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metal-organic compounds
Bromido({2-[2-(diphenylphosphanyl)benzylidene]hydrazin-1-ylidene}(4-methoxyanilino)methanethiolato)palladium(II) acetone monosolvate
aDepartment of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia, bIbnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia, and cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: hkfun@usm.my
In the title compound, [PdBr(C27H23N3OPS)]·C3H6O, the coordination geometry about the PdII atom is distorted square-planar, arising from the attached Br, S, P and N atoms (N and Br are trans), the maximum deviation from the plane being 0.2053 (4) Å for the N atom. The three benzene rings attached to the P atom make dihedral angles of 69.78 (7), 87.05 (7) and 77.50 (7)° with each other. An intramolecular C—H⋯N hydrogen bond forms an S(6) ring motif. In the crystal, the complex molecules form infinite chains along the a-axis direction through C—H⋯Br interactions, and a C—H⋯O interaction links the main molecule with the acetone solvent molecule.
Related literature
For the properties of palladium(II)–iminophosphine complexes, see: Mahamo et al. (2012); Nobre & Monteiro (2009
); Scrivanti et al. (2009
); Sánchez et al. (2010
); Mogorosi et al. (2011
). For hydrogen-bond motifs, see: Bernstein et al. (1995
).
Experimental
Crystal data
|
Refinement
|
|
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009
); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009
).
Supporting information
https://doi.org/10.1107/S1600536812028760/hb6867sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028760/hb6867Isup2.hkl
The title complex was prepared by a metathesis reaction of the chlorido({2-[2-(diphenylphosphanyl)benzylidene]hydrazin-1-ylidene}(4-methoxyanilino)methanethiolato)palladium(II) complex. Potassium bromide (70 mg, 0.57 mmol) was added to a solution of the chloropalladium(II) complex (30 mg, 0.06 mmol) in acetone (6 ml). The reaction mixture was allowed to stand at room temperature for 20 h. Orange blocks of the title compound, which precipitated out were filtered off, washed with cold methanol and dried in vacuo (yield: 80%). Melting point: 157–159 °C.
N bound H atom were located from a difference Fourier map and freely refined. The remaining H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.98 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating group model was applied to the methyl group.
Iminophosphines containing heteroatoms such as nitrogen, oxygen or sulfur have attracted considerable attention with the expectation that the functionality could participate in the chemistry. These functionalized ligands may act as chelating ligands, using phosphorus and other atom(s), for example, the nitrogen, oxygen or sulfur as donor atoms. Interest in the metal complexes of these hemilabile ligands and their applications in catalysis have been steadily growing as the different features associated with each donor atom offer properties unique to their metal. In particular, the palladium(II)-iminophosphine complexes have shown great potential as catalysts for the formation of new C—C bonds in organic synthesis (Mahamo et al., 2012, Nobre et al., 2009, Scrivanti et al., 2009, Sánchez et al., 2010) and in
reactions (Mogorosi et al., 2011).All parameters in (I), are within normal ranges. The coordination environment around PdII atom is in a distorted square-planar configuration, formed by Br1, S1, P1 and N1 atoms with maximum deviation from the plane form by these atoms being 0.2053 (4) Å for the N1 atom. The coordination bond distances between PdII with Br1, S1, P1 and N1 atoms are 2.42015 (17), 2.3260 (4), 2.2470 (4) and 2.0243 (12) Å, respectively with angles 93.17 (1)° for Br1—Pd1—P1, 94.02 (1)° for Br1—Pd1—S1, 83.9 (3)° for S1—Pd1—N1 and 90.13 (3) for P1—Pd1—N1. The three benzene rings attached to the P1 atom make dihedral angles of 69.78 (7)° (C2—C7 and C8—C13), 87.05 (7)° (C2—C7 and C14—C19) and 77.50 (7)° (C8—C13 and C14—C19). These three benzene rings make dihedral angles of 21.99 (7)°, 86.06 (7)° and 75.78 (7)° with the C21—C26 benzene ring.
