Supra­molecular hydrogen bonding of [5,10,15,20-tetra­kis(4-carboxyphenyl)porphyrinato]palladium(II) in the presence of competing solvents

The title porphyrin compound forms hydrogen-bonded adducts with methanol (1:1), [Pd(C₄₈H₂₈N₄O₈)]·CH₄O, (I), and with water and N,N-dimethyl­formamide (1:4:4), [Pd(C₄₈H₂₈N₄O₈)]·4C₃H₇NO·4H₂O, (II). In (I), the metalloporphyrin unit lies across a mirror plane in Cmca, while in (II), this unit lies across an inversion center in P. Extended supra­molecular hydrogen-bonded arrays are formed in (I) by inter­molecular inter­actions between the carboxylic acid functions, either directly or through the methanol species. These layers have a wavy topology and large inter­porphyrin pores, which are filled in the crystal structure by double inter­penetration as well as enclathration of additional non-inter­acting nitro­benzene solvent mol­ecules. The supra­molecular aggregation in (II) can be characterized by cascaded porphyrin layers, wherein adjacent porphyrin mol­ecules are hydrogen bonded to one another through mol­ecules of water that are incorporated into the hydrogen-bonding scheme. Mol­ecules of dimethyl­formamide partly solvate the carboxylic acid groups and fill the inter­porphyrin space in the crystal structure.

S1. Comment

Metalloporphyrin macrocycles when tetra-substituted with 4-carboxyphenyl groups at their meso positions (M-TCPP) provide a classical example of an organic species with multiple complementary terminal functional groups directed at four diverging directions of the equatorial molecular plane, which exhibit high a propensity for self-assembling into flat hydrogen-bonded two-dimensional nets (Goldberg, 2005, and references therein). It has been shown that the carboxylic acid functions may engage readily in two different supramolecular synthons, either catemeric (chain-type) or cyclic dimeric. In the latter case, utilization of four head-to-head (COOH)₂ cyclic dimeric associations to four neighboring porphyrin units leads to the formation of quadrangular grid arrays with large pores (Dastidar et al., 1996; Diskin-Posner & Goldberg, 1999; George & Goldberg, 2006; George et al., 2006; Lipstman, Muniappan & Goldberg, 2007). In the solid, these pores are filled either by a guest template or by self-interpenetration of the networks. Every molecule of the tetra-acid within such supramolecular layered assembly is involved simultaneously in eight nearly linear O—H···O interactions, or four (COOH)₂ R²₂(8)-type (Etter, 1990; Bernstein et al., 1995) synthons.

In non-interwoven structures the two-dimensional multiporphyrin layers form offset stacks along the normal direction, held together by van der Waals forces. In addition to supramolecular isomerism of the catenane type (occurrence of interwoven versus. non-interpenetrating networks), conformational isomerism, where arrays of identical composition reveal different grid shapes, has also been observed in these systems (George et al., 2006). The neat networking of the M-TCPP units into homogeneous multi-porphyrin nets can be readily disrupted by competing solvation that can modify or prevent supramolecular association. This is common with strong Lewis base reagents, e.g. dimethyl sulfoxide and pyridine, which each have a higher proton affinity than the carbonyl fragments of the carboxylic acid (Lipstman et al., 2006; George et al., 2006). Correspondingly, the actual outcome of a given supramolecular synthesis with the M-TCPP building blocks via hydrogen bonding is not always predictable.

In the above context we describe here the structures of the solid products (Fig. 1), (I) and (II), obtained by crystallizing Pd-TCPP from (i) a mixture of methanol (used to dissolve the porphyrin) and nitrobenzene (an inert reagent that commonly fills effectively intra-lattice voids in porphyrin framework solids), and (ii) a mixture of methanol and N,N'-dimethylformamide (DMF).

In the presence of alcohols (although they represent relatively weak hydrogen-bond donors and acceptors), the supramolecular hydrogen bonding of organic carboxylic acids does not always preserve the (COOH)₂ intermolecular synthon. On some occasions incorporation of the hydroxy group into the intermolecular hydrogen-bonding scheme has been observed (Dale et al., 2004). Not surprisingly, the same phenomenon characterizes the hydrogen-bonded assembly in (I). Two cis-related carboxylic acid groups of Pd-TCPP are involved in R₂²(8) direct interaction synthons (Fig. 2a) with the carboxylic acid functions of neighboring species. However, the two other carboxylic acid residues bind to their neighbors via the R₃³(10) synthon (Fig. 2b), in which there is one methanol molecule inserted between the two carboxylic acid groups (Table 1). This modification maintains a continuous hydrogen-bonding pattern throughout the crystal structures, where every porphyrin unit is interacting with four different neighbouring species.

