cis-Dichlorido[4,4,5,5-tetra-methyl-2-(2-pyrid-yl)-2-imidazoline-1-ox-yl]-palladium(II) tetra-hydro-furan hemi-solvate.

The asymmetric unit of the title complex, [PdCl(2)(C(12)H(16)N(3)O)]·0.5C(4)H(8)O, consists of one palladium complex in a general position and one half tetra-hydro-furan (THF) solvent mol-ecule, with the O atom lying on a twofold rotation axis. The Pd(II) atom is bound to one chelating imino nitroxide radical through two N atoms, one from the pyridyl ring and the other from the imidazoline ring. The coordination of the metal centre is completed by two Cl atoms in a cis configuration, leading to a quasi-square-planar coordination of the metal centre. The four atoms that define the Pd(II) coordination environment and the eight atoms that belong to the pyridylimine fragment are coplanar, with no deviation larger than 0.087 (5) Å. In the crystal structure, inter-molecular inter-actions shorter than the corresponding van der Waals radii sum are observed only between Pd(II) complexes, and no short contact is observed around the THF mol-ecule. Weak C-H⋯O and C-H⋯Cl inter-actions yield a two-dimensional network of complexes in the (101) plane.

Related literature

For related literature, see: Caneschi et al. (1991 ▶); Davis et al. (1972 ▶); Evans et al. (1968 ▶); Fettouhi et al. (2003 ▶); Li et al. (2004 ▶); Ma et al. (2006 ▶, 2007 ▶); Oshio et al. (1996 ▶); Ueda et al. (2003 ▶, 2005 ▶); Ullman & Holm (1970 ▶); Xu et al. (2007 ▶).

Experimental

Crystal data

[PdCl2(C12H16N3O)]·0.5C4H8O

M = 431.65

Monoclinic,

a = 19.1398 (10) Å

b = 15.2061 (12) Å

c = 13.8291 (10) Å

β = 123.415 (3)°

V = 3359.6 (4) Å3

Z = 8

Mo Kα radiation

μ = 1.43 mm−1

T = 293 (2) K

0.7 × 0.3 × 0.3 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

5707 measured reflections

3065 independent reflections

2049 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.152

S = 1.03

3065 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.95 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004406/dn2318sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004406/dn2318Isup2.hkl

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

[PdCl2(C12H16N3O)]·0.5C4H8O	F000 = 1736
Mr = 431.65	Dx = 1.707 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2981 reflections
a = 19.1398 (10) Å	θ = 2.6–25.4º
b = 15.2061 (12) Å	µ = 1.43 mm−1
c = 13.8291 (10) Å	T = 293 (2) K
β = 123.415 (3)º	Thick plate, brown
V = 3359.6 (4) Å3	0.7 × 0.3 × 0.3 mm
Z = 8

Nonius KappaCCD diffractometer	2049 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Monochromator: graphite	θmax = 25.4º
T = 293(2) K	θmin = 3.0º
φ and ω scans	h = −22→22
Absorption correction: none	k = −17→18
5707 measured reflections	l = −16→16
3065 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057	H-atom parameters constrained
wR(F2) = 0.152	w = 1/[σ2(Fo2) + (0.0709P)2 + 4.5052P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3065 reflections	Δρmax = 0.61 e Å−3
199 parameters	Δρmin = −0.95 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. Multiscan absorption correction methods did not yield a better refinement agreement, then no correction was applied.

