Ni₁P₃S	850129	1.253 (3)	1.707 (2)	142.2 (2)	Huang et al. (2013)
C₁₆H₃₂Cl₁Ir₁N₁P₃S₁	1027097	1.256 (7)	1.757 (6)	137.2 (4)	This work

4. Synthesis and crystallization

The crystal used in this experiment was obtained from a reaction between [Ir(COD)(PMe₃)₃]Cl (COD = 1,5-cyclooctadiene) and phenyl isothiocyanate in toluene solution. Suitable single crystals were grown from dichloromethane by the layering of diethyl ether.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were placed at calculated positions and refined using a model in which the hydrogen rides on the atom to which it is attached. For methyl hydrogen atoms U_iso(H) = 1.5Ueq(C) and for the phenyl hydrogen atoms, U_iso(H) = 1.2Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[IrCl(C₇H₅NS)(C₃H₉P)₃]
M_r	591.05
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.964 (2), 27.074 (7), 9.721 (2)
β (°)	102.054 (19)
V (Å³)	2307.3 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.20
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Siemens P4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.757, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	5294, 5294, 4133
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 0.93
No. of reflections	5294
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −1.19
Computer programs: XSCANS (Siemens, 1994 ), SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1027097

Crystal structure: contains datablock I. DOI: 10.1107/S160053681402162X/zl2576sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681402162X/zl2576Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681402162X/zl2576Isup4.mol

checkCIF report

Chemical context top

Various other phenyl isothiocyanate complexes of metals have been characterized, all showing the effect of complexation of lengthening of N—C and C—S bonds and the bending of the N—C—S angle away from linearity. Complexation of an aryl isothiocyanate to a metal has a similar effect across a wide range of metal systems with the N—C bond length averaging about 1.26 Å, the C—S distance averaging about 1.74 Å and the N—C—S bond angle ranging from 137 to 142°.

Structural commentary top

The title compound is a distorted octahedral iridium complex with three PMe₃ ligands arranged in a meridional geometry, a chloride ion cis to all three PMe₃ groups and the phenyl isothiocyanate bonded in an η² fashion to the C and S atoms. The C atom is trans to the chloride ion and the S atom is significantly off from an ideal octahedral geometry [the P2—Ir1—S1 angle is 144.51 (5)° instead of the expected angle near 180°].

Upon complexation to the iridium in the title compound, the N—C bond in phenyl isothiocyanate lengthens to 1.256 (7) Å, the C—S bond lengthens to 1.757 (6) Å and the N—C—S bond angle bends to 137.2 (4)°. These significant changes in geometry reflect the normal consequences of π-bonding of the C–S π electrons to the metal and π back-bonding from the metal to the π* orbitals of the ligand.

Database survey top

A search of the Cambridge Crystallographic Database (Groom & Allen, 2014) on 28 January 2014 found 16 aryl isothiocyanates in which the SCN group is not disordered or coordinated to a metal. All of those structures display a nearly linear N—C—S geometry (ranging from 174–179° with an average of 176°). The multiply bonded nature of both the C—S and C—N bonds is seen in the bond lengths. For C—N, the distances range from 1.14 to 1.17 Å with an average of 1.16 Å and the C—S distances range from 1.54 to 1.59 Å with an average of 1.57 Å. Of those 16, four structures of good precision with no disorder, ionic interactions or other complex interactions that could affect the geometry of the N—C—S group were chosen for comparison to contrast `free' versus `complexed' isothiocyanates. The first entry in Table 1 shows the average values for all 16 structures, the next four entries are the specific non-complexed aryl isothiocyanates, the next six entries are other examples from the CCDC in which phenyl isothiocyanate is complexed to a metal and the last entry is the data from the title compound. For the structures of several uncomplexed aryl isothiocyanates, see: Majewska et al. (2007, 2008); Laliberté et al. (2004); Biswas et al. (2007). For the structures of a cobalt and a nickel complex of phenyl isothiocyanate, see: Bianchini et al. (1984). For the structure of a vanadium complex of phenyl isothiocyanate see: Gambarotta et al. (1984). For a phenyl isothiocyanate complex of molybdenum, see: Ohnishi et al. (2005). For a phenyl isothiocyanate complex of osmium, see: Flügel et al. (1996). For a tris-trimethylphosphine nickel complex of phenyl isothiocyanate, see: Huang et al. (2013).