Evidently, in the present case, the hydrogen-bonded networks thus formed are no longer flat. Rather, they adopt a wavy shape, as illustrated in Fig. 3. While intermolecular aggregation via the (COOH)₂ bonds is associated with coplanarity of the interacting components, that via the COOH(MeOH)COOH R₃³(10) synthons effects a nearly perpendicular orientation of the species involved. Thus, in the observed assemblies there is a strong kink either up or down every two rows of the interlinked Pd-TCPP units. The supramolecular networks are characterized by wide interporphyrin voids. These voids are filled in the solid phase by double interpenetration, as well as by incorporation into the structure of nitrobenzene from the solvent mixture. The crystal packing of (I) is illustrated in Fig. 4. It is further stabilized by stacking interactions at an interplanar distance of approximately 4 Å between parallel porphyrin segments of the interweaved networks.

The disruption of the interporphyrin hydrogen-bonding scheme is much more severe in (II). Here the two carboxylic acid groups of adjacent porphyrin species are solvated by two molecules of water and one molecule of DMF. One of the water molecules (O33) bridges by hydrogen bonding between two adjacent carbonyl fragments (O21 and O31), while the other water molecule (O32) and the DMF molecule (through O34) serve as H-atom acceptors from the two adjacent hydroxy residues O30 and O22 (Fig. 2c and Table 2). Moreover, every porphyrin unit connects via the first water molecule only to two neighboring porphyrins (and not to four neighbors as in the preceding example), giving rise to the formation of hydrogen-bonded one-dimensional chains as the primary supramolecular motif with coplanar porphyrin components (Fig. 5). These chain motifs further interconnect by hydrogen bonding between the O32 and O33 species of adjacent chains, yielding an extended two-dimensional hydrogen-bonded pattern in the crystal structure, which propagates parallel to the (011) plane (Fig. 5 and Table 2). The observed hydrogen-bonding scheme corresponds (when the side hydrogen bonds to the DMF molecules are ingnored) to the C₃³(8) graph-set representation. The packing arrangement of (II) is shown in Fig. 6. The porphyrin frameworks displaced along the a axis are arranged in an offset stacked manner with a minor overlap between adjacent molecules along the stack and average spacing of about 4.6 Å. Additional molecules of the DMF solvent are included in the interface between the hydrogen-bonded layers centered at z = 0 and z = 1 in a disordered manner (fragments O39A–C43A and O39B–C43B). They form hydrogen bonds to the O32 water molecule.

In summary, this study describes the effects of competing solvation on the self assembly of TCPP-type porphyrin building blocks by hydrogen bonding, where solvent components with comparable H-atom donating or accepting capacity interfere with direct assembly of the porphyrin units into homogeneous single-component arrays. It should be noted that Pd-TCPP and related metalloporphyrins are also excellent building blocks for networking through external metal ion bridging auxiliaries, which can coordinate to the peripheral carboxylic acid groups, and yield by multiple coordination robust supramolecular arrays (Goldberg, 2005,and references therein; Shmilovits et al., 2003; Lipstman, Muniappan, George & Goldberg, 2007).

Related literature

For related literature, see: Bernstein et al. (1995); Dale et al. (2004); Dastidar et al. (1996); Diskin-Posner & Goldberg (1999); Etter (1990); George & Goldberg (2006); George, Lipstman, Muniappan & Goldberg (2006); Goldberg (2005); Lipstman et al. (2006); Lipstman, Muniappan & Goldberg (2007); Lipstman, Muniappan, George & Goldberg (2007); Shmilovits et al. (2003); Spek (2003).

S2. Experimental

Pd-TCPP was obtained commercially from Porphyrin Systems GbR. Compound (I) was obtained by dissolving the metalloporphyrin (2.7 mg, 0.003 mmol) in a minimal amount of methanol. To this, six drops of nitrobenzene were added. Slow evaporation of the resulting mixture yielded after one month X-ray quality red rhombus-like crystals. Reaction of Pd-TCPP (2 mg, 0.002 mmol) with a minimal amount of methanol and a few drops of DMF yielded crystals of (II) under otherwise similar crystallization conditions.

