Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019575/bt2350sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019575/bt2350Isup2.hkl |
CCDC reference: 646647
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (C-C) = 0.012 Å
- Disorder in main residue
- R factor = 0.037
- wR factor = 0.079
- Data-to-parameter ratio = 13.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.94 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.38 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 C10 PLAT301_ALERT_3_C Main Residue Disorder ......................... 18.00 Perc. PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 12 PLAT733_ALERT_1_C Torsion Calc -93.7(4), Rep -93.72(9) ...... 4.44 su-Ra CL1 -IR1 -C11 -C11 1.555 1.555 1.555 7.565 PLAT751_ALERT_4_C Bond Calc 0.00000, Rep 0.00(2) ...... Senseless su O2 -O2 1.555 1.555 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.27 Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 0.00 Deg. O2 -S1 -O2 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 0.00 Deg. O2 -O2 -S1 1.555 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C F3 O3 S
Alert level G ABSTY01_ALERT_1_G Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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
For related literature, see: Allen (2002); Bergs et al. (1997); Dadci et al. (1995); Gencaslan & Sheldrick (2005); Gleichmann et al. (1995); Grant et al. (2005); Korn & Sheldrick (1997); Poth et al. (2001); Schäfer & Sheldrick (2007); Scharwitz et al. (2007, 2007a,b,c); Youinou & Ziessel (1989).
Ag(CF3SO3) (25.7 mg, 0.1 mmol) was added to a solution of [(η5-C5Me5)IrCl2]2 (39.8 mg, 0.05 mmol) in acetone (10 ml) and stirred at room temperature for 30 min. After centrifugation of the precipitated AgCl and solvent removal from the resulting solution, the yellow residue was redissolved in CH3OH/CH2Cl2 (10 ml, 1:1) and treated with 6.1 µl ethylendiamine (0.1 mmol). The reaction solution was heated for 2 h at 348 K and the solvent subsequently removed to afford (I), which was dissolved in methanol (3 ml) and reprecipitated with diethyl ether prior to drying in vacuum (yield 89%). Suitable crystals for X-ray analysis were grown by slow evaporation of a solution of (I) in CH3OH/H2O (1:). Elemental analysis found: C 27.4, H 4.5, N 5.2%; calculated for C13H23ClF3IrN2O3S: C 27.3, H 4.1, N 4.9%. FAB-MS on a VG Autospec instrument (m/z): 537 (30) [M—Cl]+, 423 (100) [M—CF3SO3]+, 387 (60) [M—CF3SO3—Cl]+.
H atoms were constrained to idealized positions and refined using a riding model, with C—H distances of 0.97 Å for the methylene C atoms and 0.96 Å for the methyl groups; Uiso(H) = 1.2 Uiso(C) for methylene and 1.5 Uiso(C) for methyl groups. The methyl groups were allowed to rotate but not tip.
Although many (pentamethylcyclopentadienyl)iridium(III) complexes with bidentate aromatic N-donor ligands such as 2,2-bipyridine (Dadci et al., 1995; Youinou & Ziessel, 1989) or 1,10-phenanthroline (Gencaslan & Sheldrick, 2005) have been structurally characterized, few examples are known for ligands containing two or three amino or alkylamino N-donor functions. The Cambridge Structural Database (Version 5.27, December 2006; Allen, 2002) contain two entries [(η5-C5Me5)Ir(1,2-diaminocyclohexane-κ2N)](ClO4)2*2H2O (Poth et al., 2001) and [(η5-C5Me5)IrCl(2-amino-3-dimethylaminopropionate-κ2N)] *H2O (Bergs et al., 1997) for bidentate ligands of this type. Crystal structures have also been reported for [(η5-C5Me5)Ir(1,4,7-triazacyclononane-κ3N)](PF6)2 *CH3NO2 (Grant et al., 2005) and [(η5-C5Me5)Ir(dien-κ3N)](CF3SO3)2 (dien is diethylenetriamine) (Scharwitz et al., 2007c), both of which contain κ3N amino ligands. As part of our continuing studies on organoruthenium(II) and organoiridium(III) half-sandwhich complexes with N and S donor ligands (Gleichmann et al., 1995, Korn & Sheldrick, 1997; Schäfer & Sheldrick, 2007; Scharwitz et al., 2007a,b,c, Scharwitz et al., 2007) we have now determined the structure of the title compound [(η5-C5Me5)IrCl(en-κ2N)](CF3SO3), (I).