Synthesis and crystallization top

Refinement top

H atoms were placed at calculated positions and refined using a model in which the hydrogen rides on the atom to which it is attached. For methyl hydrogen atoms U_iso(H) = 1.5Ueq(C) and for the phenyl hydrogen atoms, U_iso(H) = 1.2Ueq(C).

Related literature top

For related literature, see: Bianchini et al. (1984); Biswas et al. (2007); Flügel et al. (1996); Gambarotta et al. (1984); Groom & Allen (2014); Huang et al. (2013); Laliberté et al. (2004); Majewska et al. (2007, 2008); Ohnishi et al. (2005).

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS (Siemens, 1994); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. Displacement ellipsoid drawing of the title compound. Ellipsoids are drawn at the 50% probability level and hydrogen atoms are omitted for clarity.

Chlorido(η²-phenyl isothiocyanate-κ²C,S)-mer-tris(trimethylphosphane-κP)iridium(I) top

Crystal data top

[IrCl(C₇H₅NS)(C₃H₉P)₃]	F(000) = 1160
M_r = 591.05	D_x = 1.701 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.964 (2) Å	Cell parameters from 45 reflections
b = 27.074 (7) Å	θ = 2–22°
c = 9.721 (2) Å	µ = 6.20 mm⁻¹
β = 102.054 (19)°	T = 293 K
V = 2307.3 (10) Å³	Prism, yellow
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Siemens P4 diffractometer	4133 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.0000
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→35
T_min = 0.757, T_max = 0.891	l = 0→12
5294 measured reflections	2 standard reflections every 400 reflections
5294 independent reflections	intensity decay: 0.0 (1)

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0433P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max = 0.002
5294 reflections	Δρ_max = 1.00 e Å⁻³
218 parameters	Δρ_min = −1.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: heavy-atom method	Extinction coefficient: 0.00040 (9)

Crystal data top

[IrCl(C₇H₅NS)(C₃H₉P)₃]	V = 2307.3 (10) Å³
M_r = 591.05	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.964 (2) Å	µ = 6.20 mm⁻¹
b = 27.074 (7) Å	T = 293 K
c = 9.721 (2) Å	0.3 × 0.2 × 0.2 mm
β = 102.054 (19)°

