Bis(acetyl-acetonato-κO,O')-aqua-(diacetyl-methanido-κC)iridium(III).

In the crystal structure of the title compound, [Ir(C(5)H(7)O(2))(3)(H(2)O)], the Ir(III) atom is six-coordinated and situated in a slightly distorted octa-hedral environment. The complex contains both Ir-O and Ir-C bonds and was isolated from a reaction mixture of IrCl(3)(H(2)O)(x), pentane-2,5-dione and NaHCO(3). O-H⋯O hydrogen bonding between the water molecules and the carbonyl O atoms of adjacent molecules leads to a layered motif extending parallel to (010).

Related literature

For background to the title compound, see: Bennett & Mitchell (1976 ▶); Bhalla et al. (2005 ▶); Gibson (1969 ▶); Matsumoto et al. (2000 ▶); Periana et al. (2002 ▶); Wong-Foy et al. (2003 ▶). For a related structure, see: Isakova et al. (1999 ▶); For background on hydrogen bonding, see: Desiraju (1996 ▶).

Experimental

Crystal data

[Ir(C5H7O2)3(H2O)]

M = 507.54

Triclinic,

a = 7.7853 (13) Å

b = 7.9461 (13) Å

c = 16.362 (3) Å

α = 77.295 (2)°

β = 77.927 (2)°

γ = 60.918 (1)°

V = 856.7 (3) Å3

Z = 2

Mo Kα radiation

μ = 7.82 mm−1

T = 293 K

0.15 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.387, T max = 0.539

7435 measured reflections

3900 independent reflections

2885 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.127

S = 1.03

3900 reflections

215 parameters

H-atom parameters constrained

Δρmax = 2.37 e Å−3

Δρmin = −1.88 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903760X/er2069sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903760X/er2069Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ir(C5H7O2)3(H2O)]	Z = 2
Mr = 507.54	F(000) = 492
Triclinic, P1	Dx = 1.968 Mg m−3
a = 7.7853 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9461 (13) Å	Cell parameters from 1164 reflections
c = 16.362 (3) Å	θ = 1.3–28.4°
α = 77.295 (2)°	µ = 7.82 mm−1
β = 77.927 (2)°	T = 293 K
γ = 60.918 (1)°	Block, orange
V = 856.7 (3) Å3	0.15 × 0.13 × 0.09 mm

Bruker APEXII CCD area-detector diffractometer	3900 independent reflections
Radiation source: fine-focus sealed tube	2885 reflections with I > 2σ(I)
graphite	Rint = 0.061
φ and ω scans	θmax = 28.4°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.387, Tmax = 0.539	k = −10→10
7435 measured reflections	l = −21→21

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)] = 0.058	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0469P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3900 reflections	Δρmax = 2.37 e Å−3
215 parameters	Δρmin = −1.87 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (5)

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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
Ir1	0.36783 (6)	0.62096 (6)	0.25137 (3)	0.02612 (17)
O1	0.3350 (11)	0.7800 (11)	0.1361 (5)	0.0327 (18)
O2	0.6421 (11)	0.4122 (11)	0.2154 (5)	0.0355 (19)
O3	0.1042 (10)	0.8433 (10)	0.2871 (5)	0.0315 (17)
O4	0.4064 (11)	0.4697 (11)	0.3682 (5)	0.0334 (18)
O5	0.5066 (10)	0.7689 (10)	0.2858 (5)	0.0337 (18)
H5D	0.5577	0.8115	0.2430	0.050*
H5E	0.5997	0.6857	0.3187	0.050*
O6	−0.0934 (12)	0.5794 (12)	0.2823 (6)	0.046 (2)
O7	0.4419 (13)	0.1349 (12)	0.2185 (5)	0.048 (2)
C1	0.4627 (18)	0.7249 (17)	0.0700 (7)	0.035 (3)
C2	0.402 (2)	0.8478 (19)	−0.0103 (7)	0.047 (3)
H2A	0.3312	0.8038	−0.0347	0.070*
H2B	0.5167	0.8398	−0.0483	0.070*
H2C	0.3172	0.9801	−0.0006	0.070*
C3	0.6452 (19)	0.5594 (18)	0.0726 (8)	0.046 (3)
H3	0.7256	0.5384	0.0212	0.055*
C4	0.7252 (17)	0.4194 (15)	0.1418 (8)	0.034 (3)
C5	0.9347 (19)	0.256 (2)	0.1293 (9)	0.055 (4)
H5A	0.9385	0.1353	0.1578	0.083*
H5B	1.0224	0.2819	0.1519	0.083*
H5C	0.9756	0.2480	0.0701	0.083*
C6	0.2844 (19)	0.5342 (18)	0.4321 (7)	0.040 (3)
C7	0.334 (2)	0.402 (2)	0.5146 (8)	0.055 (4)
H7A	0.2550	0.3352	0.5289	0.083*
H7B	0.3074	0.4781	0.5582	0.083*
H7C	0.4718	0.3091	0.5092	0.083*
C8	0.1094 (19)	0.7063 (19)	0.4332 (8)	0.044 (3)
H8	0.0380	0.7318	0.4860	0.052*
C9	0.0265 (18)	0.8459 (17)	0.3658 (7)	0.036 (3)
C10	−0.1719 (19)	1.0193 (19)	0.3801 (8)	0.054 (4)
H10A	−0.1759	1.1296	0.3405	0.080*
H10B	−0.1923	1.0475	0.4365	0.080*
H10C	−0.2742	0.9916	0.3725	0.080*
C11	0.2348 (16)	0.4738 (15)	0.2148 (8)	0.034 (3)
H11	0.2784	0.4669	0.1544	0.041*
C12	0.0184 (17)	0.5990 (16)	0.2220 (8)	0.033 (3)
C13	−0.0656 (19)	0.7536 (19)	0.1483 (8)	0.051 (3)
H13A	−0.0591	0.6933	0.1022	0.076*
H13B	0.0101	0.8241	0.1309	0.076*
H13C	−0.2009	0.8417	0.1649	0.076*
C14	0.3079 (17)	0.2716 (16)	0.2559 (7)	0.030 (2)
C15	0.226 (2)	0.2179 (18)	0.3450 (8)	0.046 (3)
H15A	0.3341	0.1330	0.3776	0.070*
H15B	0.1511	0.1529	0.3428	0.070*
H15C	0.1427	0.3337	0.3707	0.070*

	U11	U22	U33	U12	U13	U23
Ir1	0.0211 (2)	0.0223 (2)	0.0273 (2)	−0.00479 (17)	−0.00288 (16)	−0.00175 (15)
O1	0.028 (4)	0.031 (4)	0.035 (4)	−0.012 (4)	0.001 (4)	−0.007 (4)
O2	0.030 (4)	0.030 (4)	0.039 (5)	−0.008 (4)	0.000 (4)	−0.006 (4)
O3	0.025 (4)	0.027 (4)	0.032 (4)	−0.002 (3)	−0.007 (3)	−0.007 (3)
O4	0.033 (4)	0.041 (5)	0.024 (4)	−0.017 (4)	−0.004 (3)	0.003 (3)
O5	0.021 (4)	0.032 (4)	0.038 (4)	−0.008 (3)	−0.006 (3)	0.003 (4)
O6	0.026 (5)	0.044 (5)	0.058 (6)	−0.010 (4)	−0.005 (4)	0.000 (4)
O7	0.056 (6)	0.028 (4)	0.048 (5)	−0.011 (4)	0.009 (4)	−0.016 (4)
C1	0.045 (7)	0.039 (7)	0.024 (6)	−0.021 (6)	−0.007 (5)	−0.003 (5)
C2	0.059 (9)	0.051 (8)	0.030 (7)	−0.028 (7)	−0.018 (6)	0.011 (6)
C3	0.052 (8)	0.043 (8)	0.029 (7)	−0.012 (7)	−0.003 (6)	−0.004 (6)
C4	0.030 (6)	0.020 (5)	0.049 (7)	−0.009 (5)	0.004 (6)	−0.015 (5)
C5	0.039 (8)	0.054 (9)	0.060 (9)	−0.010 (7)	0.011 (7)	−0.029 (7)
C6	0.046 (8)	0.048 (8)	0.029 (6)	−0.029 (7)	0.002 (6)	0.002 (6)
C7	0.054 (9)	0.078 (11)	0.039 (7)	−0.036 (8)	−0.011 (7)	0.002 (7)
C8	0.044 (8)	0.055 (8)	0.031 (7)	−0.023 (7)	0.009 (6)	−0.016 (6)
C9	0.039 (7)	0.033 (7)	0.036 (7)	−0.017 (6)	0.003 (6)	−0.012 (5)
C10	0.038 (8)	0.049 (8)	0.043 (8)	0.001 (7)	−0.001 (6)	−0.005 (7)
C11	0.021 (6)	0.022 (6)	0.050 (7)	−0.002 (5)	−0.005 (5)	−0.003 (5)
C12	0.030 (6)	0.026 (6)	0.043 (7)	−0.010 (5)	−0.011 (6)	−0.009 (5)
C13	0.043 (8)	0.047 (8)	0.049 (8)	−0.015 (7)	−0.006 (6)	0.003 (6)
C14	0.038 (7)	0.030 (6)	0.032 (6)	−0.021 (5)	−0.009 (5)	−0.006 (5)
C15	0.058 (9)	0.041 (7)	0.042 (7)	−0.024 (7)	−0.003 (6)	−0.005 (6)

