(Acetonitrile-κN)chloridobis[2-(pyridin-2-yl)phenyl-κ2C1,N]iridium(III)

Blasberg, F.; Bats, J.W.; Wagner, M.; Lerner, H.-W.

doi:10.1107/S1600536811049373

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1837-m1838

https://doi.org/10.1107/S1600536811049373

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(Acetonitrile-κN)chloridobis[2-(pyridin-2-yl)phenyl-κ²C¹,N]iridium(III)

Florian Blasberg,^a Jan W. Bats,^b ^* Matthias Wagner ^a and Hans-Wolfram Lerner ^a

^aInstitut für Anorganische Chemie der Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, and ^bInstitut für Organische Chemie, Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bats@chemie.uni-frankfurt.de

(Received 17 November 2011; accepted 18 November 2011; online 25 November 2011)

The Ir^III atom of the title compound, [Ir(C₁₁H₈N)₂Cl(CH₃CN)], displays a distorted octahedral coordination. The pyridyl groups are in trans positions [N—Ir—N = 173.07 (10)°], while the phenyl groups are trans with respect to the acetonitrile and chloride groups [C—Ir—N = 178.13 (11) and C—Ir—Cl = 176.22 (9)°]. The pyridylphenyl groups only show a small deviation from planarity, with the dihedral angle between the planes of the two six-membered rings in each pyridylphenyl group being 5.6 (2) and 5.8 (1)°. The crystal packing shows intermolecular C—H⋯Cl, C—H⋯π(acetonitrile) and C—H⋯π(pyridylphenyl) contacts.

Related literature

For our work on redox active ligands, see: Jäkle et al. (1996 ); Guo et al. (2001 ); Margraf et al. (2006 ); Kretz et al. (2006 ); Phan et al. (2011 ); Scheuermann et al. (2008 , 2009 ); Blasberg et al. (2010 , 2011 ). For the synthesis of the starting materials, see: Blasberg et al. (2011); Lowry et al. (2004 ). For related structures, see: Yang et al. (2009 ); Shu et al. (2011 ); McGee & Mann (2007 ); Garces et al. (1993 ).

Experimental

Crystal data

[Ir(C₁₁H₈N)₂Cl(C₂H₃N)]
M_r = 577.07
Orthorhombic, P b c a
a = 16.5255 (8) Å
b = 14.6588 (7) Å
c = 17.0536 (8) Å
V = 4131.1 (3) Å³
Z = 8
Mo Kα radiation
μ = 6.61 mm⁻¹
T = 171 K
0.38 × 0.34 × 0.20 mm

Data collection

Siemens SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.176, T_max = 0.267
44325 measured reflections
4772 independent reflections
3899 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.040
S = 1.07
4772 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected bond lengths (Å)

Ir1—C11	2.004 (3)
Ir1—C22	2.007 (3)
Ir1—N1	2.043 (2)
Ir1—N2	2.047 (2)
Ir1—N3	2.129 (3)
Ir1—Cl1	2.4839 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1ⁱ	0.95	2.78	3.600 (3)	145
C14—H14A⋯Cl1ⁱⁱ	0.95	2.80	3.470 (3)	129
C14—H14A⋯C23ⁱⁱⁱ	0.95	2.69	3.431 (4)	135
C8—H8A⋯C16^iv	0.95	2.79	3.595 (4)	143
C8—H8A⋯C17^iv	0.95	2.72	3.628 (4)	159
C8—H8A⋯C18^iv	0.95	2.79	3.705 (4)	163
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811049373/tk5023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049373/tk5023Isup2.hkl