Data collection top

Siemens P4 diffractometer	4133 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.0000
T_min = 0.757, T_max = 0.891	2 standard reflections every 400 reflections
5294 measured reflections	intensity decay: 0.0 (1)
5294 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 0.93	Δρ_max = 1.00 e Å⁻³
5294 reflections	Δρ_min = −1.19 e Å⁻³
218 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ir1	0.43752 (2)	0.345208 (7)	0.04153 (2)	0.02506 (7)
Cl1	0.46057 (19)	0.27098 (5)	−0.10524 (16)	0.0442 (4)
P1	0.39424 (18)	0.28837 (5)	0.20883 (16)	0.0331 (3)
P2	0.68593 (17)	0.35657 (5)	0.13576 (17)	0.0352 (3)
P3	0.43328 (19)	0.38958 (5)	−0.16484 (16)	0.0355 (3)
S1	0.17603 (16)	0.37728 (5)	0.03289 (17)	0.0377 (3)
C1A	0.5316 (8)	0.2394 (2)	0.2543 (7)	0.0543 (17)
H1AA	0.5381	0.2210	0.1713	0.082*
H1AB	0.5002	0.2178	0.3213	0.082*
H1AC	0.6296	0.2532	0.2946	0.082*
C1B	0.3641 (9)	0.3133 (2)	0.3741 (7)	0.0578 (19)
H1BA	0.4540	0.3305	0.4207	0.087*
H1BB	0.3430	0.2868	0.4328	0.087*
H1BC	0.2792	0.3357	0.3562	0.087*
C1C	0.2226 (7)	0.2537 (2)	0.1451 (7)	0.0500 (16)
H1CA	0.1409	0.2759	0.1075	0.075*
H1CB	0.1968	0.2352	0.2211	0.075*
H1CC	0.2385	0.2314	0.0727	0.075*
C2A	0.7354 (8)	0.3558 (3)	0.3284 (7)	0.060 (2)
H2AA	0.6775	0.3806	0.3646	0.091*
H2AB	0.8423	0.3624	0.3596	0.091*
H2AC	0.7122	0.3239	0.3618	0.091*
C2B	0.8222 (8)	0.3143 (3)	0.0871 (9)	0.065 (2)
H2BA	0.8001	0.2813	0.1129	0.097*
H2BB	0.9233	0.3232	0.1352	0.097*
H2BC	0.8156	0.3159	−0.0127	0.097*
C2C	0.7610 (8)	0.4167 (2)	0.1038 (8)	0.0579 (19)
H2CA	0.7478	0.4219	0.0043	0.087*
H2CB	0.8676	0.4181	0.1466	0.087*
H2CC	0.7074	0.4418	0.1435	0.087*
C3A	0.5891 (9)	0.3812 (3)	−0.2562 (8)	0.0586 (19)
H3AA	0.6814	0.3943	−0.1998	0.088*
H3AB	0.5660	0.3983	−0.3447	0.088*
H3AC	0.6022	0.3466	−0.2723	0.088*
C3B	0.2699 (8)	0.3716 (2)	−0.2991 (7)	0.0528 (17)
H3BA	0.2793	0.3375	−0.3228	0.079*
H3BB	0.2656	0.3916	−0.3813	0.079*
H3BC	0.1783	0.3761	−0.2642	0.079*
C3C	0.4144 (9)	0.4560 (2)	−0.1565 (7)	0.0536 (18)
H3CA	0.3149	0.4641	−0.1412	0.080*
H3CB	0.4276	0.4704	−0.2435	0.080*
H3CC	0.4907	0.4688	−0.0805	0.080*
C1	0.3493 (6)	0.39985 (18)	0.1318 (6)	0.0295 (11)
N1	0.3916 (5)	0.43280 (15)	0.2224 (5)	0.0330 (10)
C3	0.2897 (6)	0.4657 (2)	0.2672 (6)	0.0336 (12)
C4	0.3135 (9)	0.4781 (2)	0.4081 (7)	0.0576 (19)
H4	0.3936	0.4634	0.4710	0.069*
C5	0.2239 (12)	0.5111 (3)	0.4568 (7)	0.086 (3)
H5	0.2426	0.5181	0.5525	0.103*
C6	0.1056 (10)	0.5344 (3)	0.3676 (8)	0.068 (2)
H6	0.0451	0.5573	0.4018	0.081*
C7	0.0792 (8)	0.5232 (2)	0.2275 (8)	0.0567 (19)
H7	−0.0013	0.5382	0.1658	0.068*
C8	0.1712 (7)	0.4895 (2)	0.1760 (7)	0.0448 (15)
H8	0.1535	0.4829	0.0801	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.02846 (11)	0.01590 (10)	0.03174 (11)	−0.00011 (9)	0.00841 (7)	−0.00018 (8)
Cl1	0.0563 (9)	0.0274 (7)	0.0530 (9)	−0.0037 (6)	0.0206 (7)	−0.0132 (6)
P1	0.0430 (8)	0.0220 (7)	0.0358 (8)	0.0002 (6)	0.0115 (6)	0.0035 (6)
P2	0.0300 (7)	0.0232 (7)	0.0522 (9)	−0.0020 (5)	0.0081 (7)	−0.0023 (6)
P3	0.0502 (9)	0.0229 (7)	0.0355 (8)	−0.0011 (6)	0.0140 (7)	0.0003 (6)
S1	0.0295 (7)	0.0297 (7)	0.0525 (9)	0.0006 (6)	0.0055 (6)	−0.0032 (6)
C1A	0.062 (4)	0.033 (3)	0.066 (4)	0.012 (3)	0.009 (4)	0.014 (3)
C1B	0.093 (6)	0.040 (4)	0.048 (4)	0.004 (4)	0.032 (4)	0.002 (3)
C1C	0.045 (4)	0.043 (4)	0.063 (4)	−0.008 (3)	0.015 (3)	0.006 (3)
C2A	0.053 (4)	0.064 (5)	0.055 (4)	−0.011 (4)	−0.011 (3)	−0.002 (4)
C2B	0.042 (4)	0.058 (5)	0.099 (6)	0.022 (3)	0.025 (4)	0.010 (4)
C2C	0.048 (4)	0.028 (3)	0.090 (5)	−0.012 (3)	−0.003 (4)	0.006 (3)
C3A	0.073 (5)	0.046 (4)	0.067 (5)	−0.001 (4)	0.039 (4)	0.002 (3)
C3B	0.068 (5)	0.043 (4)	0.044 (4)	−0.005 (3)	0.003 (3)	0.003 (3)
C3C	0.083 (5)	0.026 (3)	0.055 (4)	0.004 (3)	0.021 (4)	0.008 (3)
C1	0.033 (3)	0.021 (2)	0.035 (3)	0.006 (2)	0.007 (2)	0.003 (2)
N1	0.033 (2)	0.021 (2)	0.044 (3)	0.0041 (19)	0.007 (2)	−0.0039 (19)
C3	0.040 (3)	0.028 (3)	0.034 (3)	0.002 (2)	0.010 (2)	−0.001 (2)
C4	0.079 (5)	0.049 (4)	0.043 (4)	0.027 (4)	0.008 (4)	0.003 (3)
C5	0.138 (9)	0.090 (6)	0.034 (4)	0.049 (6)	0.029 (5)	−0.001 (4)
C6	0.084 (6)	0.055 (5)	0.073 (5)	0.028 (4)	0.036 (5)	−0.008 (4)
C7	0.043 (4)	0.042 (4)	0.080 (5)	0.016 (3)	0.002 (4)	−0.007 (4)
C8	0.057 (4)	0.033 (3)	0.042 (3)	0.010 (3)	0.006 (3)	−0.007 (3)

