(3-Allyl-oxypicolinato-κN,O)bis-[3,5-difluoro-2-(2-pyrid-yl)phenyl-κC,N]iridium(III).

The title complex, [Ir(C(11)H(6)F(2)N)(2)(C(9)H(8)NO(3))], consists of one Ir(III) ion, two C,N-bidentate 3,5-difluoro-2-(2-pyrid-yl)phenyl (F(2)ppy) ligands and one N,O-bidentate 3-allyl-oxypicolinate (pic-3-Oall) ligand. The Ir(III) ion is hexa-coordinated by two C atoms and two N atoms from the F(2)ppy ligands and one N atom and one carboxyl-ate O atom from the pic-3-Oall ligand, displaying a distorted octa-hedral geometry. In the crystal structure, weak inter-molecular C-H⋯F and C-H⋯O hydrogen bonds link the complex mol-ecules into a three-dimensional supra-molecular structure.

Related literature

For general background to phospho­rescent materials, see: Baldo et al. (1998 ▶, 2000 ▶); Liang et al. (2006 ▶); Thompson (2007 ▶); Tsuboyama et al. (2003 ▶). For bond lengths in organic compounds, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ir(C11H6F2N)2(C9H8NO3)]

M = 750.70

Monoclinic,

a = 33.429 (4) Å

b = 9.9117 (12) Å

c = 16.0265 (19) Å

β = 94.107 (2)°

V = 5296.5 (11) Å3

Z = 8

Mo Kα radiation

μ = 5.11 mm−1

T = 185 K

0.31 × 0.23 × 0.03 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.305, T max = 0.862

14169 measured reflections

5087 independent reflections

4364 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.080

S = 1.05

5087 reflections

379 parameters

H-atom parameters constrained

Δρmax = 1.72 e Å−3

Δρmin = −0.59 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046479/hy2251sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046479/hy2251Isup2.hkl

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

[Ir(C11H6F2N)2(C9H8NO3)]	F(000) = 2912
Mr = 750.70	Dx = 1.883 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7056 reflections
a = 33.429 (4) Å	θ = 2.4–25.8°
b = 9.9117 (12) Å	µ = 5.11 mm−1
c = 16.0265 (19) Å	T = 185 K
β = 94.107 (2)°	Plate, yellow
V = 5296.5 (11) Å3	0.31 × 0.23 × 0.03 mm
Z = 8

Bruker SMART APEX CCD diffractometer	5087 independent reflections
Radiation source: sealed tube	4364 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 25.8°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −40→36
Tmin = 0.305, Tmax = 0.862	k = −12→12
14169 measured reflections	l = −11→19

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3
5087 reflections	(Δ/σ)max = 0.002
379 parameters	Δρmax = 1.72 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

