Chlorido[3,3'-dibutyl-5,5'-(pyridine-2,6-di-yl)dipyrazol-1-ido]gold(III).

The Au atom in the C2-symmetric pincer-type title complex, [AuCl(C(19)H(23)N(5))], is in the +3 oxidation state. The ligand is composed of one pyridine unit and two n-butyl-substituted pyrazoles (pyrz). Both pyrazoles are deprotonated, thus forming a neutral compound. To the best of our knowledge, this is the first Au(III)-bis-pyrazolate complex. According to the special geometry in the N,N',N''-tridentate ligand, containing two five-membered heterocycles, the complex deviates from an ideal square-planar coordination geometry; the N(pyrz)-Au-N(pyrz) angle is 160.8 (3)°, indicating a distortion of nearly 20°.

Related literature

For the importance of gold catalysis, see: Hashmi & Hutchings (2006a ▶,b ▶); Hashmi (2007 ▶). For the role of the gold(I) oxidation state, see: Ito et al. (1986 ▶) and for the use of gold(III) pre-catalysts, see: Hashmi et al. (2004a ▶,b ▶).

Experimental

Crystal data

[AuCl(C19H23N5)]

M = 553.84

Monoclinic,

a = 9.0003 (3) Å

b = 24.2220 (7) Å

c = 9.3042 (3) Å

β = 101.372 (1)°

V = 1988.54 (11) Å3

Z = 4

Mo Kα radiation

μ = 7.55 mm−1

T = 200 K

0.16 × 0.04 × 0.04 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan SADABS (Sheldrick, 2008b ▶) T min = 0.378, T max = 0.752

19560 measured reflections

4539 independent reflections

3103 reflections with I > 2σ(I)

R int = 0.091

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.089

S = 1.07

4539 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.91 e Å−3

Δρmin = −1.01 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008a ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050995/hg2593sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050995/hg2593Isup2.hkl

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

[AuCl(C19H23N5)]	Z = 4
Mr = 553.84	F(000) = 1072
Monoclinic, P21/c	Dx = 1.850 Mg m−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.0003 (3) Å	Cell parameters from 6701 reflections
b = 24.2220 (7) Å	µ = 7.55 mm−1
c = 9.3042 (3) Å	T = 200 K
β = 101.372 (1)°	Polyhedron, orange
V = 1988.54 (11) Å3	0.16 × 0.04 × 0.04 mm

Bruker SMART CCD diffractometer	4539 independent reflections
Radiation source: fine-focus sealed tube	3103 reflections with I > 2σ(I)
graphite	Rint = 0.091
ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan SADABS (Sheldrick, 2008b)	h = −11→11
Tmin = 0.378, Tmax = 0.752	k = −31→31
19560 measured reflections	l = −12→12

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0241P)2 + 2.5681P] where P = (Fo2 + 2Fc2)/3
4539 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.91 e Å−3
0 restraints	Δρmin = −1.01 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.