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
C1	0.4332 (5)	0.2973 (4)	0.6038 (6)	0.0604 (18)
H1	0.4196	0.3511	0.6214	0.073*
C2	0.4905 (5)	0.2955 (5)	0.5741 (8)	0.072 (2)
H2	0.5154	0.3475	0.5723	0.087*
C3	0.5113 (5)	0.2173 (5)	0.5470 (6)	0.0603 (18)
H3	0.5497	0.2151	0.5258	0.072*
C4	0.4733 (5)	0.1419 (4)	0.5520 (6)	0.0558 (18)
H4	0.4851	0.0877	0.5330	0.067*
C5	0.4172 (4)	0.1475 (4)	0.5858 (5)	0.0443 (14)
C6	0.3741 (4)	0.0747 (4)	0.5988 (5)	0.0445 (14)
C7	0.3264 (5)	−0.0669 (4)	0.6000 (6)	0.0560 (17)
C8	0.2934 (4)	0.0028 (4)	0.6501 (6)	0.0498 (16)
C9	0.2604 (6)	−0.0980 (6)	0.4783 (7)	0.081 (2)
H9A	0.2328	−0.0479	0.4294	0.122*
H9B	0.2201	−0.1339	0.4806	0.122*
H9C	0.2867	−0.1317	0.4480	0.122*
C10	0.3725 (5)	−0.1451 (5)	0.6789 (8)	0.078 (2)
H10A	0.3899	−0.1843	0.6415	0.117*
H10B	0.3359	−0.1757	0.6946	0.117*
H10C	0.4208	−0.1246	0.7503	0.117*
C11	0.1983 (5)	0.0032 (5)	0.5897 (7)	0.076 (2)
H11A	0.1824	0.0501	0.6202	0.114*
H11B	0.1805	−0.0520	0.6030	0.114*
H11C	0.1723	0.0116	0.5080	0.114*
C12	0.3364 (5)	−0.0032 (5)	0.7811 (6)	0.067 (2)
H12A	0.3951	−0.0143	0.8167	0.101*
H12B	0.3121	−0.0502	0.7994	0.101*
H12C	0.3292	0.0513	0.8098	0.101*
N1	0.3961 (3)	0.2250 (3)	0.6084 (5)	0.0470 (12)
N2	0.3857 (4)	−0.0129 (3)	0.5888 (5)	0.0512 (13)
N3	0.3211 (3)	0.0884 (3)	0.6270 (5)	0.0509 (13)
O1	0.4363 (3)	−0.0447 (3)	0.5657 (5)	0.0687 (14)
Cl1	0.21890 (16)	0.20499 (14)	0.7093 (2)	0.0865 (7)
Cl2	0.30744 (14)	0.36626 (13)	0.67356 (19)	0.0761 (6)
Pd1	0.30983 (3)	0.21827 (3)	0.65241 (5)	0.0534 (2)
O1S	0.5000	0.4980 (7)	0.7500	0.177 (7)
C2S	0.5251 (8)	0.5487 (7)	0.6926 (10)	0.108 (3)
H2S1	0.4949	0.5319	0.6116	0.130*
H2S2	0.5845	0.5408	0.7263	0.130*
C3S	0.5078 (9)	0.6386 (6)	0.7032 (11)	0.118 (4)
H3S1	0.4590	0.6595	0.6312	0.142*
H3S2	0.5552	0.6758	0.7235	0.142*

	U11	U22	U33	U12	U13	U23
C1	0.069 (5)	0.050 (4)	0.066 (5)	0.003 (3)	0.040 (4)	−0.004 (3)
C2	0.077 (6)	0.059 (5)	0.091 (6)	−0.023 (4)	0.052 (5)	−0.002 (4)
C3	0.060 (4)	0.068 (5)	0.065 (5)	−0.006 (4)	0.041 (4)	0.000 (4)
C4	0.071 (5)	0.053 (4)	0.064 (5)	0.003 (3)	0.050 (4)	0.003 (3)
C5	0.050 (4)	0.045 (3)	0.039 (3)	−0.002 (3)	0.026 (3)	−0.002 (3)
C6	0.050 (4)	0.046 (3)	0.048 (4)	0.004 (3)	0.034 (3)	0.003 (3)
C7	0.068 (5)	0.046 (3)	0.073 (5)	−0.006 (3)	0.050 (4)	0.001 (3)
C8	0.050 (4)	0.053 (4)	0.054 (4)	0.000 (3)	0.034 (4)	0.008 (3)
C9	0.095 (7)	0.079 (5)	0.083 (6)	−0.018 (5)	0.057 (6)	−0.017 (5)
C10	0.100 (7)	0.060 (5)	0.105 (7)	0.009 (4)	0.075 (6)	0.022 (4)
C11	0.061 (5)	0.085 (6)	0.091 (6)	−0.010 (4)	0.048 (5)	0.000 (5)
C12	0.074 (5)	0.078 (5)	0.060 (5)	−0.003 (4)	0.044 (4)	0.005 (4)
N1	0.051 (3)	0.043 (3)	0.049 (3)	−0.002 (2)	0.029 (3)	0.002 (2)
N2	0.059 (3)	0.043 (3)	0.067 (4)	0.006 (3)	0.044 (3)	0.006 (2)
N3	0.056 (3)	0.052 (3)	0.057 (3)	0.006 (3)	0.039 (3)	0.005 (2)
O1	0.083 (4)	0.052 (3)	0.103 (4)	0.014 (3)	0.072 (4)	0.004 (3)
Cl1	0.0970 (17)	0.0960 (15)	0.1066 (18)	0.0216 (13)	0.0814 (16)	0.0034 (12)
Cl2	0.0873 (15)	0.0578 (10)	0.0865 (15)	0.0200 (10)	0.0499 (13)	−0.0037 (9)
Pd1	0.0586 (4)	0.0552 (3)	0.0549 (4)	0.0116 (3)	0.0366 (3)	−0.0002 (2)
O1S	0.249 (17)	0.068 (6)	0.35 (2)	0.000	0.246 (18)	0.000
C2S	0.116 (9)	0.094 (7)	0.134 (10)	−0.007 (6)	0.081 (8)	−0.014 (7)
C3S	0.178 (12)	0.073 (6)	0.142 (10)	−0.025 (7)	0.113 (10)	−0.009 (6)