	x	y	z	Uiso*/Ueq
Ir1	0.365597 (4)	0.187358 (14)	0.693663 (9)	0.03540 (8)
N1	0.32777 (11)	0.0250 (3)	0.6890 (2)	0.0416 (8)
N2	0.39933 (11)	0.3598 (4)	0.7072 (2)	0.0426 (8)
N3	0.38322 (11)	0.1393 (3)	0.5719 (2)	0.0401 (8)
O1	0.41710 (9)	0.0620 (3)	0.71739 (17)	0.0441 (7)
O2	0.45390 (11)	−0.0942 (4)	0.6590 (2)	0.0706 (10)
O3	0.45584 (9)	−0.0840 (3)	0.4921 (2)	0.0564 (8)
C1	0.33883 (15)	−0.1008 (4)	0.7107 (3)	0.0485 (11)
H1	0.3663	−0.1186	0.7259	0.058*
C2	0.31159 (19)	−0.2054 (5)	0.7119 (4)	0.0617 (14)
H2	0.3203	−0.2935	0.7280	0.074*
C3	0.2721 (2)	−0.1808 (5)	0.6897 (4)	0.0640 (16)
H3	0.2531	−0.2520	0.6897	0.077*
C4	0.25994 (15)	−0.0520 (5)	0.6672 (3)	0.0585 (12)
H4	0.2324	−0.0342	0.6521	0.070*
C5	0.28811 (13)	0.0521 (4)	0.6665 (3)	0.0441 (10)
C6	0.28083 (15)	0.1936 (4)	0.6436 (3)	0.0453 (11)
C7	0.31502 (13)	0.2809 (4)	0.6563 (3)	0.0409 (10)
C8	0.30985 (14)	0.4155 (4)	0.6320 (3)	0.0503 (11)
H8	0.3314	0.4776	0.6405	0.060*
C9	0.27359 (16)	0.4575 (5)	0.5961 (3)	0.0582 (12)
C10	0.24033 (16)	0.3774 (5)	0.5840 (3)	0.0613 (14)
H10	0.2156	0.4105	0.5592	0.074*
C11	0.24501 (13)	0.2484 (5)	0.6095 (3)	0.0536 (12)
C12	0.41786 (14)	0.4204 (4)	0.6459 (3)	0.0521 (11)
H12	0.4174	0.3770	0.5930	0.062*
C13	0.43741 (16)	0.5417 (5)	0.6554 (4)	0.0663 (14)
H13	0.4494	0.5824	0.6097	0.080*
C14	0.43921 (18)	0.6028 (5)	0.7324 (4)	0.0722 (16)
H14	0.4527	0.6865	0.7409	0.087*
C15	0.42135 (16)	0.5422 (5)	0.7969 (3)	0.0639 (14)
H15	0.4229	0.5834	0.8505	0.077*
C16	0.40075 (13)	0.4197 (4)	0.7843 (3)	0.0458 (10)
C17	0.37829 (14)	0.3462 (4)	0.8450 (3)	0.0446 (10)
C18	0.35732 (12)	0.2308 (4)	0.8132 (3)	0.0378 (9)
C19	0.33531 (14)	0.1565 (4)	0.8687 (3)	0.0434 (10)
H19	0.3199	0.0808	0.8492	0.052*
C20	0.33618 (17)	0.1936 (4)	0.9511 (3)	0.0525 (13)
C21	0.35735 (19)	0.3014 (5)	0.9836 (4)	0.0683 (16)
H21	0.3583	0.3225	1.0416	0.082*
C22	0.37700 (17)	0.3773 (5)	0.9289 (3)	0.0649 (14)
C23	0.43021 (13)	−0.0015 (4)	0.6533 (3)	0.0446 (10)
C24	0.41319 (12)	0.0496 (4)	0.5690 (3)	0.0383 (9)
C25	0.42684 (13)	0.0104 (4)	0.4908 (3)	0.0437 (10)
C26	0.41040 (14)	0.0726 (5)	0.4191 (3)	0.0542 (12)
H26	0.4201	0.0518	0.3663	0.065*
C27	0.38003 (17)	0.1647 (5)	0.4247 (3)	0.0535 (13)
H27	0.3682	0.2063	0.3756	0.064*
C28	0.36687 (15)	0.1963 (4)	0.5008 (3)	0.0458 (11)
H28	0.3457	0.2598	0.5040	0.055*
C29	0.46854 (15)	−0.1295 (6)	0.4130 (3)	0.0619 (13)
H29A	0.4832	−0.0568	0.3858	0.074*
H29B	0.4450	−0.1555	0.3754	0.074*
C30	0.49507 (17)	−0.2473 (7)	0.4297 (5)	0.0751 (17)
H30	0.5047	−0.2911	0.3824	0.090*
C31	0.5065 (2)	−0.2967 (5)	0.5026 (5)	0.080 (2)
H31A	0.4976	−0.2565	0.5518	0.097*
H31B	0.5237	−0.3731	0.5067	0.097*
F1	0.27033 (10)	0.5876 (3)	0.5693 (2)	0.0866 (10)
F2	0.21199 (9)	0.1647 (3)	0.5980 (2)	0.0759 (9)
F3	0.31653 (10)	0.1165 (3)	1.00528 (17)	0.0748 (9)
F4	0.39817 (14)	0.4857 (3)	0.9610 (2)	0.1073 (14)