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
Au1	0.28448 (3)	0.481560 (12)	0.61190 (3)	0.03110 (10)
Cl1	0.3449 (3)	0.44522 (9)	0.8400 (2)	0.0514 (6)
N1	0.2300 (7)	0.5101 (2)	0.4082 (6)	0.0347 (15)
C2	0.1273 (8)	0.5513 (3)	0.3826 (8)	0.0328 (17)
C3	0.0815 (9)	0.5696 (3)	0.2393 (8)	0.040 (2)
H3	0.0069	0.5977	0.2156	0.048*
C4	0.1478 (11)	0.5458 (3)	0.1317 (9)	0.050 (2)
H4	0.1166	0.5578	0.0331	0.060*
C5	0.2585 (10)	0.5050 (3)	0.1635 (9)	0.044 (2)
H5	0.3070	0.4906	0.0897	0.053*
C6	0.2952 (8)	0.4865 (3)	0.3063 (8)	0.0344 (18)
C11	0.0767 (8)	0.5693 (3)	0.5158 (7)	0.0316 (18)
N12	0.1375 (7)	0.5411 (2)	0.6419 (6)	0.0319 (14)
N13	0.0917 (6)	0.5633 (2)	0.7583 (6)	0.0293 (14)
C14	−0.0014 (8)	0.6050 (3)	0.7037 (8)	0.0311 (17)
C15	−0.0165 (8)	0.6099 (3)	0.5537 (8)	0.0328 (18)
H15	−0.0773	0.6355	0.4906	0.039*
C16	−0.0734 (9)	0.6395 (3)	0.8036 (8)	0.040 (2)
H16A	0.0009	0.6458	0.8958	0.048*
H16B	−0.1601	0.6190	0.8284	0.048*
C17	−0.1289 (9)	0.6948 (3)	0.7383 (9)	0.042 (2)
H17A	−0.2064	0.6882	0.6485	0.050*
H17B	−0.0429	0.7142	0.7085	0.050*
C18	−0.1964 (9)	0.7326 (3)	0.8389 (9)	0.048 (2)
H18A	−0.1224	0.7370	0.9322	0.057*
H18B	−0.2881	0.7149	0.8618	0.057*
C19	−0.2390 (11)	0.7898 (4)	0.7739 (11)	0.066 (3)
H19A	−0.1466	0.8108	0.7709	0.098*
H19B	−0.2990	0.8094	0.8349	0.098*
H19C	−0.2986	0.7858	0.6743	0.098*
C21	0.3986 (9)	0.4418 (3)	0.3670 (8)	0.041 (2)
N22	0.4106 (7)	0.4319 (3)	0.5137 (7)	0.0386 (16)
N23	0.5062 (8)	0.3898 (3)	0.5598 (8)	0.0465 (18)
C24	0.5559 (9)	0.3730 (3)	0.4398 (11)	0.049 (2)
C25	0.4926 (9)	0.4040 (3)	0.3161 (10)	0.049 (2)
H25	0.5099	0.4002	0.2191	0.058*
C26	0.6668 (11)	0.3245 (4)	0.4558 (13)	0.071 (3)
H26A	0.7227	0.3261	0.3744	0.085*
H26B	0.7416	0.3291	0.5484	0.085*
C27	0.6011 (12)	0.2719 (4)	0.4563 (15)	0.093 (4)
H27A	0.5352	0.2656	0.3592	0.112*
H27B	0.5353	0.2718	0.5299	0.112*
C28	0.7134 (12)	0.2229 (5)	0.4898 (16)	0.094 (4)
H28A	0.7856	0.2244	0.4221	0.113*
H28B	0.7723	0.2265	0.5911	0.113*
C29	0.6347 (14)	0.1689 (5)	0.4739 (15)	0.114 (5)
H29A	0.5526	0.1693	0.5293	0.171*
H29B	0.7069	0.1396	0.5119	0.171*
H29C	0.5924	0.1620	0.3701	0.171*

