Azido-(η(5)-penta-methyl-cyclo-penta-dien-yl)[2-(pyridin-2-yl)phen-yl]iridium(III).

In the title compound, [Ir(C10H15)(C11H8N)(N3)], the Ir(III) ion is coordinated by three anionic ligands, namely, penta-methyl-cyclo-penta-dienyl (Cp*(-)), 2-(pyridin-2-yl)phenyl (ppy(-)) and azide (N3 (-)), and adopts a three-legged piano-stool geometry The coordination mode of N3 (-) is typical for Cp*Ir(III)-N3 complexes, with an Ir-N(N3) bond length of 2.125 (2) Å and an Ir-N=N bond angle of 116.5 (2)°. The N3 (-) ligand is almost linear [N=N=N = 176.0 (3)°], and the N=N bond length between the central and coordinating N atom and that between the central and non-coordinating terminal N atom are 1.194 (3) and 1.157 (3) Å, respectively. For the ppy(-) ligand, the Ir-C and Ir-N bond lengths are 2.066 (3) and 2.079 (3) Å, respectively, which are rather close to each other, compared to the related Ir(III)- or Rh(III)-ppy complexes. The Ir-C(Cp*) bond lengths vary in the range 2.163 (2)-2.232 (2) Å, indicating a strong trans influence of the cyclo-metallated C-donor atom of the ppy(-) ligand.

Related literature

For crystallographic analyses of [Cp*IrIII(N3)(L–L′)] (L–L′ = bidentate chelate ligands; e.g., bpy, 2-Spy, etc.) complexes, see: Suzuki et al. (2009 ▶); Suzuki (2005 ▶). For crystallographic analyses of mononuclear [Cp*Ir(ppy)X] complexes (X = Cl, I, MeCN4, etc.), see: Boutadla et al. (2009 ▶); Park-Gehrke et al. (2009 ▶); Takayama et al. (2013 ▶). For photochemistry of [Cp*IrIII(N3)(L–L′)] complexes, see: Sekioka et al. (2005 ▶); Kotera et al. (2008 ▶).

Experimental

Crystal data

[Ir(C10H15)(C11H8N)(N3)]

M = 523.63

Monoclinic,

a = 15.4821 (18) Å

b = 7.3938 (9) Å

c = 15.7137 (18) Å

β = 91.477 (4)°

V = 1798.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 7.44 mm−1

T = 193 K

0.30 × 0.30 × 0.20 mm

Data collection

Rigaku R-AXIS RAPIDII diffractometer

Absorption correction: numerical (NUMABS; Rigaku, 1999 ▶) T min = 0.103, T max = 0.225

27640 measured reflections

4115 independent reflections

4022 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.042

S = 1.13

4115 reflections

240 parameters

H-atom parameters constrained

Δρmax = 1.61 e Å−3

Δρmin = −0.65 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2006 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: DIRDIF99-PATTY (Beurskens et al., 1999 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813026159/is5306sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026159/is5306Isup2.hkl

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

[Ir(C10H15)(C11H8N)(N3)]	F(000) = 1016
Mr = 523.63	Dx = 1.934 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
a = 15.4821 (18) Å	Cell parameters from 17777 reflections
b = 7.3938 (9) Å	θ = 3.0–27.5°
c = 15.7137 (18) Å	µ = 7.44 mm−1
β = 91.477 (4)°	T = 193 K
V = 1798.2 (4) Å3	Needle, orange
Z = 4	0.30 × 0.30 × 0.20 mm

Rigaku R-AXIS RAPIDII diffractometer	4022 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm-1	Rint = 0.045
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −20→20
Tmin = 0.103, Tmax = 0.225	k = −9→9
27640 measured reflections	l = −20→20
4115 independent reflections