In the molecule, an intramolecular hydrogen bond of C26—H26A···N2 (Table 1) forms an S(6) hydrogen ring motif (Bernstein et al., 1995).In the
the main molecules form infinite chains along the a-direction through the intermolecular interaction of C3—H3A···Br1i whereas the C9—H9A···O2ii bond links the main molecule with the acetone (Fig. 2).For the properties of palladium(II)–iminophosphine complexes, see: Mahamo et al. (2012); Nobre & Monteiro (2009); Scrivanti et al. (2009); Sánchez et al. (2010); Mogorosi et al. (2011). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).[PdBr(C27H23N3OPS)]·C3H6O | F(000) = 1432 |
Mr = 712.90 | Dx = 1.658 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9855 reflections |
a = 9.7594 (1) Å | θ = 2.6–32.7° |
b = 13.7946 (2) Å | µ = 2.21 mm−1 |
c = 21.8681 (3) Å | T = 100 K |
β = 104.092 (1)° | Block, orange |
V = 2855.44 (6) Å3 | 0.34 × 0.29 × 0.28 mm |
Z = 4 |
Bruker SMART APEXII CCD diffractometer | 10415 independent reflections |
Radiation source: fine-focus sealed tube | 8861 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 32.7°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −14→13 |
Tmin = 0.519, Tmax = 0.581 | k = −20→20 |
39886 measured reflections | l = −33→31 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0214P)2 + 1.9887P] where P = (Fo2 + 2Fc2)/3 |
10415 reflections | (Δ/σ)max = 0.003 |
359 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
[PdBr(C27H23N3OPS)]·C3H6O | V = 2855.44 (6) Å3 |
Mr = 712.90 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7594 (1) Å | µ = 2.21 mm−1 |
b = 13.7946 (2) Å | T = 100 K |
c = 21.8681 (3) Å | 0.34 × 0.29 × 0.28 mm |
β = 104.092 (1)° |
Bruker SMART APEXII CCD diffractometer | 10415 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 8861 reflections with I > 2σ(I) |
Tmin = 0.519, Tmax = 0.581 | Rint = 0.020 |
39886 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.57 e Å−3 |
10415 reflections | Δρmin = −0.51 e Å−3 |
359 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
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 | ||
Pd1 | 0.704790 (10) | 0.779680 (8) | 0.641136 (5) | 0.01125 (3) | |
Br1 | 0.488416 (14) | 0.688667 (11) | 0.631039 (7) | 0.01661 (3) | |
S1 | 0.60716 (4) | 0.88536 (3) | 0.559230 (18) | 0.01615 (7) | |
P1 | 0.80778 (4) | 0.71221 (3) | 0.734540 (17) | 0.01189 (6) | |
O1 | 1.14215 (11) | 1.29985 (8) | 0.48277 (6) | 0.0204 (2) | |
N1 | 0.88698 (12) | 0.84952 (9) | 0.64072 (5) | 0.0121 (2) | |
N2 | 0.88304 (12) | 0.93600 (9) | 0.60730 (6) | 0.0141 (2) | |
N3 | 0.74780 (13) | 1.03604 (9) | 0.53199 (6) | 0.0163 (2) | |
C1 | 1.01540 (14) | 0.82094 (11) | 0.66483 (7) | 0.0142 (3) | |
H1A | 1.0873 | 0.8613 | 0.6562 | 0.017* | |
C2 | 1.06536 (14) | 0.73545 (10) | 0.70334 (7) | 0.0132 (2) | |
C3 | 1.20598 (14) | 0.70940 (11) | 0.70649 (7) | 0.0156 (3) | |
H3A | 1.2597 | 0.7471 | 0.6844 | 0.019* | |