	U11	U22	U33	U12	U13	U23
Au1	0.03813 (17)	0.03202 (16)	0.02527 (15)	0.00177 (16)	0.01141 (11)	−0.00274 (16)
Cl1	0.0686 (15)	0.0563 (14)	0.0304 (11)	0.0218 (12)	0.0125 (10)	0.0075 (10)
N1	0.051 (4)	0.032 (4)	0.024 (3)	−0.006 (3)	0.015 (3)	−0.003 (3)
C2	0.039 (5)	0.034 (4)	0.029 (4)	−0.008 (4)	0.016 (3)	−0.001 (3)
C3	0.053 (5)	0.040 (5)	0.026 (4)	0.001 (4)	0.005 (4)	0.005 (4)
C4	0.079 (7)	0.041 (5)	0.032 (5)	−0.014 (5)	0.019 (5)	−0.003 (4)
C5	0.072 (6)	0.039 (5)	0.030 (4)	−0.021 (4)	0.031 (4)	−0.012 (4)
C6	0.045 (5)	0.040 (5)	0.024 (4)	−0.014 (4)	0.021 (3)	−0.010 (4)
C11	0.043 (5)	0.034 (4)	0.019 (4)	−0.003 (3)	0.010 (3)	0.008 (3)
N12	0.038 (4)	0.033 (3)	0.027 (3)	0.007 (3)	0.013 (3)	−0.002 (3)
N13	0.029 (3)	0.039 (4)	0.022 (3)	0.001 (3)	0.010 (3)	−0.008 (3)
C14	0.032 (4)	0.037 (5)	0.024 (4)	0.000 (3)	0.007 (3)	0.000 (3)
C15	0.041 (5)	0.035 (4)	0.021 (4)	0.005 (4)	0.003 (3)	0.002 (3)
C16	0.041 (5)	0.048 (5)	0.031 (4)	0.005 (4)	0.006 (4)	−0.003 (4)
C17	0.045 (5)	0.041 (5)	0.038 (5)	0.011 (4)	0.004 (4)	−0.006 (4)
C18	0.051 (6)	0.050 (5)	0.039 (5)	0.009 (4)	0.003 (4)	−0.014 (4)
C19	0.080 (7)	0.042 (6)	0.067 (7)	0.018 (5)	−0.005 (5)	−0.018 (5)
C21	0.054 (5)	0.041 (5)	0.031 (5)	−0.012 (4)	0.020 (4)	−0.014 (4)
N22	0.046 (4)	0.032 (4)	0.041 (4)	0.002 (3)	0.018 (3)	−0.007 (3)
N23	0.047 (4)	0.034 (4)	0.067 (5)	0.001 (3)	0.031 (4)	0.001 (4)
C24	0.046 (5)	0.031 (5)	0.079 (7)	−0.007 (4)	0.036 (5)	−0.016 (5)
C25	0.050 (6)	0.040 (5)	0.064 (6)	−0.007 (4)	0.031 (5)	−0.016 (5)
C26	0.075 (7)	0.041 (6)	0.106 (9)	−0.002 (5)	0.041 (6)	−0.018 (6)
C27	0.055 (7)	0.064 (8)	0.170 (13)	0.009 (6)	0.042 (7)	0.025 (8)
C28	0.062 (7)	0.071 (9)	0.152 (12)	0.032 (6)	0.027 (7)	0.030 (8)
C29	0.104 (11)	0.092 (11)	0.141 (13)	0.044 (9)	0.011 (9)	0.018 (10)

