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May 18, 2016 - C7–C11, C12–C17 and C30–C35 rings, respectively; symmetry research communications. Acta Cryst. (2016). E72, 838–840. Goo et al.
research communications

ISSN 2056-9890

Crystal structure of {(E)-2-[(phenylimino)methyl]phenolato-j2N,O}bis[2-(pyridin-2-yl)phenylj2C 1,N]iridium(III) dichloromethane monosolvate Moo-Sung Goo,a Ki-Min Parkb* and Hee-Joon Kima* a

Received 28 April 2016 Accepted 18 May 2016

Edited by M. Weil, Vienna University of Technology, Austria Keywords: crystal structure; iridium(III) complex; C2N3O coordination set. CCDC reference: 1480710 Supporting information: this article has supporting information at journals.iucr.org/e

Department of Applied Chemistry, Kumoh National Institute of Technology, Gumi 39177, Republic of Korea, and Research institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea. *Correspondence e-mail: [email protected], [email protected] b

In the title compound, [Ir(C11H8N)2(C13H10NO)]CH2Cl2, the IrIII ion is sixcoordinated by two C,N-bidentate 2-(pyridin-2-yl)phenyl ligands and one N,Obidentate 2-[(phenylimino)methyl]phenolate anion, giving rise to a distorted octahedral environment. The C,N-bidentate ligands, in which the C and N atoms are statistically disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other, are almost perpendicular to each other [the dihedral angle between the least-square planes is 87.00 (4) ]. An intramolecular C—H  O hydrogen bond, as well as intermolecular C—H   interactions and – interactions, contribute to the stabilization of the molecular and crystal structure.

1. Chemical context Cyclometallated IrIII complexes are of great interest due to their excellent phosphorescent properties and electroluminescence applications. In particular, heteroleptic IrIII complexes with imine-based ancillary ligands exhibit aggregation-induced phosphorescent emission (AIPE), resulting in enhanced phosphorescence phenomena in the solid state (Howarth et al., 2014; You et al., 2008; Zhao et al., 2008). To uncover the origin of the intriguing AIPE, it is crucial to analyse the solid-state structures of relevant IrIII complexes besides undertaking spectroscopic and theoretical investigations. Here we report the crystal structure of the title compound, [Ir(C11H8N)2(C13H10NO)]CH2Cl2, a heteroleptic IrIII complex with an ancillary salicylimine ligand.

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http://dx.doi.org/10.1107/S2056989016008100

Acta Cryst. (2016). E72, 838–840

research communications Table 1

Table 2

˚ ,  ). Selected geometric parameters (A

˚ ,  ). Hydrogen-bond geometry (A

Ir1—C12 Ir1—C1 Ir1—N2 C12—Ir1—C1 C12—Ir1—N2 C1—Ir1—N2 C12—Ir1—N1 C1—Ir1—N1 N2—Ir1—N1 C12—Ir1—O1 C1—Ir1—O1

1.997 (2) 2.004 (2) 2.0302 (18) 87.97 (9) 80.69 (8) 96.62 (8) 95.15 (8) 80.42 (8) 175.02 (7) 175.01 (7) 90.14 (8)

Ir1—N1 Ir1—O1 Ir1—N3 N2—Ir1—O1 N1—Ir1—O1 C12—Ir1—N3 C1—Ir1—N3 N2—Ir1—N3 N1—Ir1—N3 O1—Ir1—N3

2.0424 (18) 2.1409 (16) 2.1551 (19) 94.95 (7) 89.08 (7) 94.96 (8) 176.86 (7) 84.99 (7) 98.16 (7) 87.04 (7)

2. Structural commentary The molecular components of the title structure are shown in Fig. 1. The asymmetric unit consists of one IrIII ion, two 2-(pyridin-2-yl)phenyl ligands, and one 2-[(phenylimino)methyl]phenolate anion. The IrIII ion adopts a distorted octahedral coordination geometry, being N,O-chelated by the 2-[(phenylimino)methyl]phenolate ligand and C,N-chelated by two 2-(pyridin-2-yl)phenyl ligands, in which the C and N atoms are equally disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other. The equatorial plane is formed by N1/O1/N2/C12 atoms, the mean deviation from the least-squares plane being ˚ . The IrIII ion is displaced by 0.0481 (9) A ˚ from the 0.002 A

Cg2 and Cg3 are the centroids of the C1–C6 and C12–C17 rings, respectively. D—H  A

D—H

H  A

D  A

D—H  A

C22—H22  O1 C21—H21  Cg2i C36—H36A  Cg2 C36—H36B  Cg3

0.95 0.95 0.99 0.99

2.54 2.90 2.62 2.59

3.132 (3) 3.658 (3) 3.444 (4) 3.498 (4)

121 138 140 153

Symmetry code: (i) x þ 1; y þ 1; z þ 1.