C4 | 1.26828 (15) | 0.62984 (11) | 0.74116 (7) | 0.0175 (3) | |
H4A | 1.3628 | 0.6125 | 0.7417 | 0.021* | |
C5 | 1.19220 (15) | 0.57571 (11) | 0.77498 (7) | 0.0183 (3) | |
H5A | 1.2348 | 0.5216 | 0.7991 | 0.022* | |
C6 | 1.05325 (15) | 0.60090 (11) | 0.77346 (7) | 0.0162 (3) | |
H6A | 1.0020 | 0.5642 | 0.7972 | 0.019* | |
C7 | 0.98815 (14) | 0.67937 (10) | 0.73746 (7) | 0.0133 (2) | |
C8 | 0.73152 (14) | 0.60811 (11) | 0.76440 (7) | 0.0139 (2) | |
C9 | 0.71690 (15) | 0.52162 (11) | 0.73022 (7) | 0.0173 (3) | |
H9A | 0.7438 | 0.5185 | 0.6913 | 0.021* | |
C10 | 0.66292 (16) | 0.44031 (11) | 0.75344 (8) | 0.0198 (3) | |
H10A | 0.6544 | 0.3810 | 0.7307 | 0.024* | |
C11 | 0.62110 (16) | 0.44505 (12) | 0.80996 (8) | 0.0216 (3) | |
H11A | 0.5845 | 0.3890 | 0.8257 | 0.026* | |
C12 | 0.63286 (16) | 0.53128 (12) | 0.84311 (8) | 0.0214 (3) | |
H12A | 0.6029 | 0.5348 | 0.8813 | 0.026* | |
C13 | 0.68869 (15) | 0.61310 (11) | 0.82056 (7) | 0.0176 (3) | |
H13A | 0.6975 | 0.6722 | 0.8435 | 0.021* | |
C14 | 0.81635 (14) | 0.80673 (10) | 0.79286 (7) | 0.0134 (2) | |
C15 | 0.69068 (15) | 0.85482 (11) | 0.79408 (7) | 0.0170 (3) | |
H15A | 0.6055 | 0.8383 | 0.7644 | 0.020* | |
C16 | 0.69001 (16) | 0.92636 (12) | 0.83842 (8) | 0.0195 (3) | |
H16A | 0.6044 | 0.9584 | 0.8394 | 0.023* | |
C17 | 0.81496 (17) | 0.95120 (12) | 0.88152 (8) | 0.0221 (3) | |
H17A | 0.8146 | 1.0002 | 0.9120 | 0.026* | |
C18 | 0.94000 (17) | 0.90461 (12) | 0.88012 (8) | 0.0225 (3) | |
H18A | 1.0252 | 0.9222 | 0.9095 | 0.027* | |
C19 | 0.94167 (15) | 0.83214 (11) | 0.83592 (7) | 0.0182 (3) | |
H19A | 1.0275 | 0.8003 | 0.8351 | 0.022* | |
C20 | 0.76103 (14) | 0.95539 (10) | 0.56883 (7) | 0.0137 (2) | |
C21 | 0.85096 (15) | 1.10329 (11) | 0.52262 (7) | 0.0148 (3) | |
C22 | 0.80186 (15) | 1.18361 (11) | 0.48507 (7) | 0.0181 (3) | |
H22A | 0.7031 | 1.1919 | 0.4687 | 0.022* | |
C23 | 0.89460 (16) | 1.25220 (12) | 0.47100 (7) | 0.0182 (3) | |
H23A | 0.8592 | 1.3071 | 0.4459 | 0.022* | |
C24 | 1.03915 (15) | 1.23961 (11) | 0.49406 (7) | 0.0166 (3) | |
C25 | 1.08861 (15) | 1.15945 (11) | 0.53156 (7) | 0.0166 (3) | |
H25A | 1.1875 | 1.1509 | 0.5472 | 0.020* | |
C26 | 0.99713 (15) | 1.09190 (11) | 0.54654 (7) | 0.0155 (3) | |
H26A | 1.0330 | 1.0382 | 0.5728 | 0.019* | |
C27 | 1.09781 (17) | 1.38688 (12) | 0.44904 (8) | 0.0215 (3) | |
H27A | 1.1808 | 1.4238 | 0.4449 | 0.032* | |
H27B | 1.0425 | 1.4257 | 0.4719 | 0.032* | |
H27C | 1.0395 | 1.3711 | 0.4070 | 0.032* | |
O2 | 0.28740 (16) | 0.89352 (14) | 0.89867 (9) | 0.0568 (5) | |
C28 | 0.5216 (2) | 0.88159 (18) | 0.96035 (10) | 0.0389 (5) | |
H28A | 0.5261 | 0.9520 | 0.9552 | 0.058* | |
H28B | 0.6047 | 0.8514 | 0.9506 | 0.058* | |
H28C | 0.5200 | 0.8665 | 1.0040 | 0.058* | |
C29 | 0.39116 (18) | 0.84330 (15) | 0.91678 (9) | 0.0294 (4) | |
C30 | 0.3951 (3) | 0.74038 (17) | 0.89679 (11) | 0.0439 (5) | |
