Conformational change induced by hydration: trans-dichloro­bis­[(1R,2R,3R,5S)-(–)-isopinocampheylamine]palladium(II) and trans-dichloro­bis[(1S,2S,3S,5R)-(+)-isopinocampheylamine]palladium(II) hemihydrate

The title compounds, trans-dichloro­bis[(1R,2R,3R,5S)-(−)-2,6,6-trimethyl­bicyclo­[3.1.1]heptan-3-amine]palladium(II), [PdCl₂(C₁₀H₁₉N)₂], and trans-dichloro­bis[(1S,2S,3S,5R)-(+)-2,6,6-trimethyl­bicyclo­[3.1.1]heptan-3-amine]palladium(II) hemihydrate, [PdCl₂(C₁₀H₁₉N)₂]·0.5H₂O, present different arrangements of the amine ligands coordinated to Pd^II, viz. antiperiplanar in the former case and (−)anticlinal in the latter. The hemihydrate is an inclusion compound, with a Pd coordination complex and disordered water mol­ecules residing on crystallographic twofold axes. The crystal structure for the hemihydrate includes a short Pd...Pd separation of 3.4133 (13) Å.

S1. Comment

The use and applications of chiral complexes of transition metals have experienced an exponential growth in recent years (e.g. Maire et al., 2005). The combined use of organometallic and coordination chemistry has allowed the development of a number of new and powerful synthetic methods for important classes of compounds in general and for optically active substances in particular (e.g. Gamez et al., 1995). Along this line, N-containing ligands are increasingly used, since they present many advantages (accessibility, easy recovery etc.) over their P analogs (Fache et al., 2000). As such, chiral amines have highlighted the use of such N-donors and are nowadays widely employed. Our interest has recently been focused on new chiral Pd complexes derived from optically pure α-diimines (Martínez-García et al., 2000; Peláez et al., 2004) and, in this regard, in the synthesis of new Pd^II complexes with optically pure α-diimines derived from pyruvaldehyde and a variety of chiral amines (Vázquez-García et al., 2000; Vázquez-García, 2002). However, a limitation observed during this work was a tendency of some α-diimines to decompose in solution, the only crystallizable products being the coordination compounds including chiral amines as ligands instead of the expected α-diimines. We have now characterized two complexes of general formula [PdL₂Cl₂].nH₂O, where ligand L is a commercially available diastereoisomer of isopinocampheylamine. For compound (I), L is (-)-isopinocampheylamine and n = 0, while for (II), L is (+)-isopinocampheylamine and n = 0.5 (see Scheme).

Complex (I) is based on a classical trans-[PdN₂Cl₂] plane rectangular coordination geometry (Fig. 1 and Table 1). The molecule lies on a general position and amine ligands, (1R,2R,3R,5S)-(-)-isopinocampheylamine, adopt an antiperiplanar arrangement, as described by the C3—N1—N2—C13 torsion angle [−167.2 (2)°]. The complex approximately exhibits a C₂ point symmetry, with the symmetry axis within the coordination plane (Cl—Pd—Cl line), minimizing steric hindrance and giving a relatively well packed crystal structure in space group P2₁2₁2₁ (Fig. 2), as reflected by the packing index of 0.666 (Spek, 2003). Metallic centers are well separated in the cell; the shortest Pd···Pd separations are 6.6037 (5) Å [Pd1···Pd1ⁱ; symmetry code: (i) 1 + x, y, z] and 6.7037 (5) Å [Pd1···Pd1ⁱⁱ; symmetry code: (ii) 1 − x, y − 1/2, 1/2 − z]. No voids are available for solvent molecules in the structure of (I).

Complex (II), based on (1S,2S,3S,5R)-(+)-isopinocampheylamine coordinated to the PdCl₂ central core, presents a different molecular structure (Fig. 3 and Table 2). The metal center resides on a twofold axis and amine ligands are arranged in an (-)anticlinal configuration, as described by the C3—N1—N1ⁱ—C3ⁱ torsion angle [−106.0 (9)°; symmetry code: (i) 1 − x, y, 1 − z]. By comparison with (I), one amine ligand is thus rotated around the σ bond Pd1—N1, giving a boat-like conformation for the whole molecule. The [PdL₂Cl₂] complex in (II) actually belongs to the C₂ point symmetry group, with the molecular axis normal to the coordination plane [PdN₂Cl₂ ] and coincident with the [010] crystallographic twofold axis.

The main difference between (I) and (II) consists in the presence of disordered water molecules, lying on a twofold rotation axis along [100]. These water molecules are located in the cavities allowed by the boat geometry of the complex (Fig. 4). Indeed, omitting these water molecules would result in a very low packing index for (II), 0.592. Moreover, it should be noted that the reported refinement for (II) probably underestimates water content, as suggested by the SQUEEZE option available in PLATON (Spek, 2003); starting from a water-free model, this option recovered 116 electrons belonging to diffusely diffracting solvent molecules, equally distributed in two voids located close to (0, 0, 0) and (0, 1/2, 1/2), each void having a volume of 156 ų. The actual estimation of the water content was based on the refinement of the site occupation factors, which converged to 1/8 for both water molecules, and were fixed in the last least-squares cycles. The ca sixfold difference between the refined and SQUEEZE calculated amounts of water (0.5 versus 2.9 water molecules per complex) may appear unrealistic. However, it is worth noting that available voids, estimated by SQUEEZE to be 78 ų per asymmetric unit, can accommodate no more than two water molecules, assuming a streric volume of 40 ų for a water molecule. These observations are consistent with the presence of strongly disordered water molecules in the structure of (II), to an extent that cannot be estimated accurately on the basis of the currently available X-ray data. However, (II) may be safely formulated as [PdL₂Cl₂](OH₂)_n, with 0.5 < n < 2.0. Thermal studies or related techniques would help for an accurate determination of n.