Refinement on F2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.042	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0078P)2 + 2.039P] where P = (Fo2 + 2Fc2)/3
4115 reflections	(Δ/σ)max = 0.002
240 parameters	Δρmax = 1.61 e Å−3
0 restraints	Δρmin = −0.65 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ir1	0.50470 (2)	0.26864 (2)	0.74054 (2)	0.01605 (4)
N22	0.42229 (13)	0.3666 (3)	0.64468 (14)	0.0241 (4)
N1	0.55974 (13)	0.5315 (3)	0.73529 (14)	0.0252 (4)
N2	0.58798 (13)	0.5919 (3)	0.80076 (14)	0.0247 (4)
N3	0.61722 (17)	0.6587 (3)	0.86156 (16)	0.0384 (6)
C1	0.51540 (15)	−0.0120 (3)	0.70066 (15)	0.0194 (5)
C2	0.50048 (15)	−0.0035 (3)	0.79079 (15)	0.0189 (5)
C3	0.57313 (15)	0.0883 (3)	0.83098 (15)	0.0217 (5)
C4	0.63164 (15)	0.1339 (3)	0.76593 (16)	0.0229 (5)
C5	0.59759 (15)	0.0731 (3)	0.68515 (16)	0.0218 (5)
C6	0.46049 (17)	−0.1057 (3)	0.63532 (16)	0.0261 (5)
H6A	0.4003	−0.1058	0.6532	0.039*
H6B	0.4805	−0.2306	0.6289	0.039*
H6C	0.4645	−0.0424	0.5808	0.039*
C7	0.42773 (16)	−0.0905 (3)	0.83631 (17)	0.0262 (5)
H7A	0.4470	−0.2067	0.8600	0.039*
H7B	0.3791	−0.1104	0.7963	0.039*
H7C	0.4094	−0.0113	0.8825	0.039*
C8	0.59008 (19)	0.1038 (4)	0.92487 (17)	0.0331 (6)
H8A	0.6274	0.2084	0.9366	0.050*
H8B	0.6187	−0.0064	0.9458	0.050*
H8C	0.5352	0.1195	0.9537	0.050*
C9	0.71557 (18)	0.2319 (4)	0.7806 (2)	0.0329 (7)
H9A	0.7603	0.1457	0.7992	0.049*
H9B	0.7085	0.3242	0.8246	0.049*
H9C	0.7327	0.2899	0.7275	0.049*
C10	0.64306 (17)	0.0740 (4)	0.60188 (17)	0.0314 (6)
H10A	0.6575	−0.0504	0.5859	0.047*
H10B	0.6962	0.1454	0.6076	0.047*
H10C	0.6052	0.1274	0.5577	0.047*
C11	0.40789 (14)	0.3875 (3)	0.80932 (14)	0.0169 (4)
C12	0.40386 (17)	0.3927 (3)	0.89675 (16)	0.0266 (5)
H12	0.4490	0.3388	0.9300	0.032*
C13	0.33557 (18)	0.4749 (4)	0.93770 (17)	0.0294 (6)
H13	0.3340	0.4748	0.9981	0.035*
C14	0.27000 (17)	0.5567 (3)	0.89033 (18)	0.0296 (6)
H14	0.2231	0.6130	0.9179	0.036*
C15	0.27330 (16)	0.5559 (3)	0.80278 (18)	0.0267 (5)
H15	0.2288	0.6129	0.7698	0.032*
C16	0.34190 (15)	0.4715 (3)	0.76237 (16)	0.0208 (5)
C17	0.35097 (15)	0.4629 (3)	0.67030 (16)	0.0210 (5)
C18	0.29488 (16)	0.5441 (3)	0.61069 (17)	0.0265 (5)
H18	0.2469	0.6122	0.6293	0.032*
C19	0.30904 (16)	0.5255 (4)	0.52521 (18)	0.0298 (6)
H19	0.2706	0.5792	0.4845	0.036*
C20	0.38019 (17)	0.4273 (4)	0.49885 (17)	0.0295 (6)
H20	0.3907	0.4128	0.4399	0.035*
C21	0.43519 (16)	0.3516 (3)	0.55904 (16)	0.0251 (5)
H21	0.4841	0.2862	0.5405	0.030*