Ir1—O1	2.015 (8)	C5—H5C	0.9600
Ir1—O4	2.017 (7)	C6—C8	1.384 (17)
Ir1—O3	2.026 (7)	C6—C7	1.508 (16)
Ir1—O2	2.029 (7)	C7—H7A	0.9600
Ir1—C11	2.131 (11)	C7—H7B	0.9600
Ir1—O5	2.155 (7)	C7—H7C	0.9600
O1—C1	1.297 (13)	C8—C9	1.388 (17)
O2—C4	1.245 (13)	C8—H8	0.9300
O3—C9	1.302 (13)	C9—C10	1.504 (16)
O4—C6	1.266 (13)	C10—H10A	0.9600
O5—H5D	0.8200	C10—H10B	0.9600
O5—H5E	0.8900	C10—H10C	0.9600
O6—C12	1.208 (13)	C11—C14	1.468 (14)
O7—C14	1.252 (13)	C11—C12	1.477 (15)
C1—C3	1.391 (16)	C11—H11	0.9800
C1—C2	1.468 (15)	C12—C13	1.513 (16)
C2—H2A	0.9600	C13—H13A	0.9600
C2—H2B	0.9600	C13—H13B	0.9600
C2—H2C	0.9600	C13—H13C	0.9600
C3—C4	1.406 (16)	C14—C15	1.520 (15)
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.518 (16)	C15—H15B	0.9600
C5—H5A	0.9600	C15—H15C	0.9600
C5—H5B	0.9600
O1—Ir1—O4	177.1 (3)	O4—C6—C7	115.2 (11)
O1—Ir1—O3	84.6 (3)	C8—C6—C7	117.6 (11)
O4—Ir1—O3	95.1 (3)	C6—C7—H7A	109.5
O1—Ir1—O2	94.2 (3)	C6—C7—H7B	109.5
O4—Ir1—O2	85.9 (3)	H7A—C7—H7B	109.5
O3—Ir1—O2	175.4 (3)	C6—C7—H7C	109.5
O1—Ir1—C11	87.6 (4)	H7A—C7—H7C	109.5
O4—Ir1—C11	95.3 (4)	H7B—C7—H7C	109.5
O3—Ir1—C11	93.5 (4)	C6—C8—C9	128.5 (11)
O2—Ir1—C11	90.9 (4)	C6—C8—H8	115.7
O1—Ir1—O5	91.6 (3)	C9—C8—H8	115.7
O4—Ir1—O5	85.5 (3)	O3—C9—C8	126.0 (11)
O3—Ir1—O5	87.3 (3)	O3—C9—C10	113.8 (10)
O2—Ir1—O5	88.2 (3)	C8—C9—C10	120.2 (11)
C11—Ir1—O5	178.8 (4)	C9—C10—H10A	109.5
C1—O1—Ir1	123.5 (7)	C9—C10—H10B	109.5
C4—O2—Ir1	122.2 (7)	H10A—C10—H10B	109.5
C9—O3—Ir1	121.2 (7)	C9—C10—H10C	109.5
C6—O4—Ir1	121.9 (8)	H10A—C10—H10C	109.5
Ir1—O5—H5D	109.5	H10B—C10—H10C	109.5
Ir1—O5—H5E	109.5	C14—C11—C12	117.6 (10)
H5D—O5—H5E	109.2	C14—C11—Ir1	112.4 (8)
O1—C1—C3	123.7 (10)	C12—C11—Ir1	108.4 (7)
O1—C1—C2	115.6 (11)	C14—C11—H11	105.8
C3—C1—C2	120.7 (11)	C12—C11—H11	105.8
C1—C2—H2A	109.5	Ir1—C11—H11	105.8
C1—C2—H2B	109.5	O6—C12—C11	123.2 (11)
H2A—C2—H2B	109.5	O6—C12—C13	119.2 (11)
C1—C2—H2C	109.5	C11—C12—C13	117.6 (11)
H2A—C2—H2C	109.5	C12—C13—H13A	109.5
H2B—C2—H2C	109.5	C12—C13—H13B	109.5
C1—C3—C4	129.1 (11)	H13A—C13—H13B	109.5
C1—C3—H3	115.5	C12—C13—H13C	109.5
C4—C3—H3	115.5	H13A—C13—H13C	109.5