checkCIF report

Comment top

One of the highlights of our group's work is the synthesis and characterization of redox active ligands for transition metal catalyzed reactions and applications in material science. Up to now we have applied electro-active ligands with poly(pyrazol-1-yl)borate (Jäkle et al., 1996; Guo et al., 2001), diimine (Margraf et al., 2006; Kretz et al., 2006; Phan et al., 2011) and bis(pyrazol-1-yl)methane (Scheuermann et al., 2008; Scheuermann et al., 2009; Blasberg et al., 2010) donor groups. So far, ferrocenyl and mainly para-quinonyl units (quinone is used if the oxidation state is not defined) were used as the redox-active element. But recently our attention turned to ortho-quinone derivatives, since they should allow for efficient bridging of two different transition metal centers in redox-switchable catalysis. In this context, synthesis of the hetero-bimetallic complex 3 with an ortho-hydroquinone-derived bis(pyrazol-1-yl)methane ligand, a catalytically active palladium(II) and a light-switchable iridium(III) center was attempted (see Fig. 1). This molecule might allow for light-driven redox-reactions, which in turn can switch catalysis on or off. The palladium(II) complex 1 (Blasberg et al., 2010; Blasberg et al., 2011) was deprotonated twice with lithium t-butoxide (LiOtBu) in a tetrahydrofuran solution in a glove box and subsequently tetrakis-[2-(pyridin-2-yl)phenyl]-dichlorido-diiridium(III) 2 (Lowry et al., 2004) was added to the resulting dianion. After stirring overnight and recrystallization of the resulting crude material from acetonitrile, the only obtained product was (acetonitrile-N)-chlorido-bis[2-(pyridin-2-yl)phenyl-C,N]iridium(III) 4, instead of the expected compound 3.

The molecular structure of the title compound is shown in Fig. 2. The Ir(III) atom displays octahedral coordination (Table 1). The pyridyl groups are in trans positions and the phenyl groups in cis positions with respect to the central metal atom. A trans position of the pyridyl groups also has been observed in dimer 2 (McGee & Mann, 2007; Garces et al., 1993) and in related compounds (Shu et al., 2011). The bond lengths involving the Ir atom are very similar to the values reported for a closely related molecule (Yang et al., 2009). The pyridylphenyl groups only show a small deviation from planarity. The angle between the planes of the two six-membered rings is 5.6 (2) and 5.8 (1)°, respectively, for the two different pyridylphenyl groups. The crystal packing shows two intermolecular C—H···Cl contacts, an intermolecular C—H···π_acetonitrile and an intermolecular C—H···π_{pyridylphenyl} contact (Table 2). The C—H···π_acetonitrile contact points closer towards atom C23 than towards the midpoint of the C≡ N triple bond. The C—H···π_{pyridylphenyl} contact does not point towards the center of one of the six-membered rings. It rather points towards the midpoint of the C17—C18 bond.

Related literature top

For our work on redox active ligands, see: Jäkle et al. (1996); Guo et al. (2001); Margraf et al. (2006); Kretz et al. (2006); Phan et al. (2011); Scheuermann et al. (2008, 2009); Blasberg et al. (2010, 2011). For the synthesis of the starting materials, see: Blasberg et al. (2011); Lowry et al. (2004). For related structures, see: Yang et al. (2009); Shu et al. (2011); McGee & Mann (2007); Garces et al. (1993).

Experimental top

Dichlorido-[1-(bis-1H-pyrazol-1-ylmethyl)-benzene-3,4-diol-N,N']palladium(II) (50 mg, 0.12 mmol; Blasberg et al., 2011) was reacted with 19 mg (0.23 mmol) of lithium t-butoxide in tetrahydrofuran (4 ml) for 5 min, after which 62 mg (0.12 mmol) of tetrakis-[2-(pyridin-2-yl)phenyl]-dichlorido-diiridium(III) was added. After stirring overnight, the suspension which had formed, was separated by centrifugation and dried by evaporation. Recrystallization of the tan-colored powder from acetonitrile yielded yellow-brown blocks of the title compound.

Structure description top

For our work on redox active ligands, see: Jäkle et al. (1996); Guo et al. (2001); Margraf et al. (2006); Kretz et al. (2006); Phan et al. (2011); Scheuermann et al. (2008, 2009); Blasberg et al. (2010, 2011). For the synthesis of the starting materials, see: Blasberg et al. (2011); Lowry et al. (2004). For related structures, see: Yang et al. (2009); Shu et al. (2011); McGee & Mann (2007); Garces et al. (1993).

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The attempted synthesis of compound 3 and the synthesis of the title compound 4.
	Fig. 2. The molecular structure of the title molecule shown with 50% probability displacement ellipsoids. The H atoms are drawn as small spheres of arbitrary radius.