H30A | 0.2984 | 0.7168 | 0.8804 | 0.066* | |
H30B | 0.4424 | 0.7009 | 0.9330 | 0.066* | |
H30C | 0.4471 | 0.7358 | 0.8638 | 0.066* | |
H1N3 | 0.666 (2) | 1.0483 (14) | 0.5108 (9) | 0.017 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01062 (4) | 0.01195 (5) | 0.01123 (5) | 0.00014 (3) | 0.00274 (3) | 0.00117 (4) |
Br1 | 0.01181 (6) | 0.01856 (7) | 0.01935 (7) | −0.00098 (5) | 0.00360 (5) | 0.00368 (5) |
S1 | 0.01293 (14) | 0.01705 (17) | 0.01712 (17) | −0.00071 (12) | 0.00104 (12) | 0.00493 (13) |
P1 | 0.01176 (14) | 0.01188 (16) | 0.01216 (16) | −0.00036 (12) | 0.00319 (12) | 0.00106 (12) |
O1 | 0.0186 (5) | 0.0174 (5) | 0.0254 (6) | −0.0022 (4) | 0.0054 (4) | 0.0058 (4) |
N1 | 0.0139 (5) | 0.0115 (5) | 0.0110 (5) | −0.0003 (4) | 0.0030 (4) | 0.0009 (4) |
N2 | 0.0157 (5) | 0.0117 (5) | 0.0148 (6) | −0.0009 (4) | 0.0033 (4) | 0.0027 (4) |
N3 | 0.0141 (5) | 0.0155 (6) | 0.0180 (6) | 0.0006 (4) | 0.0013 (4) | 0.0060 (5) |
C1 | 0.0138 (6) | 0.0146 (7) | 0.0147 (6) | −0.0011 (5) | 0.0046 (5) | 0.0007 (5) |
C2 | 0.0127 (5) | 0.0138 (7) | 0.0131 (6) | 0.0000 (4) | 0.0029 (5) | −0.0006 (5) |
C3 | 0.0132 (6) | 0.0168 (7) | 0.0170 (7) | 0.0001 (5) | 0.0041 (5) | 0.0005 (5) |
C4 | 0.0144 (6) | 0.0186 (7) | 0.0197 (7) | 0.0023 (5) | 0.0044 (5) | 0.0011 (6) |
C5 | 0.0181 (6) | 0.0169 (7) | 0.0201 (7) | 0.0043 (5) | 0.0048 (5) | 0.0036 (6) |
C6 | 0.0163 (6) | 0.0158 (7) | 0.0168 (7) | 0.0013 (5) | 0.0046 (5) | 0.0031 (5) |
C7 | 0.0127 (5) | 0.0140 (6) | 0.0132 (6) | 0.0002 (5) | 0.0034 (5) | −0.0007 (5) |
C8 | 0.0122 (5) | 0.0148 (6) | 0.0137 (6) | −0.0007 (5) | 0.0014 (5) | 0.0037 (5) |
C9 | 0.0176 (6) | 0.0163 (7) | 0.0174 (7) | −0.0004 (5) | 0.0033 (5) | 0.0015 (5) |
C10 | 0.0194 (6) | 0.0141 (7) | 0.0242 (8) | −0.0020 (5) | 0.0018 (6) | 0.0013 (6) |
C11 | 0.0179 (6) | 0.0192 (7) | 0.0264 (8) | −0.0049 (5) | 0.0027 (6) | 0.0076 (6) |
C12 | 0.0211 (7) | 0.0246 (8) | 0.0190 (7) | −0.0037 (6) | 0.0060 (6) | 0.0050 (6) |
C13 | 0.0191 (6) | 0.0178 (7) | 0.0161 (7) | −0.0019 (5) | 0.0048 (5) | 0.0010 (5) |
C14 | 0.0152 (6) | 0.0130 (6) | 0.0124 (6) | 0.0003 (5) | 0.0044 (5) | 0.0008 (5) |
C15 | 0.0163 (6) | 0.0181 (7) | 0.0165 (7) | 0.0015 (5) | 0.0039 (5) | −0.0002 (5) |
C16 | 0.0215 (7) | 0.0180 (7) | 0.0204 (7) | 0.0028 (5) | 0.0075 (6) | −0.0020 (6) |
C17 | 0.0252 (7) | 0.0190 (8) | 0.0218 (8) | 0.0008 (6) | 0.0052 (6) | −0.0047 (6) |
C18 | 0.0210 (7) | 0.0227 (8) | 0.0212 (8) | −0.0006 (6) | 0.0002 (6) | −0.0057 (6) |
C19 | 0.0163 (6) | 0.0183 (7) | 0.0189 (7) | 0.0007 (5) | 0.0024 (5) | −0.0020 (5) |
C20 | 0.0158 (6) | 0.0129 (6) | 0.0134 (6) | 0.0001 (5) | 0.0053 (5) | 0.0001 (5) |
C21 | 0.0160 (6) | 0.0135 (6) | 0.0148 (6) | 0.0000 (5) | 0.0032 (5) | 0.0014 (5) |
C22 | 0.0162 (6) | 0.0178 (7) | 0.0190 (7) | 0.0008 (5) | 0.0018 (5) | 0.0032 (6) |
C23 | 0.0202 (6) | 0.0152 (7) | 0.0184 (7) | 0.0008 (5) | 0.0033 (5) | 0.0043 (5) |