As expected, inclusion of water in (II) results in lower density for the crystal compared with (I), viz. 1.295 and 1.417 g/cm³, respectively. Weak hydrogen bonds involving Cl⁻ ions and water molecules are observed in the crystal (Table 3). Another consequence of the conformational change observed in (II) is the occurance of a short metal–metal separation, Pd1···Pd1ⁱ = 3.4133 (13) Å [symmetry code: (i) 1 − x, 2 − y, z], a distance close to the sum of the van der Waals radii (3.26 Å; Bondi, 1964).

It is worth noting that (I) crystallizes in the most common space group for chiral molecules, P2₁2₁2₁, while (II) crystallizes in I222, a space group poorly represented in the Cambridge Structural Database (CSD; Version 5.26, updated May 2005; Allen, 2002), with 91 entries to date. An examination of these hits shows that 45% are flagged as disordered structures, a frequency more than twice of that observed for the entire database (18%). Moreover, 33% of the structures reported in space group I222 are solvates, including hydrates. These observations suggest that symmetry I222 fits crystal structures featuring disorder, hindered conformations or solvatation, as in the case of (II).

Defining the complex [PdL₂Cl₂] as a templating host molecule, (II) may be considered as an inclusion compound with water as guest (Fig. 4). On the other hand, we assume that two crystals of [PdL₂Cl₂] prepared with both enantiomers of L ligands should crystallize as isostructural species (e.g. Leung et al., 1999), as two enantiomeric compounds do, unless a true polymorphism occur. Therefore, regardless of the handedness of chiral amines L used in the present work, the variety of conformations observed for complex [PdL₂Cl₂] probably depends on the presence or absence of water molecules in the crystal structure.

S2. Experimental

A solution of bis[(1R,2R,3R,5S)-isopinocampheyl]-1,2-propanediimine (0.120 g, 0.35 mmol) in benzene (20 ml) was treated with dichloro(1,5-cyclooctadiene) palladium(II) (0.100 g, 0.35 mmol) with stirring at 298 K for 10 min. A yellow precipitate was collected, and orange crystals of (I) were grown from the filtered solution by slow evaporation (9% yield). The same procedure was repeated with bis[(1S,2S,3S,5R)-isopinocampheyl]-1,2-propandiimine, affording (II) by slow evaporation in a non-controlled atmosphere, with a low yield of ca 5%.

S3. Refinement

In the case of (I), the highest residual peak found in the last difference map is located in the vicinity of atom Cl2. Attempts to refine this residual as a water molecule with a partial occupation factor were definitively unsuccessful. In the case of (II), site occupation factors for the two water molecules were fixed to 1/8. Corresponding O atoms were refined isotropically, otherwise they converged to non-positive definite displacement ellipsoids. H atoms for water molecules were found in difference maps and their positions were refined with a restrained geometry [O—H = 0.85 (1) Å]. In the final cycles, water H atoms were constrained to ride on their carrier O atoms, with U_iso = 1.5U_eq(carrier O atom). For both compounds, H atoms bonded to C and N atoms were placed in idealized positions and refined using a riding-model approximation, with U_iso = xU_eq(carrier atom); constrained distances and x parameters: methine C—H = 0.98 Å and x = 1.2; methylene C—H = 0.97 Å and x = 1.2; methyl C—H = 0.96 Å and x = 1.5; amine N—H = 0.90 Å and x = 1.5. The methyl groups were allowed to rotate about their C—C bonds, in order to obtain the correct torsion angles for these groups.

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are shown at the 25% probability level and H atoms bonded to C atoms have been omitted for clarity.
	Fig. 2. Part of the crystal structure of (I), viewed approximately down the [100] axis. Eight symmetry-related molecules are included.
	Fig. 3. The structure of (II), with the atom-numbering scheme for the asymmetric unit. Displacement ellipsoids for non-H atoms are shown at the 25% probability level and H atoms bonded to C atoms have been omitted for clarity.
	Fig. 4. Part of the crystal structure of (II), viewed approximately down the [100] axis. 14 symmetry-related coordination complexes and 28 disordered water molecules are represented, in order to emphasize the host character of the coordination complex. The short Pd···Pd contact is indicated with a dashed line.

(I) trans-dichlorobis[(1R,2R,3R,5S)-(-)-2,6,6-trimethylbicyclo[3.1.1]heptan-3- amine]palladium(II)

Crystal data

[PdCl2(C10H19N)2]	F(000) = 1008
Mr = 483.82	Dx = 1.417 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 76 reflections
a = 6.6037 (5) Å	θ = 4.8–13.9°
b = 11.3935 (10) Å	µ = 1.06 mm^−1
c = 30.143 (2) Å	T = 296 K
V = 2267.9 (3) Å^3	Plate, yellow
Z = 4	0.60 × 0.42 × 0.12 mm

Data collection

Bruker P4 diffractometer	5860 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.020
Graphite monochromator	θmax = 30.0°, θmin = 1.9°
ω scans	h = −9→9
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −16→1
Tmin = 0.703, Tmax = 0.879	l = −1→42
7901 measured reflections	3 standard reflections every 97 reflections
6612 independent reflections	intensity decay: 1.5%