S3. Refinement

H atoms bound to C atoms were located in calculated positions and were constrained to ride on their parent atoms with C—H distances of 0.95 and 0.98 Å and with U_iso(H) values of 1.2 or 1.5 times U_eq(C). H atoms bound to O atoms were either located in difference Fourier maps or placed in calculated positions to correspond to idealized hydrogen-bonding geometries, with O—H distances within the range 0.84–0.99 Å. Their atomic positions were not refined, and they were constrained to ride on their parent atoms with U_iso(H) values of 1.2 or 1.5 times U_eq(O) [should this be just 1.2?]. In (I), the porphyrin and methanol components are located on mirror planes and twofold axes, respectively. The hydrogen-bonding scheme is characterized by a twofold disorder about the rotation axes. Correspondingly, the methanol molecule and the carboxylic acid groups also exhibit partial disorder. The nitrobenzene solvent incorporated into the crystal structure of (I) is also positioned on, and severely disordered about, the (1/2 y z) mirror plane, being centered approximately at (1/2, 0.1, 0.4). It could not be reliably modeled by discrete atoms. Correspondingly, its contribution was subtracted from the diffraction data by the SQUEEZE procedure (PLATON; Spek, 2003). In (II), one of the DMF species (O39/C40/N41/C42/C43) exhibits a twofold orientational disorder, which could be modeled, and it was refined with restrained geometry in order to avoid irregular values for bond lengths and bond angles. The Pd-TCPP reference unit is located on an inversion centre at (0, 0, 1).

Computing details

For both compounds, data collection: Collect (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997). Data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (I); DENZO (Otwinowski & Minor, 1997) for (II). For both compounds, program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (a) compound (I) and (b) compound (II), showing the atom labeling scheme. Atomic ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. H atoms have been omitted.
	Fig. 2. Schematic representations of the different hydrogen-bonding synthons between the carboxylic acid substituents. (a) The R2^2(8) pattern encountered in a variety of TCPP-based hydrogen-bonded networks (Dastidar et al., 1996; Diskin-Posner & Goldberg, 1999; George & Goldberg, 2006; George et al., 2006; Lipstman, Muniappan & Goldberg, 2007). (b) The R3^3(10) pattern observed in (I). (c) The solvation pattern of the carboxylic acid groups in (II) (see text).
	Fig. 3. The supramolecular hydrogen-bonded wavy layers in (I). Hydrogen bonds are marked by dotted lines. The palladium ions and the methanol O atoms are indicated by small spheres. H atoms are not shown.
	Fig. 4. The crystal structure of (I). The palladium ions and the methanol molecule are indicated by small spheres. H atoms as well as the disordered nitrobenzene solvent molecule have been omitted.
	Fig. 5. Illustration of the supramolecular hydrogen bonding in (II). The Pd atoms and water molecules are indicated by small spheres. Hydrogen bonds are marked by dotted lines. The disordered DMF molecule and the H atoms have been omitted. Crystallographic translation along a relates the two shown rows of the porphyrin molecules. Atomic labels identify the O atoms (or their symmetry equivalents) that are involved in the hydrogen bonds.
	Fig. 6. The crystal packing of (II), projected down the a axis. Pd atoms and water molecules are indicated by spheres. The disordered DMF species located between neighboring hydrogen-bonded layers (only a single orientation of each is shown) are marked by an asterisk. They reside near x = 0.26, y = 0.51, z = 0.45, filling the interporphyrin space.

(I) [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]palladium(II) methanol solvate

Crystal data

[Pd(C48H28N4O8)]·CH4O	F(000) = 3776
Mr = 927.21	Dx = 1.354 Mg m^−3
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 4588 reflections
a = 31.0347 (6) Å	θ = 2.6–25.6°
b = 15.9441 (11) Å	µ = 0.47 mm^−1
c = 18.3824 (7) Å	T = 110 K
V = 9096.0 (7) Å^3	Rhomb, red
Z = 8	0.30 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer	2688 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.098
Graphite monochromator	θmax = 25.6°, θmin = 2.6°
Detector resolution: 12.8 pixels mm^-1	h = 0→37
0.5 deg. ϕ scans	k = 0→19
20365 measured reflections	l = −22→0
4344 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0724P)^2 + 2.4049P] where P = (Fo^2 + 2Fc^2)/3
4344 reflections	(Δ/σ)max = 0.008
291 parameters	Δρmax = 0.50 e Å^−3
12 restraints	Δρmin = −0.77 e Å^−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.

