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.
Supporting information
CCDC reference: 206737
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (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.
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
top
Crystal data top
[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) Å3 | Block, yellow |
Z = 4 | 0.16 × 0.12 × 0.10 mm |
F(000) = 912 | |
Data collection top
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 top
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.0291P)2] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.93 | 2.09 | 3.017 (4) | 176 |
Symmetry code: (i) x−1, y, z. |