(Acetonitrile-κN)chloridobis[2-(pyridin-2-yl)phenyl- κ²C¹,N]iridium(III) top

Crystal data top

[Ir(C₁₁H₈N)₂Cl(C₂H₃N)]	F(000) = 2224
M_r = 577.07	D_x = 1.856 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8192 reflections
a = 16.5255 (8) Å	θ = 3–26°
b = 14.6588 (7) Å	µ = 6.61 mm⁻¹
c = 17.0536 (8) Å	T = 171 K
V = 4131.1 (3) Å³	Block, yellow-brown
Z = 8	0.38 × 0.34 × 0.20 mm

Data collection top

Siemens SMART 1K CCD diffractometer	4772 independent reflections
Radiation source: normal-focus sealed tube	3899 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 28.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −21→21
T_min = 0.176, T_max = 0.267	k = −18→19
44325 measured reflections	l = −21→21

Refinement top

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.040	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.01P)² + 6P] where P = (F_o² + 2F_c²)/3
4772 reflections	(Δ/σ)_max = 0.002
263 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Ir(C₁₁H₈N)₂Cl(C₂H₃N)]	V = 4131.1 (3) Å³
M_r = 577.07	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 16.5255 (8) Å	µ = 6.61 mm⁻¹
b = 14.6588 (7) Å	T = 171 K
c = 17.0536 (8) Å	0.38 × 0.34 × 0.20 mm