equatorial plane towards the axial imino N3 atom. The C,Nbidentate ligands are nearly perpendicular to each other, with a dihedral angle between the least-squares planes of 87.00 (4) . Within the C,N-bidentate ligands, the dihedral angles between the aromatic rings are 3.70 (10) (between rings C1–C6 and N1/C7–C11) and 7.67 (16) (between rings C12– C17 and N2/C18–C22). As shown in Table 1, the Ir—C, Ir—N and Ir—O bond lengths of the title compound are within the ranges reported for similar IrIII compounds, e.g. {(E)-2-[(2,6diisopropylphenylimino)methyl]phenolato-2N,O}bis(2-phenylpyridine-2C,N)iridium(III) (Howarth et al., 2014), {(E)-2[(naphthalene-1-ylimino)methyl]phenolato-2 N,O}bis(2phenylpyridine-2C,N)iridium(III) (Zhao et al., 2008), or {(E)2-[(phenylimino)methyl]phenolato-2N,O}bis[2-(2,4-difluorophenyl)pyridine-2C,N]iridium(III) (You et al., 2008).

3. Supramolecular features The molecular structure of the title compound is stabilized by an intramolecular C—H  O hydrogen bond and intermolecular C—H   interactions between the dichloromethane solvent molecule and the phenyl rings of the C,Nbidentate ligand (Fig. 1 and Table 2). Additionally, intermolecular C—H   interactions (Table 2) and – inter˚ and Cg3  Cg4 = actions [Cg1  Cg1ii = 3.6231 (12) A ˚ ; Cg1, Cg3 and Cg4 are the centroids of the N1/ 3.8873 (17) A C7–C11, C12–C17 and C30–C35 rings, respectively; symmetry

Figure 1

Figure 2

View of the molecular structure of the title compound, showing the atomnumbering scheme. Displacement ellipsoids are drawn at the 50% probability level; red and sky-blue dashed lines represent intermolecular C—H   hydrogen bonds and intramolecular – interactions, respectively. H atoms have been omitted for clarity.

Packing plot of the molecular components in the title compound. Yellow and black dashed lines represent intermolecular C—H   and – stacking interactions, respectively. H atoms not involved in intermolecular interactions and dichloromethane solvent molecules have been omitted for clarity.

Acta Cryst. (2016). E72, 838–840

Goo et al.



[Ir(C11H8N)2(C13H10NO)]CH2Cl2

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research communications Table 3

diffraction were grown by slow diffusion of n-hexane into a CH2Cl2 solution of the title compound at room temperature.

Experimental details. Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A , ,  ( ) ˚ 3) V (A Z Radiation type  (mm1) Crystal size (mm) Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin / )max (A Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters H-atom treatment ˚ 3)  max,  min (e A

[Ir(C11H8N)2(C13H10NO)]CH2Cl2 781.71 Triclinic, P1 130 11.8318 (2), 12.0638 (4), 12.3169 (2) 98.260 (1), 114.283 (1), 101.418 (1) 1520.15 (6) 2 Mo K 4.60 0.15  0.09  0.05

Bruker APEXII CCD Multi-scan (SADABS; Bruker, 2013) 0.614, 0.877 25306, 7425, 6973 0.020 0.666

code: (ii) x + 1, y + 2, z + 1] contribute to the stabilization of the crystal structure (Fig. 2).

4. Synthesis and crystallization The title compound was prepared according to a reported procedure (You et al., 2008). Single crystals suitable for X-ray

Goo et al.



Crystal data, data collection and structure refinement details are summarized in Table 3. The positions of the N atoms in the 2-(pyridin-2-yl)phenyl unit could not be discriminated from the difference in the displacement parameters, and free refinement of the N and C atoms revealed a lower and higher electron density, respectively, as expected for full occupancy and without disorder. Therefore, atoms N1 and C1A, C11 and N1A, N2 and C2A, and C22 and N2A were refined at the same sites with site occupancy factors of 0.5 using EXYZ/EADP constrains. All H atoms were positioned geometrically and ˚ for Csp2—H refined using a riding model, with C—H = 0.95 A ˚ and 0.99 A for methylene C—H. For all H atoms, Uiso(H) = 1.2Ueq of the parent atom.

Acknowledgements 0.019, 0.047, 1.08 7425 388 H-atom parameters constrained 1.45, 1.25

Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and DIAMOND (Brandenburg, 2010).

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5. Refinement

[Ir(C11H8N)2(C13H10NO)]CH2Cl2

This work was supported by Kumoh National Institute of Technology.

References Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Howarth, A. J., Patia, R., Davies, D. L., Lelj, F., Wolf, M. O. & Singh, K. (2014). Eur. J. Inorg. Chem. pp. 3657–3664. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. You, Y., Huh, H. S., Kim, K. S., Lee, S. W., Kim, D. & Park, S. Y. (2008). Chem. Commun. pp. 3998–4000. Zhao, Q., Li, L., Li, F., Yu, M., Liu, Z., Yi, T. & Huang, C. (2008). Chem. Commun. pp. 685–687.

