Crystal structure of di-μ-chlorido-bis­[di­chlorido­bis­(methanol-κO)iridium(III)] dihydrate: a surprisingly simple chlorido­iridium(III) dinuclear complex with methanol ligands

While attempting to synthesize a cyclo­penta­dienyl iridium complex by the reaction between IrCl₃·xH₂O in methanol, several well-shaped crystals formed from the reaction mixture. Surprisingly, the crystals were of di-μ-chlorido-bis­[di­chlorido­bis­(methanol-κO)iridium(III)] dihydrate, [Ir₂Cl₆(CH₃OH)₄]·2H₂O. This is a surprising result in that, while many reactions of iridium chloride hydrate are carried out in alcoholic solvents, especially methanol and ethanol, this is the first structure of a chlorido-iridium compound with only methanol ligands.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](O-C) = 0.007 Å
• R factor = 0.028
• wR factor = 0.055
• Data-to-parameter ratio = 30.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ...          5 Report
PLAT971_ALERT_2_C Check Calcd Residual Density  0.68A From     Ir1       1.61 eA-3
PLAT971_ALERT_2_C Check Calcd Residual Density  0.75A From     Ir1       1.52 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.79A From     Ir1      -1.76 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.69A From     Ir1      -1.57 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          4 Report
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        206 Note

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

   2 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
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-chlorido-bis[dichloridobis(methanol-κO)iridium(III)] dihydrate

Crystal data

[Ir2Cl6(CH4O)4]·2H2O	Z = 2
Mr = 380.68	F(000) = 348
Triclinic, P1	Dx = 2.951 Mg m^−3
a = 7.1445 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4876 (5) Å	Cell parameters from 3445 reflections
c = 8.6362 (7) Å	θ = 4.0–32.1°
α = 73.597 (6)°	µ = 16.46 mm^−1
β = 75.596 (5)°	T = 100 K
γ = 89.404 (5)°	Prism, clear light orange
V = 428.37 (5) Å^3	0.14 × 0.11 × 0.09 mm

Data collection

Agilent Xcalibur Eos Gemini ultra diffractometer	2817 independent reflections
Radiation source: Enhance (Mo) X-ray Source, Agilent	2575 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 16.0122 pixels mm^-1	θmax = 32.2°, θmin = 4.0°
ω scans	h = −10→10
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	k = −11→11
Tmin = 0.184, Tmax = 0.342	l = −12→12
7987 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.055	w = 1/[σ^2(Fo^2) + (0.0194P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
2817 reflections	Δρmax = 1.67 e Å^−3
93 parameters	Δρmin = −1.94 e Å^−3
6 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ir1	0.64307 (2)	0.65568 (2)	0.81418 (2)	0.01042 (5)
Cl1	0.82335 (16)	0.93834 (15)	0.74853 (14)	0.0167 (2)
Cl2	0.72146 (16)	0.65918 (17)	0.53518 (13)	0.0177 (2)
Cl3	0.45411 (15)	0.36814 (14)	0.89543 (12)	0.01298 (19)
O1	0.9022 (5)	0.5412 (5)	0.8390 (4)	0.0169 (7)
H1	1.0118 (19)	0.603 (3)	0.785 (5)	0.025*
O2	0.3880 (4)	0.7770 (5)	0.7908 (4)	0.0151 (6)
H2	0.328 (5)	0.759 (4)	0.720 (4)	0.023*
C1	0.9356 (7)	0.3485 (7)	0.8412 (6)	0.0208 (10)
H1A	0.9287	0.3317	0.7366	0.031*
H1B	0.8388	0.2669	0.9302	0.031*
H1C	1.0615	0.3197	0.8584	0.031*
C2	0.3605 (8)	0.9702 (7)	0.7877 (7)	0.0274 (12)
H2A	0.4497	1.0503	0.6912	0.041*
H2B	0.3835	0.9897	0.8868	0.041*
H2C	0.2303	0.9984	0.7831	0.041*
O3	0.2082 (5)	0.7157 (5)	0.5754 (4)	0.0182 (7)
H3A	0.2516	0.6327	0.5284	0.027*
H3B	0.2060	0.8178	0.5013	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.01073 (8)	0.01068 (8)	0.00999 (8)	−0.00075 (6)	−0.00180 (6)	−0.00389 (6)
Cl1	0.0172 (5)	0.0126 (5)	0.0189 (5)	−0.0039 (4)	−0.0030 (4)	−0.0034 (4)
Cl2	0.0209 (5)	0.0215 (6)	0.0104 (5)	0.0007 (4)	−0.0018 (4)	−0.0058 (4)
Cl3	0.0167 (5)	0.0117 (5)	0.0113 (4)	−0.0021 (4)	−0.0022 (4)	−0.0056 (4)
O1	0.0149 (15)	0.0173 (17)	0.0199 (16)	0.0019 (13)	−0.0048 (13)	−0.0074 (13)
O2	0.0152 (15)	0.0185 (17)	0.0161 (15)	0.0035 (13)	−0.0073 (12)	−0.0092 (13)
C1	0.018 (2)	0.020 (2)	0.025 (2)	0.0057 (19)	−0.0036 (19)	−0.009 (2)
C2	0.028 (3)	0.017 (2)	0.036 (3)	0.003 (2)	−0.009 (2)	−0.006 (2)
O3	0.0196 (17)	0.0180 (17)	0.0184 (16)	0.0041 (14)	−0.0076 (13)	−0.0051 (14)