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 0.6075P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6612 reflections	Δρmax = 1.08 e Å^−3
232 parameters	Δρmin = −0.80 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2839 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (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	0.23901 (3)	0.635874 (18)	0.262902 (6)	0.03033 (6)
Cl1	0.49969 (12)	0.74568 (8)	0.29337 (3)	0.04635 (19)
Cl2	−0.01763 (12)	0.51991 (8)	0.23388 (3)	0.04665 (18)
N1	0.0352 (4)	0.7136 (2)	0.30505 (8)	0.0344 (5)
H1A	0.0377	0.7915	0.3002	0.041*
H1B	−0.0895	0.6880	0.2979	0.041*
N2	0.4371 (4)	0.5635 (2)	0.21858 (8)	0.0325 (5)
H2A	0.5641	0.5758	0.2283	0.039*
H2B	0.4167	0.4854	0.2178	0.039*
C1	−0.1617 (5)	0.6819 (3)	0.42157 (11)	0.0406 (7)
H1C	−0.2514	0.7213	0.4428	0.049*
C2	−0.0928 (5)	0.7587 (3)	0.38259 (10)	0.0332 (6)
H2C	−0.2117	0.7712	0.3637	0.040*
C3	0.0674 (5)	0.6929 (3)	0.35376 (10)	0.0313 (6)
H3A	0.2000	0.7259	0.3613	0.038*
C4	0.0799 (6)	0.5599 (3)	0.36199 (12)	0.0439 (8)
H4A	0.0219	0.5191	0.3368	0.053*
H4B	0.2212	0.5373	0.3641	0.053*
C5	−0.0290 (6)	0.5212 (3)	0.40369 (12)	0.0473 (8)
H5A	−0.0155	0.4376	0.4108	0.057*
C6	0.0094 (7)	0.6062 (3)	0.44325 (11)	0.0511 (9)
C7	−0.0185 (7)	0.8794 (3)	0.39667 (13)	0.0528 (9)
H7A	−0.1233	0.9189	0.4129	0.079*
H7B	0.0159	0.9244	0.3708	0.079*
H7C	0.0990	0.8710	0.4152	0.079*
C8	−0.2471 (7)	0.5668 (3)	0.40198 (14)	0.0559 (9)
H8A	−0.3402	0.5256	0.4214	0.067*
H8B	−0.3017	0.5745	0.3723	0.067*
C9	0.2218 (8)	0.6557 (4)	0.45043 (15)	0.0725 (13)
H9A	0.3072	0.5961	0.4629	0.109*
H9B	0.2150	0.7214	0.4703	0.109*
H9C	0.2768	0.6808	0.4225	0.109*
C10	−0.0650 (11)	0.5545 (5)	0.48730 (14)	0.0874 (18)
H10A	0.0286	0.4956	0.4973	0.131*
H10B	−0.1960	0.5197	0.4831	0.131*
H10C	−0.0741	0.6157	0.5091	0.131*
C11	0.5916 (5)	0.7757 (3)	0.12980 (11)	0.0418 (7)
H11A	0.6179	0.8599	0.1262	0.050*
C12	0.4739 (5)	0.7433 (3)	0.17170 (11)	0.0396 (7)
H12A	0.5648	0.7571	0.1969	0.047*
C13	0.4191 (4)	0.6109 (2)	0.17237 (9)	0.0317 (6)
H13A	0.2760	0.6049	0.1640	0.038*
C14	0.5396 (5)	0.5349 (3)	0.13901 (11)	0.0408 (7)
H14A	0.6384	0.4887	0.1552	0.049*
H14B	0.4472	0.4808	0.1246	0.049*
C15	0.6488 (5)	0.6061 (3)	0.10362 (11)	0.0447 (8)
H15A	0.7172	0.5601	0.0806	0.054*
C16	0.5230 (5)	0.7115 (3)	0.08669 (10)	0.0368 (6)
C17	0.2897 (7)	0.8228 (3)	0.17839 (13)	0.0621 (12)
H17A	0.3342	0.9022	0.1828	0.093*