The molecular structure of (I) is depicted in Fig. 1. Both the cation and anion exhibit crystallographic Cs symmetry with the ethylenediamine carbon atoms C2 and C3 being disordered (s.o.f.s = 1/2) with symmetry-equivalent sites (i) [(i) = x, 0.5 - y, z] generated by the mirror plane. A twist δ conformation is observed for the five-membered chelate ring containing C2 and C3 with a λ conformation for the alternative disordered ring with C2i and C3i. Carbon atoms C2 and C3 are displaced respectively 0.258 (9) and -0.292 (19) Å from the best plane through the ring atoms. The Ir1—C13 distance of 2.127 (10) Å is somewhat shorter than the Ir1—C11 and Ir1—C12 distances of respectively 2.156 (7) and 2.162 (7) Å. Participation of the N1 atoms in N1—H1···O2 hydrogen bonds of length 2.954 (9) Å (H1···O2 = 2.09 Å, N1—H1···O2 = 161.8°) to symmetry-related trifluoromethanesulfonate counter-anions is observed (Fig. 1). Hydrogen bonding interactions of the type N1—H2···Cl1i [(i) = 1 - x, -y, -z] (Table 1) link the cations and anions of (I) (Fig. 2).
For related literature, see: Allen (2002); Bergs et al. (1997); Dadci et al. (1995); Gencaslan & Sheldrick (2005); Gleichmann et al. (1995); Grant et al. (2005); Korn & Sheldrick (1997); Poth et al. (2001); Schäfer & Sheldrick (2007); Scharwitz et al. (2007, 2007a,b,c); Youinou & Ziessel (1989).
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.
[Ir(C10H15)Cl(C2H8N2)](CF3O3S) | F(000) = 1104 |
Mr = 572.04 | Dx = 2.027 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 14 reflections |
a = 15.400 (5) Å | θ = 3.5–12.7° |
b = 8.5728 (16) Å | µ = 7.42 mm−1 |
c = 14.202 (5) Å | T = 292 K |
V = 1874.9 (10) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.20 × 0.16 mm |
Siemens P4 four-circle diffractometer | 1308 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 25.0°, θmin = 2.7° |
ω scans | h = −1→18 |
Absorption correction: ψ scan (XPREP; Sheldrick, 1995) | k = −1→10 |
Tmin = 0.211, Tmax = 0.308 | l = −1→16 |
2309 measured reflections | 3 standard reflections every 97 reflections |
1743 independent reflections | intensity decay: 0.0% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0415P)2] where P = (Fo2 + 2Fc2)/3 |
1743 reflections | (Δ/σ)max < 0.001 |
133 parameters | Δρmax = 0.77 e Å−3 |
3 restraints | Δρmin = −0.93 e Å−3 |
[Ir(C10H15)Cl(C2H8N2)](CF3O3S) | V = 1874.9 (10) Å3 |