Geometric parameters (Å, º) top

Ir1—Cl1	2.4982 (14)	C2B—H2BA	0.9600
Ir1—P1	2.3297 (15)	C2B—H2BB	0.9600
Ir1—P2	2.2450 (16)	C2B—H2BC	0.9600
Ir1—P3	2.3319 (15)	C2C—H2CA	0.9600
Ir1—S1	2.4846 (15)	C2C—H2CB	0.9600
Ir1—C1	1.968 (5)	C2C—H2CC	0.9600
P1—C1A	1.801 (6)	C3A—H3AA	0.9600
P1—C1B	1.814 (6)	C3A—H3AB	0.9600
P1—C1C	1.799 (6)	C3A—H3AC	0.9600
P2—C2A	1.832 (7)	C3B—H3BA	0.9600
P2—C2B	1.808 (6)	C3B—H3BB	0.9600
P2—C2C	1.813 (6)	C3B—H3BC	0.9600
P3—C3A	1.819 (6)	C3C—H3CA	0.9600
P3—C3B	1.813 (7)	C3C—H3CB	0.9600
P3—C3C	1.810 (6)	C3C—H3CC	0.9600
S1—C1	1.757 (6)	C1—N1	1.256 (7)
C1A—H1AA	0.9600	N1—C3	1.408 (6)
C1A—H1AB	0.9600	C3—C4	1.383 (8)
C1A—H1AC	0.9600	C3—C8	1.391 (8)
C1B—H1BA	0.9600	C4—H4	0.9300
C1B—H1BB	0.9600	C4—C5	1.351 (9)
C1B—H1BC	0.9600	C5—H5	0.9300
C1C—H1CA	0.9600	C5—C6	1.375 (10)
C1C—H1CB	0.9600	C6—H6	0.9300
C1C—H1CC	0.9600	C6—C7	1.368 (10)
C2A—H2AA	0.9600	C7—H7	0.9300
C2A—H2AB	0.9600	C7—C8	1.391 (8)
C2A—H2AC	0.9600	C8—H8	0.9300

