The asymmetric unit of the title complex, trans-[PdCl2(NH2tBu)2], consists of two independent square-planar molecules, linked together in a hydrogen-bonding network, with the resultant alignment of the tert-butyl groups defining a two-dimensional layered structure approximately parallel to (001)

Boag, NM

Clapham, S

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metal-organic papersm2172 Boag and Clapham  [PdCl2(C4H11N)2] doi:10.1107/S1600536805030047 Acta Cryst. (2005). E61, m2172–m2173Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368trans-Bis(tert-butylamine)dichloropalladium(II)Neil M. Boag* andSarah ClaphamChemistry and Nanotechnology, Institute forMaterials Research, Cockcroft Building,University of Salford, Salford, M5 4WT, EnglandCorrespondence e-mail:N.M.Boag@salford.ac.ukKey indicatorsSingle-crystal X-ray studyT = 223 KMean (C–C) = 0.008 ÅR factor = 0.038wR factor = 0.098Data-to-parameter ratio = 22.8For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2005 International Union of CrystallographyPrinted in Great Britain – all rights reservedThe asymmetric unit of the title complex, trans-[PdCl2(NH2tBu)2], consists of two independent square-planarmolecules, linked together in a hydrogen-bonding network,with the resultant alignment of the tert-butyl groups defining atwo-dimensional layered structure approximately parallel to(001).CommentWe have noted that the chemistry of tert-butylamine deriva-tives of palladium frequently differs from other primary aminecomplexes due to the steric bulk of the tert-butyl group. Theavailability of crystals of the title complex, (I), allowedcomparison with other bis(primary amine)dichloro complexesof palladium to determine the structural consequences ofsteric bulk.Complex (I) exists as two independent square-planar mol-ecules in the asymmetric unit. The orientation of the tert-butylamine groups is such that both molecules are pseudo-centrosymmetric. Analysis of the 14 previously reportedbis(primary amine)dichloropalladium(II) structures (Fletcheret al., 1996) gives averages of 2.300 (8) Å and 2.047 (9) Å forthe Pd—Cl and the Pd—N bonds, respectively, with a meandeviation of the N—Pd—Cl angles of ca 1.4 from the ideal90. The Pd—Cl and Pd—N bond lengths in (I) range from2.3015 (11) to 2.3072 (12) and 2.046 (4) to 2.058 (4) Å,respectively; this indicates that, in this complex, the bulky tert-butyl group has no obvious structural consequence, althoughthe average N—Pd—Cl angle in complex (I) does show asignificantly smaller deviation from the 90 required by idealsquare-planar geometry [0.46 (molecule 1), 0.37 (molecule2). The molecules are linked together in a hydrogen-bondingnetwork, resulting in the formation of a two-dimensionallayered structure, externally defined by the tert-butyl groupsand approximately parallel to (001).ExperimentalComplex (I) crystallized from a dichloromethane/hexane solution oftrans-[Pd(1-C5H5)(NH2tBu)2Cl] and [Pd(5-C5H5)(NH2tBu)Cl] andwas spectroscopically identical to the material synthesized accordingto the literature method (Nakayama et al., 1984).Received 23 August 2005Accepted 20 September 2005Online 30 September 2005Crystal data[PdCl2(C4H11N)2]Mr = 323.58Triclinic, P1a = 6.2357 (10) Åb = 10.6500 (11) Åc = 20.472 (2) Å = 94.641 (8) = 90.978 (13) = 93.824 (11)V = 1351.7 (3) Å3Z = 4Dx = 1.590 Mg m3Mo K radiationCell parameters from 34reflections = 5.1–12.5 = 1.73 mm1T = 223 (2) KBlock, orange0.6  0.3  0.3 mmData collectionSiemens P4 diffractometerProfile fitting of !