Crystal structure of trans-di­chloridobis­[N-(5,5-di­methyl-4,5-di­hydro-3H-pyrrol-2-yl-κN)acetamide]palladium(II) dihydrate

This is an electronic reprint of the original article. This reprint may differ from the original in pagination and typographic detail. Author(s): Title: Year: Version: Please cite the original version: All material supplied via JYX is protected by copyright and other intellectual property rights, and duplication or sale of all or part of any of the repository collections is not permitted, except that material may be duplicated by you for your research use or educational purposes in electronic or print form. You must obtain permission for any other use. Electronic or print copies may not be offered, whether for sale or otherwise to anyone who is not an authorised user. Crystal structure of trans-di-chloridobis-[N-(5,5-di-methyl-4,5-di-hydro-3H-pyrrol-2-yl- κN)acetamide]palladium(II) dihydrate Lasri, J.; Eltayeb, N. E.; Haukka, Matti; Babgi, B. A. Lasri, J., Eltayeb, N. E., Haukka, M., & Babgi, B. A. (2017). Crystal structure of transdi-chloridobis-[N-(5,5-di-methyl-4,5-di-hydro-3H-pyrrol-2-yl- κN)acetamide]palladium(II) dihydrate. Acta Crystallographica Section E : Crystallographic Communications, E73(4), 528-530. https://doi.org/10.1107/S2056989017003929 2017 528 https://doi.org/10.1107/S2056989017003929 Acta Cryst. (2017). E73, 528–530 research communications Received 6 March 2017 Accepted 10 March 2017 Edited by C. Rizzoli, Universita degli Studi di Parma, Italy ‡ Additional correspondence author, e-mail: [email protected]. Keywords: crystal structure; palladium; nitrile; nitrone; cycloaddition; N—O bond cleavage. CCDC reference:1537327 Supporting information:this article has supporting information at journals.iucr.org/e Crystal structure of trans-dichloridobis[N-(5,5-di- methyl-4,5-dihydro-3H-pyrrol-2-yl-jN)acetamide]- palladium(II) dihydrate Jamal Lasri, a * Naser Eltaher Eltayeb, a Matti Haukka b ‡ and Bandar A. Babgi a a Department of Chemistry, Rabigh College of Science and Arts, PO Box 344, King Abdulaziz University, Jeddah, Saudi Arabia, and b University of Jyva ¨skyla ¨, Department of Chemistry, University of Jyva ¨skyla ¨, PO Box 35, FI-40014, Finland. *Correspondence e-mail: [email protected] The title complex, [PdCl 2 (C 8 H 14 N 2 O) 2 ]2H 2 O, was obtained by N–O bond cleavage of the oxadiazoline rings of the trans-[dichlorido-bis(2,5,5-trimethyl- 5,6,7,7a-tetrahydropyrrolo[1,2-b][1,2,4]oxadiazole-N 1 )]palladium(II) complex. The palladium(II) atom exhibits an almost square-planar coordination provided by two trans-arranged chloride anions and a nitrogen atom from each of the two neutral organic ligands. In the crystal, N—HO, O—HO and O—HCl hydrogen bonds link complex molecules into double layers parallel to the bc plane. 