Dichlorido(9-methyl-adenine-κN)(η-penta-methyl-cyclo-penta-dien-yl)iridium(III) dichloromethane solvate.

In the title complex, [Ir(C(10)H(15))Cl(2)(C(6)H(7)N(5))]·CH(2)Cl(2) or [Ir(η(5)-C(5)Me(5))Cl(2)(9-MeAde-κN(7))]·CH(2)Cl(2) (9-MeAde = 9-methyl-adenine), the coordination geometry of the Ir(III) atom approximates to a three-legged piano stool. The 9-methyl-adenine ligand is coordinated in a monodentate fashion to the Ir centre through its N-7 atom. The crystal structure contains centrosymmetric pairs of mol-ecules, inter-acting through two N-H⋯N hydrogen bonds. An intra-molecular N-H⋯Cl hydrogen bond is formed between the H atom of an NH(2) group and a chlorido ligand. Further short intra- and inter-molecular C-H⋯Cl contacts are observed.

Related literature

For background information, see: Lippert (2000 ▶); Houlton (2002 ▶). For related literature, see: Zhu et al. (2002 ▶); Gaballa et al. (2004 ▶, 2008 ▶); Aakeröy et al. (1999 ▶); Baldovino-Pantaleon et al. (2007 ▶); Davies et al. (2003 ▶); Huang et al. (1998 ▶); Jeffrey & Saenger (1994 ▶); Kistenmacher & Rossi (1977 ▶); McMullan et al. (1980 ▶).

Experimental

Crystal data

[Ir(C10H15)Cl2(C6H7N5)]·CH2Cl2

M = 632.41

Triclinic,

a = 7.294 (2) Å

b = 11.8698 (14) Å

c = 13.649 (3) Å

α = 71.338 (15)°

β = 83.83 (3)°

γ = 78.003 (14)°

V = 1094.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 6.60 mm−1

T = 200 (2) K

0.19 × 0.15 × 0.13 mm

Data collection

Stoe STADI-4 diffractometer

Absorption correction: multi-scan (X-RED; Stoe & Cie, 2002 ▶) T min = 0.32, T max = 0.43

4132 measured reflections

3807 independent reflections

3246 reflections with I > 2σ(I)

R int = 0.068

1 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.125

S = 1.13

3807 reflections

250 parameters

H-atom parameters constrained

Δρmax = 2.87 e Å−3

Δρmin = −3.41 e Å−3

Data collection: STADI4 (Stoe & Cie, 2002 ▶); cell refinement: STADI4 (Stoe & Cie, 2002 ▶); data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003760/fj2096sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003760/fj2096Isup2.hkl

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

[Ir(C10H15)Cl2(C6H7N5)]·CH2Cl2	Z = 2
Mr = 632.41	F(000) = 612
Triclinic, P1	Dx = 1.920 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.294 (2) Å	Cell parameters from 32 reflections
b = 11.8698 (14) Å	θ = 6.5–18.9°
c = 13.649 (3) Å	µ = 6.60 mm−1
α = 71.338 (15)°	T = 200 K
β = 83.83 (3)°	Block, colourless
γ = 78.003 (14)°	0.19 × 0.15 × 0.13 mm
V = 1094.0 (4) Å3

Stoe STADI-4 diffractometer	3246 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
graphite	θmax = 25.0°, θmin = 1.6°
profile data from ω/2θ scans	h = −8→8
Absorption correction: multi-scan (X-RED; Stoe & Cie, 2002)	k = −13→14
Tmin = 0.32, Tmax = 0.43	l = −8→16
4132 measured reflections	1 standard reflections every 60 min
3807 independent reflections	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0666P)2] where P = (Fo2 + 2Fc2)/3
3807 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 2.87 e Å−3
0 restraints	Δρmin = −3.41 e Å−3
0 constraints