Data collection top

Siemens SMART 1K CCD diffractometer	4772 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	3899 reflections with I > 2σ(I)
T_min = 0.176, T_max = 0.267	R_int = 0.043
44325 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.040	H-atom parameters constrained
S = 1.07	Δρ_max = 0.70 e Å⁻³
4772 reflections	Δρ_min = −0.67 e Å⁻³
263 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ir1	0.120571 (6)	0.443245 (7)	0.139275 (6)	0.01422 (4)
Cl1	0.10742 (5)	0.35418 (5)	0.01602 (4)	0.02214 (17)
N1	0.15302 (14)	0.55553 (17)	0.07570 (14)	0.0168 (5)
N2	0.09788 (15)	0.33598 (17)	0.21296 (14)	0.0173 (6)
N3	−0.00690 (15)	0.46420 (16)	0.13721 (15)	0.0180 (5)
C1	0.10024 (19)	0.6140 (2)	0.04170 (19)	0.0208 (7)
H1A	0.0442	0.5995	0.0419	0.025*
C2	0.1253 (2)	0.6939 (2)	0.00676 (19)	0.0271 (7)
H2A	0.0872	0.7336	−0.0172	0.032*
C3	0.2071 (2)	0.7156 (2)	0.0070 (2)	0.0269 (8)
H3A	0.2255	0.7715	−0.0148	0.032*
C4	0.2612 (2)	0.6548 (2)	0.03935 (19)	0.0227 (7)
H4A	0.3174	0.6682	0.0389	0.027*
C5	0.23377 (18)	0.5736 (2)	0.07272 (18)	0.0188 (7)
C6	0.28432 (19)	0.5020 (2)	0.10731 (18)	0.0183 (7)
C7	0.3682 (2)	0.5025 (2)	0.10645 (19)	0.0262 (8)
H7A	0.3960	0.5525	0.0835	0.031*
C8	0.4118 (2)	0.4314 (2)	0.1385 (2)	0.0314 (8)
H8A	0.4693	0.4323	0.1378	0.038*
C9	0.3706 (2)	0.3584 (2)	0.1717 (2)	0.0287 (8)
H9A	0.4001	0.3090	0.1937	0.034*
C10	0.2866 (2)	0.3570 (2)	0.17310 (19)	0.0224 (7)
H10A	0.2595	0.3067	0.1964	0.027*
C11	0.24108 (18)	0.4280 (2)	0.14108 (18)	0.0184 (6)
C12	0.07559 (19)	0.2516 (2)	0.1899 (2)	0.0234 (7)
H12A	0.0702	0.2393	0.1354	0.028*
C13	0.0605 (2)	0.1831 (2)	0.2425 (2)	0.0286 (8)
H13A	0.0438	0.1246	0.2249	0.034*
C14	0.0697 (2)	0.2002 (2)	0.3214 (2)	0.0294 (8)
H14A	0.0605	0.1531	0.3586	0.035*
C15	0.0923 (2)	0.2858 (2)	0.34593 (19)	0.0256 (8)
H15A	0.0991	0.2979	0.4003	0.031*
C16	0.10527 (18)	0.3545 (2)	0.29141 (18)	0.0183 (7)
C17	0.12382 (17)	0.4502 (2)	0.30864 (17)	0.0180 (6)
C18	0.1296 (2)	0.4849 (2)	0.38490 (18)	0.0234 (7)
H18A	0.1232	0.4452	0.4285	0.028*
C19	0.1446 (2)	0.5767 (2)	0.3970 (2)	0.0294 (8)
H19A	0.1488	0.6004	0.4487	0.035*
C20	0.1534 (2)	0.6340 (2)	0.3325 (2)	0.0298 (8)
H20A	0.1635	0.6972	0.3403	0.036*
C21	0.1477 (2)	0.5998 (2)	0.2570 (2)	0.0246 (8)
H21A	0.1545	0.6400	0.2139	0.030*
C22	0.13213 (18)	0.5074 (2)	0.24265 (17)	0.0171 (6)
C23	−0.07549 (19)	0.4705 (2)	0.1405 (2)	0.0216 (7)
C24	−0.1632 (2)	0.4813 (3)	0.1439 (2)	0.0344 (9)
H24A	−0.1805	0.5251	0.1038	0.052*
H24B	−0.1787	0.5039	0.1959	0.052*
H24C	−0.1892	0.4223	0.1343	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01496 (6)	0.01404 (6)	0.01367 (6)	0.00062 (5)	−0.00041 (5)	0.00067 (5)
Cl1	0.0257 (4)	0.0242 (4)	0.0165 (4)	0.0035 (3)	−0.0032 (3)	−0.0025 (3)
N1	0.0193 (12)	0.0163 (12)	0.0148 (12)	0.0023 (11)	0.0007 (10)	0.0020 (12)
N2	0.0202 (14)	0.0168 (13)	0.0149 (13)	0.0008 (10)	0.0016 (10)	0.0009 (11)
N3	0.0201 (14)	0.0152 (13)	0.0186 (13)	−0.0005 (10)	−0.0010 (12)	0.0001 (11)
C1	0.0192 (17)	0.0222 (17)	0.0211 (17)	0.0020 (13)	−0.0020 (13)	−0.0001 (14)
C2	0.0330 (19)	0.0214 (17)	0.0267 (18)	0.0051 (16)	−0.0036 (16)	0.0070 (14)
C3	0.036 (2)	0.0189 (17)	0.0263 (19)	−0.0037 (15)	0.0020 (16)	0.0081 (15)
C4	0.0227 (17)	0.0223 (17)	0.0232 (18)	−0.0061 (14)	0.0014 (14)	0.0016 (14)
C5	0.0189 (16)	0.0225 (18)	0.0149 (15)	−0.0008 (12)	−0.0010 (12)	−0.0017 (13)
C6	0.0201 (16)	0.0193 (16)	0.0156 (16)	−0.0011 (13)	−0.0019 (13)	−0.0003 (13)
C7	0.0222 (18)	0.0309 (19)	0.0255 (17)	−0.0054 (15)	0.0003 (14)	0.0014 (15)
C8	0.0149 (15)	0.042 (2)	0.037 (2)	0.0031 (15)	−0.0031 (16)	0.001 (2)
C9	0.0236 (19)	0.0290 (19)	0.0335 (19)	0.0084 (15)	−0.0064 (16)	0.0032 (15)
C10	0.0241 (17)	0.0168 (17)	0.0263 (18)	0.0010 (13)	−0.0024 (14)	0.0018 (14)
C11	0.0184 (15)	0.0202 (16)	0.0167 (14)	0.0022 (12)	−0.0021 (14)	−0.0059 (15)
C12	0.0259 (18)	0.0228 (18)	0.0216 (19)	−0.0010 (14)	−0.0003 (14)	−0.0030 (15)
C13	0.042 (2)	0.0162 (18)	0.028 (2)	−0.0037 (15)	0.0050 (16)	−0.0002 (15)
C14	0.043 (2)	0.0213 (19)	0.0240 (19)	−0.0031 (16)	0.0048 (16)	0.0089 (15)
C15	0.0321 (18)	0.0248 (18)	0.0200 (19)	−0.0001 (14)	0.0007 (14)	0.0026 (14)
C16	0.0177 (16)	0.0183 (16)	0.0188 (16)	0.0039 (12)	−0.0001 (13)	0.0013 (13)
C17	0.0158 (14)	0.0215 (15)	0.0167 (14)	0.0014 (14)	−0.0013 (12)	−0.0006 (13)
C18	0.0253 (18)	0.0269 (17)	0.0181 (16)	0.0000 (15)	−0.0009 (14)	−0.0004 (13)
C19	0.034 (2)	0.033 (2)	0.0207 (18)	−0.0021 (15)	−0.0022 (15)	−0.0096 (15)
C20	0.040 (2)	0.0200 (18)	0.030 (2)	−0.0014 (15)	−0.0027 (16)	−0.0084 (15)
C21	0.0303 (19)	0.0207 (18)	0.0229 (18)	−0.0002 (14)	−0.0012 (15)	−0.0001 (14)
C22	0.0137 (15)	0.0199 (15)	0.0176 (15)	0.0028 (13)	−0.0011 (12)	−0.0005 (13)
C23	0.0243 (18)	0.0211 (16)	0.0193 (16)	0.0008 (12)	−0.0011 (15)	−0.0014 (15)
C24	0.0205 (18)	0.042 (2)	0.041 (2)	0.0020 (15)	0.0023 (17)	0.003 (2)

Geometric parameters (Å, º) top

Ir1—C11	2.004 (3)	C9—H9A	0.9500
Ir1—C22	2.007 (3)	C10—C11	1.394 (4)
Ir1—N1	2.043 (2)	C10—H10A	0.9500
Ir1—N2	2.047 (2)	C12—C13	1.370 (5)
Ir1—N3	2.129 (3)	C12—H12A	0.9500
Ir1—Cl1	2.4839 (7)	C13—C14	1.376 (5)
N1—C1	1.353 (4)	C13—H13A	0.9500
N1—C5	1.361 (4)	C14—C15	1.374 (5)
N2—C12	1.349 (4)	C14—H14A	0.9500
N2—C16	1.371 (4)	C15—C16	1.388 (4)
N3—C23	1.139 (4)	C15—H15A	0.9500
C1—C2	1.378 (4)	C16—C17	1.466 (4)
C1—H1A	0.9500	C17—C18	1.399 (4)
C2—C3	1.389 (5)	C17—C22	1.410 (4)
C2—H2A	0.9500	C18—C19	1.385 (5)
C3—C4	1.378 (5)	C18—H18A	0.9500
C3—H3A	0.9500	C19—C20	1.392 (5)
C4—C5	1.394 (4)	C19—H19A	0.9500
C4—H4A	0.9500	C20—C21	1.384 (5)
C5—C6	1.465 (4)	C20—H20A	0.9500
C6—C7	1.386 (4)	C21—C22	1.400 (4)
C6—C11	1.422 (4)	C21—H21A	0.9500
C7—C8	1.380 (5)	C23—C24	1.459 (4)
C7—H7A	0.9500	C24—H24A	0.9800
C8—C9	1.389 (5)	C24—H24B	0.9800
C8—H8A	0.9500	C24—H24C	0.9800
C9—C10	1.389 (5)