P1—Ir1—Cl1	85.01 (6)	H2AA—C2A—H2AB	109.5
P1—Ir1—P3	164.96 (6)	H2AA—C2A—H2AC	109.5
P1—Ir1—S1	87.77 (5)	H2AB—C2A—H2AC	109.5
P2—Ir1—Cl1	98.62 (5)	P2—C2B—H2BA	109.5
P2—Ir1—P1	95.81 (6)	P2—C2B—H2BB	109.5
P2—Ir1—P3	96.72 (6)	P2—C2B—H2BC	109.5
P2—Ir1—S1	144.51 (5)	H2BA—C2B—H2BB	109.5
P3—Ir1—Cl1	84.92 (5)	H2BA—C2B—H2BC	109.5
P3—Ir1—S1	86.85 (6)	H2BB—C2B—H2BC	109.5
S1—Ir1—Cl1	116.86 (5)	P2—C2C—H2CA	109.5
C1—Ir1—Cl1	161.48 (16)	P2—C2C—H2CB	109.5
C1—Ir1—P1	92.54 (16)	P2—C2C—H2CC	109.5
C1—Ir1—P2	99.88 (16)	H2CA—C2C—H2CB	109.5
C1—Ir1—P3	93.46 (15)	H2CA—C2C—H2CC	109.5
C1—Ir1—S1	44.63 (16)	H2CB—C2C—H2CC	109.5
C1A—P1—Ir1	116.9 (2)	P3—C3A—H3AA	109.5
C1A—P1—C1B	106.1 (3)	P3—C3A—H3AB	109.5
C1B—P1—Ir1	116.8 (2)	P3—C3A—H3AC	109.5
C1C—P1—Ir1	111.1 (2)	H3AA—C3A—H3AB	109.5
C1C—P1—C1A	101.0 (3)	H3AA—C3A—H3AC	109.5
C1C—P1—C1B	103.0 (3)	H3AB—C3A—H3AC	109.5
C2A—P2—Ir1	115.0 (3)	P3—C3B—H3BA	109.5
C2B—P2—Ir1	118.2 (3)	P3—C3B—H3BB	109.5
C2B—P2—C2A	103.2 (4)	P3—C3B—H3BC	109.5
C2B—P2—C2C	103.2 (3)	H3BA—C3B—H3BB	109.5
C2C—P2—Ir1	115.2 (2)	H3BA—C3B—H3BC	109.5
C2C—P2—C2A	99.6 (3)	H3BB—C3B—H3BC	109.5
C3A—P3—Ir1	118.7 (2)	P3—C3C—H3CA	109.5
C3B—P3—Ir1	110.3 (2)	P3—C3C—H3CB	109.5
C3B—P3—C3A	101.7 (4)	P3—C3C—H3CC	109.5
C3C—P3—Ir1	117.3 (2)	H3CA—C3C—H3CB	109.5
C3C—P3—C3A	103.5 (3)	H3CA—C3C—H3CC	109.5
C3C—P3—C3B	103.3 (3)	H3CB—C3C—H3CC	109.5
C1—S1—Ir1	51.90 (17)	S1—C1—Ir1	83.5 (2)
P1—C1A—H1AA	109.5	N1—C1—Ir1	139.2 (4)
P1—C1A—H1AB	109.5	N1—C1—S1	137.2 (4)
P1—C1A—H1AC	109.5	C1—N1—C3	123.1 (5)
H1AA—C1A—H1AB	109.5	C4—C3—N1	119.0 (5)
H1AA—C1A—H1AC	109.5	C4—C3—C8	117.2 (5)
H1AB—C1A—H1AC	109.5	C8—C3—N1	123.7 (5)
P1—C1B—H1BA	109.5	C3—C4—H4	119.1
P1—C1B—H1BB	109.5	C5—C4—C3	121.9 (6)
P1—C1B—H1BC	109.5	C5—C4—H4	119.1
H1BA—C1B—H1BB	109.5	C4—C5—H5	119.4
H1BA—C1B—H1BC	109.5	C4—C5—C6	121.3 (7)
H1BB—C1B—H1BC	109.5	C6—C5—H5	119.4
P1—C1C—H1CA	109.5	C5—C6—H6	120.8
P1—C1C—H1CB	109.5	C7—C6—C5	118.4 (6)
P1—C1C—H1CC	109.5	C7—C6—H6	120.8
H1CA—C1C—H1CB	109.5	C6—C7—H7	119.6
H1CA—C1C—H1CC	109.5	C6—C7—C8	120.8 (6)
H1CB—C1C—H1CC	109.5	C8—C7—H7	119.6
P2—C2A—H2AA	109.5	C3—C8—H8	119.8
P2—C2A—H2AB	109.5	C7—C8—C3	120.4 (6)
P2—C2A—H2AC	109.5	C7—C8—H8	119.8