H17B	0.2149	0.7971	0.2039	0.093*
H17C	0.2046	0.8192	0.1526	0.093*
C18	0.7828 (5)	0.6969 (4)	0.12792 (15)	0.0632 (12)
H18A	0.8920	0.7285	0.1100	0.076*
H18B	0.8312	0.6712	0.1567	0.076*
C19	0.2994 (5)	0.6928 (3)	0.07636 (12)	0.0458 (8)
H19A	0.2864	0.6427	0.0509	0.069*
H19B	0.2368	0.7671	0.0703	0.069*
H19C	0.2342	0.6569	0.1014	0.069*
C20	0.6178 (6)	0.7691 (4)	0.04540 (13)	0.0580 (10)
H20A	0.6028	0.7178	0.0204	0.087*
H20B	0.7590	0.7834	0.0507	0.087*
H20C	0.5506	0.8422	0.0394	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03117 (9)	0.03435 (10)	0.02548 (9)	−0.00059 (10)	0.00157 (9)	0.00016 (8)
Cl1	0.0368 (4)	0.0570 (5)	0.0453 (4)	−0.0064 (4)	−0.0016 (3)	−0.0133 (4)
Cl2	0.0423 (4)	0.0525 (4)	0.0451 (4)	−0.0114 (3)	0.0020 (4)	−0.0101 (4)
N1	0.0338 (12)	0.0391 (13)	0.0303 (12)	0.0025 (11)	0.0030 (10)	0.0022 (10)
N2	0.0380 (13)	0.0311 (11)	0.0283 (11)	0.0021 (10)	0.0012 (10)	0.0049 (10)
C1	0.0480 (17)	0.0386 (16)	0.0354 (16)	0.0012 (14)	0.0114 (14)	−0.0062 (13)
C2	0.0349 (14)	0.0324 (14)	0.0324 (14)	0.0026 (12)	0.0033 (11)	−0.0041 (12)
C3	0.0330 (14)	0.0344 (14)	0.0266 (13)	−0.0011 (12)	0.0022 (11)	−0.0009 (11)
C4	0.059 (2)	0.0336 (16)	0.0395 (17)	0.0091 (14)	0.0095 (16)	−0.0006 (13)
C5	0.070 (2)	0.0285 (14)	0.0429 (18)	0.0016 (16)	0.0085 (17)	0.0033 (14)
C6	0.078 (3)	0.0419 (18)	0.0337 (16)	0.0079 (18)	0.0010 (17)	0.0057 (14)
C7	0.068 (2)	0.0328 (17)	0.058 (2)	−0.0023 (17)	0.0078 (19)	−0.0056 (16)
C8	0.057 (2)	0.0441 (17)	0.066 (2)	−0.017 (2)	0.016 (2)	−0.0039 (15)
C9	0.086 (3)	0.075 (3)	0.056 (2)	0.009 (3)	−0.026 (2)	−0.004 (2)
C10	0.148 (5)	0.072 (3)	0.043 (2)	0.020 (3)	0.022 (3)	0.020 (2)
C11	0.0464 (18)	0.0376 (17)	0.0414 (17)	−0.0118 (14)	−0.0013 (14)	0.0090 (14)
C12	0.0522 (18)	0.0318 (14)	0.0346 (15)	−0.0025 (14)	0.0029 (14)	−0.0043 (13)
C13	0.0316 (13)	0.0331 (15)	0.0304 (13)	0.0031 (11)	0.0039 (10)	0.0020 (11)
C14	0.0536 (19)	0.0356 (16)	0.0331 (15)	0.0105 (14)	0.0098 (14)	−0.0001 (13)
C15	0.0468 (17)	0.052 (2)	0.0354 (16)	0.0149 (15)	0.0164 (14)	0.0089 (14)
C16	0.0379 (15)	0.0401 (15)	0.0324 (14)	0.0042 (13)	0.0075 (12)	0.0045 (12)
C17	0.099 (3)	0.0441 (17)	0.0429 (18)	0.027 (2)	0.017 (2)	0.0049 (15)
C18	0.0303 (17)	0.095 (3)	0.064 (2)	−0.0050 (19)	0.0042 (16)	0.031 (2)
C19	0.0467 (19)	0.0524 (19)	0.0382 (16)	0.0056 (15)	−0.0042 (14)	0.0023 (14)
C20	0.067 (2)	0.066 (3)	0.0406 (19)	0.003 (2)	0.0185 (17)	0.0162 (18)

