Chlorido(η⁵-penta­methyl­cyclo­penta­dien­yl)(1,10-phenanthroline-κ²N,N′)iridium(III) trifluoro­methane­sulfonate

The cation of the title compound, [Ir(η⁵-C₅Me₅)Cl(C₁₂H₈N₂)]CF₃SO₃, contains a half-sandwich (η⁵-C₅Me₅)Ir^III fragment coordinated in a κ²N manner by the N atoms of a 1,10-phenanthroline ligand. The diimine ligand is inclined at an angle of 62.6 (4)° to the plane of the penta­methyl­cyclo­penta­dienyl ligand.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.018 Å
• R factor = 0.043
• wR factor = 0.075
• Data-to-parameter ratio = 9.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom C50     has ADP max/min Ratio .............       3.30 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.59 Ratio
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         C1
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         18
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10    ..  O2      ..       2.61 Ang.

Alert level G
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               2997
           Count of symmetry unique reflns         2454
           Completeness (_total/calc)            122.13%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       543
           Fraction of Friedel pairs measured     0.221
           Are heavy atom types Z>Si present        yes

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

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: Siemens R3m/V (Siemens, 1989); cell refinement: Siemens 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.

Chlorido(η⁵-pentamethylcyclopentadienyl)(1,10-phenanthroline- κ²N,N')iridium(III) trifluoromethanesulfonate

Crystal data

[Ir(C10H15)Cl(C12H8N2)]CF3SO3	F(000) = 1344
Mr = 692.14	Dx = 1.884 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 13 reflections
a = 8.266 (4) Å	θ = 2.9–9.6°
b = 12.848 (7) Å	µ = 5.72 mm^−1
c = 22.977 (12) Å	T = 292 K
V = 2440 (2) Å^3	Block, yellow
Z = 4	0.10 × 0.08 × 0.06 mm

Data collection

Siemens P4 four-circle diffractometer	2346 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω scans	h = −1→9
Absorption correction: ψ scan (XPREP; Sheldrick, 1995)	k = −1→15
Tmin = 0.570, Tmax = 0.718	l = −1→27
3200 measured reflections	3 standard reflections every 97 reflections
2997 independent reflections	intensity decay: 0.0%

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0189P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.003
2997 reflections	Δρmax = 0.67 e Å^−3
312 parameters	Δρmin = −1.03 e Å^−3
0 restraints	Absolute structure: Flack (1983), 548 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.039 (14)