	U11	U22	U33	U12	U13	U23
Ir1	0.01507 (6)	0.01433 (6)	0.01873 (6)	0.00073 (3)	−0.00018 (4)	0.00032 (3)
N22	0.0226 (10)	0.0210 (10)	0.0287 (11)	−0.0024 (8)	−0.0007 (8)	0.0020 (8)
N1	0.0248 (10)	0.0208 (11)	0.0298 (12)	−0.0029 (8)	−0.0020 (9)	0.0012 (8)
N2	0.0207 (10)	0.0181 (10)	0.0353 (12)	0.0013 (8)	0.0010 (9)	0.0027 (9)
N3	0.0418 (14)	0.0316 (13)	0.0412 (14)	0.0002 (11)	−0.0107 (11)	−0.0059 (11)
C1	0.0219 (11)	0.0142 (11)	0.0220 (12)	0.0027 (9)	0.0001 (9)	0.0005 (8)
C2	0.0198 (11)	0.0151 (11)	0.0218 (12)	0.0022 (9)	−0.0003 (9)	0.0014 (8)
C3	0.0207 (11)	0.0203 (12)	0.0239 (12)	0.0051 (9)	−0.0037 (9)	−0.0010 (9)
C4	0.0175 (11)	0.0162 (11)	0.0348 (14)	0.0037 (9)	−0.0022 (10)	0.0007 (9)
C5	0.0201 (11)	0.0186 (11)	0.0267 (12)	0.0041 (9)	0.0011 (9)	0.0027 (9)
C6	0.0292 (13)	0.0216 (12)	0.0273 (13)	−0.0001 (10)	−0.0050 (10)	−0.0043 (9)
C7	0.0234 (12)	0.0239 (13)	0.0317 (14)	−0.0005 (10)	0.0049 (10)	0.0051 (10)
C8	0.0354 (15)	0.0388 (16)	0.0247 (13)	0.0093 (12)	−0.0077 (11)	−0.0064 (11)
C9	0.0187 (13)	0.0269 (14)	0.053 (2)	−0.0019 (10)	−0.0026 (13)	−0.0053 (11)
C10	0.0271 (13)	0.0379 (15)	0.0295 (14)	0.0073 (11)	0.0077 (11)	0.0069 (11)
C11	0.0166 (10)	0.0131 (10)	0.0210 (11)	−0.0014 (8)	0.0018 (9)	−0.0014 (8)
C12	0.0279 (13)	0.0241 (13)	0.0278 (13)	0.0031 (10)	0.0006 (10)	−0.0011 (10)
C13	0.0338 (14)	0.0270 (13)	0.0279 (13)	−0.0006 (11)	0.0070 (11)	−0.0043 (10)
C14	0.0253 (12)	0.0240 (13)	0.0400 (15)	0.0005 (10)	0.0103 (11)	−0.0068 (11)
C15	0.0192 (11)	0.0205 (12)	0.0403 (15)	0.0014 (10)	0.0011 (10)	−0.0028 (10)
C16	0.0184 (11)	0.0144 (11)	0.0296 (13)	−0.0015 (8)	0.0006 (9)	0.0003 (9)
C17	0.0172 (10)	0.0148 (11)	0.0309 (13)	−0.0041 (9)	−0.0014 (9)	0.0014 (9)
C18	0.0178 (11)	0.0219 (12)	0.0395 (15)	−0.0014 (9)	−0.0021 (10)	0.0074 (10)
C19	0.0233 (12)	0.0302 (14)	0.0354 (15)	−0.0058 (10)	−0.0096 (11)	0.0134 (11)
C20	0.0307 (13)	0.0323 (14)	0.0253 (13)	−0.0062 (11)	−0.0036 (11)	0.0071 (10)
C21	0.0241 (12)	0.0248 (13)	0.0266 (13)	−0.0013 (10)	0.0022 (10)	0.0034 (10)