Geometric parameters (Å, º)

Pd1—N2	2.044 (2)	C9—H9B	0.9600
Pd1—N1	2.052 (3)	C9—H9C	0.9600
Pd1—Cl1	2.3177 (8)	C10—H10A	0.9600
Pd1—Cl2	2.3201 (8)	C10—H10B	0.9600
N1—C3	1.502 (4)	C10—H10C	0.9600
N1—H1A	0.9000	C11—C12	1.528 (5)
N1—H1B	0.9000	C11—C18	1.551 (5)
N2—C13	1.499 (4)	C11—C16	1.559 (5)
N2—H2A	0.9000	C11—H11A	0.9800
N2—H2B	0.9000	C12—C17	1.530 (5)
C1—C2	1.534 (4)	C12—C13	1.550 (4)
C1—C8	1.546 (5)	C12—H12A	0.9800
C1—C6	1.564 (5)	C13—C14	1.548 (4)
C1—H1C	0.9800	C13—H13A	0.9800
C2—C7	1.520 (4)	C14—C15	1.522 (4)
C2—C3	1.561 (4)	C14—H14A	0.9700
C2—H2C	0.9800	C14—H14B	0.9700
C3—C4	1.538 (4)	C15—C18	1.546 (6)
C3—H3A	0.9800	C15—C16	1.546 (5)
C4—C5	1.514 (5)	C15—H15A	0.9800
C4—H4A	0.9700	C16—C19	1.524 (5)
C4—H4B	0.9700	C16—C20	1.540 (4)
C5—C8	1.532 (6)	C17—H17A	0.9600
C5—C6	1.557 (5)	C17—H17B	0.9600
C5—H5A	0.9800	C17—H17C	0.9600
C6—C9	1.527 (7)	C18—H18A	0.9700
C6—C10	1.533 (5)	C18—H18B	0.9700
C7—H7A	0.9600	C19—H19A	0.9600
C7—H7B	0.9600	C19—H19B	0.9600
C7—H7C	0.9600	C19—H19C	0.9600
C8—H8A	0.9700	C20—H20A	0.9600
C8—H8B	0.9700	C20—H20B	0.9600
C9—H9A	0.9600	C20—H20C	0.9600
N2—Pd1—N1	177.28 (10)	C6—C9—H9C	109.5
N2—Pd1—Cl1	90.09 (7)	H9A—C9—H9C	109.5
N1—Pd1—Cl1	90.51 (8)	H9B—C9—H9C	109.5
N2—Pd1—Cl2	89.50 (8)	C6—C10—H10A	109.5
N1—Pd1—Cl2	90.00 (8)	C6—C10—H10B	109.5
Cl1—Pd1—Cl2	177.86 (3)	H10A—C10—H10B	109.5
C3—N1—Pd1	116.39 (19)	C6—C10—H10C	109.5
C3—N1—H1A	108.2	H10A—C10—H10C	109.5
Pd1—N1—H1A	108.2	H10B—C10—H10C	109.5
C3—N1—H1B	108.2	C12—C11—C18	107.7 (3)
Pd1—N1—H1B	108.2	C12—C11—C16	115.3 (3)
H1A—N1—H1B	107.3	C18—C11—C16	86.2 (3)
C13—N2—Pd1	114.28 (17)	C12—C11—H11A	114.7
C13—N2—H2A	108.7	C18—C11—H11A	114.7
Pd1—N2—H2A	108.7	C16—C11—H11A	114.7
C13—N2—H2B	108.7	C11—C12—C17	111.7 (3)
Pd1—N2—H2B	108.7	C11—C12—C13	111.4 (3)
H2A—N2—H2B	107.6	C17—C12—C13	112.9 (3)
C2—C1—C8	107.4 (3)	C11—C12—H12A	106.8
C2—C1—C6	114.9 (3)	C17—C12—H12A	106.8
C8—C1—C6	87.4 (3)	C13—C12—H12A	106.8
C2—C1—H1C	114.7	N2—C13—C12	110.2 (2)
C8—C1—H1C	114.7	N2—C13—C14	111.2 (2)
C6—C1—H1C	114.7	C12—C13—C14	114.6 (2)
C7—C2—C1	113.4 (3)	N2—C13—H13A	106.8
C7—C2—C3	111.8 (3)	C12—C13—H13A	106.8
C1—C2—C3	110.7 (2)	C14—C13—H13A	106.8
C7—C2—H2C	106.8	C15—C14—C13	113.6 (3)
C1—C2—H2C	106.8	C15—C14—H14A	108.8
C3—C2—H2C	106.8	C13—C14—H14A	108.8
N1—C3—C4	108.7 (3)	C15—C14—H14B	108.8
N1—C3—C2	111.9 (2)	C13—C14—H14B	108.8
C4—C3—C2	114.8 (3)	H14A—C14—H14B	107.7
N1—C3—H3A	107.0	C14—C15—C18	107.2 (3)
C4—C3—H3A	107.0	C14—C15—C16	113.0 (3)
C2—C3—H3A	107.0	C18—C15—C16	86.8 (3)
C5—C4—C3	113.3 (3)	C14—C15—H15A	115.4
C5—C4—H4A	108.9	C18—C15—H15A	115.4
C3—C4—H4A	108.9	C16—C15—H15A	115.4
C5—C4—H4B	108.9	C19—C16—C20	106.7 (3)
C3—C4—H4B	108.9	C19—C16—C15	118.7 (3)
H4A—C4—H4B	107.7	C20—C16—C15	112.3 (3)
C4—C5—C8	108.6 (3)	C19—C16—C11	121.2 (3)