Ir1—S1—C1—N1	−175.8 (7)	P3—Ir1—P2—C2B	−85.8 (3)
Ir1—C1—N1—C3	−176.7 (4)	P3—Ir1—P2—C2C	36.8 (3)
Cl1—Ir1—P1—C1A	52.0 (3)	P3—Ir1—S1—C1	−98.1 (2)
Cl1—Ir1—P1—C1B	179.2 (3)	P3—Ir1—C1—S1	81.98 (17)
Cl1—Ir1—P1—C1C	−63.2 (2)	P3—Ir1—C1—N1	−102.4 (6)
Cl1—Ir1—P2—C2A	−122.4 (3)	S1—Ir1—P1—C1A	169.2 (3)
Cl1—Ir1—P2—C2B	0.0 (3)	S1—Ir1—P1—C1B	−63.6 (3)
Cl1—Ir1—P2—C2C	122.6 (3)	S1—Ir1—P1—C1C	54.0 (2)
Cl1—Ir1—P3—C3A	−55.1 (3)	S1—Ir1—P2—C2A	57.8 (3)
Cl1—Ir1—P3—C3B	61.5 (3)	S1—Ir1—P2—C2B	−179.8 (3)
Cl1—Ir1—P3—C3C	179.3 (3)	S1—Ir1—P2—C2C	−57.2 (3)
Cl1—Ir1—S1—C1	179.2 (2)	S1—Ir1—P3—C3A	−172.4 (3)
Cl1—Ir1—C1—S1	−2.4 (6)	S1—Ir1—P3—C3B	−55.8 (3)
Cl1—Ir1—C1—N1	173.2 (4)	S1—Ir1—P3—C3C	62.0 (3)
P1—Ir1—P2—C2A	−36.6 (3)	S1—Ir1—C1—N1	175.6 (8)
P1—Ir1—P2—C2B	85.8 (3)	S1—C1—N1—C3	−3.2 (9)
P1—Ir1—P2—C2C	−151.5 (3)	C1—Ir1—P1—C1A	−146.4 (3)
P1—Ir1—P3—C3A	−103.2 (3)	C1—Ir1—P1—C1B	−19.2 (3)
P1—Ir1—P3—C3B	13.3 (3)	C1—Ir1—P1—C1C	98.4 (3)
P1—Ir1—P3—C3C	131.2 (3)	C1—Ir1—P2—C2A	57.1 (3)
P1—Ir1—S1—C1	95.9 (2)	C1—Ir1—P2—C2B	179.5 (3)
P1—Ir1—C1—S1	−84.23 (17)	C1—Ir1—P2—C2C	−57.9 (3)
P1—Ir1—C1—N1	91.4 (6)	C1—Ir1—P3—C3A	143.4 (3)
P2—Ir1—P1—C1A	−46.2 (3)	C1—Ir1—P3—C3B	−100.0 (3)
P2—Ir1—P1—C1B	81.0 (3)	C1—Ir1—P3—C3C	17.8 (3)
P2—Ir1—P1—C1C	−161.4 (2)	C1—N1—C3—C4	140.5 (6)
P2—Ir1—P3—C3A	43.0 (3)	C1—N1—C3—C8	−44.4 (8)
P2—Ir1—P3—C3B	159.6 (3)	N1—C3—C4—C5	177.1 (7)
P2—Ir1—P3—C3C	−82.6 (3)	N1—C3—C8—C7	−177.1 (6)
P2—Ir1—S1—C1	−1.0 (2)	C3—C4—C5—C6	−1.0 (14)
P2—Ir1—C1—S1	179.42 (14)	C4—C3—C8—C7	−1.9 (9)
P2—Ir1—C1—N1	−5.0 (6)	C4—C5—C6—C7	0.7 (14)
P3—Ir1—P1—C1A	100.1 (3)	C5—C6—C7—C8	−1.0 (12)
P3—Ir1—P1—C1B	−132.7 (3)	C6—C7—C8—C3	1.7 (11)
P3—Ir1—P1—C1C	−15.1 (3)	C8—C3—C4—C5	1.6 (11)
P3—Ir1—P2—C2A	151.8 (3)