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
C2	0.9961 (15)	−0.0640 (10)	0.7978 (9)	0.030 (2)
H2	1.0628	−0.1450	0.8165	0.036*
C4	0.8452 (14)	0.0945 (9)	0.6832 (8)	0.023 (2)
C5	0.7931 (13)	0.1571 (8)	0.7549 (7)	0.019 (2)
C6	0.8617 (15)	0.0991 (9)	0.8549 (8)	0.026 (2)
C8	0.6814 (13)	0.2726 (9)	0.6092 (8)	0.020 (2)
H8	0.6198	0.3402	0.5573	0.024*
C9	0.7869 (16)	0.1435 (10)	0.4929 (8)	0.029 (2)
H9A	0.7137	0.2109	0.4416	0.035*
H9B	0.7375	0.0696	0.5034	0.035*
H9C	0.9185	0.1318	0.4682	0.035*
C10	0.2376 (14)	0.3257 (10)	0.7454 (8)	0.028 (2)
C11	0.3065 (16)	0.2573 (10)	0.8485 (9)	0.030 (3)
C12	0.2955 (15)	0.3417 (11)	0.9036 (8)	0.031 (3)
C13	0.2174 (16)	0.4615 (11)	0.8368 (10)	0.037 (3)
C14	0.1805 (14)	0.4482 (10)	0.7419 (9)	0.030 (3)
C15	0.213 (2)	0.2713 (14)	0.6624 (11)	0.053 (4)
H15A	0.2482	0.3242	0.5945	0.064*
H15B	0.0821	0.2632	0.6635	0.064*
H15C	0.2941	0.1914	0.6754	0.064*
C16	0.3688 (18)	0.1234 (10)	0.8885 (11)	0.045 (3)
H16A	0.4789	0.1048	0.9301	0.054*
H16B	0.4014	0.0907	0.8301	0.054*
H16C	0.2671	0.0869	0.9315	0.054*
C17	0.3513 (19)	0.3108 (14)	1.0118 (9)	0.050 (4)
H17A	0.4030	0.3772	1.0197	0.060*
H17B	0.4465	0.2366	1.0282	0.060*
H17C	0.2412	0.2982	1.0591	0.060*
C18	0.180 (2)	0.5756 (12)	0.8658 (13)	0.060 (4)
H18A	0.2126	0.6420	0.8067	0.072*
H18B	0.2555	0.5651	0.9243	0.072*
H18C	0.0464	0.5946	0.8855	0.072*
C19	0.0889 (17)	0.5477 (13)	0.6515 (12)	0.056 (4)
H19A	0.0830	0.6263	0.6621	0.068*
H19B	−0.0383	0.5361	0.6462	0.068*
H19C	0.1627	0.5454	0.5876	0.068*
C20	0.331 (2)	0.2130 (12)	0.3148 (10)	0.045 (3)
H20A	0.2167	0.2111	0.2826	0.053*
H20B	0.3533	0.2972	0.2903	0.053*
Cl1	0.5584 (4)	0.5480 (2)	0.6167 (2)	0.0268 (5)
Cl2	0.7133 (4)	0.4366 (2)	0.8520 (2)	0.0289 (6)
Cl3	0.2938 (5)	0.1691 (3)	0.4491 (3)	0.0505 (8)
Cl4	0.5213 (6)	0.1194 (4)	0.2750 (4)	0.0745 (12)
N1	0.9631 (12)	−0.0139 (8)	0.8738 (7)	0.027 (2)
N3	0.9494 (13)	−0.0174 (7)	0.6998 (7)	0.029 (2)
N6	0.8322 (13)	0.1512 (8)	0.9311 (7)	0.031 (2)
H6A	0.8789	0.1115	0.9921	0.037*
H6B	0.7663	0.2249	0.9199	0.037*
N7	0.6850 (11)	0.2692 (7)	0.7069 (6)	0.0188 (17)
N9	0.7732 (12)	0.1709 (8)	0.5912 (6)	0.0233 (18)
Ir	0.47641 (5)	0.39087 (3)	0.76639 (3)	0.01833 (15)