C4—C5—C6	112.2 (3)	C20—C16—C11	110.8 (3)
C8—C5—C6	88.1 (3)	C15—C16—C11	86.2 (3)
C4—C5—H5A	115.0	C12—C17—H17A	109.5
C8—C5—H5A	115.0	C12—C17—H17B	109.5
C6—C5—H5A	115.0	H17A—C17—H17B	109.5
C9—C6—C10	108.3 (4)	C12—C17—H17C	109.5
C9—C6—C5	119.2 (3)	H17A—C17—H17C	109.5
C10—C6—C5	111.8 (3)	H17B—C17—H17C	109.5
C9—C6—C1	121.2 (3)	C15—C18—C11	86.5 (3)
C10—C6—C1	110.0 (4)	C15—C18—H18A	114.2
C5—C6—C1	84.6 (3)	C11—C18—H18A	114.2
C2—C7—H7A	109.5	C15—C18—H18B	114.2
C2—C7—H7B	109.5	C11—C18—H18B	114.2
H7A—C7—H7B	109.5	H18A—C18—H18B	111.4
C2—C7—H7C	109.5	C16—C19—H19A	109.5
H7A—C7—H7C	109.5	C16—C19—H19B	109.5
H7B—C7—H7C	109.5	H19A—C19—H19B	109.5
C5—C8—C1	86.1 (3)	C16—C19—H19C	109.5
C5—C8—H8A	114.3	H19A—C19—H19C	109.5
C1—C8—H8A	114.3	H19B—C19—H19C	109.5
C5—C8—H8B	114.3	C16—C20—H20A	109.5
C1—C8—H8B	114.3	C16—C20—H20B	109.5
H8A—C8—H8B	111.4	H20A—C20—H20B	109.5
C6—C9—H9A	109.5	C16—C20—H20C	109.5
C6—C9—H9B	109.5	H20A—C20—H20C	109.5
H9A—C9—H9B	109.5	H20B—C20—H20C	109.5
Cl1—Pd1—N1—C3	−62.6 (2)	C2—C1—C8—C5	87.6 (3)
Cl2—Pd1—N1—C3	115.3 (2)	C6—C1—C8—C5	−27.6 (3)
Cl1—Pd1—N2—C13	−104.72 (19)	C18—C11—C12—C17	175.8 (3)
Cl2—Pd1—N2—C13	77.38 (19)	C16—C11—C12—C17	−90.0 (4)
C8—C1—C2—C7	175.9 (3)	C18—C11—C12—C13	−56.9 (4)
C6—C1—C2—C7	−88.8 (4)	C16—C11—C12—C13	37.3 (4)
C8—C1—C2—C3	−57.5 (4)	Pd1—N2—C13—C12	63.9 (3)
C6—C1—C2—C3	37.8 (4)	Pd1—N2—C13—C14	−168.0 (2)
Pd1—N1—C3—C4	−53.6 (3)	C11—C12—C13—N2	142.0 (3)
Pd1—N1—C3—C2	178.51 (18)	C17—C12—C13—N2	−91.3 (3)
C7—C2—C3—N1	−92.5 (3)	C11—C12—C13—C14	15.8 (4)
C1—C2—C3—N1	140.0 (3)	C17—C12—C13—C14	142.4 (3)
C7—C2—C3—C4	143.0 (3)	N2—C13—C14—C15	−140.7 (3)
C1—C2—C3—C4	15.5 (4)	C12—C13—C14—C15	−15.0 (4)
N1—C3—C4—C5	−139.7 (3)	C13—C14—C15—C18	54.6 (4)
C2—C3—C4—C5	−13.5 (4)	C13—C14—C15—C16	−39.3 (4)
C3—C4—C5—C8	53.6 (4)	C14—C15—C16—C19	−44.3 (4)
C3—C4—C5—C6	−42.2 (5)	C18—C15—C16—C19	−151.7 (3)
C4—C5—C6—C9	−41.0 (5)	C14—C15—C16—C20	−169.7 (3)
C8—C5—C6—C9	−150.4 (3)	C18—C15—C16—C20	82.9 (3)
C4—C5—C6—C10	−168.6 (4)	C14—C15—C16—C11	79.3 (3)
C8—C5—C6—C10	82.0 (4)	C18—C15—C16—C11	−28.0 (2)
C4—C5—C6—C1	81.9 (3)	C12—C11—C16—C19	41.6 (4)
C8—C5—C6—C1	−27.5 (2)	C18—C11—C16—C19	149.4 (3)
C2—C1—C6—C9	40.2 (5)	C12—C11—C16—C20	167.7 (3)
C8—C1—C6—C9	148.2 (4)	C18—C11—C16—C20	−84.5 (3)
C2—C1—C6—C10	167.9 (3)	C12—C11—C16—C15	−79.9 (3)
C8—C1—C6—C10	−84.1 (4)	C18—C11—C16—C15	27.9 (2)
C2—C1—C6—C5	−80.8 (3)	C14—C15—C18—C11	−84.9 (3)
C8—C1—C6—C5	27.2 (3)	C16—C15—C18—C11	28.2 (2)
C4—C5—C8—C1	−85.0 (3)	C12—C11—C18—C15	87.4 (3)
C6—C5—C8—C1	27.8 (3)	C16—C11—C18—C15	−28.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1^i	0.90	2.79	3.572 (3)	146
N1—H1A···Cl2^ii	0.90	2.80	3.683 (3)	167
N2—H2B···Cl1^iii	0.90	2.81	3.663 (3)	159
N2—H2A···Cl2^iv	0.90	2.84	3.664 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1, y, z.