C24 | 0.0186 (6) | 0.0155 (7) | 0.0158 (7) | −0.0019 (5) | 0.0046 (5) | −0.0001 (5) |
C25 | 0.0157 (6) | 0.0172 (7) | 0.0162 (7) | 0.0000 (5) | 0.0026 (5) | 0.0010 (5) |
C26 | 0.0174 (6) | 0.0133 (6) | 0.0151 (6) | 0.0007 (5) | 0.0028 (5) | 0.0024 (5) |
C27 | 0.0247 (7) | 0.0168 (7) | 0.0222 (8) | −0.0033 (6) | 0.0044 (6) | 0.0047 (6) |
O2 | 0.0318 (8) | 0.0650 (12) | 0.0747 (13) | 0.0166 (8) | 0.0149 (8) | 0.0380 (10) |
C28 | 0.0411 (11) | 0.0494 (13) | 0.0270 (10) | −0.0042 (9) | 0.0097 (8) | −0.0033 (9) |
C29 | 0.0239 (8) | 0.0400 (11) | 0.0266 (9) | 0.0040 (7) | 0.0105 (7) | 0.0133 (8) |
C30 | 0.0570 (14) | 0.0432 (13) | 0.0313 (11) | −0.0085 (11) | 0.0107 (10) | −0.0021 (9) |
Pd1—N1 | 2.0243 (12) | C12—C13 | 1.395 (2) |
Pd1—P1 | 2.2470 (4) | C12—H12A | 0.9500 |
Pd1—S1 | 2.3260 (4) | C13—H13A | 0.9500 |
Pd1—Br1 | 2.4202 (2) | C14—C19 | 1.394 (2) |
S1—C20 | 1.7547 (14) | C14—C15 | 1.400 (2) |
P1—C7 | 1.8037 (14) | C15—C16 | 1.385 (2) |
P1—C8 | 1.8109 (15) | C15—H15A | 0.9500 |
P1—C14 | 1.8115 (15) | C16—C17 | 1.390 (2) |
O1—C24 | 1.3722 (18) | C16—H16A | 0.9500 |
O1—C27 | 1.4203 (19) | C17—C18 | 1.386 (2) |
N1—C1 | 1.2971 (17) | C17—H17A | 0.9500 |
N1—N2 | 1.3945 (17) | C18—C19 | 1.393 (2) |
N2—C20 | 1.3075 (18) | C18—H18A | 0.9500 |
N3—C20 | 1.3610 (19) | C19—H19A | 0.9500 |
N3—C21 | 1.4202 (19) | C21—C22 | 1.393 (2) |
N3—H1N3 | 0.836 (19) | C21—C26 | 1.4035 (19) |
C1—C2 | 1.462 (2) | C22—C23 | 1.394 (2) |
C1—H1A | 0.9500 | C22—H22A | 0.9500 |
C2—C3 | 1.4040 (19) | C23—C24 | 1.389 (2) |
C2—C7 | 1.413 (2) | C23—H23A | 0.9500 |
C3—C4 | 1.387 (2) | C24—C25 | 1.391 (2) |
C3—H3A | 0.9500 | C25—C26 | 1.384 (2) |
C4—C5 | 1.387 (2) | C25—H25A | 0.9500 |
C4—H4A | 0.9500 | C26—H26A | 0.9500 |
C5—C6 | 1.392 (2) | C27—H27A | 0.9800 |
C5—H5A | 0.9500 | C27—H27B | 0.9800 |
C6—C7 | 1.397 (2) | C27—H27C | 0.9800 |
C6—H6A | 0.9500 | O2—C29 | 1.211 (2) |
C8—C13 | 1.392 (2) | C28—C29 | 1.489 (3) |
C8—C9 | 1.397 (2) | C28—H28A | 0.9800 |
C9—C10 | 1.387 (2) | C28—H28B | 0.9800 |
C9—H9A | 0.9500 | C28—H28C | 0.9800 |
C10—C11 | 1.394 (2) | C29—C30 | 1.489 (3) |
C10—H10A | 0.9500 | C30—H30A | 0.9800 |
C11—C12 | 1.383 (2) | C30—H30B | 0.9800 |
C11—H11A | 0.9500 | C30—H30C | 0.9800 |
N1—Pd1—P1 | 90.13 (3) | C19—C14—C15 | 119.75 (14) |
N1—Pd1—S1 | 83.90 (3) | C19—C14—P1 | 122.61 (11) |
P1—Pd1—S1 | 165.537 (15) | C15—C14—P1 | 117.64 (11) |
N1—Pd1—Br1 | 173.90 (3) | C16—C15—C14 | 120.30 (14) |
P1—Pd1—Br1 | 93.172 (10) | C16—C15—H15A | 119.9 |
S1—Pd1—Br1 | 94.023 (10) | C14—C15—H15A | 119.9 |
C20—S1—Pd1 | 94.29 (5) | C15—C16—C17 | 119.83 (14) |
C7—P1—C8 | 105.74 (7) | C15—C16—H16A | 120.1 |
C7—P1—C14 | 106.17 (7) | C17—C16—H16A | 120.1 |
C8—P1—C14 | 105.63 (7) | C18—C17—C16 | 120.15 (15) |
C7—P1—Pd1 | 110.66 (5) | C18—C17—H17A | 119.9 |
C8—P1—Pd1 | 121.60 (5) | C16—C17—H17A | 119.9 |