Mr = 572.04 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 15.400 (5) Å | µ = 7.42 mm−1 |
b = 8.5728 (16) Å | T = 292 K |
c = 14.202 (5) Å | 0.22 × 0.20 × 0.16 mm |
Siemens P4 four-circle diffractometer | 1308 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XPREP; Sheldrick, 1995) | Rint = 0.037 |
Tmin = 0.211, Tmax = 0.308 | 3 standard reflections every 97 reflections |
2309 measured reflections | intensity decay: 0.0% |
1743 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 3 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.77 e Å−3 |
1743 reflections | Δρmin = −0.93 e Å−3 |
133 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ir1 | 0.40783 (2) | 0.2500 | 0.10854 (3) | 0.03035 (15) | |
Cl1 | 0.4968 (2) | 0.2500 | −0.0318 (2) | 0.0512 (8) | |
N1 | 0.5019 (3) | 0.0926 (8) | 0.1612 (4) | 0.0391 (16) | 0.50 |
H1 | 0.4808 | 0.0464 | 0.2133 | 0.047* | 0.50 |
H2 | 0.5112 | 0.0177 | 0.1179 | 0.047* | 0.50 |
C2 | 0.5844 (9) | 0.166 (3) | 0.1841 (14) | 0.054 (5) | 0.50 |
H21 | 0.6193 | 0.1805 | 0.1279 | 0.065* | 0.50 |
H22 | 0.6168 | 0.1034 | 0.2287 | 0.065* | 0.50 |
C3 | 0.5607 (14) | 0.321 (3) | 0.2265 (13) | 0.068 (8) | 0.50 |
H31 | 0.5318 | 0.3051 | 0.2864 | 0.081* | 0.50 |
H32 | 0.6128 | 0.3818 | 0.2377 | 0.081* | 0.50 |
N1' | 0.5019 (3) | 0.0926 (8) | 0.1612 (4) | 0.0391 (16) | 0.50 |
H1' | 0.4756 | 0.0139 | 0.1920 | 0.047* | 0.50 |
H2' | 0.5328 | 0.0520 | 0.1133 | 0.047* | 0.50 |
C11 | 0.2866 (5) | 0.1665 (10) | 0.0516 (5) | 0.053 (2) | |
C111 | 0.2773 (7) | 0.0629 (15) | −0.0350 (6) | 0.106 (4) | |
H111 | 0.2170 | 0.0526 | −0.0509 | 0.159* | |
H112 | 0.3012 | −0.0382 | −0.0219 | 0.159* | |
H113 | 0.3080 | 0.1090 | −0.0869 | 0.159* | |
C12 | 0.2946 (5) | 0.1144 (9) | 0.1460 (6) | 0.0400 (19) | |
C121 | 0.2943 (6) | −0.0504 (9) | 0.1767 (7) | 0.070 (3) | |
H121 | 0.3197 | −0.0581 | 0.2383 | 0.105* | |
H122 | 0.3274 | −0.1119 | 0.1331 | 0.105* | |
H123 | 0.2356 | −0.0881 | 0.1787 | 0.105* | |
C13 | 0.3020 (7) | 0.2500 | 0.2048 (7) | 0.036 (3) | |
C131 | 0.3134 (8) | 0.2500 | 0.3093 (8) | 0.063 (4) | |
H13A | 0.3650 | 0.1932 | 0.3254 | 0.095* | 0.50 |
H13B | 0.2640 | 0.2013 | 0.3383 | 0.095* | 0.50 |
H13C | 0.3184 | 0.3555 | 0.3313 | 0.095* | 0.50 |
S1 | 0.5106 (2) | −0.2500 | 0.3332 (2) | 0.0544 (9) | |
O1 | 0.5902 (7) | −0.2500 | 0.2830 (8) | 0.105 (4) | |
O2 | 0.4614 (5) | −0.1126 (9) | 0.3224 (5) | 0.099 (3) | |
C10 | 0.5384 (16) | −0.2500 | 0.4557 (12) | 0.096 (6) | |