(II) trans-dichlorobis[(1S,2S,3S,5R)-(+)-2,6,6-trimethylbicyclo[3.1.1]heptan-3- amino]palladium(II) hemihydrate

Crystal data

[PdCl2(C10H19N)2]·0.5H2O	F(000) = 1028
Mr = 492.83	Dx = 1.295 Mg m^−3
Orthorhombic, I222	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2 2	Cell parameters from 68 reflections
a = 6.6873 (8) Å	θ = 4.2–12.5°
b = 13.427 (2) Å	µ = 0.95 mm^−1
c = 28.159 (4) Å	T = 296 K
V = 2528.4 (6) Å^3	Needle, yellow
Z = 4	0.60 × 0.18 × 0.18 mm

Data collection

Bruker P4 diffractometer	1750 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.029
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
ω scans	h = −8→1
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→17
Tmin = 0.735, Tmax = 0.842	l = −1→36
2145 measured reflections	3 standard reflections every 97 reflections
2029 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: See text
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0664P)^2 + 1.4484P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2029 reflections	Δρmax = 0.88 e Å^−3
121 parameters	Δρmin = −0.67 e Å^−3
0 restraints	Absolute structure: Flack (1983), 349 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

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	Occ. (<1)
Pd1	0.5000	0.87289 (4)	0.5000	0.04686 (18)
Cl1	0.77115 (18)	0.8743 (3)	0.44952 (5)	0.0625 (4)
N1	0.2963 (6)	0.8762 (7)	0.44519 (14)	0.0549 (10)
H1A	0.1785	0.8550	0.4568	0.066*
H1B	0.2798	0.9404	0.4368	0.066*
C1	0.1271 (12)	0.7458 (5)	0.3352 (2)	0.0640 (18)
H1C	0.0401	0.7566	0.3077	0.077*
C2	0.1799 (9)	0.8404 (4)	0.36188 (18)	0.0528 (13)
H2A	0.0585	0.8623	0.3784	0.063*
C3	0.3373 (9)	0.8177 (4)	0.40026 (17)	0.0508 (12)
H3A	0.4667	0.8403	0.3880	0.061*
C4	0.3597 (14)	0.7070 (5)	0.4127 (3)	0.080 (2)
H4A	0.5008	0.6910	0.4151	0.096*
H4B	0.2996	0.6950	0.4436	0.096*
C5	0.2633 (13)	0.6382 (5)	0.3765 (3)	0.0769 (19)
H5A	0.2840	0.5669	0.3822	0.092*
C6	0.3070 (12)	0.6732 (5)	0.3254 (3)	0.0727 (19)
C7	0.2475 (14)	0.9266 (5)	0.3304 (2)	0.079 (2)
H7A	0.1485	0.9388	0.3065	0.118*
H7B	0.3724	0.9100	0.3156	0.118*
H7C	0.2642	0.9853	0.3495	0.118*
C8	0.0487 (13)	0.6691 (6)	0.3701 (3)	0.086 (2)
H8A	−0.0123	0.6973	0.3984	0.104*
H8B	−0.0359	0.6185	0.3560	0.104*
C9	0.5140 (13)	0.7108 (7)	0.3128 (3)	0.100 (3)
H9A	0.6029	0.6552	0.3090	0.150*
H9B	0.5625	0.7532	0.3377	0.150*
H9C	0.5078	0.7477	0.2836	0.150*
C10	0.2471 (16)	0.5942 (6)	0.2874 (3)	0.113 (3)
H10A	0.3377	0.5388	0.2890	0.169*
H10B	0.2534	0.6236	0.2564	0.169*
H10C	0.1134	0.5714	0.2935	0.169*
O1	0.359 (6)	0.5000	0.5000	0.111 (10)*	0.25
H1	0.4009	0.5441	0.5192	0.167*	0.25
O2	0.119 (9)	0.5000	0.5000	0.19 (2)*	0.25
H2	0.1961	0.4587	0.5136	0.281*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0350 (2)	0.0722 (3)	0.0334 (2)	0.000	0.0023 (2)	0.000
Cl1	0.0397 (6)	0.1029 (10)	0.0450 (5)	0.0052 (11)	0.0080 (5)	−0.0023 (10)
N1	0.0393 (19)	0.086 (3)	0.0396 (18)	0.006 (4)	−0.0045 (17)	−0.006 (3)
C1	0.053 (4)	0.085 (4)	0.054 (3)	0.005 (3)	−0.009 (3)	−0.014 (3)
C2	0.048 (3)	0.072 (3)	0.039 (2)	0.007 (3)	−0.005 (2)	−0.002 (2)
C3	0.044 (3)	0.069 (3)	0.039 (2)	0.007 (3)	−0.003 (2)	−0.002 (2)
C4	0.099 (6)	0.070 (4)	0.072 (4)	0.012 (4)	−0.020 (4)	0.004 (3)
C5	0.087 (5)	0.060 (4)	0.083 (4)	−0.005 (4)	−0.009 (4)	−0.002 (3)
C6	0.067 (4)	0.077 (4)	0.075 (4)	0.009 (4)	−0.008 (4)	−0.026 (3)
C7	0.103 (6)	0.075 (4)	0.058 (3)	0.006 (4)	−0.007 (4)	0.009 (3)
C8	0.085 (6)	0.083 (4)	0.091 (5)	−0.024 (4)	0.007 (5)	−0.011 (4)
C9	0.078 (5)	0.120 (6)	0.102 (5)	0.016 (7)	0.027 (6)	−0.035 (5)
C10	0.116 (7)	0.112 (6)	0.111 (6)	0.010 (6)	−0.021 (6)	−0.062 (5)

Geometric parameters (Å, º)