O2—C4—C3	126.9 (11)	H13B—C13—H13C	109.5
O2—C4—C5	114.0 (11)	O7—C14—C11	120.8 (10)
C3—C4—C5	119.1 (11)	O7—C14—C15	117.0 (10)
C4—C5—H5A	109.5	C11—C14—C15	122.2 (10)
C4—C5—H5B	109.5	C14—C15—H15A	109.5
H5A—C5—H5B	109.5	C14—C15—H15B	109.5
C4—C5—H5C	109.5	H15A—C15—H15B	109.5
H5A—C5—H5C	109.5	C14—C15—H15C	109.5
H5B—C5—H5C	109.5	H15A—C15—H15C	109.5
O4—C6—C8	127.1 (11)	H15B—C15—H15C	109.5
O4—Ir1—O1—C1	96 (6)	C1—C3—C4—C5	−176.5 (12)
O3—Ir1—O1—C1	−179.7 (9)	Ir1—O4—C6—C8	2.3 (17)
O2—Ir1—O1—C1	4.8 (9)	Ir1—O4—C6—C7	179.4 (8)
C11—Ir1—O1—C1	−85.9 (9)	O4—C6—C8—C9	1(2)
O5—Ir1—O1—C1	93.2 (9)	C7—C6—C8—C9	−176.4 (13)
O1—Ir1—O2—C4	0.1 (9)	Ir1—O3—C9—C8	1.1 (16)
O4—Ir1—O2—C4	−177.0 (9)	Ir1—O3—C9—C10	−178.4 (8)
O3—Ir1—O2—C4	−76 (4)	C6—C8—C9—O3	−3(2)
C11—Ir1—O2—C4	87.7 (9)	C6—C8—C9—C10	176.9 (13)
O5—Ir1—O2—C4	−91.4 (9)	O1—Ir1—C11—C14	149.4 (8)
O1—Ir1—O3—C9	−176.0 (8)	O4—Ir1—C11—C14	−30.7 (8)
O4—Ir1—O3—C9	1.1 (8)	O3—Ir1—C11—C14	−126.1 (8)
O2—Ir1—O3—C9	−100 (4)	O2—Ir1—C11—C14	55.2 (8)
C11—Ir1—O3—C9	96.8 (9)	O5—Ir1—C11—C14	101 (17)
O5—Ir1—O3—C9	−84.1 (8)	O1—Ir1—C11—C12	−78.8 (8)
O1—Ir1—O4—C6	81 (6)	O4—Ir1—C11—C12	101.0 (8)
O3—Ir1—O4—C6	−2.7 (9)	O3—Ir1—C11—C12	5.6 (8)
O2—Ir1—O4—C6	172.7 (9)	O2—Ir1—C11—C12	−173.0 (8)
C11—Ir1—O4—C6	−96.8 (9)	O5—Ir1—C11—C12	−127 (16)
O5—Ir1—O4—C6	84.2 (9)	C14—C11—C12—O6	30.9 (17)
Ir1—O1—C1—C3	−6.4 (16)	Ir1—C11—C12—O6	−98.0 (11)
Ir1—O1—C1—C2	172.5 (8)	C14—C11—C12—C13	−146.7 (11)
O1—C1—C3—C4	2(2)	Ir1—C11—C12—C13	84.4 (11)
C2—C1—C3—C4	−176.5 (13)	C12—C11—C14—O7	135.2 (12)
Ir1—O2—C4—C3	−3.7 (17)	Ir1—C11—C14—O7	−97.9 (11)
Ir1—O2—C4—C5	176.3 (7)	C12—C11—C14—C15	−45.0 (16)
C1—C3—C4—O2	3(2)	Ir1—C11—C14—C15	82.0 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5D···O7i	0.82	2.24	2.706 (11)	116
O5—H5E···O6ii	0.89	2.11	2.715 (11)	125

Table 1

Selected bond lengths (Å)

Ir1—O1	2.015 (8)
Ir1—O4	2.017 (7)
Ir1—O3	2.026 (7)
Ir1—O2	2.029 (7)
Ir1—C11	2.131 (11)
Ir1—O5	2.155 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5D⋯O7i	0.82	2.24	2.706 (11)	116
O5—H5E⋯O6ii	0.89	2.11	2.715 (11)	125

Symmetry codes: (i) ; (ii) .