(S-Methyl­cysteinato)(η⁵-penta­methyl­cyclopenta­dien­yl)iridium(III) trifluoro­methanesulfonate hemihydrate

The cation of the title compound, [Ir(C₁₀H₁₅)(C₄H₈NO₂S)](CF₃SO₃)·0.5H₂O, contains a half-sandwich [Ir(C₅Me₅)]²⁺ fragment, the Ir^III atom of which is coordinated by the tridentate S-methyl­cysteinate ligand (S-MecysO) in a κ³N,O,S manner. An R_Ir configuration is observed for the transition metal and an S_S configuration for the chiral thio­ether S atom.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.016 Å
• H-atom completeness 96%
• Disorder in solvent or counterion
• R factor = 0.032
• wR factor = 0.080
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.12 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ir1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        S1'
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for       C10'
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................       6.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         16
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C15 H24 F3 Ir1 N1 O5.5 S2
            Atom count from _chemical_formula_moiety:C30 H48 F6 Ir2 N2 O11 S4
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C15 H24 F3 Ir1 N1 O5.5 S2
            Atom count from the _atom_site data:  C15 H23 F3 Ir1 N1 O5.5 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C15 H24 F3 Ir1 N1 O5.5 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         60.00     60.00    0.00
           H         96.00     92.00    4.00
           F         12.00     12.00    0.00
           Ir         4.00      4.00    0.00
           N          4.00      4.00    0.00
           O         22.00     22.00    0.00
           S          8.00      8.00    0.00
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               2681
           Count of symmetry unique reflns         2191
           Completeness (_total/calc)            122.36%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       490
           Fraction of Friedel pairs measured     0.224
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

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

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Computing details

Data collection: R3m/V (Siemens, 1989); cell refinement: R3m/V; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

(S-Methylcysteinato)(η⁵-pentamethylcyclopentadienyl)iridium(III) trifluoromethanesulfonate hemihydrate

Crystal data

[Ir(C10H15)(C4H8NO2S)](CF3SO3)·0.5H2O	F(000) = 1204
Mr = 619.67	Dx = 1.905 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 35 reflections
a = 8.510 (5) Å	θ = 5.3–17.4°
b = 10.728 (3) Å	µ = 6.43 mm^−1
c = 23.664 (4) Å	T = 292 K
V = 2160.4 (14) Å^3	Prism, yellow
Z = 4	0.49 × 0.28 × 0.23 mm

Data collection

Siemens P4 four-circle diffractometer	2487 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω scans	h = −10→1
Absorption correction: psi-scan (XPREP in SHELXTL; Sheldrick, 1995)	k = −1→12
Tmin = 0.130, Tmax = 0.230	l = −1→28
2865 measured reflections	3 standard reflections every 100 reflections
2677 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 2.2565P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2677 reflections	Δρmax = 1.37 e Å^−3
256 parameters	Δρmin = −0.83 e Å^−3
16 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.007 (16)