	U11	U22	U33	U12	U13	U23
Ir1	0.03972 (12)	0.03992 (11)	0.02690 (11)	−0.00128 (6)	0.00483 (8)	−0.00145 (6)
N1	0.051 (2)	0.0460 (19)	0.0293 (19)	−0.0108 (16)	0.0137 (16)	−0.0091 (15)
N2	0.045 (2)	0.0455 (18)	0.038 (2)	−0.0053 (17)	0.0091 (17)	0.0043 (17)
N3	0.047 (2)	0.0424 (17)	0.0316 (19)	0.0009 (16)	0.0072 (16)	−0.0010 (16)
O1	0.0496 (17)	0.0548 (16)	0.0270 (15)	0.0049 (14)	−0.0033 (13)	0.0029 (14)
O2	0.085 (3)	0.074 (2)	0.053 (2)	0.038 (2)	0.0088 (19)	0.0119 (18)
O3	0.0536 (19)	0.0692 (19)	0.0477 (19)	0.0164 (16)	0.0118 (16)	−0.0069 (16)
C1	0.064 (3)	0.049 (2)	0.034 (2)	−0.008 (2)	0.009 (2)	−0.0010 (19)
C2	0.087 (4)	0.055 (3)	0.045 (3)	−0.016 (3)	0.013 (3)	−0.004 (2)
C3	0.078 (4)	0.065 (3)	0.051 (3)	−0.026 (3)	0.019 (3)	−0.009 (2)
C4	0.053 (3)	0.074 (3)	0.049 (3)	−0.019 (3)	0.009 (2)	−0.010 (3)
C5	0.046 (2)	0.058 (2)	0.030 (2)	−0.010 (2)	0.0149 (19)	−0.009 (2)
C6	0.042 (3)	0.061 (3)	0.034 (3)	0.002 (2)	0.008 (2)	−0.012 (2)
C7	0.045 (2)	0.051 (2)	0.028 (2)	0.0021 (19)	0.0061 (19)	−0.0085 (18)
C8	0.050 (3)	0.053 (2)	0.048 (3)	0.005 (2)	0.004 (2)	−0.009 (2)
C9	0.065 (3)	0.055 (3)	0.055 (3)	0.018 (2)	0.004 (3)	−0.011 (2)
C10	0.055 (3)	0.076 (3)	0.052 (3)	0.024 (3)	0.002 (2)	−0.016 (3)
C11	0.040 (3)	0.074 (3)	0.047 (3)	0.003 (2)	0.008 (2)	−0.015 (3)
C12	0.057 (3)	0.057 (3)	0.044 (3)	−0.010 (2)	0.015 (2)	0.008 (2)
C13	0.074 (4)	0.067 (3)	0.060 (3)	−0.021 (3)	0.016 (3)	0.013 (3)
C14	0.082 (4)	0.054 (3)	0.082 (4)	−0.025 (3)	0.011 (3)	0.003 (3)
C15	0.082 (4)	0.052 (3)	0.058 (3)	−0.022 (3)	0.010 (3)	−0.006 (2)
C16	0.055 (3)	0.042 (2)	0.040 (2)	−0.003 (2)	0.003 (2)	−0.0020 (19)
C17	0.056 (3)	0.045 (2)	0.034 (2)	−0.005 (2)	0.008 (2)	−0.0061 (19)
C18	0.042 (2)	0.0404 (19)	0.031 (2)	0.0027 (18)	0.0018 (18)	−0.0042 (18)
C19	0.050 (3)	0.049 (2)	0.032 (2)	−0.006 (2)	0.011 (2)	−0.0047 (19)
C20	0.067 (3)	0.055 (3)	0.038 (3)	−0.007 (2)	0.020 (3)	−0.003 (2)
C21	0.089 (4)	0.077 (4)	0.041 (3)	−0.016 (3)	0.019 (3)	−0.013 (3)
C22	0.097 (4)	0.055 (3)	0.044 (3)	−0.022 (3)	0.012 (3)	−0.020 (2)
C23	0.047 (3)	0.048 (2)	0.040 (3)	0.003 (2)	0.011 (2)	0.002 (2)
C24	0.042 (2)	0.0396 (19)	0.034 (2)	−0.0034 (18)	0.0066 (18)	−0.0004 (18)
C25	0.041 (2)	0.048 (2)	0.042 (3)	−0.0038 (19)	0.010 (2)	−0.005 (2)
C26	0.057 (3)	0.068 (3)	0.039 (3)	−0.006 (2)	0.013 (2)	−0.006 (2)
C27	0.062 (3)	0.071 (3)	0.027 (2)	0.007 (2)	0.000 (2)	0.003 (2)
C28	0.053 (3)	0.052 (2)	0.033 (2)	0.0068 (19)	0.004 (2)	−0.0005 (19)
C29	0.058 (3)	0.077 (3)	0.053 (3)	0.008 (3)	0.015 (3)	−0.021 (3)
C30	0.059 (3)	0.081 (4)	0.087 (5)	0.011 (3)	0.017 (3)	−0.022 (4)
C31	0.071 (4)	0.063 (3)	0.110 (6)	0.009 (3)	0.025 (4)	0.000 (3)
F1	0.090 (2)	0.0581 (16)	0.109 (3)	0.0262 (16)	−0.015 (2)	−0.0043 (17)
F2	0.0428 (16)	0.101 (2)	0.082 (3)	−0.0054 (15)	−0.0077 (16)	−0.0100 (18)
F3	0.100 (2)	0.087 (2)	0.0399 (16)	−0.0301 (18)	0.0257 (16)	−0.0026 (15)
F4	0.177 (4)	0.092 (2)	0.055 (2)	−0.071 (2)	0.024 (2)	−0.0337 (18)

