Dichlorido{2,6-diisopropyl-N-[(S)-pyrrolidin-2-ylmeth-yl]aniline-κ(2) N,N'}palladium(II).

In the title compound, [PdCl2(C17H28N2)], the Pd(II) atom displays a square-planar coordination involving two N atoms of a 2,6-diisopropyl-N-[(S)-pyrrolidin-2-ylmeth-yl]aniline ligand and two chloride ligands, with a deviation of 0.090 (1) Å for the Pd(II) atom from the best plane. The absolute configuration of the chiral C atom of the pyrrolidine ring is S, which induces R configurations at the two N atoms of the aniline ligand. Optical isomerism arising from the chelate five-membered ring is configured as δ. The Pd-N bond lengths are 2.040 (3) and 2.072 (2) Å, and the Pd-Cl bond lengths are 2.3055 (8) and 2.3160 (8) Å. In the crystal, pairs of N-H⋯Cl hydrogen bonds link mol-ecules into discrete dimers.

Related literature

For background to the use of palladium complexes bearing enanti­opure ligands in asymmetric synthesis, see: Sodeoka & Hamashima (2006 ▶); Quintard et al. (2008 ▶); Tan et al. (2009 ▶) and as anti­cancer drugs, see: Barnham et al. (1994 ▶). For the synthesis of the 2,6-diisopropyl-N-[(S)-pyrrolidin-2-ylmeth­yl]aniline ligand, see: Shifeng et al. (2010 ▶). For related structures, see: Rafii et al. (2007 ▶). For a description of the Cambridge Structural Database, see: Allen et al. (2002 ▶).

Experimental

Crystal data

[PdCl2(C17H28N2)]

M = 437.71

Monoclinic,

a = 24.287 (3) Å

b = 8.6534 (12) Å

c = 18.355 (2) Å

β = 94.851 (9)°

V = 3843.7 (8) Å3

Z = 8

Mo Kα radiation

μ = 1.24 mm−1

T = 293 K

0.45 × 0.40 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 four-circle diffractometer

Absorption correction: ψ scan (ABSCALC; McArdle & Daly, 1999 ▶) T min = 0.578, T max = 0.608

3790 measured reflections

3580 independent reflections

3089 reflections with I > 2σ(I)

R int = 0.018

3 standard reflections every 60 min intensity decay: 0.2%

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.105

S = 1.08

3580 reflections

199 parameters

H-atom parameters constrained

Δρmax = 1.33 e Å−3

Δρmin = −1.56 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1999 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008271/fk2069sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008271/fk2069Isup2.hkl

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

[PdCl2(C17H28N2)]	F(000) = 1792
Mr = 437.71	Dx = 1.513 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 24.287 (3) Å	θ = 9.0–13.0°
b = 8.6534 (12) Å	µ = 1.24 mm−1
c = 18.355 (2) Å	T = 293 K
β = 94.851 (9)°	Brick, orange
V = 3843.7 (8) Å3	0.45 × 0.40 × 0.40 mm
Z = 8