F1 | 0.4739 (11) | −0.2500 | 0.5110 (7) | 0.149 (6) | |
F2 | 0.5861 (6) | −0.1274 (14) | 0.4760 (7) | 0.192 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.0303 (2) | 0.0298 (2) | 0.0309 (2) | 0.000 | 0.0003 (2) | 0.000 |
Cl1 | 0.0616 (19) | 0.0525 (19) | 0.0396 (15) | 0.000 | 0.0153 (14) | 0.000 |
N1 | 0.038 (3) | 0.042 (4) | 0.038 (4) | 0.003 (3) | 0.008 (3) | 0.002 (3) |
C2 | 0.039 (10) | 0.065 (12) | 0.059 (13) | 0.006 (11) | 0.002 (10) | 0.003 (14) |
C3 | 0.056 (13) | 0.093 (19) | 0.054 (14) | −0.017 (13) | −0.008 (10) | −0.018 (14) |
N1' | 0.038 (3) | 0.042 (4) | 0.038 (4) | 0.003 (3) | 0.008 (3) | 0.002 (3) |
C11 | 0.032 (4) | 0.074 (6) | 0.053 (4) | −0.005 (5) | −0.008 (4) | −0.006 (5) |
C111 | 0.084 (8) | 0.154 (12) | 0.079 (7) | −0.010 (9) | −0.024 (7) | −0.070 (8) |
C12 | 0.026 (4) | 0.031 (4) | 0.063 (5) | −0.003 (4) | −0.001 (4) | 0.005 (4) |
C121 | 0.056 (6) | 0.032 (5) | 0.122 (8) | −0.011 (5) | 0.010 (6) | 0.015 (6) |
C13 | 0.032 (6) | 0.036 (6) | 0.039 (6) | 0.000 | 0.007 (5) | 0.000 |
C131 | 0.040 (7) | 0.106 (12) | 0.044 (7) | 0.000 | 0.005 (6) | 0.000 |
S1 | 0.059 (2) | 0.059 (2) | 0.0449 (18) | 0.000 | −0.0136 (17) | 0.000 |
O1 | 0.080 (8) | 0.139 (11) | 0.098 (9) | 0.000 | 0.011 (7) | 0.000 |
O2 | 0.122 (6) | 0.093 (6) | 0.081 (5) | 0.046 (5) | −0.004 (5) | 0.030 (5) |
C10 | 0.142 (18) | 0.093 (15) | 0.052 (10) | 0.000 | −0.033 (12) | 0.000 |
F1 | 0.217 (15) | 0.173 (13) | 0.057 (6) | 0.000 | 0.017 (8) | 0.000 |
F2 | 0.206 (9) | 0.233 (12) | 0.137 (7) | −0.095 (8) | −0.065 (7) | −0.045 (8) |
Ir1—N1'i | 2.116 (6) | C111—H112 | 0.9600 |
Ir1—N1i | 2.116 (6) | C111—H113 | 0.9600 |
Ir1—N1 | 2.116 (6) | C12—C13 | 1.436 (9) |
Ir1—C13 | 2.127 (10) | C12—C121 | 1.479 (10) |
Ir1—C11 | 2.156 (7) | C121—H121 | 0.9600 |
Ir1—C11i | 2.156 (7) | C121—H122 | 0.9600 |
Ir1—C12 | 2.162 (7) | C121—H123 | 0.9600 |
Ir1—C12i | 2.162 (7) | C13—C12i | 1.436 (9) |
Ir1—Cl1 | 2.419 (3) | C13—C131 | 1.494 (14) |
N1—C2 | 1.455 (10) | C131—H13A | 0.9600 |
N1—H1 | 0.9000 | C131—H13B | 0.9600 |
N1—H2 | 0.9000 | C131—H13C | 0.9600 |
C2—C3 | 1.503 (13) | S1—O2ii | 1.409 (7) |
C2—H21 | 0.9700 | S1—O2 | 1.409 (7) |
C2—H22 | 0.9700 | S1—O2 | 1.409 (7) |
C3—N1i | 1.49 (2) | S1—O1 | 1.417 (11) |
C3—H31 | 0.9700 | S1—C10 | 1.791 (16) |
C3—H32 | 0.9700 | O2—O2 | 0.00 (2) |
C11—C12 | 1.417 (10) | C10—F1 | 1.27 (2) |
C11—C11i | 1.431 (18) | C10—F2 | 1.315 (15) |
C11—C111 | 1.525 (11) | C10—F2ii | 1.315 (15) |