Ir1—C7	1.983 (4)	C12—C13	1.371 (6)
Ir1—C18	2.002 (4)	C12—H12	0.9500
Ir1—N1	2.045 (3)	C13—C14	1.373 (8)
Ir1—N2	2.051 (4)	C13—H13	0.9500
Ir1—N3	2.132 (3)	C14—C15	1.368 (7)
Ir1—O1	2.135 (3)	C14—H14	0.9500
N1—C1	1.339 (5)	C15—C16	1.404 (6)
N1—C5	1.375 (6)	C15—H15	0.9500
N2—C12	1.341 (5)	C16—C17	1.465 (6)
N2—C16	1.367 (6)	C17—C22	1.384 (6)
N3—C24	1.343 (5)	C17—C18	1.417 (6)
N3—C28	1.352 (6)	C18—C19	1.404 (6)
O1—C23	1.307 (5)	C19—C20	1.369 (7)
O2—C23	1.212 (5)	C19—H19	0.9500
O3—C25	1.346 (5)	C20—F3	1.361 (5)
O3—C29	1.438 (6)	C20—C21	1.365 (7)
C1—C2	1.381 (7)	C21—C22	1.359 (7)
C1—H1	0.9500	C21—H21	0.9500
C2—C3	1.364 (9)	C22—F4	1.367 (5)
C2—H2	0.9500	C23—C24	1.514 (6)
C3—C4	1.380 (7)	C24—C25	1.419 (6)
C3—H3	0.9500	C25—C26	1.383 (6)
C4—C5	1.398 (6)	C26—C27	1.373 (7)
C4—H4	0.9500	C26—H26	0.9500
C5—C6	1.465 (6)	C27—C28	1.362 (7)
C6—C11	1.391 (7)	C27—H27	0.9500
C6—C7	1.436 (6)	C28—H28	0.9500
C7—C8	1.397 (6)	C29—C30	1.479 (8)
C8—C9	1.369 (7)	C29—H29A	0.9900
C8—H8	0.9500	C29—H29B	0.9900
C9—F1	1.360 (5)	C30—C31	1.299 (10)
C9—C10	1.369 (7)	C30—H30	0.9500
C10—C11	1.349 (8)	C31—H31A	0.9500
C10—H10	0.9500	C31—H31B	0.9500
C11—F2	1.382 (5)
C7—Ir1—C18	90.86 (17)	C13—C12—H12	118.2
C7—Ir1—N1	81.10 (16)	C12—C13—C14	118.5 (5)
C18—Ir1—N1	94.43 (15)	C12—C13—H13	120.7
C7—Ir1—N2	95.32 (15)	C14—C13—H13	120.7
C18—Ir1—N2	80.32 (16)	C15—C14—C13	119.4 (5)
N1—Ir1—N2	173.64 (13)	C15—C14—H14	120.3
C7—Ir1—N3	96.53 (15)	C13—C14—H14	120.3
C18—Ir1—N3	171.88 (15)	C14—C15—C16	120.5 (5)
N1—Ir1—N3	90.06 (13)	C14—C15—H15	119.7
N2—Ir1—N3	95.59 (14)	C16—C15—H15	119.7
C7—Ir1—O1	170.11 (14)	N2—C16—C15	119.3 (4)
C18—Ir1—O1	96.88 (14)	N2—C16—C17	113.4 (3)
N1—Ir1—O1	92.13 (13)	C15—C16—C17	127.2 (4)
N2—Ir1—O1	92.06 (13)	C22—C17—C18	118.7 (4)
N3—Ir1—O1	76.16 (12)	C22—C17—C16	126.0 (4)
C1—N1—C5	119.6 (4)	C18—C17—C16	115.2 (4)
C1—N1—Ir1	124.4 (3)	C19—C18—C17	117.6 (4)
C5—N1—Ir1	116.0 (3)	C19—C18—Ir1	127.5 (3)
C12—N2—C16	118.7 (4)	C17—C18—Ir1	114.8 (3)
C12—N2—Ir1	125.1 (3)	C20—C19—C18	119.7 (4)
C16—N2—Ir1	116.1 (3)	C20—C19—H19	120.2
C24—N3—C28	120.4 (4)	C18—C19—H19	120.2
C24—N3—Ir1	115.8 (3)	F3—C20—C21	117.2 (5)
C28—N3—Ir1	123.8 (3)	F3—C20—C19	119.1 (4)