Enraf–Nonius CAD-4 four-circle diffractometer	3089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 25.5°, θmin = 1.7°
ω/2θ scans	h = 0→29
Absorption correction: ψ scan (ABSCALC; McArdle & Daly, 1999)	k = −10→0
Tmin = 0.578, Tmax = 0.608	l = −22→22
3790 measured reflections	3 standard reflections every 60 min
3580 independent reflections	intensity decay: 0.2%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0819P)2 + 0.2845P] where P = (Fo2 + 2Fc2)/3
3580 reflections	(Δ/σ)max = 0.004
199 parameters	Δρmax = 1.33 e Å−3
0 restraints	Δρmin = −1.56 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
Pd	0.792743 (8)	0.79819 (2)	0.934349 (11)	0.02593 (12)
Cl1	0.71265 (3)	0.92407 (9)	0.89218 (4)	0.0389 (2)
Cl2	0.83021 (3)	1.01710 (9)	0.99173 (5)	0.0391 (2)
N1	0.76098 (10)	0.5922 (3)	0.89652 (14)	0.0320 (5)
H1	0.7308	0.5786	0.9169	0.038*
N2	0.86249 (10)	0.6681 (3)	0.96516 (14)	0.0296 (5)
H2	0.8597	0.6456	1.0103	0.035*
C1	0.74724 (15)	0.5713 (4)	0.81664 (19)	0.0448 (8)
H1A	0.7770	0.6075	0.7889	0.054*
H1B	0.7135	0.6253	0.8001	0.054*
C2	0.74001 (19)	0.3971 (4)	0.8098 (2)	0.0560 (10)
H2A	0.7043	0.3650	0.8245	0.067*
H2B	0.7436	0.3629	0.7601	0.067*
C3	0.78631 (16)	0.3348 (4)	0.8613 (2)	0.0518 (10)
H3A	0.8189	0.3156	0.8356	0.062*
H3B	0.7754	0.2388	0.8833	0.062*
C4	0.79815 (12)	0.4599 (4)	0.92021 (18)	0.0352 (7)
H4	0.7888	0.4211	0.9678	0.042*
C5	0.85712 (12)	0.5168 (3)	0.92571 (19)	0.0362 (7)
H5A	0.8808	0.4409	0.9515	0.043*
H5B	0.8692	0.5287	0.8770	0.043*
C6	0.91821 (11)	0.7313 (3)	0.96309 (17)	0.0291 (6)
C7	0.95576 (13)	0.7160 (3)	1.02479 (18)	0.0327 (7)
C8	0.93964 (13)	0.6498 (4)	1.09665 (17)	0.0372 (7)
H8	0.9095	0.5762	1.0852	0.045*
C9	0.9180 (2)	0.7757 (5)	1.1435 (3)	0.0637 (12)
H9A	0.9469	0.8491	1.1562	0.096*
H9B	0.9058	0.7311	1.1873	0.096*
H9C	0.8876	0.8270	1.1169	0.096*
C10	0.98669 (18)	0.5623 (6)	1.1401 (2)	0.0643 (11)
H10A	1.0162	0.6329	1.1544	0.096*
H10B	1.0002	0.4822	1.1101	0.096*
H10C	0.9732	0.5173	1.1829	0.096*
C11	1.00930 (14)	0.7704 (4)	1.0203 (2)	0.0406 (8)
H11	1.0347	0.7629	1.0610	0.049*
C12	1.02549 (14)	0.8350 (5)	0.9571 (2)	0.0463 (8)
H12	1.0616	0.8691	0.9548	0.056*
C13	0.98797 (13)	0.8487 (4)	0.8975 (2)	0.0410 (7)
H13	0.9993	0.8927	0.8550	0.049*
C14	0.93362 (13)	0.7992 (3)	0.89800 (18)	0.0319 (7)
C15	0.89514 (13)	0.8238 (4)	0.82901 (18)	0.0383 (7)
H15	0.8582	0.7891	0.8393	0.046*
C16	0.89141 (18)	0.9966 (5)	0.8104 (3)	0.0623 (11)
H16A	0.9274	1.0348	0.8020	0.093*
H16B	0.8776	1.0520	0.8504	0.093*
H16C	0.8668	1.0113	0.7672	0.093*
C17	0.91266 (18)	0.7291 (6)	0.7649 (2)	0.0580 (11)
H17A	0.9496	0.7572	0.7552	0.087*
H17B	0.8879	0.7492	0.7224	0.087*
H17C	0.9116	0.6211	0.7768	0.087*

	U11	U22	U33	U12	U13	U23
Pd	0.02146 (17)	0.02124 (17)	0.03568 (17)	0.00033 (7)	0.00598 (10)	−0.00046 (8)
Cl1	0.0303 (4)	0.0360 (4)	0.0503 (5)	0.0077 (3)	0.0037 (3)	0.0045 (3)
Cl2	0.0330 (4)	0.0265 (4)	0.0583 (5)	−0.0053 (3)	0.0064 (3)	−0.0055 (3)
N1	0.0259 (12)	0.0289 (13)	0.0417 (14)	−0.0020 (10)	0.0056 (10)	−0.0027 (11)
N2	0.0253 (12)	0.0252 (11)	0.0385 (14)	0.0003 (10)	0.0048 (10)	0.0039 (11)
C1	0.054 (2)	0.0314 (17)	0.0469 (19)	0.0011 (14)	−0.0072 (15)	−0.0049 (14)
C2	0.077 (3)	0.0322 (18)	0.057 (2)	−0.0009 (18)	−0.0068 (19)	−0.0135 (17)
C3	0.053 (2)	0.0223 (15)	0.079 (3)	−0.0006 (15)	−0.0031 (19)	−0.0053 (17)
C4	0.0348 (15)	0.0246 (15)	0.0461 (17)	−0.0013 (12)	0.0030 (13)	0.0054 (13)
C5	0.0317 (15)	0.0245 (15)	0.0526 (19)	0.0015 (12)	0.0054 (13)	−0.0026 (13)
C6	0.0207 (13)	0.0271 (14)	0.0399 (16)	0.0026 (11)	0.0048 (11)	−0.0020 (12)
C7	0.0309 (15)	0.0262 (15)	0.0409 (17)	0.0031 (11)	0.0027 (13)	−0.0018 (12)
C8	0.0385 (17)	0.0371 (17)	0.0354 (16)	−0.0002 (14)	−0.0005 (13)	0.0023 (14)
C9	0.075 (3)	0.057 (3)	0.063 (3)	0.006 (2)	0.029 (2)	−0.005 (2)
C10	0.063 (3)	0.065 (3)	0.064 (3)	0.013 (2)	−0.003 (2)	0.016 (2)
C11	0.0279 (15)	0.0421 (19)	0.050 (2)	−0.0007 (13)	−0.0054 (14)	−0.0020 (16)
C12	0.0281 (16)	0.0480 (19)	0.064 (2)	−0.0051 (15)	0.0089 (15)	0.0036 (18)
C13	0.0302 (15)	0.0403 (18)	0.054 (2)	−0.0019 (14)	0.0116 (14)	0.0073 (15)
C14	0.0289 (15)	0.0274 (16)	0.0404 (17)	0.0013 (10)	0.0079 (13)	−0.0007 (12)
C15	0.0319 (16)	0.0445 (19)	0.0402 (18)	0.0028 (13)	0.0133 (14)	0.0112 (15)
C16	0.056 (2)	0.059 (3)	0.071 (3)	0.0042 (19)	0.003 (2)	0.028 (2)
C17	0.048 (2)	0.083 (3)	0.043 (2)	0.006 (2)	0.0075 (17)	−0.004 (2)

Pd—N1	2.040 (3)	C7—C8	1.519 (5)
Pd—N2	2.072 (2)	C8—C9	1.510 (5)
Pd—Cl1	2.3055 (8)	C8—C10	1.536 (5)
Pd—Cl2	2.3160 (8)	C8—H8	0.9800
N1—C1	1.487 (4)	C9—H9A	0.9600
N1—C4	1.500 (4)	C9—H9B	0.9600
N1—H1	0.8600	C9—H9C	0.9600
N2—C6	1.463 (4)	C10—H10A	0.9600
N2—C5	1.497 (4)	C10—H10B	0.9600
N2—H2	0.8600	C10—H10C	0.9600
C1—C2	1.521 (5)	C11—C12	1.375 (5)
C1—H1A	0.9700	C11—H11	0.9300
C1—H1B	0.9700	C12—C13	1.369 (5)
C2—C3	1.507 (5)	C12—H12	0.9300
C2—H2A	0.9700	C13—C14	1.388 (4)
C2—H2B	0.9700	C13—H13	0.9300
C3—C4	1.539 (5)	C14—C15	1.524 (5)
C3—H3A	0.9700	C15—C17	1.524 (5)
C3—H3B	0.9700	C15—C16	1.535 (5)
C4—C5	1.510 (4)	C15—H15	0.9800
C4—H4	0.9800	C16—H16A	0.9600
C5—H5A	0.9700	C16—H16B	0.9600
C5—H5B	0.9700	C16—H16C	0.9600
C6—C7	1.399 (4)	C17—H17A	0.9600
C6—C14	1.410 (4)	C17—H17B	0.9600
C7—C11	1.392 (5)	C17—H17C	0.9600
N1—Pd—N2	83.98 (10)	C11—C7—C6	117.9 (3)
N1—Pd—Cl1	90.83 (7)	C11—C7—C8	119.3 (3)
N2—Pd—Cl1	174.45 (7)	C6—C7—C8	122.7 (3)
N1—Pd—Cl2	172.72 (7)	C9—C8—C7	110.5 (3)
N2—Pd—Cl2	92.27 (8)	C9—C8—C10	109.8 (3)
Cl1—Pd—Cl2	93.10 (3)	C7—C8—C10	113.6 (3)
C1—N1—C4	105.8 (2)	C9—C8—H8	107.5
C1—N1—Pd	119.3 (2)	C7—C8—H8	107.5
C4—N1—Pd	111.56 (18)	C10—C8—H8	107.5
C1—N1—H1	106.5	C8—C9—H9A	109.5
C4—N1—H1	106.5	C8—C9—H9B	109.5
Pd—N1—H1	106.5	H9A—C9—H9B	109.5
C6—N2—C5	111.0 (2)	C8—C9—H9C	109.5
C6—N2—Pd	121.74 (19)	H9A—C9—H9C	109.5
C5—N2—Pd	107.90 (18)	H9B—C9—H9C	109.5
C6—N2—H2	104.9	C8—C10—H10A	109.5
C5—N2—H2	104.9	C8—C10—H10B	109.5
Pd—N2—H2	104.9	H10A—C10—H10B	109.5
N1—C1—C2	102.5 (3)	C8—C10—H10C	109.5
N1—C1—H1A	111.3	H10A—C10—H10C	109.5
C2—C1—H1A	111.3	H10B—C10—H10C	109.5
N1—C1—H1B	111.3	C12—C11—C7	121.5 (3)
C2—C1—H1B	111.3	C12—C11—H11	119.3
H1A—C1—H1B	109.2	C7—C11—H11	119.3
C3—C2—C1	103.2 (3)	C13—C12—C11	119.4 (3)
C3—C2—H2A	111.1	C13—C12—H12	120.3
C1—C2—H2A	111.1	C11—C12—H12	120.3
C3—C2—H2B	111.1	C12—C13—C14	122.5 (3)
C1—C2—H2B	111.1	C12—C13—H13	118.8
H2A—C2—H2B	109.1	C14—C13—H13	118.8
C2—C3—C4	105.9 (3)	C13—C14—C6	117.1 (3)
C2—C3—H3A	110.6	C13—C14—C15	117.9 (3)
C4—C3—H3A	110.6	C6—C14—C15	125.0 (3)
C2—C3—H3B	110.6	C17—C15—C14	112.0 (3)
C4—C3—H3B	110.6	C17—C15—C16	111.6 (3)
H3A—C3—H3B	108.7	C14—C15—C16	110.0 (3)
N1—C4—C5	108.3 (2)	C17—C15—H15	107.7
N1—C4—C3	105.2 (3)	C14—C15—H15	107.7
C5—C4—C3	113.3 (3)	C16—C15—H15	107.7
N1—C4—H4	110.0	C15—C16—H16A	109.5
C5—C4—H4	110.0	C15—C16—H16B	109.5
C3—C4—H4	110.0	H16A—C16—H16B	109.5
N2—C5—C4	111.2 (2)	C15—C16—H16C	109.5
N2—C5—H5A	109.4	H16A—C16—H16C	109.5
C4—C5—H5A	109.4	H16B—C16—H16C	109.5
N2—C5—H5B	109.4	C15—C17—H17A	109.5
C4—C5—H5B	109.4	C15—C17—H17B	109.5
H5A—C5—H5B	108.0	H17A—C17—H17B	109.5
C7—C6—C14	121.6 (3)	C15—C17—H17C	109.5
C7—C6—N2	119.0 (3)	H17A—C17—H17C	109.5
C14—C6—N2	119.4 (3)	H17B—C17—H17C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2i	0.86	2.47	3.283 (3)	158
N2—H2···Cl1i	0.86	2.68	3.410 (3)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2i	0.86	2.47	3.283 (3)	158
N2—H2⋯Cl1i	0.86	2.68	3.410 (3)	144

Symmetry code: (i) .