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
Ir1	0.73319 (6)	0.42617 (3)	0.899921 (17)	0.03639 (14)
Cl1	0.4898 (5)	0.3307 (3)	0.88120 (16)	0.0550 (11)
N1	0.5724 (13)	0.5513 (8)	0.9171 (4)	0.045 (3)
C2	0.5089 (15)	0.5803 (14)	0.9681 (5)	0.041 (3)
H2	0.5432	0.5461	1.0016	0.049*
C3	0.3953 (16)	0.6580 (11)	0.9738 (5)	0.053 (4)
H3	0.3529	0.6751	1.0100	0.063*
C4	0.3459 (17)	0.7102 (11)	0.9242 (5)	0.052 (4)
H4	0.2710	0.7639	0.9272	0.063*
C5	0.4061 (16)	0.6834 (10)	0.8705 (5)	0.041 (4)
C6	0.3644 (19)	0.7319 (11)	0.8169 (6)	0.062 (4)
H6	0.2870	0.7844	0.8175	0.075*
C7	0.4294 (16)	0.7066 (11)	0.7661 (6)	0.053 (4)
H7	0.3978	0.7418	0.7326	0.064*
C8	0.5469 (16)	0.6263 (10)	0.7624 (5)	0.042 (4)
C9	0.6304 (18)	0.5944 (10)	0.7122 (5)	0.054 (4)
H9	0.6124	0.6290	0.6772	0.065*
C10	0.7368 (19)	0.5141 (9)	0.7138 (4)	0.053 (3)
H10	0.7882	0.4926	0.6798	0.064*
C11	0.7693 (18)	0.4635 (8)	0.7663 (4)	0.044 (3)
H11	0.8413	0.4079	0.7667	0.053*
N12	0.6966 (12)	0.4944 (7)	0.8174 (3)	0.038 (3)
C13	0.5882 (13)	0.5735 (11)	0.8146 (4)	0.031 (3)
C14	0.5223 (15)	0.6030 (9)	0.8694 (5)	0.036 (3)
C20	0.9418 (16)	0.3231 (11)	0.8932 (7)	0.047 (4)
C21	0.9916 (19)	0.2512 (11)	0.8464 (5)	0.065 (5)
H211	1.0157	0.2903	0.8119	0.098*
H212	0.9054	0.2032	0.8385	0.098*
H213	1.0861	0.2135	0.8585	0.098*
C30	0.9935 (15)	0.4301 (13)	0.9025 (6)	0.059 (4)
C31	1.1057 (16)	0.4878 (12)	0.8595 (6)	0.076 (5)
H311	1.0893	0.5615	0.8631	0.114*
H312	1.0813	0.4663	0.8205	0.114*
H313	1.2164	0.4714	0.8683	0.114*
C40	0.9271 (17)	0.4684 (11)	0.9565 (6)	0.050 (4)
C41	0.9580 (17)	0.5741 (14)	0.9826 (7)	0.083 (6)
H411	0.8639	0.5965	1.0036	0.125*
H412	0.9813	0.6230	0.9521	0.125*
H413	1.0485	0.5702	1.0087	0.125*
C50	0.8402 (16)	0.3830 (11)	0.9818 (5)	0.048 (4)
C51	0.766 (2)	0.3848 (11)	1.0430 (4)	0.074 (5)
H511	0.7793	0.4527	1.0597	0.111*
H512	0.8192	0.3342	1.0670	0.111*
H513	0.6528	0.3685	1.0406	0.111*
C60	0.8477 (19)	0.2950 (11)	0.9448 (5)	0.054 (4)
C61	0.778 (2)	0.1910 (9)	0.9594 (6)	0.074 (5)
H611	0.8595	0.1482	0.9768	0.111*
H612	0.7389	0.1583	0.9245	0.111*
H613	0.6896	0.1998	0.9861	0.111*
S1	0.9057 (6)	0.8385 (4)	0.85387 (16)	0.0664 (13)
O1	0.8165 (15)	0.7647 (9)	0.8845 (4)	0.103 (4)
O2	1.0102 (13)	0.8980 (10)	0.8900 (4)	0.098 (4)
O3	0.9753 (13)	0.8067 (11)	0.7998 (5)	0.100 (4)
C1	0.758 (3)	0.9340 (14)	0.8300 (8)	0.091 (5)
F1	0.8259 (16)	1.0144 (8)	0.8051 (6)	0.147 (5)
F2	0.6589 (13)	0.8949 (9)	0.7902 (6)	0.141 (5)