C11—Ir1—C22	86.81 (12)	C10—C9—H9A	119.7
C11—Ir1—N1	80.64 (11)	C9—C10—C11	121.5 (3)
C22—Ir1—N1	93.65 (11)	C9—C10—H10A	119.3
C11—Ir1—N2	94.97 (11)	C11—C10—H10A	119.3
C22—Ir1—N2	80.69 (11)	C10—C11—C6	117.2 (3)
N1—Ir1—N2	173.07 (10)	C10—C11—Ir1	128.7 (2)
C11—Ir1—N3	178.13 (11)	C6—C11—Ir1	114.1 (2)
C22—Ir1—N3	92.36 (11)	N2—C12—C13	122.0 (3)
N1—Ir1—N3	97.75 (9)	N2—C12—H12A	119.0
N2—Ir1—N3	86.54 (9)	C13—C12—H12A	119.0
C11—Ir1—Cl1	92.36 (9)	C12—C13—C14	119.1 (3)
C22—Ir1—Cl1	176.22 (9)	C12—C13—H13A	120.4
N1—Ir1—Cl1	89.85 (7)	C14—C13—H13A	120.4
N2—Ir1—Cl1	95.72 (7)	C15—C14—C13	119.6 (3)
N3—Ir1—Cl1	88.58 (7)	C15—C14—H14A	120.2
C1—N1—C5	119.5 (3)	C13—C14—H14A	120.2
C1—N1—Ir1	124.6 (2)	C14—C15—C16	120.0 (3)
C5—N1—Ir1	115.7 (2)	C14—C15—H15A	120.0
C12—N2—C16	119.4 (3)	C16—C15—H15A	120.0
C12—N2—Ir1	125.1 (2)	N2—C16—C15	119.8 (3)
C16—N2—Ir1	115.5 (2)	N2—C16—C17	113.8 (3)
C23—N3—Ir1	174.8 (3)	C15—C16—C17	126.4 (3)
N1—C1—C2	122.0 (3)	C18—C17—C22	121.3 (3)
N1—C1—H1A	119.0	C18—C17—C16	123.2 (3)
C2—C1—H1A	119.0	C22—C17—C16	115.4 (3)
C1—C2—C3	119.1 (3)	C19—C18—C17	120.3 (3)
C1—C2—H2A	120.4	C19—C18—H18A	119.9
C3—C2—H2A	120.4	C17—C18—H18A	119.9
C4—C3—C2	118.9 (3)	C18—C19—C20	119.2 (3)
C4—C3—H3A	120.5	C18—C19—H19A	120.4
C2—C3—H3A	120.5	C20—C19—H19A	120.4
C3—C4—C5	120.3 (3)	C21—C20—C19	120.6 (3)
C3—C4—H4A	119.8	C21—C20—H20A	119.7
C5—C4—H4A	119.8	C19—C20—H20A	119.7
N1—C5—C4	120.0 (3)	C20—C21—C22	121.7 (3)
N1—C5—C6	113.8 (3)	C20—C21—H21A	119.1
C4—C5—C6	126.2 (3)	C22—C21—H21A	119.1
C7—C6—C11	120.7 (3)	C21—C22—C17	116.9 (3)
C7—C6—C5	124.2 (3)	C21—C22—Ir1	128.7 (2)
C11—C6—C5	115.1 (3)	C17—C22—Ir1	114.4 (2)
C8—C7—C6	121.0 (3)	N3—C23—C24	178.3 (4)
C8—C7—H7A	119.5	C23—C24—H24A	109.5
C6—C7—H7A	119.5	C23—C24—H24B	109.5
C7—C8—C9	119.1 (3)	H24A—C24—H24B	109.5
C7—C8—H8A	120.4	C23—C24—H24C	109.5
C9—C8—H8A	120.4	H24A—C24—H24C	109.5
C8—C9—C10	120.5 (3)	H24B—C24—H24C	109.5
C8—C9—H9A	119.7