1. Chemical context The [2 + 3]-cycloaddition of nitrones with nitriles is one of the most important routes for the synthesis of 1,2,4-oxadiazolines (Bokach et al., 2011). However, there are some limitations for this method, as only electrophilically activated nitriles react with nitrones under harsh conditions and/or long reaction times (Eberson et al., 1998; Lasri et al., 2008). The coordination of nitriles to a suitable metal atom becomes a convenient methodology and facile metal-mediated route for the synthesis of a large number of compounds, inaccessible directly by pure organic chemistry (Bokach et al., 2011). The N—O bond cleavage of oxadiazoline rings can be promoted by thermal heating to furnish the derived ketoimine complexes (Lasri et al., 2011). Moreover, the oxadiazoline ligands are opened by N—O bond cleavage to form pyrrolylbenzamide derivatives in which the N atoms of the pyrrolyl moieties coordinate to the palladium atom in the trans positions (Lasri et al., 2009). In this work, we report the synthesis and crystal structure of the title complex trans-[dichlorido-bis(N-(4,5-dihydro-5,5- dimethyl-3H-pyrrol-2-yl)acetamide)]palladium(II) dihydrate, 2. The fused bicyclic 1,2,4-oxadiazoline palladium(II) complex trans-[PdCl 2 {N=C(Me)ONC(H)CH 2 CH 2 CMe 2 } 2 ](1) was previously synthesized by one of us (Lasri et al., 2009), in good yield (ca 75%), by treatment of trans-[PdCl 2 (NCMe) 2 ] with pyrroline N-oxide  O + NCHCH 2 CH 2 CMe 2 (Scheme, reaction a). Interestingly, refluxing complex 1in CHCl 3 for one week affords a mixture of compounds from which the title compound 2was isolated by mechanical separation of the crystals obtained from slow evaporation of an acetone/toluene (30:1 v/v) solution. Compound 2was characterized by IR spectroscopy and also by X-ray diffraction, which shows that the oxadiazoline ligands of 1have opened by N—O bond ISSN 2056-9890 cleavage to form a pyrrolylacetamide derivative, i.e. N-(4,5- dihydro-5,5-dimethyl-3H-pyrrol-2-yl)acetamide, in which the N-atoms of the pyrrolyl moieties coordinate to palladium in the trans position (Scheme, reaction b). 2. Structural commentary The slightly distorted square-planar coordination sphere around the Pd II atom comprises two chloride anions and two nitrogen atoms from two neutral organic ligands (Fig. 1). The Cl—Pd—Cl, N—Pd—N, and Cl—Pd—N angles all deviate by less that 5from the ideal 90or 180angles. The Pd—N [mean value 2.0783 (16) A ˚] and Pd—Cl [mean value 2.336 (12) A ˚] bond lengths fall in the range of typical distances found in similar types of Pd II complexes. The five-membered heterocyclic rings each have a twist conformation, with puckering parameters Q= 0.238 (4) A ˚,’=108.8 (8)and Q = 0.245 (4) A ˚,’= 69.9 (8)for N1/C1–C4 and N3/C9–C12, respectively. The crystal structures of the 2-ethyl and 2-(4- bromophenyl) analogues of the title compounds have been reported elsewhere (Lasri et al., 2009). 