The crystal contains severely disordered molecules of the nitrobenzene solvent, which couldn't be modeled reliably by discrete atoms. One molecule of nitrobenzene is located on and disordered about the mirror plane at 1/2,y,z, being centered at 1/2,0.1,0.4. Correspondingly, the contribution of the disordered solvent was subtracted from the diffraction data by the SQUEEZE procedure (Spek, 2003). The results below are based on thus modified intensity data. The two independent carboxylic groups also reveal partial rotational disorder about the C-COOH bond and SIMU restratrains were applied to their ADP's. The methanol is also partly disordered.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.0000	0.03589 (4)	0.35956 (3)	0.0237 (2)
C2	0.02189 (18)	0.1673 (4)	0.5582 (3)	0.0309 (14)
H2	0.0401	0.1876	0.5958	0.037*
C3	0.03551 (18)	0.1305 (4)	0.4903 (3)	0.0293 (14)
C4	0.07828 (17)	0.1262 (4)	0.4667 (3)	0.0255 (13)
C5	0.09124 (18)	0.0853 (4)	0.4028 (3)	0.0265 (13)
C6	0.13500 (17)	0.0824 (4)	0.3773 (3)	0.0309 (15)
H6	0.1591	0.1099	0.3983	0.037*
C7	0.13524 (17)	0.0327 (4)	0.3172 (3)	0.0311 (14)
H7	0.1598	0.0178	0.2891	0.037*
C8	0.09142 (18)	0.0067 (4)	0.3040 (3)	0.0283 (14)
C9	0.07875 (17)	−0.0460 (4)	0.2478 (3)	0.0278 (13)
C10	0.03559 (18)	−0.0646 (4)	0.2321 (3)	0.0294 (14)
C11	0.02210 (18)	−0.1147 (4)	0.1706 (3)	0.0334 (15)
H11	0.0403	−0.1423	0.1367	0.040*
N12	0.0000	0.1062 (5)	0.4506 (3)	0.0271 (16)
N13	0.06496 (13)	0.0403 (3)	0.3576 (2)	0.0258 (10)
N14	0.0000	−0.0358 (5)	0.2700 (3)	0.0264 (15)
C15	0.11126 (17)	0.1686 (4)	0.5126 (3)	0.0281 (14)
C16	0.11155 (18)	0.2557 (4)	0.5201 (3)	0.0327 (15)
H16	0.0915	0.2887	0.4935	0.039*
C17	0.14104 (19)	0.2949 (5)	0.5662 (3)	0.0405 (17)
H17	0.1420	0.3543	0.5695	0.049*
C18	0.16916 (18)	0.2456 (5)	0.6075 (3)	0.0360 (15)
C19	0.1693 (2)	0.1591 (5)	0.6009 (3)	0.0436 (18)
H19	0.1889	0.1262	0.6285	0.052*
C20	0.14048 (19)	0.1207 (5)	0.5534 (3)	0.0380 (16)
H20	0.1406	0.0614	0.5486	0.046*
C21	0.1996 (2)	0.2884 (5)	0.6601 (3)	0.0395 (17)
O22	0.19883 (16)	0.3654 (4)	0.6649 (4)	0.091 (2)
H22	0.2156	0.3929	0.6926	0.109*	0.50
O23	0.22375 (15)	0.2398 (4)	0.6969 (2)	0.0738 (19)
H23	0.2422	0.2624	0.7237	0.089*	0.50
C24	0.11290 (17)	−0.0826 (4)	0.2009 (3)	0.0300 (14)
C25	0.1340 (2)	−0.0354 (5)	0.1482 (3)	0.0462 (16)
H25	0.1268	0.0220	0.1416	0.055*
C26	0.1659 (2)	−0.0728 (5)	0.1048 (4)	0.0461 (19)
H26	0.1803	−0.0400	0.0691	0.055*
C27	0.17659 (19)	−0.1556 (5)	0.1130 (4)	0.0385 (16)
C28	0.1563 (2)	−0.2028 (5)	0.1647 (4)	0.0445 (17)
H28	0.1637	−0.2602	0.1706	0.053*
C29	0.12447 (19)	−0.1666 (5)	0.2095 (3)	0.0388 (17)
H29	0.1108	−0.1996	0.2458	0.047*