C14—P1—Pd1 | 106.00 (5) | C17—C18—C19 | 120.47 (14) |
C24—O1—C27 | 117.48 (12) | C17—C18—H18A | 119.8 |
C1—N1—N2 | 111.94 (11) | C19—C18—H18A | 119.8 |
C1—N1—Pd1 | 128.05 (10) | C18—C19—C14 | 119.49 (14) |
N2—N1—Pd1 | 119.82 (8) | C18—C19—H19A | 120.3 |
C20—N2—N1 | 114.64 (12) | C14—C19—H19A | 120.3 |
C20—N3—C21 | 130.61 (12) | N2—C20—N3 | 119.24 (13) |
C20—N3—H1N3 | 115.7 (13) | N2—C20—S1 | 125.67 (11) |
C21—N3—H1N3 | 113.7 (13) | N3—C20—S1 | 115.09 (10) |
N1—C1—C2 | 129.27 (13) | C22—C21—C26 | 118.78 (13) |
N1—C1—H1A | 115.4 | C22—C21—N3 | 116.77 (13) |
C2—C1—H1A | 115.4 | C26—C21—N3 | 124.40 (13) |
C3—C2—C7 | 118.33 (13) | C21—C22—C23 | 121.41 (14) |
C3—C2—C1 | 114.81 (12) | C21—C22—H22A | 119.3 |
C7—C2—C1 | 126.86 (12) | C23—C22—H22A | 119.3 |
C4—C3—C2 | 121.49 (14) | C24—C23—C22 | 119.45 (14) |
C4—C3—H3A | 119.3 | C24—C23—H23A | 120.3 |
C2—C3—H3A | 119.3 | C22—C23—H23A | 120.3 |
C5—C4—C3 | 119.80 (13) | O1—C24—C23 | 125.66 (14) |
C5—C4—H4A | 120.1 | O1—C24—C25 | 115.03 (13) |
C3—C4—H4A | 120.1 | C23—C24—C25 | 119.31 (14) |
C4—C5—C6 | 119.85 (14) | C26—C25—C24 | 121.57 (13) |
C4—C5—H5A | 120.1 | C26—C25—H25A | 119.2 |
C6—C5—H5A | 120.1 | C24—C25—H25A | 119.2 |
C5—C6—C7 | 120.90 (14) | C25—C26—C21 | 119.47 (14) |
C5—C6—H6A | 119.6 | C25—C26—H26A | 120.3 |
C7—C6—H6A | 119.6 | C21—C26—H26A | 120.3 |
C6—C7—C2 | 119.60 (13) | O1—C27—H27A | 109.5 |
C6—C7—P1 | 121.37 (11) | O1—C27—H27B | 109.5 |
C2—C7—P1 | 119.02 (11) | H27A—C27—H27B | 109.5 |
C13—C8—C9 | 120.06 (14) | O1—C27—H27C | 109.5 |
C13—C8—P1 | 121.13 (12) | H27A—C27—H27C | 109.5 |
C9—C8—P1 | 118.81 (11) | H27B—C27—H27C | 109.5 |
C10—C9—C8 | 119.56 (14) | C29—C28—H28A | 109.5 |
C10—C9—H9A | 120.2 | C29—C28—H28B | 109.5 |
C8—C9—H9A | 120.2 | H28A—C28—H28B | 109.5 |
C9—C10—C11 | 120.39 (15) | C29—C28—H28C | 109.5 |
C9—C10—H10A | 119.8 | H28A—C28—H28C | 109.5 |
C11—C10—H10A | 119.8 | H28B—C28—H28C | 109.5 |
C12—C11—C10 | 120.00 (14) | O2—C29—C30 | 121.9 (2) |
C12—C11—H11A | 120.0 | O2—C29—C28 | 121.5 (2) |
C10—C11—H11A | 120.0 | C30—C29—C28 | 116.55 (18) |
C11—C12—C13 | 120.04 (15) | C29—C30—H30A | 109.5 |
C11—C12—H12A | 120.0 | C29—C30—H30B | 109.5 |
C13—C12—H12A | 120.0 | H30A—C30—H30B | 109.5 |
C8—C13—C12 | 119.93 (15) | C29—C30—H30C | 109.5 |
C8—C13—H13A | 120.0 | H30A—C30—H30C | 109.5 |
C12—C13—H13A | 120.0 | H30B—C30—H30C | 109.5 |
N1—Pd1—S1—C20 | −8.51 (6) | Pd1—P1—C8—C9 | 62.03 (12) |
P1—Pd1—S1—C20 | 57.59 (7) | C13—C8—C9—C10 | −1.6 (2) |
Br1—Pd1—S1—C20 | 177.24 (5) | P1—C8—C9—C10 | 177.93 (11) |
N1—Pd1—P1—C7 | −38.54 (6) | C8—C9—C10—C11 | 1.1 (2) |
S1—Pd1—P1—C7 | −103.92 (7) | C9—C10—C11—C12 | 0.2 (2) |
Br1—Pd1—P1—C7 | 136.33 (5) | C10—C11—C12—C13 | −1.1 (2) |
N1—Pd1—P1—C8 | −163.47 (7) | C9—C8—C13—C12 | 0.8 (2) |
S1—Pd1—P1—C8 | 131.15 (7) | P1—C8—C13—C12 | −178.73 (11) |
Br1—Pd1—P1—C8 | 11.40 (6) | C11—C12—C13—C8 | 0.5 (2) |
N1—Pd1—P1—C14 | 76.16 (6) | C7—P1—C14—C19 | −9.13 (15) |