3. Supramolecular features In the asymmetric unit, both the N2 and N4 atoms act as hydrogen-bond donors for the O3 atom of a water molecule (Table 1). The water molecule including the O3 atom also acts as a hydrogen-bond donor to Cl2 and to a second water molecule (O4) which, in turn, forms hydrogen bonds with the Cl1 and O3 atoms of neighboring metal complexes. A view of the crystal packing (Fig. 2) shows that the molecules are organized in such a way that hydrogen bonds form double layers of metal complexes parallel to the bc plane, mainly connected by weak van der Waals interactions. 4. Synthesis and crystallization A solution of bis(1,2,4-oxadiazoline) palladium(II) (complex 1; 100 mg, 0.206 mmol; Lasri et al., 2009) in CHCl 3 (10 mL) was refluxed for one week. The solvent was then removed in vacuo and the resulting solid was washed with three 10 mL portions of diethyl ether and dried under air to give a yellow research communications Acta Cryst. (2017). E73, 528–530 Lasri et al. [PdCl 2 (C 8 H 14 N 2 O) 2 ]2H 2 O529 Table 1 Hydrogen-bond geometry (A ˚,). D—HAD—H HADAD—HA O4—H1Cl1 i 0.98 (10) 1.99 (9) 2.952 (4) 169 (8) O4—H2O3 0.69 (3) 2.22 (3) 2.909 (5) 171 (3) O3—H3Cl2 ii 0.71 (6) 2.58 (7) 3.269 (5) 163 (8) O3—H4O2 0.81 (7) 2.19 (7) 2.994 (6) 169 (7) N4—H5O4 iii 0.87 (3) 2.19 (4) 3.010 (5) 159 (3) N2—H6O4 iii 0.88 (3) 2.40 (3) 3.194 (5) 151 (3) Symmetry codes: (i) xþ1;yþ1 2;zþ3 2; (ii) xþ1;yþ1;zþ1; (iii) xþ1;y1 2;zþ3 2. Figure 2 Packing diagram of the title compound viewed down the caxis. Figure 1 The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Dashed lines indicate hydrogen bonds solid. The 1 H and 13 C NMR spectra in CDCl 3 of the obtained solid show the presence of a mixture of compounds. However, the pyrrolylacetamide product 2was isolated by mechanical separation of the crystals obtained from slow evaporation of an acetone/toluene (30:1 v/v) solution. The IR spectrum of 2 shows strong (NC O) and (N C) vibrations at 1729 and 1644 cm 1 , respectively, and (NH) at 3300 cm 1 . 5. Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. The amine and water hydrogen atoms were located in a difference-Fourier map and refined isotropically. All other hydrogen atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.96–0.97 A ˚, and with U iso =1.2U eq (C) or 1.5U eq (C) for methyl H atoms. A rotating model was applied to the methyl groups. The maximum electron density is located 0.97 A ˚from atom Pd1 and the minimum electron density is located 0.95 A ˚from atom Pd1. Two outliers (102 and 002) were omitted in the last cycles of refinement. Acknowledgements The authors acknowledge with thanks the Deanship of Scientific Research (DSR) at King Abdulaziz University, Jeddah, for technical and financial support. Funding information Funding for this research was provided by: Deanship of Scientific Research (DSR) at King Abdulaziz University (award No. G-100-662-37). References Bokach, N. A., Kuznetsov, M. L. & Kukushkin, V. Yu. (2011). Coord. Chem. Rev. 255, 2946–2967. Bruker (2016). APEX3,SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Eberson, L., McCullough, J. J., Hartshorn, C. M. & Hartshorn, M. P. (1998). J. Chem. Soc. Perkin Trans. 