C30	0.2105 (2)	−0.1966 (5)	0.0644 (3)	0.0391 (16)
O31	0.23083 (13)	−0.1452 (3)	0.0237 (2)	0.0509 (13)
H31	0.2487	−0.1723	−0.0063	0.061*
O32	0.21594 (14)	−0.2735 (3)	0.0659 (2)	0.0475 (13)
C33	0.2500	−0.0366 (8)	0.2500	0.077 (4)
H33A	0.2797	−0.0571	0.2530	0.116*	0.50
H33B	0.2367	−0.0571	0.2051	0.116*	0.50
H33C	0.2336	−0.0571	0.2920	0.116*	0.50
O34	0.2500	0.0498 (6)	0.2500	0.124 (4)
H34	0.2677	0.0787	0.2795	0.149*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0213 (3)	0.0260 (4)	0.0238 (3)	0.000	0.000	−0.0054 (3)
C2	0.033 (3)	0.030 (4)	0.030 (3)	−0.008 (3)	−0.007 (2)	−0.003 (3)
C3	0.034 (3)	0.035 (4)	0.019 (3)	−0.006 (3)	−0.006 (3)	−0.003 (3)
C4	0.027 (3)	0.028 (4)	0.021 (3)	−0.001 (3)	−0.003 (2)	−0.006 (2)
C5	0.028 (3)	0.024 (4)	0.027 (3)	0.001 (3)	0.000 (2)	0.000 (3)
C6	0.021 (3)	0.031 (4)	0.040 (4)	−0.003 (3)	−0.002 (3)	0.000 (3)
C7	0.023 (3)	0.037 (4)	0.033 (3)	−0.001 (3)	0.012 (2)	−0.004 (3)
C8	0.028 (3)	0.027 (4)	0.030 (3)	0.002 (3)	−0.006 (3)	0.002 (3)
C9	0.033 (3)	0.024 (4)	0.027 (3)	−0.003 (3)	0.003 (2)	0.000 (3)
C10	0.032 (3)	0.032 (4)	0.025 (3)	0.005 (3)	0.007 (3)	−0.005 (3)
C11	0.035 (3)	0.036 (4)	0.029 (3)	0.004 (3)	0.003 (3)	−0.013 (3)
N12	0.024 (3)	0.029 (4)	0.029 (4)	0.000	0.000	−0.008 (3)
N13	0.028 (2)	0.025 (3)	0.025 (2)	−0.002 (2)	0.004 (2)	−0.011 (2)
N14	0.027 (3)	0.026 (4)	0.027 (3)	0.000	0.000	0.002 (3)
C15	0.026 (3)	0.035 (4)	0.023 (3)	−0.006 (3)	−0.001 (2)	−0.004 (3)
C16	0.025 (3)	0.035 (4)	0.038 (3)	−0.001 (3)	−0.002 (3)	−0.004 (3)
C17	0.034 (3)	0.038 (5)	0.049 (4)	−0.008 (3)	0.001 (3)	−0.010 (3)
C18	0.029 (3)	0.050 (5)	0.029 (3)	−0.002 (3)	0.001 (3)	−0.012 (3)
C19	0.042 (4)	0.053 (5)	0.036 (4)	−0.004 (4)	−0.008 (3)	0.007 (3)
C20	0.037 (3)	0.036 (4)	0.041 (4)	−0.008 (3)	−0.009 (3)	0.006 (3)
C21	0.027 (3)	0.054 (5)	0.037 (4)	−0.006 (3)	−0.001 (3)	−0.011 (3)
O22	0.047 (3)	0.089 (5)	0.136 (6)	0.005 (3)	−0.027 (3)	−0.080 (5)
O23	0.046 (3)	0.139 (6)	0.036 (3)	−0.028 (3)	−0.016 (2)	0.004 (3)
C24	0.023 (3)	0.032 (4)	0.034 (3)	−0.001 (3)	0.003 (3)	−0.005 (3)
C25	0.049 (4)	0.045 (4)	0.045 (4)	0.004 (4)	0.011 (3)	0.004 (4)
C26	0.044 (4)	0.060 (5)	0.034 (4)	−0.009 (4)	0.020 (3)	−0.003 (3)
C27	0.028 (3)	0.041 (5)	0.046 (4)	0.002 (3)	0.001 (3)	−0.008 (3)
C28	0.042 (4)	0.043 (5)	0.048 (4)	0.006 (3)	0.005 (3)	−0.002 (3)
C29	0.034 (3)	0.048 (5)	0.035 (3)	0.003 (3)	0.009 (3)	−0.011 (3)
C30	0.035 (3)	0.044 (5)	0.039 (4)	−0.001 (3)	−0.001 (3)	−0.008 (3)
O31	0.035 (2)	0.066 (4)	0.052 (3)	−0.002 (3)	0.014 (2)	−0.011 (3)
O32	0.043 (3)	0.045 (4)	0.055 (3)	0.005 (2)	0.004 (2)	−0.011 (2)
C33	0.065 (7)	0.038 (8)	0.129 (11)	0.000	−0.022 (7)	0.000
O34	0.113 (8)	0.049 (7)	0.211 (12)	0.000	−0.104 (8)	0.000

Geometric parameters (Å, º)

Pd1—N14	2.004 (7)	C17—C18	1.398 (9)
Pd1—N12	2.015 (6)	C17—H17	0.9500
Pd1—N13	2.018 (4)	C18—C19	1.386 (10)
Pd1—N13^i	2.018 (4)	C18—C21	1.515 (9)
C2—C2^i	1.359 (11)	C19—C20	1.391 (9)
C2—C3	1.442 (8)	C19—H19	0.9500
C2—H2	0.9500	C20—H20	0.9500
C3—N12	1.377 (6)	C21—O22	1.230 (9)
C3—C4	1.398 (7)	C21—O23	1.272 (8)
C4—C5	1.402 (7)	O22—H22	0.8506
C4—C15	1.489 (7)	O23—H23	0.8359
C5—N13	1.368 (7)	C24—C25	1.390 (9)
C5—C6	1.438 (8)	C24—C29	1.396 (9)
C6—C7	1.359 (8)	C25—C26	1.405 (9)
C6—H6	0.9500	C25—H25	0.9500
C7—C8	1.442 (8)	C26—C27	1.370 (10)
C7—H7	0.9500	C26—H26	0.9500
C8—C9	1.389 (8)	C27—C28	1.367 (9)
C8—N13	1.390 (7)	C27—C30	1.528 (9)
C9—C10	1.402 (8)	C28—C29	1.410 (8)
C9—C24	1.485 (8)	C28—H28	0.9500
C10—N14	1.385 (7)	C29—H29	0.9500
C10—C11	1.446 (8)	C30—O32	1.238 (8)
C11—C11^i	1.372 (11)	C30—O31	1.274 (8)
C11—H11	0.9500	O31—H31	0.8945
N12—C3^i	1.377 (6)	C33—O34	1.378 (14)
N14—C10^i	1.385 (6)	C33—H33A	0.9800
C15—C16	1.396 (9)	C33—H33B	0.9800
C15—C20	1.403 (8)	C33—H33C	0.9800
C16—C17	1.395 (8)	O34—H34	0.8984
C16—H16	0.9500
N14—Pd1—N12	179.1 (3)	C15—C16—H16	119.7
N14—Pd1—N13	90.30 (13)	C17—C16—H16	119.7
N12—Pd1—N13	89.73 (13)	C16—C17—C18	119.2 (7)
N14—Pd1—N13^i	90.30 (13)	C16—C17—H17	120.4
N12—Pd1—N13^i	89.73 (13)	C18—C17—H17	120.4
N13—Pd1—N13^i	175.5 (3)	C19—C18—C17	120.9 (6)
C2^i—C2—C3	107.0 (3)	C19—C18—C21	120.1 (6)
C2^i—C2—H2	126.5	C17—C18—C21	118.9 (7)
C3—C2—H2	126.5	C18—C19—C20	119.4 (6)
N12—C3—C4	125.6 (5)	C18—C19—H19	120.3
N12—C3—C2	109.7 (5)	C20—C19—H19	120.3
C4—C3—C2	124.5 (5)	C19—C20—C15	120.7 (7)
C3—C4—C5	123.7 (5)	C19—C20—H20	119.6
C3—C4—C15	117.1 (5)	C15—C20—H20	119.6
C5—C4—C15	119.2 (5)	O22—C21—O23	125.5 (7)
N13—C5—C4	125.6 (5)	O22—C21—C18	118.8 (7)
N13—C5—C6	110.3 (5)	O23—C21—C18	115.7 (7)
C4—C5—C6	124.0 (5)	C21—O22—H22	123.1
C7—C6—C5	106.8 (5)	C21—O23—H23	117.0
C7—C6—H6	126.6	C25—C24—C29	118.5 (6)
C5—C6—H6	126.6	C25—C24—C9	121.9 (6)
C6—C7—C8	107.4 (5)	C29—C24—C9	119.6 (5)
C6—C7—H7	126.3	C24—C25—C26	120.0 (7)
C8—C7—H7	126.3	C24—C25—H25	120.0
C9—C8—N13	126.4 (5)	C26—C25—H25	120.0
C9—C8—C7	124.4 (5)	C27—C26—C25	121.1 (7)
N13—C8—C7	109.1 (5)	C27—C26—H26	119.5
C8—C9—C10	123.5 (5)	C25—C26—H26	119.5
C8—C9—C24	117.9 (5)	C28—C27—C26	119.8 (6)
C10—C9—C24	118.6 (5)	C28—C27—C30	119.3 (7)
N14—C10—C9	126.0 (5)	C26—C27—C30	120.9 (6)
N14—C10—C11	110.2 (5)	C27—C28—C29	120.2 (7)
C9—C10—C11	123.7 (5)	C27—C28—H28	119.9
C11^i—C11—C10	106.8 (3)	C29—C28—H28	119.9
C11^i—C11—H11	126.6	C24—C29—C28	120.5 (6)
C10—C11—H11	126.6	C24—C29—H29	119.7
C3^i—N12—C3	106.3 (6)	C28—C29—H29	119.7
C3^i—N12—Pd1	126.6 (3)	O32—C30—O31	125.6 (6)
C3—N12—Pd1	126.6 (3)	O32—C30—C27	120.2 (6)
C5—N13—C8	106.3 (4)	O31—C30—C27	114.1 (7)
C5—N13—Pd1	127.1 (4)	C30—O31—H31	111.0
C8—N13—Pd1	126.1 (4)	O34—C33—H33A	109.5
C10—N14—C10^i	105.8 (6)	O34—C33—H33B	109.5
C10—N14—Pd1	127.1 (3)	H33A—C33—H33B	109.5
C10^i—N14—Pd1	127.1 (3)	O34—C33—H33C	109.5
C16—C15—C20	119.0 (5)	H33A—C33—H33C	109.5
C16—C15—C4	120.8 (5)	H33B—C33—H33C	109.5
C20—C15—C4	119.9 (6)	C33—O34—H34	120.8
C15—C16—C17	120.6 (6)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O23—H23···O23^ii	0.84	1.84	2.542 (9)	141
O31—H31···O32^iii	0.89	1.77	2.669 (6)	180
O34—H34···O22^iv	0.90	1.71	2.608 (7)	179