F3	0.6717 (17)	0.9653 (11)	0.8753 (7)	0.189 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0374 (3)	0.0359 (2)	0.03589 (18)	0.0009 (3)	−0.0010 (3)	0.0010 (2)
Cl1	0.051 (2)	0.052 (2)	0.062 (2)	−0.015 (2)	0.0007 (19)	−0.005 (2)
N1	0.053 (8)	0.045 (7)	0.038 (5)	0.000 (6)	−0.009 (5)	−0.001 (5)
C2	0.043 (8)	0.047 (9)	0.033 (6)	0.007 (10)	−0.009 (6)	−0.005 (8)
C3	0.046 (10)	0.067 (10)	0.045 (7)	0.013 (9)	0.002 (7)	−0.025 (7)
C4	0.042 (10)	0.058 (9)	0.057 (7)	0.004 (8)	−0.001 (7)	0.006 (7)
C5	0.030 (9)	0.045 (8)	0.048 (7)	−0.019 (8)	0.000 (7)	0.000 (7)
C6	0.065 (11)	0.053 (9)	0.068 (9)	0.016 (9)	0.007 (9)	0.016 (8)
C7	0.046 (10)	0.061 (10)	0.053 (8)	0.013 (9)	−0.009 (8)	0.017 (8)
C8	0.043 (9)	0.048 (8)	0.035 (6)	−0.016 (8)	0.000 (7)	0.016 (7)
C9	0.069 (11)	0.046 (9)	0.046 (7)	−0.008 (9)	0.015 (8)	0.009 (7)
C10	0.063 (10)	0.061 (8)	0.035 (5)	0.002 (11)	0.005 (9)	0.005 (6)
C11	0.041 (9)	0.038 (6)	0.053 (6)	−0.004 (9)	−0.023 (8)	−0.002 (5)
N12	0.043 (8)	0.036 (5)	0.036 (5)	−0.010 (6)	0.000 (5)	0.003 (4)
C13	0.021 (7)	0.035 (6)	0.039 (6)	0.001 (8)	0.007 (5)	0.008 (7)
C14	0.031 (8)	0.039 (9)	0.039 (7)	0.006 (7)	−0.002 (6)	0.011 (6)
C20	0.051 (9)	0.033 (8)	0.058 (9)	0.023 (7)	−0.013 (9)	−0.004 (8)
C21	0.080 (12)	0.061 (11)	0.055 (8)	0.037 (10)	0.000 (9)	0.001 (8)
C30	0.050 (8)	0.086 (11)	0.041 (6)	−0.001 (11)	−0.012 (8)	−0.001 (11)
C31	0.040 (10)	0.100 (13)	0.088 (11)	−0.002 (10)	−0.005 (9)	0.028 (11)
C40	0.042 (10)	0.049 (9)	0.059 (8)	0.003 (8)	−0.010 (7)	−0.018 (8)
C41	0.079 (12)	0.082 (13)	0.087 (12)	−0.022 (14)	−0.019 (10)	−0.031 (13)
C50	0.032 (9)	0.074 (10)	0.039 (6)	0.029 (8)	−0.008 (6)	0.019 (7)
C51	0.067 (11)	0.115 (11)	0.040 (6)	0.033 (13)	−0.012 (9)	0.013 (7)
C60	0.072 (11)	0.062 (9)	0.027 (6)	0.008 (9)	−0.013 (7)	0.006 (6)
C61	0.072 (13)	0.044 (7)	0.106 (10)	−0.007 (11)	0.004 (12)	0.006 (7)
S1	0.062 (3)	0.085 (3)	0.052 (2)	−0.011 (3)	−0.001 (2)	0.010 (2)
O1	0.121 (11)	0.109 (8)	0.078 (7)	−0.035 (9)	−0.012 (7)	0.032 (6)
O2	0.089 (8)	0.129 (11)	0.077 (7)	−0.054 (8)	−0.028 (7)	0.018 (8)
O3	0.076 (9)	0.141 (12)	0.082 (7)	−0.002 (9)	0.018 (7)	−0.019 (9)
C1	0.091 (15)	0.069 (10)	0.112 (12)	−0.02 (2)	0.002 (15)	0.001 (11)
F1	0.151 (13)	0.083 (7)	0.206 (12)	−0.018 (8)	−0.056 (11)	0.032 (8)
F2	0.083 (8)	0.120 (11)	0.221 (13)	0.005 (8)	−0.061 (9)	−0.003 (10)
F3	0.158 (14)	0.176 (14)	0.233 (14)	0.038 (11)	0.098 (12)	−0.042 (11)