S1—Pd1—P1—C14 | 10.78 (8) | C8—P1—C14—C19 | 102.87 (13) |
Br1—Pd1—P1—C14 | −108.97 (5) | Pd1—P1—C14—C19 | −126.86 (12) |
P1—Pd1—N1—C1 | 31.57 (12) | C7—P1—C14—C15 | 171.21 (11) |
S1—Pd1—N1—C1 | −161.62 (13) | C8—P1—C14—C15 | −76.79 (13) |
P1—Pd1—N1—N2 | −153.83 (10) | Pd1—P1—C14—C15 | 53.48 (12) |
S1—Pd1—N1—N2 | 12.97 (9) | C19—C14—C15—C16 | −1.0 (2) |
C1—N1—N2—C20 | 163.04 (13) | P1—C14—C15—C16 | 178.68 (12) |
Pd1—N1—N2—C20 | −12.37 (16) | C14—C15—C16—C17 | 0.6 (2) |
N2—N1—C1—C2 | 179.29 (14) | C15—C16—C17—C18 | 0.1 (3) |
Pd1—N1—C1—C2 | −5.8 (2) | C16—C17—C18—C19 | −0.4 (3) |
N1—C1—C2—C3 | 162.00 (15) | C17—C18—C19—C14 | 0.1 (3) |
N1—C1—C2—C7 | −19.1 (3) | C15—C14—C19—C18 | 0.6 (2) |
C7—C2—C3—C4 | 1.1 (2) | P1—C14—C19—C18 | −179.03 (12) |
C1—C2—C3—C4 | −179.93 (14) | N1—N2—C20—N3 | −177.19 (12) |
C2—C3—C4—C5 | −1.7 (2) | N1—N2—C20—S1 | 2.55 (19) |
C3—C4—C5—C6 | 0.7 (2) | C21—N3—C20—N2 | 6.7 (2) |
C4—C5—C6—C7 | 1.0 (2) | C21—N3—C20—S1 | −173.09 (13) |
C5—C6—C7—C2 | −1.6 (2) | Pd1—S1—C20—N2 | 6.11 (13) |
C5—C6—C7—P1 | 179.50 (12) | Pd1—S1—C20—N3 | −174.14 (10) |
C3—C2—C7—C6 | 0.6 (2) | C20—N3—C21—C22 | −175.16 (15) |
C1—C2—C7—C6 | −178.32 (14) | C20—N3—C21—C26 | 7.3 (3) |
C3—C2—C7—P1 | 179.52 (11) | C26—C21—C22—C23 | 0.0 (2) |
C1—C2—C7—P1 | 0.6 (2) | N3—C21—C22—C23 | −177.65 (14) |
C8—P1—C7—C6 | −16.37 (14) | C21—C22—C23—C24 | 1.0 (2) |
C14—P1—C7—C6 | 95.55 (13) | C27—O1—C24—C23 | 5.6 (2) |
Pd1—P1—C7—C6 | −149.86 (11) | C27—O1—C24—C25 | −175.06 (14) |
C8—P1—C7—C2 | 164.69 (11) | C22—C23—C24—O1 | 178.40 (15) |
C14—P1—C7—C2 | −83.39 (12) | C22—C23—C24—C25 | −0.9 (2) |
Pd1—P1—C7—C2 | 31.20 (13) | O1—C24—C25—C26 | −179.49 (14) |
C7—P1—C8—C13 | 114.45 (12) | C23—C24—C25—C26 | −0.1 (2) |
C14—P1—C8—C13 | 2.16 (13) | C24—C25—C26—C21 | 1.1 (2) |
Pd1—P1—C8—C13 | −118.39 (11) | C22—C21—C26—C25 | −1.0 (2) |
C7—P1—C8—C9 | −65.12 (12) | N3—C21—C26—C25 | 176.44 (14) |
C14—P1—C8—C9 | −177.42 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26A···N2 | 0.95 | 2.29 | 2.890 (2) | 121 |
C3—H3A···Br1i | 0.95 | 2.87 | 3.5520 (14) | 129 |
C9—H9A···O2ii | 0.95 | 2.58 | 3.318 (2) | 135 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [PdBr(C27H23N3OPS)]·C3H6O |
Mr | 712.90 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 9.7594 (1), 13.7946 (2), 21.8681 (3) |
β (°) | 104.092 (1) |
V (Å3) | 2855.44 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.21 |
Crystal size (mm) | 0.34 × 0.29 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.519, 0.581 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39886, 10415, 8861 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.761 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.055, 1.04 |
No. of reflections | 10415 |
No. of parameters | 359 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.51 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Pd1—N1 | 2.0243 (12) | Pd1—S1 | 2.3260 (4) |