	U11	U22	U33	U12	U13	U23
C2	0.030 (6)	0.026 (6)	0.033 (6)	0.002 (5)	−0.006 (5)	−0.011 (5)
C4	0.025 (5)	0.024 (5)	0.026 (5)	−0.008 (4)	−0.003 (4)	−0.011 (4)
C5	0.022 (5)	0.017 (5)	0.017 (5)	−0.004 (4)	0.001 (4)	−0.006 (4)
C6	0.028 (6)	0.023 (5)	0.021 (5)	0.002 (4)	−0.003 (4)	−0.003 (4)
C8	0.014 (5)	0.017 (5)	0.025 (5)	0.002 (4)	−0.004 (4)	−0.004 (4)
C9	0.043 (7)	0.025 (6)	0.022 (5)	−0.009 (5)	0.006 (5)	−0.011 (4)
C10	0.018 (5)	0.040 (7)	0.029 (6)	−0.016 (5)	0.005 (4)	−0.011 (5)
C11	0.033 (6)	0.025 (6)	0.035 (6)	−0.017 (5)	0.016 (5)	−0.009 (5)
C12	0.026 (6)	0.043 (7)	0.025 (6)	−0.013 (5)	0.010 (4)	−0.012 (5)
C13	0.023 (6)	0.030 (6)	0.053 (8)	0.005 (5)	0.012 (5)	−0.015 (6)
C14	0.018 (5)	0.028 (6)	0.037 (6)	0.006 (4)	−0.002 (4)	−0.004 (5)
C15	0.055 (9)	0.069 (10)	0.053 (9)	−0.046 (8)	0.006 (7)	−0.026 (8)
C16	0.048 (8)	0.015 (6)	0.064 (9)	−0.014 (5)	0.005 (6)	0.001 (6)
C17	0.041 (7)	0.074 (10)	0.029 (7)	−0.006 (7)	0.006 (6)	−0.013 (7)
C18	0.054 (9)	0.041 (8)	0.092 (12)	0.003 (7)	0.027 (8)	−0.047 (8)
C19	0.019 (6)	0.057 (9)	0.068 (10)	−0.001 (6)	0.000 (6)	0.012 (7)
C20	0.054 (8)	0.037 (7)	0.047 (8)	−0.007 (6)	−0.001 (6)	−0.020 (6)
Cl1	0.0323 (14)	0.0227 (13)	0.0256 (13)	−0.0081 (10)	−0.0010 (10)	−0.0057 (10)
Cl2	0.0349 (14)	0.0274 (13)	0.0295 (14)	−0.0074 (11)	−0.0051 (11)	−0.0136 (11)
Cl3	0.055 (2)	0.0467 (19)	0.058 (2)	−0.0206 (16)	0.0060 (16)	−0.0227 (16)
Cl4	0.071 (3)	0.081 (3)	0.072 (3)	0.008 (2)	0.009 (2)	−0.042 (2)
N1	0.028 (5)	0.018 (4)	0.033 (5)	0.000 (4)	−0.002 (4)	−0.008 (4)
N3	0.032 (5)	0.015 (4)	0.040 (6)	0.001 (4)	0.000 (4)	−0.013 (4)
N6	0.043 (6)	0.023 (5)	0.023 (5)	0.011 (4)	−0.009 (4)	−0.011 (4)
N7	0.021 (4)	0.010 (4)	0.020 (4)	0.004 (3)	−0.002 (3)	−0.001 (3)
N9	0.029 (5)	0.022 (4)	0.019 (4)	−0.006 (4)	0.005 (3)	−0.008 (4)
Ir	0.0201 (2)	0.0154 (2)	0.0201 (2)	−0.00199 (14)	0.00201 (14)	−0.00814 (15)