C1—N1	1.329 (8)	C10—H10A	0.9600
C1—C2	1.367 (11)	C10—H10B	0.9600
C1—H1	0.9300	C10—H10C	0.9600
C2—C3	1.370 (10)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.381 (9)	C11—H11C	0.9600
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.388 (8)	C12—H12B	0.9600
C4—H4	0.9300	C12—H12C	0.9600
C5—N1	1.338 (7)	N1—Pd1	2.052 (5)
C5—C6	1.451 (8)	N2—O1	1.269 (6)
C6—N3	1.289 (7)	N3—Pd1	2.037 (5)
C6—N2	1.370 (8)	Cl1—Pd1	2.280 (2)
C7—N2	1.476 (8)	Cl2—Pd1	2.273 (2)
C7—C9	1.520 (11)	O1S—C2Si	1.370 (10)
C7—C10	1.524 (10)	O1S—C2S	1.370 (10)
C7—C8	1.576 (9)	C2S—C3S	1.433 (13)
C8—N3	1.505 (8)	C2S—H2S1	0.9700
C8—C12	1.526 (9)	C2S—H2S2	0.9700
C8—C11	1.529 (10)	C3S—C3Si	1.479 (18)
C9—H9A	0.9600	C3S—H3S1	0.9700
C9—H9B	0.9600	C3S—H3S2	0.9700
C9—H9C	0.9600
N1—C1—C2	122.5 (6)	H10B—C10—H10C	109.5
N1—C1—H1	118.8	C8—C11—H11A	109.5
C2—C1—H1	118.8	C8—C11—H11B	109.5
C1—C2—C3	120.1 (7)	H11A—C11—H11B	109.5
C1—C2—H2	120.0	C8—C11—H11C	109.5
C3—C2—H2	120.0	H11A—C11—H11C	109.5
C2—C3—C4	117.9 (6)	H11B—C11—H11C	109.5
C2—C3—H3	121.1	C8—C12—H12A	109.5
C4—C3—H3	121.1	C8—C12—H12B	109.5
C3—C4—C5	119.4 (6)	H12A—C12—H12B	109.5
C3—C4—H4	120.3	C8—C12—H12C	109.5
C5—C4—H4	120.3	H12A—C12—H12C	109.5
N1—C5—C4	121.5 (6)	H12B—C12—H12C	109.5
N1—C5—C6	112.1 (5)	C1—N1—C5	118.6 (6)
C4—C5—C6	126.3 (6)	C1—N1—Pd1	126.5 (4)
N3—C6—N2	112.8 (5)	C5—N1—Pd1	114.9 (4)
N3—C6—C5	120.7 (5)	O1—N2—C6	125.7 (5)
N2—C6—C5	126.4 (5)	O1—N2—C7	123.5 (5)
N2—C7—C9	106.0 (6)	C6—N2—C7	110.6 (5)
N2—C7—C10	109.5 (6)	C6—N3—C8	110.5 (5)
C9—C7—C10	110.5 (7)	C6—N3—Pd1	112.6 (4)
N2—C7—C8	100.9 (5)	C8—N3—Pd1	136.0 (4)
C9—C7—C8	113.9 (6)	N3—Pd1—N1	79.58 (19)
C10—C7—C8	115.1 (6)	N3—Pd1—Cl2	173.28 (15)
N3—C8—C12	106.3 (5)	N1—Pd1—Cl2	93.72 (14)
N3—C8—C11	109.4 (5)	N3—Pd1—Cl1	98.44 (15)
C12—C8—C11	110.5 (5)	N1—Pd1—Cl1	176.70 (15)
N3—C8—C7	102.5 (4)	Cl2—Pd1—Cl1	88.28 (8)
C12—C8—C7	113.4 (6)	C2Si—O1S—C2S	111.5 (11)
C11—C8—C7	114.1 (6)	O1S—C2S—C3S	107.6 (9)
C7—C9—H9A	109.5	O1S—C2S—H2S1	110.2
C7—C9—H9B	109.5	C3S—C2S—H2S1	110.2
H9A—C9—H9B	109.5	O1S—C2S—H2S2	110.2
C7—C9—H9C	109.5	C3S—C2S—H2S2	110.2
H9A—C9—H9C	109.5	H2S1—C2S—H2S2	108.5
H9B—C9—H9C	109.5	C2S—C3S—C3Si	105.0 (6)
C7—C10—H10A	109.5	C2S—C3S—H3S1	110.7
C7—C10—H10B	109.5	C3Si—C3S—H3S1	110.7
H10A—C10—H10B	109.5	C2S—C3S—H3S2	110.7
C7—C10—H10C	109.5	C3Si—C3S—H3S2	110.7
H10A—C10—H10C	109.5	H3S1—C3S—H3S2	108.8

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ii	0.93	2.61	3.307 (8)	132
C10—H10B···Cl1iii	0.96	2.77	3.691 (7)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1i	0.93	2.61	3.307 (8)	132
C10—H10B⋯Cl1ii	0.96	2.77	3.691 (7)	160

Symmetry codes: (i) ; (ii) .