Pd1—P1 | 2.2470 (4) | Pd1—Br1 | 2.4202 (2) |
N1—Pd1—P1 | 90.13 (3) | N1—Pd1—Br1 | 173.90 (3) |
N1—Pd1—S1 | 83.90 (3) | P1—Pd1—Br1 | 93.172 (10) |
P1—Pd1—S1 | 165.537 (15) | S1—Pd1—Br1 | 94.023 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26A···N2 | 0.95 | 2.29 | 2.890 (2) | 121 |
C3—H3A···Br1i | 0.95 | 2.87 | 3.5520 (14) | 129 |
C9—H9A···O2ii | 0.95 | 2.58 | 3.318 (2) | 135 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2. |
Footnotes
‡Thomson Reuters ResearcherID: A-3561-2009.
Acknowledgements
KAM and MS would like to thank Universiti Teknologi Malaysia (UTM) for the Research University Grant Q·J130000.7126.00H13. KAM also wishes to thank the Ministry of Higher Education, Malaysia, for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Iminophosphines containing heteroatoms such as nitrogen, oxygen or sulfur have attracted considerable attention with the expectation that the functionality could participate in the chemistry. These functionalized ligands may act as chelating ligands, using phosphorus and other atom(s), for example, the nitrogen, oxygen or sulfur as donor atoms. Interest in the metal complexes of these hemilabile ligands and their applications in catalysis have been steadily growing as the different features associated with each donor atom offer properties unique to their metal. In particular, the palladium(II)-iminophosphine complexes have shown great potential as catalysts for the formation of new C—C bonds in organic synthesis (Mahamo et al., 2012, Nobre et al., 2009, Scrivanti et al., 2009, Sánchez et al., 2010) and in oligomerization reactions (Mogorosi et al., 2011).
All parameters in (I), are within normal ranges. The coordination environment around PdII atom is in a distorted square-planar configuration, formed by Br1, S1, P1 and N1 atoms with maximum deviation from the plane form by these atoms being 0.2053 (4) Å for the N1 atom. The coordination bond distances between PdII with Br1, S1, P1 and N1 atoms are 2.42015 (17), 2.3260 (4), 2.2470 (4) and 2.0243 (12) Å, respectively with angles 93.17 (1)° for Br1—Pd1—P1, 94.02 (1)° for Br1—Pd1—S1, 83.9 (3)° for S1—Pd1—N1 and 90.13 (3) for P1—Pd1—N1. The three benzene rings attached to the P1 atom make dihedral angles of 69.78 (7)° (C2—C7 and C8—C13), 87.05 (7)° (C2—C7 and C14—C19) and 77.50 (7)° (C8—C13 and C14—C19). These three benzene rings make dihedral angles of 21.99 (7)°, 86.06 (7)° and 75.78 (7)° with the C21—C26 benzene ring.
In the molecule, an intramolecular hydrogen bond of C26—H26A···N2 (Table 1) forms an S(6) hydrogen ring motif (Bernstein et al., 1995).In the crystal structure, the main molecules form infinite chains along the a-direction through the intermolecular interaction of C3—H3A···Br1i whereas the C9—H9A···O2ii bond links the main molecule with the acetone (Fig. 2).