Ir1—N1	2.125 (2)	C8—H8A	0.9800
Ir1—C11	2.066 (2)	C8—H8B	0.9800
Ir1—N22	2.079 (2)	C8—H8C	0.9800
Ir1—C1	2.175 (2)	C9—H9A	0.9800
Ir1—C2	2.163 (2)	C9—H9B	0.9800
Ir1—C3	2.201 (2)	C9—H9C	0.9800
Ir1—C4	2.230 (2)	C10—H10A	0.9800
Ir1—C5	2.232 (2)	C10—H10B	0.9800
N1—N2	1.194 (3)	C10—H10C	0.9800
N2—N3	1.157 (3)	C11—C12	1.377 (3)
N22—C17	1.383 (3)	C11—C16	1.391 (3)
N22—C21	1.370 (3)	C12—C13	1.391 (4)
C1—C2	1.442 (3)	C12—H12	0.9500
C1—C5	1.446 (3)	C13—C14	1.383 (4)
C1—C6	1.487 (3)	C13—H13	0.9500
C2—C3	1.445 (3)	C14—C15	1.378 (4)
C2—C7	1.495 (3)	C14—H14	0.9500
C3—C4	1.424 (3)	C15—C16	1.398 (3)
C3—C8	1.496 (3)	C15—H15	0.9500
C4—C5	1.434 (3)	C16—C17	1.459 (3)
C4—C9	1.500 (3)	C17—C18	1.396 (3)
C5—C10	1.502 (3)	C18—C19	1.373 (4)
C6—H6A	0.9800	C18—H18	0.9500
C6—H6B	0.9800	C19—C20	1.391 (4)
C6—H6C	0.9800	C19—H19	0.9500
C7—H7A	0.9800	C20—C21	1.376 (4)
C7—H7B	0.9800	C20—H20	0.9500
C7—H7C	0.9800	C21—H21	0.9500
C11—Ir1—N22	77.94 (9)	C1—C6—H6A	109.5
C11—Ir1—N1	85.90 (8)	C1—C6—H6B	109.5
N22—Ir1—N1	83.83 (8)	H6A—C6—H6B	109.5
C11—Ir1—C1	128.17 (9)	C1—C6—H6C	109.5
N22—Ir1—C1	99.98 (9)	H6A—C6—H6C	109.5
N1—Ir1—C1	145.88 (9)	H6B—C6—H6C	109.5
C11—Ir1—C2	100.10 (9)	C2—C7—H7A	109.5
N22—Ir1—C2	124.38 (8)	C2—C7—H7B	109.5
N1—Ir1—C2	151.76 (9)	H7A—C7—H7B	109.5
C11—Ir1—C3	105.28 (9)	C2—C7—H7C	109.5
N22—Ir1—C3	162.78 (8)	H7A—C7—H7C	109.5
N1—Ir1—C3	113.11 (9)	H7B—C7—H7C	109.5
C11—Ir1—C4	138.08 (9)	C3—C8—H8A	109.5
N22—Ir1—C4	143.78 (9)	C3—C8—H8B	109.5
N1—Ir1—C4	93.62 (8)	H8A—C8—H8B	109.5
C11—Ir1—C5	164.32 (8)	C3—C8—H8C	109.5
N22—Ir1—C5	109.43 (9)	H8A—C8—H8C	109.5
N1—Ir1—C5	108.32 (9)	H8B—C8—H8C	109.5
C1—Ir1—C2	38.84 (9)	C4—C9—H9A	109.5
C1—Ir1—C3	64.47 (9)	C4—C9—H9B	109.5
C1—Ir1—C4	63.39 (9)	H9A—C9—H9B	109.5
C1—Ir1—C5	38.27 (9)	C4—C9—H9C	109.5
C2—Ir1—C3	38.66 (9)	H9A—C9—H9C	109.5
C2—Ir1—C4	63.51 (9)	H9B—C9—H9C	109.5
C2—Ir1—C5	64.25 (9)	C5—C10—H10A	109.5
C3—Ir1—C4	37.47 (9)	C5—C10—H10B	109.5
C3—Ir1—C5	63.57 (9)	H10A—C10—H10B	109.5
C4—Ir1—C5	37.50 (9)	C5—C10—H10C	109.5
N2—N1—Ir1	116.55 (17)	H10A—C10—H10C	109.5
N1—N2—N3	176.0 (3)	H10B—C10—H10C	109.5
C21—N22—Ir1	125.55 (17)	C12—C11—C16	117.7 (2)
C17—N22—Ir1	116.63 (16)	C12—C11—Ir1	125.87 (18)
C21—N22—C17	117.7 (2)	C16—C11—Ir1	116.43 (17)
C2—C1—C5	108.1 (2)	C11—C12—C13	121.9 (2)
C2—C1—C6	126.5 (2)	C11—C12—H12	119.1
C5—C1—C6	125.2 (2)	C13—C12—H12	119.1
C2—C1—Ir1	70.14 (12)	C14—C13—C12	119.9 (2)
C5—C1—Ir1	73.00 (13)	C14—C13—H13	120.1
C6—C1—Ir1	126.65 (17)	C12—C13—H13	120.1
C1—C2—C3	107.9 (2)	C15—C14—C13	119.3 (2)
C1—C2—C7	126.4 (2)	C15—C14—H14	120.3