C111—H111 | 0.9600 | ||
N1'i—Ir1—N1i | 0.0 (5) | C12—C11—C11i | 108.4 (5) |
N1'i—Ir1—N1 | 79.2 (3) | C12—C11—C111 | 126.0 (8) |
N1i—Ir1—N1 | 79.2 (3) | C11i—C11—C111 | 125.6 (6) |
N1'i—Ir1—C13 | 107.3 (3) | C12—C11—Ir1 | 71.1 (4) |
N1i—Ir1—C13 | 107.3 (3) | C11i—C11—Ir1 | 70.6 (2) |
N1—Ir1—C13 | 107.3 (3) | C111—C11—Ir1 | 125.2 (6) |
N1'i—Ir1—C11 | 159.5 (3) | C11—C111—H111 | 109.5 |
N1i—Ir1—C11 | 159.5 (3) | C11—C111—H112 | 109.5 |
N1—Ir1—C11 | 120.9 (3) | H111—C111—H112 | 109.5 |
C13—Ir1—C11 | 65.0 (3) | C11—C111—H113 | 109.5 |
N1'i—Ir1—C11i | 120.9 (3) | H111—C111—H113 | 109.5 |
N1i—Ir1—C11i | 120.9 (3) | H112—C111—H113 | 109.5 |
N1—Ir1—C11i | 159.5 (3) | C11—C12—C13 | 107.6 (7) |
C13—Ir1—C11i | 65.0 (3) | C11—C12—C121 | 125.4 (8) |
C11—Ir1—C11i | 38.8 (5) | C13—C12—C121 | 127.0 (8) |
N1'i—Ir1—C12 | 143.9 (3) | C11—C12—Ir1 | 70.6 (4) |
N1i—Ir1—C12 | 143.9 (3) | C13—C12—Ir1 | 69.1 (5) |
N1—Ir1—C12 | 97.0 (3) | C121—C12—Ir1 | 126.0 (6) |
C13—Ir1—C12 | 39.1 (2) | C12—C121—H121 | 109.5 |
C11—Ir1—C12 | 38.3 (3) | C12—C121—H122 | 109.5 |
C11i—Ir1—C12 | 64.7 (3) | H121—C121—H122 | 109.5 |
N1'i—Ir1—C12i | 97.0 (3) | C12—C121—H123 | 109.5 |
N1i—Ir1—C12i | 97.0 (3) | H121—C121—H123 | 109.5 |
N1—Ir1—C12i | 143.9 (3) | H122—C121—H123 | 109.5 |
C13—Ir1—C12i | 39.1 (2) | C12—C13—C12i | 108.1 (9) |
C11—Ir1—C12i | 64.7 (3) | C12—C13—C131 | 126.0 (4) |
C11i—Ir1—C12i | 38.3 (3) | C12i—C13—C131 | 126.0 (4) |
C12—Ir1—C12i | 65.0 (4) | C12—C13—Ir1 | 71.8 (5) |
N1'i—Ir1—Cl1 | 84.45 (17) | C12i—C13—Ir1 | 71.8 (5) |
N1i—Ir1—Cl1 | 84.45 (17) | C131—C13—Ir1 | 123.3 (8) |
N1—Ir1—Cl1 | 84.45 (17) | C13—C131—H13A | 109.5 |
C13—Ir1—Cl1 | 164.5 (3) | C13—C131—H13B | 109.5 |
C11—Ir1—Cl1 | 100.5 (2) | H13A—C131—H13B | 109.5 |
C11i—Ir1—Cl1 | 100.5 (2) | C13—C131—H13C | 109.5 |
C12—Ir1—Cl1 | 131.3 (2) | H13A—C131—H13C | 109.5 |
C12i—Ir1—Cl1 | 131.3 (2) | H13B—C131—H13C | 109.5 |
C2—N1—Ir1 | 113.6 (12) | O2ii—S1—O2 | 113.4 (7) |
C2—N1—H1 | 108.9 | O2ii—S1—O2 | 113.4 (7) |
Ir1—N1—H1 | 108.9 | O2—S1—O2 | 0.0 (8) |
C2—N1—H2 | 108.9 | O2ii—S1—O1 | 114.2 (4) |
Ir1—N1—H2 | 108.9 | O2—S1—O1 | 114.2 (4) |
H1—N1—H2 | 107.7 | O2—S1—O1 | 114.2 (4) |
N1—C2—C3 | 105.1 (18) | O2ii—S1—C10 | 103.5 (5) |
N1—C2—H21 | 110.7 | O2—S1—C10 | 103.5 (5) |
C3—C2—H21 | 110.7 | O2—S1—C10 | 103.5 (5) |
N1—C2—H22 | 110.7 | O1—S1—C10 | 106.4 (10) |
C3—C2—H22 | 110.7 | O2—O2—S1 | 0 (10) |
H21—C2—H22 | 108.8 | F1—C10—F2 | 107.6 (12) |
N1i—C3—C2 | 109.6 (18) | F1—C10—F2ii | 107.6 (12) |
N1i—C3—H31 | 109.7 | F2—C10—F2ii | 106.1 (19) |
C2—C3—H31 | 109.7 | F1—C10—S1 | 114.6 (16) |
N1i—C3—H32 | 109.7 | F2—C10—S1 | 110.3 (11) |
C2—C3—H32 | 109.7 | F2ii—C10—S1 | 110.3 (11) |
H31—C3—H32 | 108.2 | ||
N1'i—Ir1—N1—C2 | −12.7 (10) | N1'i—Ir1—C12—C121 | −93.8 (9) |
N1i—Ir1—N1—C2 | −12.7 (10) | N1i—Ir1—C12—C121 | −93.8 (9) |
C13—Ir1—N1—C2 | −117.7 (9) | N1—Ir1—C12—C121 | −12.4 (8) |
C11—Ir1—N1—C2 | 171.6 (9) | C13—Ir1—C12—C121 | −121.3 (10) |
C11i—Ir1—N1—C2 | 177.8 (9) | C11—Ir1—C12—C121 | 120.3 (10) |
C12—Ir1—N1—C2 | −156.4 (9) | C11i—Ir1—C12—C121 | 157.9 (9) |
C12i—Ir1—N1—C2 | −99.9 (9) | C12i—Ir1—C12—C121 | −159.6 (7) |
Cl1—Ir1—N1—C2 | 72.7 (9) | Cl1—Ir1—C12—C121 | 76.4 (8) |
Ir1—N1—C2—C3 | 38.5 (15) | C11—C12—C13—C12i | 2.6 (12) |
N1—C2—C3—N1i | −53.5 (14) | C121—C12—C13—C12i | −176.9 (6) |
N1'i—Ir1—C11—C12 | −109.7 (8) | Ir1—C12—C13—C12i | 63.0 (7) |
N1i—Ir1—C11—C12 | −109.7 (8) | C11—C12—C13—C131 | −178.7 (9) |
N1—Ir1—C11—C12 | 58.2 (5) | C121—C12—C13—C131 | 1.8 (16) |
C13—Ir1—C11—C12 | −37.7 (4) | Ir1—C12—C13—C131 | −118.3 (11) |
C11i—Ir1—C11—C12 | −118.3 (4) | C11—C12—C13—Ir1 | −60.4 (6) |
C12i—Ir1—C11—C12 | −81.1 (6) | C121—C12—C13—Ir1 | 120.1 (8) |
Cl1—Ir1—C11—C12 | 148.0 (4) | N1'i—Ir1—C13—C12 | −163.5 (4) |
N1'i—Ir1—C11—C11i | 8.6 (7) | N1i—Ir1—C13—C12 | −163.5 (4) |
N1i—Ir1—C11—C11i | 8.6 (7) | N1—Ir1—C13—C12 | −79.7 (5) |
N1—Ir1—C11—C11i | 176.5 (3) | C11—Ir1—C13—C12 | 37.0 (5) |
C13—Ir1—C11—C11i | 80.56 (18) | C11i—Ir1—C13—C12 | 79.9 (6) |
C12—Ir1—C11—C11i | 118.3 (4) | C12i—Ir1—C13—C12 | 116.9 (9) |
C12i—Ir1—C11—C11i | 37.2 (3) | Cl1—Ir1—C13—C12 | 58.4 (4) |
Cl1—Ir1—C11—C11i | −93.72 (9) | N1'i—Ir1—C13—C12i | 79.7 (5) |
N1'i—Ir1—C11—C111 | 129.1 (9) | N1i—Ir1—C13—C12i | 79.7 (5) |
N1i—Ir1—C11—C111 | 129.1 (9) | N1—Ir1—C13—C12i | 163.5 (4) |
N1—Ir1—C11—C111 | −63.0 (9) | C11—Ir1—C13—C12i | −79.9 (6) |
C13—Ir1—C11—C111 | −158.9 (9) | C11i—Ir1—C13—C12i | −37.0 (5) |
C11i—Ir1—C11—C111 | 120.5 (8) | C12—Ir1—C13—C12i | −116.9 (9) |
C12—Ir1—C11—C111 | −121.2 (10) | Cl1—Ir1—C13—C12i | −58.4 (4) |
C12i—Ir1—C11—C111 | 157.7 (9) | N1'i—Ir1—C13—C131 | −41.90 (19) |
Cl1—Ir1—C11—C111 | 26.8 (8) | N1i—Ir1—C13—C131 | −41.90 (19) |
C11i—C11—C12—C13 | −1.6 (7) | N1—Ir1—C13—C131 | 41.90 (19) |
C111—C11—C12—C13 | 179.8 (8) | C11—Ir1—C13—C131 | 158.5 (3) |
Ir1—C11—C12—C13 | 59.5 (6) | C11i—Ir1—C13—C131 | −158.5 (3) |