C11—Ir1—N1—C1	176.5 (3)	C22—Ir1—C11—C10	89.2 (3)
C22—Ir1—N1—C1	−97.3 (3)	N1—Ir1—C11—C10	−176.6 (3)
N3—Ir1—N1—C1	−4.4 (3)	N2—Ir1—C11—C10	8.8 (3)
Cl1—Ir1—N1—C1	84.1 (2)	Cl1—Ir1—C11—C10	−87.1 (3)
C11—Ir1—N1—C5	−7.7 (2)	C22—Ir1—C11—C6	−88.3 (2)
C22—Ir1—N1—C5	78.5 (2)	N1—Ir1—C11—C6	5.9 (2)
N3—Ir1—N1—C5	171.4 (2)	N2—Ir1—C11—C6	−168.6 (2)
Cl1—Ir1—N1—C5	−100.1 (2)	Cl1—Ir1—C11—C6	95.4 (2)
C11—Ir1—N2—C12	−98.7 (3)	C16—N2—C12—C13	−0.4 (5)
C22—Ir1—N2—C12	175.4 (3)	Ir1—N2—C12—C13	−179.3 (2)
N3—Ir1—N2—C12	82.4 (2)	N2—C12—C13—C14	−1.2 (5)
Cl1—Ir1—N2—C12	−5.8 (2)	C12—C13—C14—C15	1.2 (5)
C11—Ir1—N2—C16	82.4 (2)	C13—C14—C15—C16	0.4 (5)
C22—Ir1—N2—C16	−3.5 (2)	C12—N2—C16—C15	2.0 (4)
N3—Ir1—N2—C16	−96.5 (2)	Ir1—N2—C16—C15	−179.0 (2)
Cl1—Ir1—N2—C16	175.28 (19)	C12—N2—C16—C17	−175.6 (3)
C5—N1—C1—C2	−2.8 (5)	Ir1—N2—C16—C17	3.3 (3)
Ir1—N1—C1—C2	172.8 (2)	C14—C15—C16—N2	−2.0 (5)
N1—C1—C2—C3	−0.6 (5)	C14—C15—C16—C17	175.3 (3)
C1—C2—C3—C4	2.6 (5)	N2—C16—C17—C18	176.5 (3)
C2—C3—C4—C5	−1.3 (5)	C15—C16—C17—C18	−1.0 (5)
C1—N1—C5—C4	4.2 (4)	N2—C16—C17—C22	−0.8 (4)
Ir1—N1—C5—C4	−171.9 (2)	C15—C16—C17—C22	−178.3 (3)
C1—N1—C5—C6	−176.3 (3)	C22—C17—C18—C19	−0.7 (5)
Ir1—N1—C5—C6	7.7 (3)	C16—C17—C18—C19	−177.8 (3)
C3—C4—C5—N1	−2.1 (5)	C17—C18—C19—C20	0.3 (5)
C3—C4—C5—C6	178.4 (3)	C18—C19—C20—C21	−0.3 (5)
N1—C5—C6—C7	175.6 (3)	C19—C20—C21—C22	0.7 (5)
C4—C5—C6—C7	−4.9 (5)	C20—C21—C22—C17	−1.0 (5)
N1—C5—C6—C11	−2.6 (4)	C20—C21—C22—Ir1	179.5 (3)
C4—C5—C6—C11	176.9 (3)	C18—C17—C22—C21	1.0 (5)
C11—C6—C7—C8	−0.2 (5)	C16—C17—C22—C21	178.3 (3)
C5—C6—C7—C8	−178.3 (3)	C18—C17—C22—Ir1	−179.5 (2)
C6—C7—C8—C9	0.2 (5)	C16—C17—C22—Ir1	−2.1 (3)
C7—C8—C9—C10	−0.3 (5)	C11—Ir1—C22—C21	86.9 (3)
C8—C9—C10—C11	0.4 (5)	N1—Ir1—C22—C21	6.5 (3)
C9—C10—C11—C6	−0.3 (5)	N2—Ir1—C22—C21	−177.5 (3)
C9—C10—C11—Ir1	−177.7 (3)	N3—Ir1—C22—C21	−91.4 (3)
C7—C6—C11—C10	0.2 (5)	C11—Ir1—C22—C17	−92.6 (2)
C5—C6—C11—C10	178.5 (3)	N1—Ir1—C22—C17	−173.0 (2)
C7—C6—C11—Ir1	178.0 (2)	N2—Ir1—C22—C17	3.0 (2)
C5—C6—C11—Ir1	−3.7 (4)	N3—Ir1—C22—C17	89.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1ⁱ	0.95	2.78	3.600 (3)	145
C14—H14A···Cl1ⁱⁱ	0.95	2.80	3.470 (3)	129
C14—H14A···C23ⁱⁱⁱ	0.95	2.69	3.431 (4)	135
C8—H8A···C16^iv	0.95	2.79	3.595 (4)	143
C8—H8A···C17^iv	0.95	2.72	3.628 (4)	159
C8—H8A···C18^iv	0.95	2.79	3.705 (4)	163

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

Experimental details

Crystal data
Chemical formula	[Ir(C₁₁H₈N)₂Cl(C₂H₃N)]
M_r	577.07
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	171
a, b, c (Å)	16.5255 (8), 14.6588 (7), 17.0536 (8)
V (Å³)	4131.1 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.61
Crystal size (mm)	0.38 × 0.34 × 0.20

Data collection
Diffractometer	Siemens SMART 1K CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.176, 0.267
No. of measured, independent and observed [I > 2σ(I)] reflections	44325, 4772, 3899
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.040, 1.07
No. of reflections	4772
No. of parameters	263
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.67

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ir1—C11	2.004 (3)	Ir1—N2	2.047 (2)
Ir1—C22	2.007 (3)	Ir1—N3	2.129 (3)
Ir1—N1	2.043 (2)	Ir1—Cl1	2.4839 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1ⁱ	0.95	2.78	3.600 (3)	145
C14—H14A···Cl1ⁱⁱ	0.95	2.80	3.470 (3)	129
C14—H14A···C23ⁱⁱⁱ	0.95	2.69	3.431 (4)	135
C8—H8A···C16^iv	0.95	2.79	3.595 (4)	143
C8—H8A···C17^iv	0.95	2.72	3.628 (4)	159
C8—H8A···C18^iv	0.95	2.79	3.705 (4)	163

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

References

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Volume 67| Part 12| December 2011| Pages m1837-m1838

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