Comparison of bond lengths and angles (Å, °) for the SCN moiety of isothiocyanate complexes top

Compound	CCDC refcode	N—C	C—S	N—C—S	Reference
Not complexing to a metal
Average of 16 compounds	N/A	1.16	1.57	176	Groom & Allen (2014)
C₂₉H₁₆N₄S₄	221549	1.152 (5)	1.566 (4)	175.7 (3)	Laliberté et al. (2004)
C₂₁H₂₃N₁O₂S₁	673469	1.174 (3)	!.584 (3)	177.6 (3)	Majewska et al. (2008)
C₂₄H₃₇N₁S₁	637960	1.134 (7)	1.543 (6)	176.1 (5)	Biswas et al. (2007)
C₂₁H₂₁N₁O₁S₁	646594	1.167 (4)	1.587 (4)	178.8 (3)	Majewska et al. (2007)
Complexing to a metal
C₄₈H₄₄N₁Ni₁P₃S	555280	1.26 (3)	1.68 (3)	142 (2)	Bianchini et al. (1984)
C₄₉H₄₇Co₁N₂P₃S	555508	1.27 (2)	1.72 (1)	141 (1)	Bianchini et al. (1984)
C₂₇H₃₅N₁S₁V₁	557730	1.265 (9)	1.745 (7)	138.6 (6)	Gambarotta et al. (1984)
C₇₀H₆₃Mo₁N₃P₄S₂	257394	1.256 (7)	1.737 (5)	134.9 (4)	Ohnishi et al. (2005)
C₂₅H₄₇ClN₂O₁Os₁P₂S₁	661980	1.253 (7)	1.764 (6)	141.2 (4)	Flügel et al. (1996)
C₁₆H₃₂N₁Ni₁P₃S	850129	1.253 (3)	1.707 (2)	142.2 (2)	Huang et al. (2013)
C₁₆H₃₂Cl₁Ir₁N₁P₃S₁	1027097	1.256 (7)	1.757 (6)	137.2 (4)	This work

Experimental details

Crystal data
Chemical formula	[IrCl(C₇H₅NS)(C₃H₉P)₃]
M_r	591.05
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.964 (2), 27.074 (7), 9.721 (2)
β (°)	102.054 (19)
V (Å³)	2307.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.20
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.757, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	5294, 5294, 4133
R_int	0.0000
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 0.93
No. of reflections	5294
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −1.19

Computer programs: XSCANS (Siemens, 1994), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

The authors thank the Virginia Tech Subvention Fund for covering the open-access fee.

References

Bianchini, C., Masi, D., Mealli, C. & Meli, A. (1984). Inorg. Chem. 23, 2838–2844. CSD CrossRef CAS Web of Science Google Scholar
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Volume 70| Part 11| November 2014| Pages 352-354

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