/2 scansAbsorption correction:  scan(XSCANS; Siemens, 1996).Tmin = 0.537, Tmax = 0.5947873 measured reflections6177 independent reflections5913 reflections with I > 2(I)Rint = 0.019max = 27.5h = 8! 1k = 13! 13l = 26! 263 standard reflectionsevery 97 reflectionsintensity decay: 4%RefinementRefinement on F 2R[F 2 > 2(F 2)] = 0.038wR(F 2) = 0.098S = 1.236177 reflections271 parametersH atoms treated by a mixture ofindependent and constrainedrefinementw = 1/[2(Fo2) + (0.0118P)2+ 6.285P]where P = (Fo2 + 2Fc2)/3(/)max = 0.001max = 1.01 e Å3min = 1.24 e Å3Table 1Selected geometric parameters (Å, ).Pd1—N12 2.046 (4)Pd1—N11 2.050 (4)Pd1—Cl11 2.3015 (11)Pd1—Cl12 2.3030 (11)Pd2—N21 2.057 (4)Pd2—N22 2.058 (4)Pd2—Cl22 2.3051 (12)Pd2—Cl21 2.3072 (12)N12—Pd1—N11 179.27 (16)N12—Pd1—Cl11 90.17 (12)N11—Pd1—Cl11 89.35 (12)N12—Pd1—Cl12 89.74 (12)N11—Pd1—Cl12 90.74 (12)Cl11—Pd1—Cl12 179.34 (5)N21—Pd2—N22 179.06 (16)N21—Pd2—Cl22 89.93 (12)N22—Pd2—Cl22 90.71 (12)N21—Pd2—Cl21 90.04 (12)N22—Pd2—Cl21 89.32 (12)Cl22—Pd2—Cl21 179.26 (6)Table 2Hydrogen-bond geometry (Å, ).D—H  A D—H H  A D  A D—H  AN11—H112  Cl11i 0.81 (6) 2.62 (6) 3.408 (4) 163 (5)N12—H121  Cl21ii 0.82 (6) 2.75 (6) 3.416 (4) 140 (5)N12—H122  Cl12iii 0.84 (6) 2.60 (6) 3.423 (4) 165 (5)N21—H211  Cl11 0.79 (6) 2.59 (6) 3.327 (4) 157 (5)N21—H212  Cl22iii 0.84 (6) 2.76 (6) 3.502 (4) 148 (5)N22—H221  Cl21i 0.80 (6) 2.71 (6) 3.481 (4) 164 (5)N22—H222  Cl12iv 0.92 (6) 2.52 (6) 3.347 (4) 149 (4)Symmetry codes: (i) xþ 1; y; z; (ii) x; y 1; z; (iii) x 1; y; z; (iv) x; yþ 1; z.Methyl-H atoms were placed in calculated positions and subse-quently constrained to an ideal geometry, with C—H distances of0.97 Å and Uiso(H) = 1.5Ueq(C), with each group allowed to rotatefreely about its C—C bond. The positions of the amine H atoms wereidentified from a difference Fourier map and allowed to refine freelywith fixed isotropic displacement parameters; N—H = 0.79 (6)–0.92 (6) Å. The highest peak is located 1.21 Å from atom Cl21 and thedeepest hole 1.47 Å from atom Cl12.Data collection: XSCANS (Siemens, 1996); cell refinement:XSCANS; data reduction: XSCANS; program(s) used to solvestructure: SHELXTL-Plus (Siemens, 1995); program(s) used torefine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:SHELXTL-Plus; software used to prepare material for publication:SHELXL97 (Sheldrick, 1997).We thank the EPSRC for a studentship and the SCI for aMessel Scholarship (SC). We acknowledge the use of theEPSRC’s Chemical Database Service at Daresbury.ReferencesFletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput.Sci. 36, 746–749.Nakayama, K., Komorita, T. & Shimura, Y. (1984). Bull. Chem. Soc. Jpn, 57,1336–1347.Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University ofGöttingen, Germany.Siemens (1995). SHELXTL-Plus. Version 5.03. Siemens Analytical X-rayInstruments Inc., Madison, Wisconsin, USA.Siemens (1996), XSCANS. Version 2.20, Siemens Analytical X-ray Instru-ments Inc., Madison, Wisconsin, USA.metal-organic papersActa Cryst. (2005). E61, m2172–m2173 Boag and Clapham  [PdCl2(C4H11N)2] m2173Figure 1A view of the two independent molecules in (I). Displacement ellipsoidsare drawn at the 50% probability level. tert-Butyl H atoms have beenomitted. The dashed line indicates a hydrogen bond.

trans-Bis(tert-butylamine)dichloropalladium(II)

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