C11i—C11—C12—C121 | 177.9 (7) | C12—Ir1—C13—C131 | 121.6 (4) |
C111—C11—C12—C121 | −0.7 (13) | C12i—Ir1—C13—C131 | −121.6 (4) |
Ir1—C11—C12—C121 | −121.0 (8) | Cl1—Ir1—C13—C131 | 180.000 (1) |
C11i—C11—C12—Ir1 | −61.1 (2) | O2ii—S1—O2—O2 | 0.00 (12) |
C111—C11—C12—Ir1 | 120.3 (8) | O1—S1—O2—O2 | 0.0 (3) |
N1'i—Ir1—C12—C11 | 146.0 (5) | C10—S1—O2—O2 | 0.0 (2) |
N1i—Ir1—C12—C11 | 146.0 (5) | O2ii—S1—C10—F1 | −59.3 (4) |
N1—Ir1—C12—C11 | −132.7 (5) | O2—S1—C10—F1 | 59.3 (4) |
C13—Ir1—C12—C11 | 118.5 (7) | O2—S1—C10—F1 | 59.3 (4) |
C11i—Ir1—C12—C11 | 37.6 (5) | O1—S1—C10—F1 | 180.000 (2) |
C12i—Ir1—C12—C11 | 80.1 (5) | O2ii—S1—C10—F2 | 179.2 (14) |
Cl1—Ir1—C12—C11 | −43.9 (5) | O2—S1—C10—F2 | −62.3 (17) |
N1'i—Ir1—C12—C13 | 27.5 (7) | O2—S1—C10—F2 | −62.3 (17) |
N1i—Ir1—C12—C13 | 27.5 (7) | O1—S1—C10—F2 | 58.4 (15) |
N1—Ir1—C12—C13 | 108.9 (5) | O2ii—S1—C10—F2ii | 62.3 (17) |
C11—Ir1—C12—C13 | −118.5 (7) | O2—S1—C10—F2ii | −179.2 (14) |
C11i—Ir1—C12—C13 | −80.9 (5) | O2—S1—C10—F2ii | −179.2 (14) |
C12i—Ir1—C12—C13 | −38.4 (5) | O1—S1—C10—F2ii | −58.4 (15) |
Cl1—Ir1—C12—C13 | −162.3 (4) |
Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.90 | 2.09 | 2.954 (9) | 162 |
C121—H121···O2 | 0.96 | 2.53 | 3.345 (12) | 143 |
N1—H2···Cl1iii | 0.90 | 2.60 | 3.464 (7) | 160 |
N1′—H1′···O2 | 0.90 | 2.16 | 2.954 (9) | 147 |
Symmetry code: (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ir(C10H15)Cl(C2H8N2)](CF3O3S) |
Mr | 572.04 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 292 |
a, b, c (Å) | 15.400 (5), 8.5728 (16), 14.202 (5) |
V (Å3) | 1874.9 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.42 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Siemens P4 four-circle |
Absorption correction | ψ scan (XPREP; Sheldrick, 1995) |
Tmin, Tmax | 0.211, 0.308 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2309, 1743, 1308 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.079, 0.99 |
No. of reflections | 1743 |
No. of parameters | 133 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.93 |
Computer programs: R3m/V (Siemens, 1989), R3m/V, XDISK (Siemens, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1995), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.90 | 2.09 | 2.954 (9) | 161.8 |
C121—H121···O2 | 0.96 | 2.53 | 3.345 (12) | 142.5 |
N1—H2···Cl1i | 0.90 | 2.60 | 3.464 (7) | 160.4 |
N1'—H1'···O2 | 0.90 | 2.16 | 2.954 (9) | 147.1 |