C23—O1—Ir1	116.9 (3)	C21—C20—C19	123.6 (5)
C25—O3—C29	117.5 (4)	C22—C21—C20	116.6 (5)
N1—C1—C2	122.2 (5)	C22—C21—H21	121.7
N1—C1—H1	118.9	C20—C21—H21	121.7
C2—C1—H1	118.9	C21—C22—F4	117.0 (5)
C3—C2—C1	119.3 (5)	C21—C22—C17	123.7 (4)
C3—C2—H2	120.4	F4—C22—C17	119.3 (5)
C1—C2—H2	120.4	O2—C23—O1	124.1 (4)
C2—C3—C4	119.7 (5)	O2—C23—C24	121.4 (4)
C2—C3—H3	120.2	O1—C23—C24	114.5 (4)
C4—C3—H3	120.2	N3—C24—C25	120.0 (4)
C3—C4—C5	119.9 (5)	N3—C24—C23	115.1 (4)
C3—C4—H4	120.0	C25—C24—C23	124.9 (4)
C5—C4—H4	120.0	O3—C25—C26	124.4 (4)
N1—C5—C4	119.4 (4)	O3—C25—C24	117.0 (4)
N1—C5—C6	113.1 (4)	C26—C25—C24	118.6 (4)
C4—C5—C6	127.5 (4)	C27—C26—C25	119.6 (4)
C11—C6—C7	118.3 (4)	C27—C26—H26	120.2
C11—C6—C5	126.5 (4)	C25—C26—H26	120.2
C7—C6—C5	115.2 (4)	C28—C27—C26	120.0 (5)
C8—C7—C6	117.0 (4)	C28—C27—H27	120.0
C8—C7—Ir1	128.1 (3)	C26—C27—H27	120.0
C6—C7—Ir1	114.4 (3)	N3—C28—C27	121.4 (4)
C9—C8—C7	119.8 (4)	N3—C28—H28	119.3
C9—C8—H8	120.1	C27—C28—H28	119.3
C7—C8—H8	120.1	O3—C29—C30	107.4 (5)
F1—C9—C8	118.0 (5)	O3—C29—H29A	110.2
F1—C9—C10	117.3 (4)	C30—C29—H29A	110.2
C8—C9—C10	124.6 (5)	O3—C29—H29B	110.2
C11—C10—C9	115.6 (4)	C30—C29—H29B	110.2
C11—C10—H10	122.2	H29A—C29—H29B	108.5
C9—C10—H10	122.2	C31—C30—C29	126.5 (6)
C10—C11—F2	117.0 (4)	C31—C30—H30	116.7
C10—C11—C6	124.6 (5)	C29—C30—H30	116.7
F2—C11—C6	118.4 (5)	C30—C31—H31A	120.0
N2—C12—C13	123.5 (5)	C30—C31—H31B	120.0
N2—C12—H12	118.2	H31A—C31—H31B	120.0

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F1i	0.95	2.60	2.997 (6)	106
C28—H28···F2ii	0.95	2.55	3.280 (6)	134
C10—H10···F3iii	0.95	2.50	3.299 (6)	142
C12—H12···F4iv	0.95	2.56	3.130 (6)	119
C26—H26···O1v	0.95	2.63	3.519 (5)	155
C14—H14···O2vi	0.95	2.54	3.275 (6)	134

Table 1

Selected bond lengths (Å)

Ir1—C7	1.983 (4)
Ir1—C18	2.002 (4)
Ir1—N1	2.045 (3)
Ir1—N2	2.051 (4)
Ir1—N3	2.132 (3)
Ir1—O1	2.135 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F1i	0.95	2.60	2.997 (6)	106
C28—H28⋯F2ii	0.95	2.55	3.280 (6)	134
C10—H10⋯F3iii	0.95	2.50	3.299 (6)	142
C12—H12⋯F4iv	0.95	2.56	3.130 (6)	119
C26—H26⋯O1v	0.95	2.63	3.519 (5)	155
C14—H14⋯O2vi	0.95	2.54	3.275 (6)	134

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .