(η³-Allyl)[(S)-(+)-(2-pyrrolidinyl­methyl)­pyrrolidine]­palladium(II) trifluoro­methane­sulfonate

The title compound, [Pd(C₃H₅)(C₉H₁₈N₂)]CF₃SO₃, crystallizes in the non-centrosymmetric space group P2₁2₁2₁ and contains only one crystallographically unique Pd metal centre, showing a pseudo-square-planar geometry. (S)-(+)-(2-Pyrrolidinyl­methyl)­pyrrolidine (pmp, C₉H₁₈N₂) acts as an N,N′-bidentate chelating ligand, leading to the formation of the chiral [Pd(η³-allyl)(pmp)]⁺ complex cation, which is hydrogen bonded to the trifluoro­methane­sulfonate anion.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.069
• Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.46
         From the CIF: _reflns_number_total               3927
         Count of symmetry unique reflns         2263
         Completeness (_total/calc)            173.53%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1664
         Fraction of Friedel pairs measured     0.735
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare at al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(η³-allyl)[(S)-(+)-(2-pyrrolidinylmethyl)pyrrolidine]palladium(II) trifluomethanesulfonate

Crystal data

[Pd(C3H5)(C9H18N2)]CF3SO3	Dx = 1.738 Mg m^−3
Mr = 450.79	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 8414 reflections
a = 9.1222 (2) Å	θ = 1.0–27.5°
b = 9.1647 (2) Å	µ = 1.24 mm^−1
c = 20.6053 (6) Å	T = 180 K
V = 1722.65 (7) Å^3	Block, yellow
Z = 4	0.16 × 0.12 × 0.10 mm
F(000) = 912

Data collection

Nonius KappaCCD diffractometer	3488 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Thin–slice ω and φ scans	θmax = 27.5°, θmin = 3.7°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −11→11
Tmin = 0.826, Tmax = 0.886	k = −10→11
11560 measured reflections	l = −26→26
3927 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0291P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
3927 reflections	Δρmax = 0.98 e Å^−3
208 parameters	Δρmin = −1.41 e Å^−3
0 restraints	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.10 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.19699 (3)	0.64111 (2)	0.934903 (12)	0.02331 (8)
N1	0.0941 (3)	0.5150 (3)	0.86229 (13)	0.0261 (6)
H1	−0.0020	0.5475	0.8579	0.031*
N2	0.2075 (3)	0.4356 (3)	0.98388 (13)	0.0243 (6)
C1	0.1645 (5)	0.5183 (4)	0.79726 (17)	0.0364 (9)
H1A	0.2726	0.5192	0.8014	0.044*
H1B	0.1335	0.6058	0.7727	0.044*
C2	0.1138 (5)	0.3814 (4)	0.76372 (18)	0.0435 (10)
H2A	0.1828	0.3525	0.7290	0.052*
H2B	0.0149	0.3945	0.7448	0.052*
C3	0.1116 (5)	0.2694 (4)	0.81811 (19)	0.0395 (10)
H3A	0.2050	0.2144	0.8193	0.047*
H3B	0.0301	0.1995	0.8119	0.047*
C4	0.0904 (4)	0.3570 (4)	0.88139 (16)	0.0275 (7)
H4	−0.0067	0.3328	0.9012	0.033*
C5	0.2116 (4)	0.3296 (3)	0.92997 (17)	0.0293 (8)
H5A	0.2017	0.2297	0.9476	0.035*
H5B	0.3076	0.3363	0.9077	0.035*
C6	0.0832 (4)	0.4131 (4)	1.02907 (18)	0.0303 (8)
H6A	0.0694	0.3081	1.0386	0.036*
H6B	−0.0088	0.4527	1.0107	0.036*
C7	0.1276 (5)	0.4963 (4)	1.08996 (18)	0.0386 (10)
H7A	0.0805	0.4540	1.1290	0.046*
H7B	0.1001	0.6005	1.0866	0.046*
C8	0.2954 (5)	0.4782 (4)	1.09278 (18)	0.0437 (10)
H8A	0.3437	0.5737	1.0996	0.052*
H8B	0.3237	0.4118	1.1286	0.052*
C9	0.3386 (4)	0.4135 (4)	1.02711 (18)	0.0321 (9)
H9A	0.4255	0.4642	1.0093	0.038*
H9B	0.3615	0.3083	1.0314	0.038*
C10	0.3275 (5)	0.7828 (4)	0.99246 (19)	0.0359 (10)
H10A	0.3107	0.7796	1.0399	0.043*
H10B	0.4322	0.7909	0.9804	0.043*
C11	0.2302 (5)	0.8648 (4)	0.9566 (2)	0.0436 (10)
H11	0.1513	0.9205	0.9794	0.052*
C12	0.2215 (5)	0.8450 (4)	0.8899 (2)	0.0458 (11)
H12A	0.3131	0.8603	0.8651	0.055*
H12B	0.1336	0.8852	0.8682	0.055*
S1	0.66628 (11)	0.51686 (10)	0.86581 (5)	0.0317 (2)
O1	0.5340 (3)	0.5891 (3)	0.88437 (16)	0.0578 (9)
O2	0.7171 (4)	0.4068 (3)	0.91030 (13)	0.0542 (8)
O3	0.7809 (3)	0.6106 (3)	0.84230 (14)	0.0446 (7)
C13	0.6127 (5)	0.4124 (5)	0.7949 (2)	0.0479 (11)
F1	0.5057 (3)	0.3189 (3)	0.80854 (16)	0.0701 (9)
F2	0.5662 (4)	0.4957 (4)	0.74726 (13)	0.0798 (9)
F3	0.7255 (3)	0.3336 (3)	0.77315 (15)	0.0814 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02360 (13)	0.02073 (13)	0.02559 (13)	−0.00068 (11)	0.00093 (12)	0.00142 (11)
N1	0.0257 (16)	0.0292 (15)	0.0234 (16)	−0.0016 (13)	−0.0003 (13)	0.0027 (13)
N2	0.0241 (15)	0.0246 (13)	0.0241 (15)	0.0016 (14)	−0.0021 (14)	−0.0007 (11)
C1	0.040 (3)	0.044 (2)	0.025 (2)	−0.0002 (18)	0.0047 (17)	0.0046 (17)
C2	0.053 (3)	0.050 (2)	0.027 (2)	−0.005 (2)	0.0003 (18)	−0.0030 (19)
C3	0.051 (3)	0.037 (2)	0.031 (2)	−0.0090 (19)	−0.001 (2)	−0.0116 (18)
C4	0.0269 (18)	0.0262 (16)	0.0295 (19)	−0.0064 (17)	0.0012 (15)	0.0014 (17)
C5	0.034 (2)	0.0249 (16)	0.0291 (19)	0.0024 (14)	0.0044 (19)	−0.0009 (14)
C6	0.028 (2)	0.0293 (19)	0.033 (2)	−0.0009 (16)	0.0042 (17)	0.0029 (16)
C7	0.052 (3)	0.040 (2)	0.024 (2)	0.0070 (19)	0.0056 (18)	−0.0014 (17)
C8	0.057 (3)	0.043 (2)	0.031 (2)	0.008 (2)	−0.014 (2)	0.0006 (17)
C9	0.030 (2)	0.0322 (19)	0.034 (2)	0.0053 (15)	−0.0115 (16)	0.0036 (16)
C10	0.042 (3)	0.0299 (19)	0.036 (2)	−0.0113 (18)	0.0005 (19)	−0.0057 (16)
C11	0.052 (3)	0.0247 (18)	0.054 (3)	−0.0070 (19)	−0.001 (2)	0.0049 (19)
C12	0.072 (3)	0.0246 (19)	0.041 (2)	−0.010 (2)	0.009 (2)	0.0113 (17)
S1	0.0336 (6)	0.0324 (5)	0.0292 (5)	0.0010 (4)	0.0027 (4)	−0.0017 (4)
O1	0.0422 (18)	0.062 (2)	0.069 (2)	0.0080 (14)	0.0115 (16)	−0.0253 (17)
O2	0.071 (2)	0.0472 (16)	0.0448 (17)	−0.0037 (15)	−0.0145 (16)	0.0145 (13)
O3	0.0360 (17)	0.0472 (17)	0.0506 (18)	−0.0046 (14)	0.0043 (14)	0.0099 (13)
C13	0.042 (3)	0.059 (3)	0.042 (3)	0.008 (2)	0.002 (2)	−0.017 (2)
F1	0.0601 (19)	0.0650 (19)	0.085 (2)	−0.0196 (15)	−0.0018 (16)	−0.0297 (16)
F2	0.095 (3)	0.103 (2)	0.0412 (16)	0.003 (2)	−0.0207 (17)	−0.0003 (17)
F3	0.068 (2)	0.100 (2)	0.076 (2)	0.0247 (18)	0.0122 (16)	−0.0457 (17)

Geometric parameters (Å, º)

Pd1—C12	2.098 (3)	C13—F3	1.335 (5)
Pd1—N1	2.111 (3)	N1—H1	0.9300
Pd1—C11	2.120 (4)	C1—H1A	0.9900
Pd1—C10	2.124 (4)	C1—H1B	0.9900
Pd1—N2	2.139 (3)	C2—H2A	0.9900
N1—C1	1.486 (4)	C2—H2B	0.9900
N1—C4	1.501 (4)	C3—H3A	0.9900
N2—C5	1.476 (4)	C3—H3B	0.9900
N2—C6	1.482 (5)	C4—H4	1.0000
N2—C9	1.504 (4)	C5—H5A	0.9900
C1—C2	1.505 (5)	C5—H5B	0.9900
C2—C3	1.520 (6)	C6—H6A	0.9900
C3—C4	1.544 (5)	C6—H6B	0.9900
C4—C5	1.513 (5)	C7—H7A	0.9900
C6—C7	1.523 (5)	C7—H7B	0.9900
C7—C8	1.541 (6)	C8—H8A	0.9900
C8—C9	1.529 (5)	C8—H8B	0.9900
C10—C11	1.377 (6)	C9—H9A	0.9900
C11—C12	1.389 (6)	C9—H9B	0.9900
S1—O1	1.429 (3)	C10—H10A	0.9900
S1—O3	1.438 (3)	C10—H10B	0.9900
S1—O2	1.440 (3)	C11—H11	1.0000
S1—C13	1.813 (4)	C12—H12A	0.9900
C13—F2	1.314 (5)	C12—H12B	0.9900
C13—F1	1.329 (5)
C12—Pd1—N1	102.83 (14)	C2—C1—H1B	110.7
C12—Pd1—C11	38.44 (15)	H1A—C1—H1B	108.8
N1—Pd1—C11	137.96 (14)	C1—C2—H2A	111.1
C12—Pd1—C10	69.04 (16)	C3—C2—H2A	111.1
N1—Pd1—C10	168.51 (14)	C1—C2—H2B	111.1
C11—Pd1—C10	37.87 (15)	C3—C2—H2B	111.1
C12—Pd1—N2	171.11 (18)	H2A—C2—H2B	109.1
N1—Pd1—N2	82.66 (10)	C2—C3—H3A	110.6
C11—Pd1—N2	138.19 (13)	C4—C3—H3A	110.6
C10—Pd1—N2	104.46 (13)	C2—C3—H3B	110.6
C1—N1—C4	105.4 (3)	C4—C3—H3B	110.6
C1—N1—Pd1	115.8 (2)	H3A—C3—H3B	108.7
C4—N1—Pd1	110.6 (2)	N1—C4—H4	109.9
C5—N2—C6	113.6 (3)	C5—C4—H4	109.9
C5—N2—C9	109.7 (3)	C3—C4—H4	109.9
C6—N2—C9	102.5 (2)	N2—C5—H5A	109.3
C5—N2—Pd1	103.03 (18)	C4—C5—H5A	109.3
C6—N2—Pd1	112.6 (2)	N2—C5—H5B	109.3
C9—N2—Pd1	115.7 (2)	C4—C5—H5B	109.3
N1—C1—C2	105.3 (3)	H5A—C5—H5B	107.9
C1—C2—C3	103.2 (3)	N2—C6—H6A	110.9
C2—C3—C4	105.8 (3)	C7—C6—H6A	110.9
N1—C4—C5	108.5 (3)	N2—C6—H6B	110.9
N1—C4—C3	106.1 (3)	C7—C6—H6B	110.9
C5—C4—C3	112.4 (3)	H6A—C6—H6B	108.9
N2—C5—C4	111.8 (3)	C6—C7—H7A	111.0
N2—C6—C7	104.1 (3)	C8—C7—H7A	111.0
C6—C7—C8	104.0 (3)	C6—C7—H7B	111.0
C9—C8—C7	105.3 (3)	C8—C7—H7B	111.0
N2—C9—C8	105.5 (3)	H7A—C7—H7B	109.0
C11—C10—Pd1	70.9 (2)	C9—C8—H8A	110.7
C10—C11—C12	119.8 (4)	C7—C8—H8A	110.7
C10—C11—Pd1	71.2 (2)	C9—C8—H8B	110.7
C12—C11—Pd1	69.9 (2)	C7—C8—H8B	110.7
C11—C12—Pd1	71.6 (2)	H8A—C8—H8B	108.8
O1—S1—O3	115.32 (18)	N2—C9—H9A	110.6
O1—S1—O2	115.2 (2)	C8—C9—H9A	110.6
O3—S1—O2	113.52 (19)	N2—C9—H9B	110.6
O1—S1—C13	103.4 (2)	C8—C9—H9B	110.6
O3—S1—C13	103.9 (2)	H9A—C9—H9B	108.8
O2—S1—C13	103.3 (2)	C11—C10—H10A	116.5
F2—C13—F1	107.2 (4)	Pd1—C10—H10A	116.5
F2—C13—F3	108.1 (4)	C11—C10—H10B	116.5
F1—C13—F3	106.7 (3)	Pd1—C10—H10B	116.5
F2—C13—S1	112.5 (3)	H10A—C10—H10B	113.5
F1—C13—S1	111.6 (3)	C10—C11—H11	119.4
F3—C13—S1	110.4 (3)	C12—C11—H11	119.4
C1—N1—H1	108.2	Pd1—C11—H11	119.4
C4—N1—H1	108.2	C11—C12—H12A	116.4
Pd1—N1—H1	108.2	Pd1—C12—H12A	116.4
N1—C1—H1A	110.7	C11—C12—H12B	116.4
C2—C1—H1A	110.7	Pd1—C12—H12B	116.4
N1—C1—H1B	110.7	H12A—C12—H12B	113.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.93	2.09	3.017 (4)	176

Symmetry code: (i) x−1, y, z.