C2—N3	1.325 (14)	C13—C18	1.494 (17)
C2—N1	1.331 (14)	C13—Ir	2.159 (11)
C2—H2	0.9500	C14—C19	1.510 (16)
C4—N3	1.348 (13)	C14—Ir	2.153 (10)
C4—N9	1.375 (13)	C15—H15A	0.9800
C4—C5	1.386 (14)	C15—H15B	0.9800
C5—N7	1.392 (12)	C15—H15C	0.9800
C5—C6	1.410 (14)	C16—H16A	0.9800
C6—N1	1.349 (13)	C16—H16B	0.9800
C6—N6	1.349 (14)	C16—H16C	0.9800
C8—N7	1.325 (13)	C17—H17A	0.9800
C8—N9	1.335 (13)	C17—H17B	0.9800
C8—H8	0.9500	C17—H17C	0.9800
C9—N9	1.467 (13)	C18—H18A	0.9800
C9—H9A	0.9800	C18—H18B	0.9800
C9—H9B	0.9800	C18—H18C	0.9800
C9—H9C	0.9800	C19—H19A	0.9800
C10—C14	1.414 (16)	C19—H19B	0.9800
C10—C11	1.463 (16)	C19—H19C	0.9800
C10—C15	1.514 (17)	C20—Cl4	1.743 (13)
C10—Ir	2.127 (10)	C20—Cl3	1.745 (13)
C11—C12	1.419 (16)	C20—H20A	0.9900
C11—C16	1.493 (15)	C20—H20B	0.9900
C11—Ir	2.165 (10)	Cl1—Ir	2.402 (3)
C12—C13	1.458 (16)	Cl2—Ir	2.423 (3)
C12—C17	1.484 (16)	N6—H6A	0.8800
C12—Ir	2.164 (10)	N6—H6B	0.8800
C13—C14	1.413 (17)	N7—Ir	2.152 (8)
N3—C2—N1	129.5 (10)	C12—C17—H17A	109.5
N3—C2—H2	115.3	C12—C17—H17B	109.5
N1—C2—H2	115.3	H17A—C17—H17B	109.5
N3—C4—N9	127.0 (9)	C12—C17—H17C	109.5
N3—C4—C5	127.0 (10)	H17A—C17—H17C	109.5
N9—C4—C5	106.0 (9)	H17B—C17—H17C	109.5
C4—C5—N7	108.9 (8)	C13—C18—H18A	109.5
C4—C5—C6	116.4 (9)	C13—C18—H18B	109.5
N7—C5—C6	134.6 (9)	H18A—C18—H18B	109.5
N1—C6—N6	119.0 (9)	C13—C18—H18C	109.5
N1—C6—C5	117.6 (9)	H18A—C18—H18C	109.5
N6—C6—C5	123.4 (9)	H18B—C18—H18C	109.5
N7—C8—N9	112.9 (8)	C14—C19—H19A	109.5
N7—C8—H8	123.5	C14—C19—H19B	109.5
N9—C8—H8	123.5	H19A—C19—H19B	109.5
N9—C9—H9A	109.5	C14—C19—H19C	109.5
N9—C9—H9B	109.5	H19A—C19—H19C	109.5
H9A—C9—H9B	109.5	H19B—C19—H19C	109.5
N9—C9—H9C	109.5	Cl4—C20—Cl3	112.3 (8)
H9A—C9—H9C	109.5	Cl4—C20—H20A	109.2
H9B—C9—H9C	109.5	Cl3—C20—H20A	109.2
C14—C10—C11	107.9 (10)	Cl4—C20—H20B	109.2
C14—C10—C15	126.5 (11)	Cl3—C20—H20B	109.2
C11—C10—C15	125.3 (11)	H20A—C20—H20B	107.9
C14—C10—Ir	71.7 (6)	C2—N1—C6	119.0 (9)
C11—C10—Ir	71.5 (6)	C2—N3—C4	110.4 (9)
C15—C10—Ir	127.3 (8)	C6—N6—H6A	120.0
C12—C11—C10	107.0 (10)	C6—N6—H6B	120.0
C12—C11—C16	126.9 (11)	H6A—N6—H6B	120.0
C10—C11—C16	126.1 (11)	C8—N7—C5	104.9 (8)
C12—C11—Ir	70.8 (6)	C8—N7—Ir	119.3 (6)