2, pp. 41–48. Lasri, J., da Silva, M. F. C. G., Kopylovich, M. N., Mukhopadhyay, S., Charmier, M. A. J. & Pombeiro, A. J. L. (2009). Dalton Trans. pp. 2210. Lasri, J., Kopylovich, M. N., Guedes da Silva, M. F. C., Charmier, M. A. & Pombeiro, A. L. (2008). Chem. Eur. J. 14, 9312–9322. Lasri, J., Mac Leod, T. C. O. & Pombeiro, A. J. L. (2011). Appl. Catal. Gen. 397, 94–102. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Spek, A. L. (2015). Acta Cryst. C71, 9–18. 530 Lasri et al. [PdCl 2 (C 8 H 14 N 2 O) 2 ]2H 2 OActa Cryst. (2017). E73, 528–530 research communications Table 2 Experimental details. Crystal data Chemical formula [PdCl 2 (C 8 H 14 N 2 O) 2 ]2H 2 O M r 521.75 Crystal system, space group Monoclinic, P2 1 /c Temperature (K) 293 a,b,c(A ˚) 15.945 (12), 8.765 (6), 16.894 (13) () 101.481 (19) V(A ˚ 3 ) 2314 (3) Z4 Radiation type Mo K (mm 1 ) 1.06 Crystal size (mm) 0.24 0.20 0.05 Data collection Diffractometer Bruker D8 Quest Absorption correction Multi-scan (SADABS; Bruker, 2016); additional spherical absorption correction applied with *r= 0.2000 T min ,T max 0.594, 0.745 No. of measured, independent and observed [I>2(I)] reflections 30712, 4239, 3546 R int 0.050 (sin /) max (A ˚ 1 ) 0.637 Refinement R[F 2 >2(F 2 )], wR(F 2 ), S0.032, 0.071, 1.07 No. of reflections 4239 No. of parameters 274 H-atom treatment H atoms treated by a mixture of independent and constrained refinement  max , min (e A ˚ 3 ) 0.56, 0.50 Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXS2014/7 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015) and PLATON (Spek, 2015). supporting information sup-1 Acta Cryst. (2017). E73, 528-530 supporting information Acta Cryst. (2017). E73, 528-530 [https://doi.org/10.1107/S2056989017003929] Crystal structure of trans-dichloridobis[N-(5,5-dimethyl-4,5-dihydro-3H- pyrrol-2-yl-κN)acetamide]palladium(II) dihydrate Jamal Lasri, Naser Eltaher Eltayeb, Matti Haukka and Bandar A. Babgi Computing details Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXL2014/7 (Sheldrick, 2015); software used to prepare material for publication: APEX3 (Bruker, 2016) and PLATON (Spek, 2015). trans-Dichloridobis[N-(5,5-dimethyl-4,5-dihydro-3H-pyrrol-2-yl-κN)acetamide]palladium(II) dihydrate Crystal data [PdCl2(C8H14N2O)2]·2H2O Mr = 521.75 Monoclinic, P21/c a = 15.945 (12) Å b = 8.765 (6) Å c = 16.894 (13) Å β = 101.481 (19)° V = 2314 (3) Å3 Z = 4 F(000) = 1072 Dx = 1.498 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9661 reflections θ = 2.5–25.4° µ = 1.06 mm−1 T = 293 K Block, yellow 0.24 × 0.20 × 0.05 mm Data