Au1—N1	1.985 (6)	C17—H17B	0.9900
Au1—N22	1.994 (6)	C18—C19	1.529 (11)
Au1—N12	2.014 (6)	C18—H18A	0.9900
Au1—Cl1	2.263 (2)	C18—H18B	0.9900
N1—C6	1.338 (8)	C19—H19A	0.9800
N1—C2	1.349 (9)	C19—H19B	0.9800
C2—C3	1.389 (10)	C19—H19C	0.9800
C2—C11	1.469 (9)	C21—N22	1.369 (9)
C3—C4	1.387 (11)	C21—C25	1.390 (11)
C3—H3	0.9500	N22—N23	1.349 (9)
C4—C5	1.394 (12)	N23—C24	1.346 (10)
C4—H4	0.9500	C24—C25	1.398 (12)
C5—C6	1.379 (10)	C24—C26	1.530 (12)
C5—H5	0.9500	C25—H25	0.9500
C6—C21	1.466 (11)	C26—C27	1.403 (12)
C11—N12	1.374 (9)	C26—H26A	0.9900
C11—C15	1.383 (10)	C26—H26B	0.9900
N12—N13	1.345 (7)	C27—C28	1.551 (13)
N13—C14	1.346 (9)	C27—H27A	0.9900
C14—C15	1.381 (9)	C27—H27B	0.9900
C14—C16	1.490 (10)	C28—C29	1.482 (15)
C15—H15	0.9500	C28—H28A	0.9900
C16—C17	1.515 (10)	C28—H28B	0.9900
C16—H16A	0.9900	C29—H29A	0.9800
C16—H16B	0.9900	C29—H29B	0.9800
C17—C18	1.519 (10)	C29—H29C	0.9800
C17—H17A	0.9900
N1—Au1—N22	80.1 (3)	C17—C18—C19	113.6 (7)
N1—Au1—N12	80.6 (2)	C17—C18—H18A	108.8
N22—Au1—N12	160.8 (3)	C19—C18—H18A	108.8
N1—Au1—Cl1	177.47 (18)	C17—C18—H18B	108.8
N22—Au1—Cl1	98.2 (2)	C19—C18—H18B	108.8
N12—Au1—Cl1	101.06 (18)	H18A—C18—H18B	107.7
C6—N1—C2	124.9 (6)	C18—C19—H19A	109.5
C6—N1—Au1	117.9 (5)	C18—C19—H19B	109.5
C2—N1—Au1	117.3 (5)	H19A—C19—H19B	109.5
N1—C2—C3	118.0 (7)	C18—C19—H19C	109.5
N1—C2—C11	112.7 (6)	H19A—C19—H19C	109.5
C3—C2—C11	129.2 (7)	H19B—C19—H19C	109.5
C4—C3—C2	118.1 (8)	N22—C21—C25	106.9 (8)
C4—C3—H3	120.9	N22—C21—C6	115.6 (6)
C2—C3—H3	120.9	C25—C21—C6	137.5 (8)
C3—C4—C5	122.2 (8)	N23—N22—C21	111.6 (6)
C3—C4—H4	118.9	N23—N22—Au1	134.0 (5)
C5—C4—H4	118.9	C21—N22—Au1	114.3 (5)
C6—C5—C4	117.5 (7)	C24—N23—N22	105.1 (7)
C6—C5—H5	121.3	N23—C24—C25	111.9 (7)
C4—C5—H5	121.3	N23—C24—C26	117.9 (9)
N1—C6—C5	119.2 (8)	C25—C24—C26	130.2 (8)
N1—C6—C21	112.1 (6)	C21—C25—C24	104.5 (8)
C5—C6—C21	128.7 (7)	C21—C25—H25	127.8
N12—C11—C15	107.2 (6)	C24—C25—H25	127.8
N12—C11—C2	115.8 (7)	C27—C26—C24	115.5 (9)
C15—C11—C2	137.0 (7)	C27—C26—H26A	108.4
N13—N12—C11	110.8 (6)	C24—C26—H26A	108.4
N13—N12—Au1	135.4 (5)	C27—C26—H26B	108.4
C11—N12—Au1	113.6 (5)	C24—C26—H26B	108.4
N12—N13—C14	105.2 (5)	H26A—C26—H26B	107.5
N13—C14—C15	112.1 (6)	C26—C27—C28	115.9 (9)
N13—C14—C16	120.0 (6)	C26—C27—H27A	108.3
C15—C14—C16	127.9 (7)	C28—C27—H27A	108.3
C14—C15—C11	104.6 (6)	C26—C27—H27B	108.3
C14—C15—H15	127.7	C28—C27—H27B	108.3
C11—C15—H15	127.7	H27A—C27—H27B	107.4
C14—C16—C17	113.3 (6)	C29—C28—C27	112.1 (9)
C14—C16—H16A	108.9	C29—C28—H28A	109.2
C17—C16—H16A	108.9	C27—C28—H28A	109.2
C14—C16—H16B	108.9	C29—C28—H28B	109.2
C17—C16—H16B	108.9	C27—C28—H28B	109.2
H16A—C16—H16B	107.7	H28A—C28—H28B	107.9
C16—C17—C18	115.2 (7)	C28—C29—H29A	109.5
C16—C17—H17A	108.5	C28—C29—H29B	109.5
C18—C17—H17A	108.5	H29A—C29—H29B	109.5
C16—C17—H17B	108.5	C28—C29—H29C	109.5
C18—C17—H17B	108.5	H29A—C29—H29C	109.5
H17A—C17—H17B	107.5	H29B—C29—H29C	109.5