Acta Cryst. (2016). E72, 838–840

supporting information

supporting information Acta Cryst. (2016). E72, 838-840

[doi:10.1107/S2056989016008100]

Crystal structure of {(E)-2-[(phenylimino)methyl]phenolato-κ2N,O}bis[2-(pyridin-2-yl)phenyl-κ2C1,N]iridium(III) dichloromethane monosolvate Moo-Sung Goo, Ki-Min Park and Hee-Joon Kim Computing details Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). {(E)-2-[(Phenylimino)methyl]phenolato-κ2N,O}bis[2-(pyridin-2-yl)phenyl-κ2C1,N]iridium(III) dichloromethane monosolvate Crystal data [Ir(C11H8N)2(C13H10NO)]·CH2Cl2 Mr = 781.71 Triclinic, P1 a = 11.8318 (2) Å b = 12.0638 (4) Å c = 12.3169 (2) Å α = 98.260 (1)° β = 114.283 (1)° γ = 101.418 (1)° V = 1520.15 (6) Å3

Z=2 F(000) = 768 Dx = 1.708 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25306 reflections θ = 1.8–28.3° µ = 4.60 mm−1 T = 130 K Plate, yellow 0.15 × 0.09 × 0.05 mm

Data collection Bruker APEXII CCD diffractometer φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2013) Tmin = 0.614, Tmax = 0.877 25306 measured reflections

7425 independent reflections 6973 reflections with I > 2σ(I) Rint = 0.020 θmax = 28.3°, θmin = 1.8° h = −15→15 k = −16→16 l = −15→16

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.019 wR(F2) = 0.047 S = 1.08 7425 reflections 388 parameters 0 restraints

Acta Cryst. (2016). E72, 838-840

Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0286P)2 + 0.6203P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.003 Δρmax = 1.45 e Å−3 Δρmin = −1.25 e Å−3

sup-1

supporting information Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Ir1 Cl1 Cl2 C36 H36A H36B O1 N1 C1A N2 C2A N3 C1 N1A C2 H2 C3 H3 C4 H4 C5 H5 C6 C7 C8 H8 C9 H9 C10 H10 C11 H11 C12 N12A C13 H13 C14 H14 C15

x

y

z

Uiso*/Ueq

0.61255 (2) 0.23841 (8) 0.13261 (10) 0.2462 (3) 0.2294 0.3341 0.62551 (15) 0.58415 (18) 0.58415 (18) 0.62991 (18) 0.62991 (18) 0.82100 (18) 0.4191 (2) 0.4191 (2) 0.3326 (2) 0.3656 0.1996 (2) 0.1437 0.1480 (2) 0.0572 0.2310 (2) 0.1968 0.3646 (2) 0.4586 (2) 0.4294 (2) 0.3417 0.5277 (2) 0.5087 0.6555 (2) 0.7250 0.6799 (2) 0.7671 0.5938 (2) 0.5938 (2) 0.5758 (2) 0.5702 0.5659 (2) 0.5557 0.5709 (2)

0.74630 (2) 0.81561 (9) 0.57002 (9) 0.7010 (3) 0.7215 0.6908 0.70735 (14) 0.90242 (16) 0.90242 (16) 0.59058 (16) 0.59058 (16) 0.80078 (16) 0.69766 (19) 0.69766 (19) 0.5863 (2) 0.5232 0.5657 (2) 0.4889 0.6570 (2) 0.6428 0.7689 (2) 0.8317 0.78903 (19) 0.90398 (19) 1.0079 (2) 1.0088 1.1096 (2) 1.1804 1.1059 (2) 1.1744 1.00236 (19) 1.0009 0.76773 (19) 0.76773 (19) 0.8649 (2) 0.9308 0.8671 (2) 0.9348 0.7710 (2)

0.71617 (2) 0.92075 (9) 0.79287 (9) 0.8194 (3) 0.7402 0.8553 0.54724 (15) 0.68412 (17) 0.68412 (17) 0.75448 (18) 0.75448 (18) 0.80795 (17) 0.6226 (2) 0.6226 (2) 0.5879 (2) 0.6112 0.5204 (2) 0.4971 0.4865 (2) 0.4407 0.5207 (2) 0.4986 0.5875 (2) 0.6250 (2) 0.6042 (2) 0.5654 0.6400 (2) 0.6249 0.6987 (2) 0.7240 0.7197 (2) 0.7606 0.8711 (2) 0.8711 (2) 0.9321 (2) 0.8983 1.0412 (2) 1.0818 1.0910 (2)

0.01224 (3) 0.0577 (2) 0.0624 (3) 0.0384 (7) 0.046* 0.046* 0.0181 (3) 0.0112 (4) 0.0112 (4) 0.0118 (4) 0.0118 (4) 0.0152 (4) 0.0212 (4) 0.0212 (4) 0.0195 (5) 0.023* 0.0233 (5) 0.028* 0.0261 (5) 0.031* 0.0226 (5) 0.027* 0.0169 (4) 0.0162 (4) 0.0209 (5) 0.025* 0.0230 (5) 0.028* 0.0216 (5) 0.026* 0.0186 (4) 0.022* 0.0200 (4) 0.0200 (4) 0.0188 (4) 0.023* 0.0217 (5) 0.026* 0.0239 (5)

Acta Cryst. (2016). E72, 838-840

Occ. (