collection Bruker D8 Quest diffractometer Radiation source: sealed X-Ray tube φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2016); additional spherical absorption correction applied with µ*r = 0.2000 Tmin = 0.594, Tmax = 0.745 30712 measured reflections 4239 independent reflections 3546 reflections with I > 2σ(I) Rint = 0.050 θmax = 26.9°, θmin = 2.6° h = −20→20 k = −10→10 l = −18→19 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.032 wR(F2) = 0.071 S = 1.07 4239 reflections 274 parameters 0 restraints Hydrogen site location: mixed H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0253P)2 + 2.688P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.56 e Å−3 Δρmin = −0.50 e Å−3 supporting information sup-2 Acta Cryst. (2017). E73, 528-530 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) xyzU iso*/Ueq Pd1 0.21183 (2) 0.43221 (3) 0.41558 (2) 0.02882 (8) Cl1 0.15431 (6) 0.28686 (10) 0.50868 (5) 0.0475 (2) Cl2 0.27918 (6) 0.56600 (11) 0.32714 (6) 0.0523 (2) O1 0.3558 (2) −0.0129 (5) 0.2615 (2) 0.1043 (13) O2 0.46851 (17) 0.6655 (3) 0.6391 (2) 0.0817 (10) O3 0.6085 (3) 0.6187 (6) 0.7839 (2) 0.0918 (13) O4 0.6653 (2) 0.6870 (4) 0.9547 (2) 0.0641 (8) N1 0.18404 (15) 0.2675 (3) 0.32579 (15) 0.0330 (6) N2 0.30573 (19) 0.1373 (3) 0.3545 (2) 0.0458 (7) N3 0.23602 (16) 0.6039 (3) 0.50208 (15) 0.0330 (6) N4 0.36553 (17) 0.5252 (4) 0.56263 (18) 0.0438 (7) C1 0.1043 (2) 0.2662 (4) 0.2637 (2) 0.0432 (8) C2 0.1062 (3) 0.1119 (5) 0.2189 (2) 0.0575 (10) H2A 0.0740 0.0350 0.2415 0.069* H2B 0.0816 0.1233 0.1619 0.069* C3 0.1936 (3) 0.0699 (4) 0.2301 (2) 0.0528 (9) H3A 0.2186 0.1003 0.1847 0.063* H3B 0.2016 −0.0388 0.2393 0.063* C4 0.2301 (2) 0.1634 (4) 0.30675 (19) 0.0368 (7) C5 0.3638 (3) 0.0430 (5) 0.3314 (3) 0.0642 (11) C6 0.4363 (3) 0.0199 (6) 0.4007 (3) 0.0914 (17) H6A 0.4398 0.1053 0.4368 0.137* H6B 0.4887 0.0114 0.3812 0.137* H6C 0.4271 −0.0718 0.4288 0.137* C7 0.0348 (2) 0.2747 (5) 0.3112 (3) 0.0652 (12) H7A −0.0198 0.2642 0.2754 0.098* H7B 0.0374 0.3714 0.3383 0.098* H7C 0.0420 0.1940 0.3504 0.098* C8 0.1026 (3) 0.3988 (5) 0.2027 (2) 0.0623 (11) H8A 0.0500 0.3957 0.1636 0.093* H8B 0.1499 0.3884 0.1757 0.093* H8C 0.1070 0.4944 0.2309 0.093* C9 0.1786 (2) 0.7343 (4) 0.5045 (2) 0.0430 (8) C10 0.2181 (3) 0.8178 (5) 0.5865 (3) 0.0696 (12) H10A 0.2118 0.9275 0.5808 0.084* H10B 0.1904 0.7841 0.6297 0.084* C11 0.3071 (2) 0.7748 (4) 0.6028 (2) 0.0557 (10) H11A 0.3284 0.7564 0.6599 0.067* H11B 0.3423 0.8515 0.5839 0.067* supporting information sup-3 Acta Cryst. (2017). E73, 528-530 C12 0.3034 (2) 0.6287 (4) 0.55392 (19) 0.0363 (7) C13 0.4437 (2) 0.5445 (5) 0.6085 (2) 0.0547 (10) C14 0.4948 (2) 0.4047 (5) 0.6150 (3) 0.0798 (15) H14A 0.4739 0.3403 0.5693 0.120* H14B 0.4905 0.3519 0.6638 0.120* H14C 0.5535 0.4303 0.6160 0.120* C15 0.0952 (3) 0.6747 (5) 0.5097 (3) 0.0810 (14) H15A 0.0571 0.7578 0.5139 0.121* H15B 0.1002 0.6107 