C3—C2—C7	125.5 (2)	C13—C14—H14	120.3
C1—C2—Ir1	71.03 (12)	C14—C15—C16	120.2 (2)
C3—C2—Ir1	72.09 (13)	C14—C15—H15	119.9
C7—C2—Ir1	127.23 (16)	C16—C15—H15	119.9
C4—C3—C2	107.5 (2)	C11—C16—C15	121.0 (2)
C4—C3—C8	126.2 (2)	C11—C16—C17	114.7 (2)
C2—C3—C8	125.6 (2)	C15—C16—C17	124.3 (2)
C4—C3—Ir1	72.38 (14)	N22—C17—C18	120.9 (2)
C2—C3—Ir1	69.26 (13)	N22—C17—C16	114.1 (2)
C8—C3—Ir1	131.27 (18)	C18—C17—C16	125.0 (2)
C3—C4—C5	109.6 (2)	C19—C18—C17	120.1 (2)
C3—C4—C9	124.7 (2)	C19—C18—H18	120.0
C5—C4—C9	125.8 (2)	C17—C18—H18	120.0
C3—C4—Ir1	70.14 (13)	C18—C19—C20	119.4 (2)
C5—C4—Ir1	71.31 (13)	C18—C19—H19	120.3
C9—C4—Ir1	124.56 (17)	C20—C19—H19	120.3
C4—C5—C1	107.0 (2)	C21—C20—C19	119.2 (3)
C4—C5—C10	126.9 (2)	C21—C20—H20	120.4
C1—C5—C10	125.7 (2)	C19—C20—H20	120.4
C4—C5—Ir1	71.19 (13)	N22—C21—C20	122.6 (2)
C1—C5—Ir1	68.73 (13)	N22—C21—H21	118.7
C10—C5—Ir1	131.16 (17)	C20—C21—H21	118.7
C5—C1—C2—C3	0.5 (2)	C6—C1—C5—C4	−175.5 (2)
C6—C1—C2—C3	175.4 (2)	Ir1—C1—C5—C4	61.27 (16)
Ir1—C1—C2—C3	−63.08 (16)	C2—C1—C5—C10	172.1 (2)
C5—C1—C2—C7	−173.7 (2)	C6—C1—C5—C10	−2.9 (4)
C6—C1—C2—C7	1.3 (4)	Ir1—C1—C5—C10	−126.2 (2)
Ir1—C1—C2—C7	122.8 (2)	C2—C1—C5—Ir1	−61.72 (15)
C5—C1—C2—Ir1	63.57 (15)	C6—C1—C5—Ir1	123.2 (2)
C6—C1—C2—Ir1	−121.5 (2)	C16—C11—C12—C13	1.5 (4)
C1—C2—C3—C4	−0.3 (3)	Ir1—C11—C12—C13	−179.50 (19)
C7—C2—C3—C4	173.9 (2)	C11—C12—C13—C14	−1.0 (4)
Ir1—C2—C3—C4	−62.72 (16)	C12—C13—C14—C15	−0.1 (4)
C1—C2—C3—C8	−171.0 (2)	C13—C14—C15—C16	0.6 (4)
C7—C2—C3—C8	3.2 (4)	C12—C11—C16—C15	−0.9 (3)
Ir1—C2—C3—C8	126.6 (2)	Ir1—C11—C16—C15	179.99 (18)
C1—C2—C3—Ir1	62.40 (15)	C12—C11—C16—C17	179.1 (2)
C7—C2—C3—Ir1	−123.4 (2)	Ir1—C11—C16—C17	0.0 (3)
C2—C3—C4—C5	0.0 (3)	C14—C15—C16—C11	−0.1 (4)
C8—C3—C4—C5	170.6 (2)	C14—C15—C16—C17	179.8 (2)
Ir1—C3—C4—C5	−60.66 (16)	C21—N22—C17—C18	−0.9 (3)
C2—C3—C4—C9	179.6 (2)	Ir1—N22—C17—C18	175.84 (17)
C8—C3—C4—C9	−9.8 (4)	C21—N22—C17—C16	179.7 (2)
Ir1—C3—C4—C9	118.9 (2)	Ir1—N22—C17—C16	−3.6 (3)
C2—C3—C4—Ir1	60.70 (16)	C11—C16—C17—N22	2.3 (3)
C8—C3—C4—Ir1	−128.7 (3)	C15—C16—C17—N22	−177.7 (2)
C3—C4—C5—C1	0.3 (3)	C11—C16—C17—C18	−177.1 (2)
C9—C4—C5—C1	−179.3 (2)	C15—C16—C17—C18	3.0 (4)
Ir1—C4—C5—C1	−59.68 (15)	N22—C17—C18—C19	1.4 (4)
C3—C4—C5—C10	−172.2 (2)	C16—C17—C18—C19	−179.2 (2)
C9—C4—C5—C10	8.2 (4)	C17—C18—C19—C20	−0.8 (4)
Ir1—C4—C5—C10	127.9 (2)	C18—C19—C20—C21	−0.3 (4)
C3—C4—C5—Ir1	59.94 (16)	C17—N22—C21—C20	−0.3 (4)
C9—C4—C5—Ir1	−119.6 (2)	Ir1—N22—C21—C20	−176.68 (19)
C2—C1—C5—C4	−0.5 (2)	C19—C20—C21—N22	0.9 (4)