Pd1—N1^i	2.059 (4)	C4—H4B	0.9700
Pd1—N1	2.059 (4)	C5—C8	1.505 (12)
Pd1—Cl1	2.3041 (12)	C5—C6	1.540 (11)
Pd1—Cl1^i	2.3041 (12)	C5—H5A	0.9800
Pd1—Pd1^ii	3.4133 (13)	C6—C9	1.516 (11)
Pd1—Pd1^iii	10.0135 (19)	C6—C10	1.561 (9)
N1—C3	1.514 (7)	C7—H7A	0.9600
N1—H1A	0.9000	C7—H7B	0.9600
N1—H1B	0.9000	C7—H7C	0.9600
C1—C2	1.516 (8)	C8—H8A	0.9700
C1—C8	1.517 (11)	C8—H8B	0.9700
C1—C6	1.573 (10)	C9—H9A	0.9600
C1—H1C	0.9800	C9—H9B	0.9600
C2—C7	1.526 (9)	C9—H9C	0.9600
C2—C3	1.539 (7)	C10—H10A	0.9600
C2—H2A	0.9800	C10—H10B	0.9600
C3—C4	1.535 (9)	C10—H10C	0.9600
C3—H3A	0.9800	O1—H1	0.8500
C4—C5	1.520 (10)	O2—H2	0.8501
C4—H4A	0.9700
N1^i—Pd1—N1	177.5 (5)	H4A—C4—H4B	107.8
N1^i—Pd1—Cl1	86.66 (12)	C8—C5—C4	108.5 (7)
N1—Pd1—Cl1	93.32 (13)	C8—C5—C6	89.2 (6)
N1^i—Pd1—Cl1^i	93.32 (13)	C4—C5—C6	111.1 (6)
N1—Pd1—Cl1^i	86.66 (12)	C8—C5—H5A	115.1
Cl1—Pd1—Cl1^i	179.04 (16)	C4—C5—H5A	115.1
N1^i—Pd1—Pd1^ii	88.8 (3)	C6—C5—H5A	115.1
N1—Pd1—Pd1^ii	88.8 (3)	C9—C6—C5	119.6 (7)
Cl1—Pd1—Pd1^ii	89.52 (8)	C9—C6—C10	107.4 (7)
Cl1^i—Pd1—Pd1^ii	89.52 (8)	C5—C6—C10	112.6 (7)
N1^i—Pd1—Pd1^iii	91.2 (3)	C9—C6—C1	122.3 (6)
N1—Pd1—Pd1^iii	91.2 (3)	C5—C6—C1	83.1 (6)
Cl1—Pd1—Pd1^iii	90.48 (8)	C10—C6—C1	110.2 (7)
Cl1^i—Pd1—Pd1^iii	90.48 (8)	C2—C7—H7A	109.5
Pd1^ii—Pd1—Pd1^iii	180.0	C2—C7—H7B	109.5
C3—N1—Pd1	119.7 (4)	H7A—C7—H7B	109.5
C3—N1—H1A	107.4	C2—C7—H7C	109.5
Pd1—N1—H1A	107.4	H7A—C7—H7C	109.5
C3—N1—H1B	107.4	H7B—C7—H7C	109.5
Pd1—N1—H1B	107.4	C5—C8—C1	86.2 (6)
H1A—N1—H1B	106.9	C5—C8—H8A	114.3
C2—C1—C8	109.2 (6)	C1—C8—H8A	114.3
C2—C1—C6	115.3 (6)	C5—C8—H8B	114.3
C8—C1—C6	87.5 (6)	C1—C8—H8B	114.3
C2—C1—H1C	114.0	H8A—C8—H8B	111.4
C8—C1—H1C	114.0	C6—C9—H9A	109.5
C6—C1—H1C	114.0	C6—C9—H9B	109.5
C1—C2—C7	114.7 (5)	H9A—C9—H9B	109.5
C1—C2—C3	110.0 (5)	C6—C9—H9C	109.5
C7—C2—C3	110.8 (5)	H9A—C9—H9C	109.5
C1—C2—H2A	107.0	H9B—C9—H9C	109.5
C7—C2—H2A	107.0	C6—C10—H10A	109.5
C3—C2—H2A	107.0	C6—C10—H10B	109.5
N1—C3—C4	109.2 (5)	H10A—C10—H10B	109.5
N1—C3—C2	111.1 (4)	C6—C10—H10C	109.5
C4—C3—C2	114.8 (5)	H10A—C10—H10C	109.5
N1—C3—H3A	107.1	H10B—C10—H10C	109.5
C4—C3—H3A	107.1	H1^iv—O1—H1	135.5
C2—C3—H3A	107.1	H1^iv—O1—H2	66.1
C5—C4—C3	113.2 (6)	H1—O1—H2	113.3
C5—C4—H4A	108.9	O2^v—O2—H2^iv	92.3
C3—C4—H4A	108.9	O2^v—O2—H2	127.6
C5—C4—H4B	108.9	H2^iv—O2—H2	48.5
C3—C4—H4B	108.9
Cl1—Pd1—N1—C3	38.1 (5)	C3—C4—C5—C6	42.5 (9)
Cl1^i—Pd1—N1—C3	−142.8 (6)	C8—C5—C6—C9	150.8 (7)
Pd1^ii—Pd1—N1—C3	127.6 (5)	C4—C5—C6—C9	41.3 (9)
Pd1^iii—Pd1—N1—C3	−52.4 (5)	C8—C5—C6—C10	−81.7 (7)
C8—C1—C2—C7	−176.0 (7)	C4—C5—C6—C10	168.8 (8)
C6—C1—C2—C7	87.5 (8)	C8—C5—C6—C1	27.4 (5)
C8—C1—C2—C3	58.4 (7)	C4—C5—C6—C1	−82.1 (7)
C6—C1—C2—C3	−38.1 (8)	C2—C1—C6—C9	−38.0 (10)
Pd1—N1—C3—C4	59.2 (7)	C8—C1—C6—C9	−148.0 (7)
Pd1—N1—C3—C2	−173.2 (4)	C2—C1—C6—C5	82.9 (6)
C1—C2—C3—N1	−141.1 (6)	C8—C1—C6—C5	−27.2 (6)
C7—C2—C3—N1	91.1 (7)	C2—C1—C6—C10	−165.5 (6)
C1—C2—C3—C4	−16.6 (7)	C8—C1—C6—C10	84.4 (8)
C7—C2—C3—C4	−144.4 (6)	C4—C5—C8—C1	83.7 (7)
N1—C3—C4—C5	140.5 (7)	C6—C5—C8—C1	−28.3 (5)
C2—C3—C4—C5	15.0 (9)	C2—C1—C8—C5	−88.3 (6)
C3—C4—C5—C8	−54.0 (9)	C6—C1—C8—C5	27.7 (5)

Symmetry codes: (i) −x+1, y, −z+1; (ii) −x+1, −y+2, z; (iii) −x+1, −y+1, z; (iv) x, −y, −z+1; (v) −x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^vi	0.90	2.74	3.514 (5)	144
N1—H1B···Cl1^ii	0.90	2.54	3.382 (7)	157

Symmetry codes: (ii) −x+1, −y+2, z; (vi) x−1, y, z.