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	Occ. (<1)
Ir1	0.22851 (4)	0.83836 (3)	0.109223 (13)	0.04355 (12)
S1	0.3311 (3)	1.0219 (3)	0.06728 (11)	0.0596 (6)
O1	0.2830 (8)	0.7527 (6)	0.0308 (2)	0.0516 (15)
O2	0.2585 (9)	0.7838 (7)	−0.0606 (2)	0.0648 (19)
N1	0.0374 (9)	0.8846 (8)	0.0574 (3)	0.0468 (19)
H11	−0.0303	0.8204	0.0549	0.056*
H12	−0.0139	0.9514	0.0711	0.056*
C1	0.2222 (12)	0.8063 (9)	−0.0126 (3)	0.051 (2)
C2	0.1074 (12)	0.9129 (10)	0.0010 (4)	0.053 (2)
H2	0.0258	0.9198	−0.0280	0.064*
C3	0.1980 (14)	1.0336 (9)	0.0066 (4)	0.063 (3)
H31	0.1257	1.1025	0.0120	0.075*
H32	0.2578	1.0490	−0.0276	0.075*
C4	0.5132 (13)	0.9839 (13)	0.0310 (5)	0.079 (4)
H41	0.5006	0.9069	0.0108	0.118*
H42	0.5963	0.9753	0.0582	0.118*
H43	0.5389	1.0493	0.0049	0.118*
C1'	0.3794 (11)	0.8130 (13)	0.1810 (5)	0.070 (4)
C2'	0.3194 (13)	0.6959 (11)	0.1652 (4)	0.068 (4)
C3'	0.1521 (13)	0.7016 (10)	0.1687 (4)	0.067 (3)
C4'	0.1116 (10)	0.8221 (12)	0.1890 (4)	0.062 (3)
C5'	0.2508 (13)	0.8929 (10)	0.1964 (4)	0.068 (3)
C11'	0.5525 (12)	0.845 (2)	0.1861 (5)	0.099 (5)
H111	0.5817	0.8474	0.2253	0.148*
H112	0.5713	0.9254	0.1694	0.148*
H113	0.6140	0.7834	0.1668	0.148*
C21'	0.413 (2)	0.5840 (14)	0.1460 (6)	0.117 (7)
H211	0.5227	0.6040	0.1462	0.175*
H212	0.3813	0.5614	0.1084	0.175*
H213	0.3937	0.5154	0.1711	0.175*
C31'	0.041 (2)	0.5939 (15)	0.1568 (7)	0.113 (6)
H311	−0.0632	0.6156	0.1693	0.169*
H312	0.0758	0.5211	0.1768	0.169*
H313	0.0389	0.5770	0.1170	0.169*
C41'	−0.0523 (12)	0.8684 (17)	0.2004 (5)	0.091 (5)
H411	−0.1199	0.8447	0.1698	0.136*
H412	−0.0510	0.9575	0.2038	0.136*
H413	−0.0904	0.8324	0.2350	0.136*
C51'	0.264 (2)	1.0228 (12)	0.2175 (5)	0.110 (5)
H511	0.3352	1.0687	0.1939	0.164*
H512	0.3032	1.0220	0.2556	0.164*
H513	0.1626	1.0618	0.2168	0.164*
S1'	0.9045 (5)	0.2216 (3)	0.11935 (18)	0.0903 (11)
O1'	0.9918 (18)	0.2425 (15)	0.1701 (6)	0.177 (7)
O2'	0.880 (2)	0.0931 (9)	0.1056 (6)	0.152 (6)
O3'	0.9385 (17)	0.3006 (14)	0.0736 (5)	0.155 (6)
C10'	0.709 (2)	0.2678 (11)	0.1383 (5)	0.104 (5)
F1'	0.7075 (17)	0.3841 (10)	0.1515 (6)	0.187 (6)
F2'	0.6096 (14)	0.2572 (13)	0.0976 (6)	0.150 (4)
F3'	0.665 (2)	0.2111 (16)	0.1827 (6)	0.223 (8)
OW1'	0.314 (5)	0.372 (4)	0.0406 (16)	0.214 (15)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.03606 (17)	0.0562 (2)	0.03839 (17)	0.00281 (16)	−0.00147 (13)	0.00189 (16)
S1	0.0590 (15)	0.0588 (15)	0.0610 (14)	−0.0100 (13)	0.0018 (12)	−0.0051 (12)
O1	0.048 (4)	0.057 (3)	0.050 (3)	0.007 (4)	0.002 (3)	−0.002 (3)
O2	0.071 (5)	0.085 (4)	0.039 (3)	0.018 (4)	0.007 (3)	−0.005 (3)
N1	0.040 (4)	0.054 (5)	0.046 (4)	0.004 (4)	−0.005 (3)	−0.016 (4)
C1	0.050 (5)	0.062 (6)	0.042 (4)	0.000 (5)	−0.006 (4)	−0.002 (4)
C2	0.046 (5)	0.068 (6)	0.045 (5)	0.006 (5)	−0.002 (4)	0.012 (5)
C3	0.076 (7)	0.053 (5)	0.059 (5)	−0.001 (6)	0.002 (6)	0.017 (5)
C4	0.054 (6)	0.104 (10)	0.078 (8)	−0.019 (7)	0.007 (6)	−0.002 (8)
C1'	0.045 (5)	0.114 (11)	0.052 (6)	0.012 (7)	−0.007 (5)	0.005 (7)
C2'	0.075 (8)	0.088 (10)	0.042 (5)	0.027 (7)	0.011 (5)	0.016 (6)
C3'	0.071 (7)	0.085 (10)	0.045 (5)	−0.004 (6)	0.001 (5)	0.016 (6)
C4'	0.042 (5)	0.106 (10)	0.036 (4)	0.013 (7)	0.009 (4)	0.016 (7)
C5'	0.061 (7)	0.101 (8)	0.042 (5)	−0.002 (7)	−0.012 (5)	0.001 (5)
C11'	0.051 (6)	0.175 (17)	0.070 (7)	−0.015 (11)	−0.014 (5)	−0.002 (11)
C21'	0.150 (16)	0.110 (13)	0.090 (10)	0.066 (12)	0.023 (11)	0.058 (9)
C31'	0.131 (15)	0.096 (12)	0.111 (13)	−0.052 (11)	−0.012 (11)	0.022 (10)
C41'	0.049 (6)	0.150 (15)	0.073 (7)	0.025 (8)	0.016 (6)	0.023 (9)
C51'	0.131 (14)	0.123 (11)	0.074 (7)	0.007 (13)	−0.017 (9)	−0.048 (8)
S1'	0.104 (3)	0.069 (2)	0.098 (3)	0.024 (2)	−0.010 (2)	−0.003 (2)
O1'	0.174 (14)	0.187 (16)	0.170 (13)	0.052 (13)	−0.102 (12)	−0.045 (12)
O2'	0.207 (16)	0.085 (7)	0.165 (12)	0.048 (9)	0.010 (13)	−0.038 (8)
O3'	0.135 (11)	0.165 (13)	0.166 (11)	0.027 (10)	0.030 (9)	0.086 (11)
C10'	0.131 (16)	0.088 (10)	0.092 (10)	0.000 (12)	0.036 (12)	−0.019 (9)
F1'	0.165 (12)	0.114 (7)	0.283 (16)	0.057 (8)	−0.019 (12)	−0.088 (9)
F2'	0.109 (8)	0.171 (11)	0.171 (11)	−0.019 (8)	−0.013 (8)	−0.009 (10)
F3'	0.28 (2)	0.242 (17)	0.150 (10)	0.012 (17)	0.101 (12)	0.005 (11)