Symmetry codes: (ii) −x+1/2, y, −z+3/2; (iii) −x+1/2, −y−1/2, −z; (iv) −x+1/2, −y+1/2, −z+1.

(II) [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]palladium(II)– N,N'-dimethylformamide–water (1/4/4)

Crystal data

[Pd(C48H28N4O8)]·4C3H7NO·4H2O	Z = 1
Mr = 1259.61	F(000) = 654
Triclinic, P1	Dx = 1.418 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7243 (2) Å	Cell parameters from 5044 reflections
b = 13.2668 (4) Å	θ = 1.4–25.7°
c = 14.5878 (5) Å	µ = 0.39 mm^−1
α = 81.3820 (16)°	T = 110 K
β = 87.3282 (17)°	Needles, red
γ = 87.0384 (17)°	0.60 × 0.10 × 0.10 mm
V = 1474.91 (8) Å^3

Data collection

Nonius KappaCCD diffractometer	4868 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 25.7°, θmin = 2.3°
Detector resolution: 12.8 pixels mm^-1	h = −9→9
1 deg. ϕ and ω scans	k = −15→16
12855 measured reflections	l = −17→17
5498 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycle	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 1.3991P] where P = (Fo^2 + 2Fc^2)/3
5498 reflections	(Δ/σ)max = 0.049
437 parameters	Δρmax = 0.31 e Å^−3
8 restraints	Δρmin = −0.72 e Å^−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.