C10—C11—Ir	68.7 (5)	C5—N7—Ir	132.2 (6)
C16—C11—Ir	127.4 (8)	C8—N9—C4	107.2 (8)
C11—C12—C13	108.4 (10)	C8—N9—C9	126.4 (9)
C11—C12—C17	125.0 (12)	C4—N9—C9	126.3 (9)
C13—C12—C17	126.6 (12)	C10—Ir—N7	97.3 (4)
C11—C12—Ir	70.9 (6)	C10—Ir—C14	38.6 (4)
C13—C12—Ir	70.1 (6)	N7—Ir—C14	130.7 (4)
C17—C12—Ir	125.7 (8)	C10—Ir—C13	65.1 (5)
C14—C13—C12	107.3 (10)	N7—Ir—C13	160.2 (4)
C14—C13—C18	127.1 (12)	C14—Ir—C13	38.3 (5)
C12—C13—C18	125.6 (13)	C10—Ir—C12	65.4 (4)
C14—C13—Ir	70.6 (6)	N7—Ir—C12	126.5 (4)
C12—C13—Ir	70.4 (6)	C14—Ir—C12	64.8 (4)
C18—C13—Ir	125.4 (9)	C13—Ir—C12	39.4 (4)
C13—C14—C10	109.4 (10)	C10—Ir—C11	39.9 (4)
C13—C14—C19	125.8 (12)	N7—Ir—C11	95.5 (4)
C10—C14—C19	124.7 (12)	C14—Ir—C11	65.2 (4)
C13—C14—Ir	71.1 (6)	C13—Ir—C11	65.3 (4)
C10—C14—Ir	69.7 (6)	C12—Ir—C11	38.3 (4)
C19—C14—Ir	126.8 (8)	C10—Ir—Cl1	112.7 (3)
C10—C15—H15A	109.5	N7—Ir—Cl1	86.0 (2)
C10—C15—H15B	109.5	C14—Ir—Cl1	93.1 (3)
H15A—C15—H15B	109.5	C13—Ir—Cl1	108.6 (3)
C10—C15—H15C	109.5	C12—Ir—Cl1	147.4 (3)
H15A—C15—H15C	109.5	C11—Ir—Cl1	152.5 (3)
H15B—C15—H15C	109.5	C10—Ir—Cl2	160.2 (3)
C11—C16—H16A	109.5	N7—Ir—Cl2	91.0 (2)
C11—C16—H16B	109.5	C14—Ir—Cl2	138.2 (3)
H16A—C16—H16B	109.5	C13—Ir—Cl2	103.0 (4)
C11—C16—H16C	109.5	C12—Ir—Cl2	95.2 (3)
H16A—C16—H16C	109.5	C11—Ir—Cl2	121.6 (3)
H16B—C16—H16C	109.5	Cl1—Ir—Cl2	85.72 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N1i	0.88	2.14	3.007 (13)	170.
N6—H6B···Cl2	0.88	2.35	3.168 (10)	155.
C8—H8···Cl1	0.95	2.77	3.237 (11)	111.
C8—H8···Cl1ii	0.95	2.65	3.537 (11)	156.
C9—H9B···Cl3iii	0.98	2.75	3.697 (13)	163.
C20—H20B···Cl1ii	0.99	2.75	3.519 (15)	135.

C10—Ir	2.127 (10)
C11—Ir	2.165 (10)
C12—Ir	2.164 (10)
C13—Ir	2.159 (11)
C14—Ir	2.153 (10)
Cl1—Ir	2.402 (3)
Cl2—Ir	2.423 (3)
N7—Ir	2.152 (8)

N7—Ir—Cl1	86.0 (2)
N7—Ir—Cl2	91.0 (2)
Cl1—Ir—Cl2	85.72 (9)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯N1i	0.88	2.14	3.007 (13)	170
N6—H6B⋯Cl2	0.88	2.35	3.168 (10)	155
C8—H8⋯Cl1	0.95	2.77	3.237 (11)	111
C8—H8⋯Cl1ii	0.95	2.65	3.537 (11)	156
C9—H9B⋯Cl3iii	0.98	2.75	3.697 (13)	163
C20—H20B⋯Cl1ii	0.99	2.75	3.519 (15)	135

Symmetry codes: (i) ; (ii) ; (iii) .