Geometric parameters (Å, º)

Ir1—N1	2.096 (7)	C3'—C4'	1.422 (13)
Ir1—O1	2.122 (6)	C3'—C31'	1.521 (12)
Ir1—C3'	2.134 (10)	C4'—C5'	1.419 (13)
Ir1—C4'	2.142 (8)	C4'—C41'	1.505 (11)
Ir1—C1'	2.147 (10)	C5'—C51'	1.485 (12)
Ir1—C5'	2.154 (9)	C11'—H111	0.9600
Ir1—C2'	2.165 (10)	C11'—H112	0.9600
Ir1—S1	2.372 (3)	C11'—H113	0.9600
S1—C4	1.818 (11)	C21'—H211	0.9600
S1—C3	1.834 (11)	C21'—H212	0.9600
O1—C1	1.286 (10)	C21'—H213	0.9600
O2—C1	1.201 (10)	C31'—H311	0.9600
N1—C2	1.493 (12)	C31'—H312	0.9600
N1—H11	0.9000	C31'—H313	0.9600
N1—H12	0.9000	C41'—H411	0.9600
C1—C2	1.538 (14)	C41'—H412	0.9600
C2—C3	1.512 (14)	C41'—H413	0.9600
C2—H2	0.9800	C51'—H511	0.9600
C3—H31	0.9700	C51'—H512	0.9600
C3—H32	0.9700	C51'—H513	0.9600
C4—H41	0.9600	S1'—O3'	1.404 (9)
C4—H42	0.9600	S1'—O2'	1.431 (10)
C4—H43	0.9600	S1'—O1'	1.430 (10)
C1'—C2'	1.406 (14)	S1'—C10'	1.794 (19)
C1'—C5'	1.438 (13)	C10'—F3'	1.271 (11)
C1'—C11'	1.518 (11)	C10'—F2'	1.286 (12)
C2'—C3'	1.427 (13)	C10'—F1'	1.287 (11)
C2'—C21'	1.511 (12)
N1—Ir1—O1	76.1 (3)	C1'—C2'—C21'	126.8 (12)
N1—Ir1—C3'	108.2 (4)	C3'—C2'—C21'	125.2 (13)
O1—Ir1—C3'	110.2 (3)	C1'—C2'—Ir1	70.3 (6)
N1—Ir1—C4'	100.1 (3)	C3'—C2'—Ir1	69.4 (6)
O1—Ir1—C4'	146.9 (4)	C21'—C2'—Ir1	124.3 (8)
C3'—Ir1—C4'	38.8 (4)	C4'—C3'—C2'	107.4 (9)
N1—Ir1—C1'	163.1 (3)	C4'—C3'—C31'	127.0 (11)
O1—Ir1—C1'	120.4 (4)	C2'—C3'—C31'	125.4 (12)
C3'—Ir1—C1'	64.8 (4)	C4'—C3'—Ir1	70.9 (5)
C4'—Ir1—C1'	64.5 (4)	C2'—C3'—Ir1	71.8 (7)
N1—Ir1—C5'	124.4 (3)	C31'—C3'—Ir1	126.2 (9)
O1—Ir1—C5'	159.5 (3)	C5'—C4'—C3'	109.1 (8)
C3'—Ir1—C5'	65.3 (4)	C5'—C4'—C41'	125.1 (12)
C4'—Ir1—C5'	38.6 (3)	C3'—C4'—C41'	125.8 (12)
C1'—Ir1—C5'	39.1 (4)	C5'—C4'—Ir1	71.2 (5)
N1—Ir1—C2'	143.3 (4)	C3'—C4'—Ir1	70.3 (5)
O1—Ir1—C2'	98.7 (3)	C41'—C4'—Ir1	124.2 (7)
C3'—Ir1—C2'	38.8 (3)	C4'—C5'—C1'	106.5 (9)
C4'—Ir1—C2'	64.4 (4)	C4'—C5'—C51'	127.5 (13)
C1'—Ir1—C2'	38.0 (4)	C1'—C5'—C51'	126.0 (13)
C5'—Ir1—C2'	64.8 (4)	C4'—C5'—Ir1	70.3 (5)
N1—Ir1—S1	81.1 (2)	C1'—C5'—Ir1	70.2 (5)