Geometric parameters (Å, º)

Ir1—Cl1	2.3400 (11)	O2—C2	1.452 (6)
Ir1—Cl2	2.3267 (11)	C1—H1A	0.9600
Ir1—Cl3^i	2.3847 (10)	C1—H1B	0.9600
Ir1—Cl3	2.3846 (11)	C1—H1C	0.9600
Ir1—O1	2.066 (3)	C2—H2A	0.9600
Ir1—O2	2.057 (3)	C2—H2B	0.9600
Cl3—Ir1^i	2.3847 (10)	C2—H2C	0.9600
O1—H1	0.864 (10)	O3—H3A	0.8500
O1—C1	1.456 (6)	O3—H3B	0.8498
O2—H2	0.867 (9)
Cl1—Ir1—Cl3^i	92.90 (4)	C1—O1—H1	105.1 (16)
Cl1—Ir1—Cl3	177.08 (4)	Ir1—O2—H2	121.2 (16)
Cl2—Ir1—Cl1	91.47 (4)	C2—O2—Ir1	121.9 (3)
Cl2—Ir1—Cl3^i	175.59 (4)	C2—O2—H2	104.7 (15)
Cl2—Ir1—Cl3	91.44 (4)	O1—C1—H1A	109.5
Cl3—Ir1—Cl3^i	84.19 (4)	O1—C1—H1B	109.5
O1—Ir1—Cl1	83.45 (10)	O1—C1—H1C	109.5
O1—Ir1—Cl2	90.01 (9)	H1A—C1—H1B	109.5
O1—Ir1—Cl3^i	91.08 (9)	H1A—C1—H1C	109.5
O1—Ir1—Cl3	96.79 (10)	H1B—C1—H1C	109.5
O2—Ir1—Cl1	94.91 (10)	O2—C2—H2A	109.5
O2—Ir1—Cl2	90.73 (9)	O2—C2—H2B	109.5
O2—Ir1—Cl3	84.81 (10)	O2—C2—H2C	109.5
O2—Ir1—Cl3^i	88.30 (9)	H2A—C2—H2B	109.5
O2—Ir1—O1	178.22 (13)	H2A—C2—H2C	109.5
Ir1—Cl3—Ir1^i	95.81 (4)	H2B—C2—H2C	109.5
Ir1—O1—H1	121.2 (16)	H3A—O3—H3B	109.5
C1—O1—Ir1	121.8 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^ii	0.86 (1)	1.96 (3)	2.752 (5)	151 (4)
O2—H2···O3	0.87 (1)	1.78 (1)	2.647 (5)	179 (2)
O3—H3A···Cl2^iii	0.85	2.39	3.208 (4)	160
O3—H3B···Cl1^iv	0.85	2.45	3.285 (3)	166

Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+2, −z+1.