0.5565 0.121* H15C 0.0729 0.6162 0.4621 0.121* C16 0.1746 (3) 0.8313 (5) 0.4258 (3) 0.0782 (14) H16A 0.1352 0.9143 0.4253 0.117* H16B 0.1556 0.7680 0.3793 0.117* H16C 0.2304 0.8709 0.4245 0.117* H1 0.727 (6) 0.706 (10) 0.968 (5) 0.23 (4)* H2 0.647 (2) 0.669 (4) 0.915 (2) 0.036 (12)* H3 0.641 (4) 0.588 (8) 0.765 (4) 0.12 (3)* H4 0.570 (5) 0.644 (8) 0.747 (4) 0.15 (3)* H5 0.353 (2) 0.434 (4) 0.544 (2) 0.036 (9)* H6 0.316 (2) 0.186 (4) 0.401 (2) 0.044 (10)* Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23 Pd1 0.02776 (12) 0.02964 (13) 0.02942 (14) 0.00102 (10) 0.00656 (9) −0.00173 (11) Cl1 0.0576 (5) 0.0483 (5) 0.0396 (5) −0.0088 (4) 0.0168 (4) 0.0040 (4) Cl2 0.0484 (5) 0.0583 (5) 0.0565 (5) −0.0123 (4) 0.0260 (4) −0.0003 (5) O1 0.101 (3) 0.116 (3) 0.101 (3) 0.047 (2) 0.034 (2) −0.027 (2) O2 0.0476 (16) 0.064 (2) 0.125 (3) −0.0168 (15) −0.0023 (17) −0.0192 (19) O3 0.076 (3) 0.122 (3) 0.072 (2) 0.015 (2) 0.002 (2) −0.035 (2) O4 0.063 (2) 0.065 (2) 0.058 (2) 0.0002 (15) −0.0035 (16) −0.0105 (17) N1 0.0315 (13) 0.0333 (14) 0.0344 (14) −0.0017 (11) 0.0070 (11) −0.0043 (12) N2 0.0457 (17) 0.0401 (17) 0.0516 (19) 0.0085 (13) 0.0100 (15) −0.0064 (15) N3 0.0363 (14) 0.0281 (14) 0.0359 (14) 0.0023 (11) 0.0102 (12) −0.0004 (11) N4 0.0343 (15) 0.0404 (18) 0.0538 (19) −0.0045 (13) 0.0018 (13) −0.0087 (14) C1 0.0386 (18) 0.050 (2) 0.0368 (18) −0.0045 (15) −0.0020 (14) −0.0042 (16) C2 0.062 (2) 0.057 (2) 0.050 (2) −0.0137 (19) 0.0011 (18) −0.0125 (19) C3 0.074 (3) 0.044 (2) 0.041 (2) 0.0026 (19) 0.0120 (18) −0.0076 (17) C4 0.0472 (19) 0.0310 (17) 0.0346 (18) −0.0012 (15) 0.0139 (15) 0.0006 (14) C5 0.061 (3) 0.048 (2) 0.089 (3) 0.016 (2) 0.030 (2) 0.002 (2) C6 0.053 (3) 0.079 (3) 0.140 (5) 0.027 (2) 0.014 (3) 0.007 (3) C7 0.0337 (19) 0.087 (3) 0.071 (3) −0.003 (2) 0.0012 (18) −0.006 (2) C8 0.060 (2) 0.059 (3) 0.058 (2) 0.001 (2) −0.0113 (19) 0.006 (2) C9 0.048 (2) 0.0326 (18) 0.050 (2) 0.0088 (15) 0.0162 (16) −0.0012 (15) C10 0.081 (3) 0.050 (2) 0.077 (3) 0.013 (2) 0.015 (2) −0.021 (2) C11 0.064 (3) 0.039 (2) 0.061 (2) −0.0030 (18) 0.0060 (19) −0.0127 (18) C12 0.0408 (18) 0.0303 (16) 0.0384 (18) −0.0032 (14) 0.0088 (15) −0.0016 (14) C13 0.0393 (19) 0.057 (3) 0.066 (3) −0.0099 (18) 0.0078 (18) −0.003 (2) supporting information sup-4 Acta Cryst. (2017). E73, 528-530 C14 0.036 (2) 0.074 (3) 0.122 (4) 0.003 (2) 0.000 (2) −0.010 (3) C15 0.053 (3) 0.066 (3) 0.130 (4) 0.020 (2) 0.034 (3) −0.001 (3) C16 0.099 (3) 0.061 (3) 0.080 (3) 0.039 (3) 0.029 (3) 0.025 (2) Geometric parameters (Å, º) Pd1—N1 2.077 (3) C5—C6 1.486 (6) Pd1—N3 2.080 (3) C6—H6A 0.9600 Pd1—Cl2 2.3238 (14) C6—H6B 0.9600 Pd1—Cl1 2.3478 (14) C6—H6C 0.9600 O1—C5 1.262 (5) C7—H7A 0.9600 O2—C13 1.211 (5) C7—H7B 0.9600 O3—H3 0.71 (6) C7—H7C 0.9600 O3—H4 0.81 (7) C8—H8A 0.9600 O4—H1 0.98 (9) C8—H8B 0.9600 O4—H2 0.70 (4) C8—H8C 0.9600 N1—C4 1.253 (4) C9—C15 1.448 (5) N1—C1 1.478 (4) C9—C16 