Geometric parameters (Å, º)

Ir1—N12	2.110 (8)	C20—C30	1.46 (2)
Ir1—N1	2.123 (11)	C20—C60	1.463 (18)
Ir1—C40	2.134 (13)	C20—C21	1.475 (18)
Ir1—C50	2.151 (11)	C21—H211	0.9600
Ir1—C30	2.153 (13)	C21—H212	0.9600
Ir1—C20	2.180 (13)	C21—H213	0.9600
Ir1—C60	2.191 (13)	C30—C40	1.443 (17)
Ir1—Cl1	2.395 (4)	C30—C31	1.544 (17)
N1—C2	1.336 (15)	C31—H311	0.9600
N1—C14	1.348 (13)	C31—H312	0.9600
C2—C3	1.377 (18)	C31—H313	0.9600
C2—H2	0.9300	C40—C50	1.434 (17)
C3—C4	1.383 (16)	C40—C41	1.51 (2)
C3—H3	0.9300	C41—H411	0.9600
C4—C5	1.374 (15)	C41—H412	0.9600
C4—H4	0.9300	C41—H413	0.9600
C5—C14	1.411 (16)	C50—C60	1.416 (16)
C5—C6	1.423 (16)	C50—C51	1.536 (15)
C6—C7	1.325 (16)	C51—H511	0.9600
C6—H6	0.9300	C51—H512	0.9600
C7—C8	1.420 (17)	C51—H513	0.9600
C7—H7	0.9300	C60—C61	1.493 (17)
C8—C9	1.405 (16)	C61—H611	0.9600
C8—C13	1.420 (15)	C61—H612	0.9600
C9—C10	1.356 (17)	C61—H613	0.9600
C9—H9	0.9300	S1—O1	1.391 (11)
C10—C11	1.396 (13)	S1—O2	1.421 (11)
C10—H10	0.9300	S1—O3	1.429 (11)
C11—N12	1.379 (13)	S1—C1	1.82 (2)
C11—H11	0.9300	C1—F1	1.308 (19)
N12—C13	1.356 (14)	C1—F2	1.324 (19)
C13—C14	1.422 (15)	C1—F3	1.32 (2)
N12—Ir1—N1	76.3 (4)	C30—C20—C21	128.0 (15)
N12—Ir1—C40	123.3 (5)	C60—C20—C21	125.7 (13)
N1—Ir1—C40	99.5 (4)	C30—C20—Ir1	69.4 (7)
N12—Ir1—C50	162.1 (5)	C60—C20—Ir1	70.8 (8)
N1—Ir1—C50	106.9 (4)	C21—C20—Ir1	130.7 (10)
C40—Ir1—C50	39.1 (5)	C20—C21—H211	109.5
N12—Ir1—C30	99.1 (5)	C20—C21—H212	109.5
N1—Ir1—C30	127.1 (5)	H211—C21—H212	109.5
C40—Ir1—C30	39.3 (5)	C20—C21—H213	109.5
C50—Ir1—C30	64.6 (5)	H211—C21—H213	109.5
N12—Ir1—C20	107.6 (5)	H212—C21—H213	109.5
N1—Ir1—C20	165.6 (4)	C40—C30—C20	109.6 (14)
C40—Ir1—C20	66.6 (5)	C40—C30—C31	128.0 (14)
C50—Ir1—C20	65.2 (5)	C20—C30—C31	122.4 (14)
C30—Ir1—C20	39.3 (5)	C40—C30—Ir1	69.6 (8)
N12—Ir1—C60	143.5 (4)	C20—C30—Ir1	71.4 (7)
N1—Ir1—C60	140.0 (4)	C31—C30—Ir1	126.5 (9)
C40—Ir1—C60	65.4 (5)	C30—C31—H311	109.5
C50—Ir1—C60	38.1 (4)	C30—C31—H312	109.5
C30—Ir1—C60	64.8 (6)	H311—C31—H312	109.5
C20—Ir1—C60	39.1 (5)	C30—C31—H313	109.5
N12—Ir1—Cl1	86.0 (3)	H311—C31—H313	109.5
N1—Ir1—Cl1	84.0 (3)	H312—C31—H313	109.5
C40—Ir1—Cl1	150.5 (4)	C50—C40—C30	106.2 (12)