O1—Ir1—S1	85.01 (19)	C51'—C5'—Ir1	125.8 (8)
C3'—Ir1—S1	163.5 (3)	C1'—C11'—H111	109.5
C4'—Ir1—S1	127.4 (4)	C1'—C11'—H112	109.5
C1'—Ir1—S1	102.5 (4)	H111—C11'—H112	109.5
C5'—Ir1—S1	98.2 (3)	C1'—C11'—H113	109.5
C2'—Ir1—S1	135.3 (3)	H111—C11'—H113	109.5
C4—S1—C3	99.9 (5)	H112—C11'—H113	109.5
C4—S1—Ir1	109.0 (5)	C2'—C21'—H211	109.5
C3—S1—Ir1	99.0 (3)	C2'—C21'—H212	109.5
C1—O1—Ir1	114.6 (6)	H211—C21'—H212	109.5
C2—N1—Ir1	105.1 (6)	C2'—C21'—H213	109.5
C2—N1—H11	110.7	H211—C21'—H213	109.5
Ir1—N1—H11	110.7	H212—C21'—H213	109.5
C2—N1—H12	110.7	C3'—C31'—H311	109.5
Ir1—N1—H12	110.7	C3'—C31'—H312	109.5
H11—N1—H12	108.8	H311—C31'—H312	109.5
O2—C1—O1	124.2 (9)	C3'—C31'—H313	109.5
O2—C1—C2	120.7 (8)	H311—C31'—H313	109.5
O1—C1—C2	114.9 (7)	H312—C31'—H313	109.5
N1—C2—C3	107.4 (8)	C4'—C41'—H411	109.5
N1—C2—C1	106.8 (8)	C4'—C41'—H412	109.5
C3—C2—C1	109.3 (8)	H411—C41'—H412	109.5
N1—C2—H2	111.0	C4'—C41'—H413	109.5
C3—C2—H2	111.0	H411—C41'—H413	109.5
C1—C2—H2	111.0	H412—C41'—H413	109.5
C2—C3—S1	109.0 (6)	C5'—C51'—H511	109.5
C2—C3—H31	109.9	C5'—C51'—H512	109.5
S1—C3—H31	109.9	H511—C51'—H512	109.5
C2—C3—H32	109.9	C5'—C51'—H513	109.5
S1—C3—H32	109.9	H511—C51'—H513	109.5
H31—C3—H32	108.3	H512—C51'—H513	109.5
S1—C4—H41	109.5	O3'—S1'—O2'	115.8 (10)
S1—C4—H42	109.5	O3'—S1'—O1'	116.4 (11)
H41—C4—H42	109.5	O2'—S1'—O1'	114.8 (9)
S1—C4—H43	109.5	O3'—S1'—C10'	102.5 (8)
H41—C4—H43	109.5	O2'—S1'—C10'	100.8 (8)
H42—C4—H43	109.5	O1'—S1'—C10'	103.2 (8)
C2'—C1'—C5'	108.9 (9)	F3'—C10'—F2'	112.5 (17)
C2'—C1'—C11'	125.3 (13)	F3'—C10'—F1'	105.0 (15)
C5'—C1'—C11'	125.6 (13)	F2'—C10'—F1'	105.2 (15)
C2'—C1'—Ir1	71.7 (6)	F3'—C10'—S1'	110.4 (14)
C5'—C1'—Ir1	70.7 (5)	F2'—C10'—S1'	113.4 (10)
C11'—C1'—Ir1	127.9 (9)	F1'—C10'—S1'	109.7 (13)
C1'—C2'—C3'	108.0 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2^i	0.90	2.12	2.984 (11)	160
N1—H12···O2′^ii	0.90	1.95	2.846 (13)	176

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