1.569 (5) N2—C4 1.330 (4) C9—C10 1.583 (5) N2—C5 1.355 (5) C10—C11 1.442 (5) N2—H6 0.88 (3) C10—H10A 0.9700 N3—C12 1.263 (4) C10—H10B 0.9700 N3—C9 1.470 (4) C11—C12 1.518 (5) N4—C12 1.329 (4) C11—H11A 0.9700 N4—C13 1.341 (5) C11—H11B 0.9700 N4—H5 0.87 (3) C13—C14 1.463 (6) C1—C7 1.494 (5) C14—H14A 0.9600 C1—C8 1.551 (5) C14—H14B 0.9600 C1—C2 1.553 (5) C14—H14C 0.9600 C2—C3 1.417 (5) C15—H15A 0.9600 C2—H2A 0.9700 C15—H15B 0.9600 C2—H2B 0.9700 C15—H15C 0.9600 C3—C4 1.545 (5) C16—H16A 0.9600 C3—H3A 0.9700 C16—H16B 0.9600 C3—H3B 0.9700 C16—H16C 0.9600 N1—Pd1—N3 177.41 (10) H7A—C7—H7B 109.5 N1—Pd1—Cl2 86.56 (9) C1—C7—H7C 109.5 N3—Pd1—Cl2 92.39 (9) H7A—C7—H7C 109.5 N1—Pd1—Cl1 93.26 (9) H7B—C7—H7C 109.5 N3—Pd1—Cl1 87.97 (9) C1—C8—H8A 109.5 Cl2—Pd1—Cl1 175.38 (3) C1—C8—H8B 109.5 H3—O3—H4 105 (7) H8A—C8—H8B 109.5 H1—O4—H2 117 (6) C1—C8—H8C 109.5 C4—N1—C1 106.2 (3) H8A—C8—H8C 109.5 C4—N1—Pd1 130.0 (2) H8B—C8—H8C 109.5 C1—N1—Pd1 123.5 (2) C15—C9—N3 107.8 (3) C4—N2—C5 121.3 (4) C15—C9—C16 111.3 (4) supporting information sup-5 Acta Cryst. (2017). E73, 528-530 C4—N2—H6 117 (2) N3—C9—C16 108.5 (3) C5—N2—H6 122 (2) C15—C9—C10 108.9 (3) C12—N3—C9 107.2 (3) N3—C9—C10 104.0 (3) C12—N3—Pd1 128.7 (2) C16—C9—C10 115.7 (3) C9—N3—Pd1 123.6 (2) C11—C10—C9 104.5 (3) C12—N4—C13 124.3 (3) C11—C10—H10A 110.8 C12—N4—H5 119 (2) C9—C10—H10A 110.8 C13—N4—H5 116 (2) C11—C10—H10B 110.8 N1—C1—C7 104.1 (3) C9—C10—H10B 110.8 N1—C1—C8 111.4 (3) H10A—C10—H10B 108.9 C7—C1—C8 113.8 (3) C10—C11—C12 100.8 (3) N1—C1—C2 104.7 (3) C10—C11—H11A 111.6 C7—C1—C2 113.1 (3) C12—C11—H11A 111.6 C8—C1—C2 109.2 (3) C10—C11—H11B 111.6 C3—C2—C1 106.0 (3) C12—C11—H11B 111.6 C3—C2—H2A 110.5 H11A—C11—H11B 109.4 C1—C2—H2A 110.5 N3—C12—N4 118.2 (3) C3—C2—H2B 110.5 N3—C12—C11 117.2 (3) C1—C2—H2B 110.5 N4—C12—C11 124.6 (3) H2A—C2—H2B 108.7 O2—C13—N4 123.0 (4) C2—C3—C4 99.8 (3) O2—C13—C14 124.9 (4) C2—C3—H3A 111.8 N4—C13—C14 112.1 (3) C4—C3—H3A 111.8 C13—C14—H14A 109.5 C2—C3—H3B 111.8 C13—C14—H14B 109.5 C4—C3—H3B 111.8 H14A—C14—H14B 109.5 H3A—C3—H3B 109.5 C13—C14—H14C 109.5 N1—C4—N2 118.5 (3) H14A—C14—H14C 109.5 N1—C4—C3 117.3 (3) H14B—C14—H14C 109.5 N2—C4—C3 124.2 (3) C9—C15—H15A 109.5 O1—C5—N2 124.0 (4) C9—C15—H15B 109.5 O1—C5—C6 127.1 (4) H15A—C15—H15B 109.5 N2—C5—C6 109.0 (4) C9—C15—H15C 109.5 C5—C6—H6A 109.5 H15A—C15—H15C 109.5 C5—C6—H6B 109.5 H15B—C15—H15C 109.5 H6A—C6—H6B 109.5 C9—C16—H16A 109.5 C5—C6—H6C 109.5 C9—C16—H16B 109.5 H6A—C6—H6C 109.5 H16A—C16—H16B 109.5 H6B—C6—H6C 109.5 C9—C16—H16C 109.5 C1—C7—H7A 109.5 H16A—C16—H16C 109.5 C1—C7—H7B 109.5 H16B—C16—H16C 109.5 C4—N1—C1—C7 133.6 (3) C12—N3—C9—C15 −130.9 (3) Pd1—N1—C1—C7 −52.9 (4) Pd1—N3—C9—C15 57.0 (4) C4—N1—C1—C8 −103.4 (3) C12—N3—C9—C16 108.4 (4) Pd1—N1—C1—C8 70.2 (3) Pd1—N3—C9—C16 −63.7 (4) C4—N1—C1—C2 14.5 (3) C12—N3—C9—C10 −15.3 (4) Pd1—N1—C1—C2 −171.9 (2) Pd1—N3—C9—C10 172.5 (2) N1—C1—C2—C3 −24.4 (4) C15—C9—C10—C11 139.3 (4)