C50—Ir1—Cl1	111.7 (4)	C50—C40—C41	127.8 (13)
C30—Ir1—Cl1	148.9 (5)	C30—C40—C41	125.8 (15)
C20—Ir1—Cl1	109.9 (4)	C50—C40—Ir1	71.1 (7)
C60—Ir1—Cl1	93.0 (4)	C30—C40—Ir1	71.0 (7)
C2—N1—C14	117.1 (11)	C41—C40—Ir1	126.8 (10)
C2—N1—Ir1	128.3 (9)	C40—C41—H411	109.5
C14—N1—Ir1	114.5 (8)	C40—C41—H412	109.5
N1—C2—C3	123.6 (12)	H411—C41—H412	109.5
N1—C2—H2	118.2	C40—C41—H413	109.5
C3—C2—H2	118.2	H411—C41—H413	109.5
C2—C3—C4	118.4 (12)	H412—C41—H413	109.5
C2—C3—H3	120.8	C60—C50—C40	110.3 (11)
C4—C3—H3	120.8	C60—C50—C51	125.4 (13)
C5—C4—C3	120.7 (13)	C40—C50—C51	124.1 (13)
C5—C4—H4	119.6	C60—C50—Ir1	72.5 (7)
C3—C4—H4	119.6	C40—C50—Ir1	69.8 (7)
C4—C5—C14	116.5 (12)	C51—C50—Ir1	129.3 (9)
C4—C5—C6	125.5 (13)	C50—C51—H511	109.5
C14—C5—C6	118.0 (12)	C50—C51—H512	109.5
C7—C6—C5	123.8 (13)	H511—C51—H512	109.5
C7—C6—H6	118.1	C50—C51—H513	109.5
C5—C6—H6	118.1	H511—C51—H513	109.5
C6—C7—C8	120.6 (13)	H512—C51—H513	109.5
C6—C7—H7	119.7	C50—C60—C20	108.2 (12)
C8—C7—H7	119.7	C50—C60—C61	124.2 (12)
C9—C8—C13	115.9 (12)	C20—C60—C61	127.5 (12)
C9—C8—C7	126.7 (12)	C50—C60—Ir1	69.5 (7)
C13—C8—C7	117.4 (12)	C20—C60—Ir1	70.0 (7)
C10—C9—C8	121.2 (12)	C61—C60—Ir1	128.8 (11)
C10—C9—H9	119.4	C60—C61—H611	109.5
C8—C9—H9	119.4	C60—C61—H612	109.5
C9—C10—C11	120.1 (12)	H611—C61—H612	109.5
C9—C10—H10	119.9	C60—C61—H613	109.5
C11—C10—H10	119.9	H611—C61—H613	109.5
N12—C11—C10	121.2 (11)	H612—C61—H613	109.5
N12—C11—H11	119.4	O1—S1—O2	113.2 (6)
C10—C11—H11	119.4	O1—S1—O3	117.3 (8)
C13—N12—C11	117.6 (9)	O2—S1—O3	114.6 (7)
C13—N12—Ir1	116.7 (7)	O1—S1—C1	104.8 (8)
C11—N12—Ir1	125.7 (8)	O2—S1—C1	102.9 (8)
N12—C13—C8	123.8 (10)	O3—S1—C1	101.6 (8)
N12—C13—C14	114.2 (10)	F1—C1—F2	105.3 (16)
C8—C13—C14	121.9 (12)	F1—C1—F3	109.6 (16)
N1—C14—C5	123.7 (11)	F2—C1—F3	109.2 (19)
N1—C14—C13	118.1 (11)	F1—C1—S1	111.9 (16)
C5—C14—C13	118.1 (11)	F2—C1—S1	111.5 (13)
C30—C20—C60	105.7 (12)	F3—C1—S1	109.1 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^i	0.93	2.56	3.467 (15)	164
C11—H11···O3^ii	0.93	2.51	3.289 (17)	141
C21—H211···O3^ii	0.96	2.58	3.445 (17)	151
C10—H10···O2^ii	0.93	2.61	3.505 (16)	161

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