Symmetry code: (i) −x+1, −y, −z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Although many (pentamethylcyclopentadienyl)iridium(III) complexes with bidentate aromatic N-donor ligands such as 2,2-bipyridine (Dadci et al., 1995; Youinou & Ziessel, 1989) or 1,10-phenanthroline (Gencaslan & Sheldrick, 2005) have been structurally characterized, few examples are known for ligands containing two or three amino or alkylamino N-donor functions. The Cambridge Structural Database (Version 5.27, December 2006; Allen, 2002) contain two entries [(η5-C5Me5)Ir(1,2-diaminocyclohexane-κ2N)](ClO4)2*2H2O (Poth et al., 2001) and [(η5-C5Me5)IrCl(2-amino-3-dimethylaminopropionate-κ2N)] *H2O (Bergs et al., 1997) for bidentate ligands of this type. Crystal structures have also been reported for [(η5-C5Me5)Ir(1,4,7-triazacyclononane-κ3N)](PF6)2 *CH3NO2 (Grant et al., 2005) and [(η5-C5Me5)Ir(dien-κ3N)](CF3SO3)2 (dien is diethylenetriamine) (Scharwitz et al., 2007c), both of which contain κ3N amino ligands. As part of our continuing studies on organoruthenium(II) and organoiridium(III) half-sandwhich complexes with N and S donor ligands (Gleichmann et al., 1995, Korn & Sheldrick, 1997; Schäfer & Sheldrick, 2007; Scharwitz et al., 2007a,b,c, Scharwitz et al., 2007) we have now determined the structure of the title compound [(η5-C5Me5)IrCl(en-κ2N)](CF3SO3), (I).
The molecular structure of (I) is depicted in Fig. 1. Both the cation and anion exhibit crystallographic Cs symmetry with the ethylenediamine carbon atoms C2 and C3 being disordered (s.o.f.s = 1/2) with symmetry-equivalent sites (i) [(i) = x, 0.5 - y, z] generated by the mirror plane. A twist δ conformation is observed for the five-membered chelate ring containing C2 and C3 with a λ conformation for the alternative disordered ring with C2i and C3i. Carbon atoms C2 and C3 are displaced respectively 0.258 (9) and -0.292 (19) Å from the best plane through the ring atoms. The Ir1—C13 distance of 2.127 (10) Å is somewhat shorter than the Ir1—C11 and Ir1—C12 distances of respectively 2.156 (7) and 2.162 (7) Å. Participation of the N1 atoms in N1—H1···O2 hydrogen bonds of length 2.954 (9) Å (H1···O2 = 2.09 Å, N1—H1···O2 = 161.8°) to symmetry-related trifluoromethanesulfonate counter-anions is observed (Fig. 1). Hydrogen bonding interactions of the type N1—H2···Cl1i [(i) = 1 - x, -y, -z] (Table 1) link the cations and anions of (I) (Fig. 2).