One of the DMF solvent molecules is orientationally disordered between two sites. The corresponding species are represented by atoms O39A through C43A and O39B through C43B, respectively. The bond distances in these disordered species were restrained to normal values to avoid irregular geometries.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.0000	0.0000	1.0000	0.01444 (8)
C2	−0.2902 (3)	−0.13339 (18)	0.96293 (17)	0.0157 (5)
C3	−0.4005 (3)	−0.15028 (18)	0.89005 (17)	0.0178 (5)
H3	−0.4784	−0.2038	0.8925	0.021*
C4	−0.3726 (3)	−0.07618 (18)	0.81786 (17)	0.0185 (5)
H4	−0.4269	−0.0680	0.7599	0.022*
C5	−0.2451 (3)	−0.01155 (17)	0.84459 (16)	0.0138 (5)
C6	−0.1837 (3)	0.07443 (18)	0.78745 (16)	0.0151 (5)
C7	−0.0485 (3)	0.13108 (17)	0.80966 (16)	0.0147 (5)
C8	0.0216 (3)	0.21695 (18)	0.75038 (17)	0.0163 (5)
H8	−0.0169	0.2454	0.6907	0.020*
C9	0.1524 (3)	0.24978 (18)	0.79508 (16)	0.0157 (5)
H9	0.2238	0.3050	0.7723	0.019*
C10	0.1635 (3)	0.18551 (18)	0.88381 (16)	0.0150 (5)
C11	0.2818 (3)	0.19532 (17)	0.95141 (17)	0.0151 (5)
N12	−0.1937 (2)	−0.04911 (14)	0.93278 (13)	0.0148 (4)
N13	0.0397 (2)	0.11294 (14)	0.89106 (13)	0.0132 (4)
C14	−0.2772 (3)	0.10618 (17)	0.69914 (16)	0.0155 (5)
C15	−0.4538 (3)	0.13467 (19)	0.70647 (17)	0.0206 (5)
H15	−0.5057	0.1424	0.7655	0.025*
C16	−0.5538 (3)	0.1517 (2)	0.62900 (18)	0.0216 (5)
H16	−0.6738	0.1700	0.6352	0.026*
C17	−0.4786 (3)	0.14203 (18)	0.54186 (17)	0.0177 (5)
C18	−0.3008 (3)	0.11919 (18)	0.53311 (18)	0.0199 (5)
H18	−0.2476	0.1164	0.4734	0.024*
C19	−0.2012 (3)	0.10041 (18)	0.61135 (17)	0.0180 (5)
H19	−0.0806	0.0835	0.6050	0.022*
C20	−0.5879 (3)	0.15329 (18)	0.45888 (18)	0.0206 (5)
O21	−0.5271 (2)	0.15510 (14)	0.37971 (12)	0.0257 (4)
O22	−0.7552 (2)	0.15908 (16)	0.47920 (13)	0.0335 (5)
H22	−0.8358	0.1584	0.4323	0.040*
C23	0.4094 (3)	0.27708 (18)	0.93129 (16)	0.0158 (5)
C24	0.3565 (3)	0.38050 (18)	0.91880 (17)	0.0182 (5)
H24	0.2368	0.3998	0.9245	0.022*
C25	0.4772 (3)	0.45474 (18)	0.89815 (17)	0.0192 (5)
H25	0.4398	0.5247	0.8899	0.023*
C26	0.6540 (3)	0.42765 (18)	0.88928 (17)	0.0170 (5)
C27	0.7077 (3)	0.32493 (18)	0.90345 (17)	0.0165 (5)
H27	0.8277	0.3058	0.8987	0.020*
C28	0.5871 (3)	0.25063 (18)	0.92442 (17)	0.0167 (5)
H28	0.6251	0.1807	0.9343	0.020*
C29	0.7804 (3)	0.50806 (19)	0.85813 (18)	0.0200 (5)
O30	0.9438 (2)	0.47405 (13)	0.85937 (14)	0.0265 (4)
H30	1.0188	0.5245	0.8220	0.032*
O31	0.7367 (2)	0.59738 (13)	0.83154 (14)	0.0283 (4)
O32	0.8576 (2)	0.42381 (14)	0.25966 (14)	0.0307 (4)
H32A	0.8245	0.4613	0.3052	0.037*
H32B	0.7551	0.3860	0.2548	0.037*
O33	0.5663 (2)	0.32050 (14)	0.25003 (15)	0.0343 (5)
H33A	0.5382	0.2612	0.2870	0.041*
H33B	0.4639	0.3520	0.2323	0.041*
O34	1.0397 (2)	0.14458 (14)	0.35328 (12)	0.0263 (4)
C35	1.0357 (3)	0.19679 (19)	0.27469 (18)	0.0206 (5)
H35	1.1119	0.2515	0.2605	0.025*
N36	0.9309 (3)	0.17978 (15)	0.21023 (14)	0.0191 (4)
C37	0.9205 (3)	0.2473 (2)	0.12174 (18)	0.0255 (6)
H37A	0.8085	0.2858	0.1194	0.038*
H37B	0.9313	0.2066	0.0708	0.038*
H37C	1.0146	0.2950	0.1156	0.038*
C38	0.8107 (3)	0.0975 (2)	0.2296 (2)	0.0246 (6)
H38A	0.8556	0.0454	0.2787	0.037*
H38B	0.7983	0.0669	0.1733	0.037*
H38C	0.6974	0.1248	0.2499	0.037*
O39A	0.1977 (8)	0.4360 (4)	0.6152 (3)	0.0574 (17)	0.460 (4)
C40A	0.2154 (10)	0.4309 (4)	0.5312 (3)	0.0418 (18)	0.460 (4)
H40A	0.2039	0.3661	0.5124	0.050*	0.460 (4)
N41A	0.2497 (6)	0.5099 (3)	0.4642 (3)	0.0285 (13)	0.460 (4)
C42A	0.2842 (11)	0.6100 (4)	0.4874 (5)	0.050 (2)	0.460 (4)
H42A	0.1749	0.6506	0.4903	0.074*	0.460 (4)
H42B	0.3627	0.6450	0.4397	0.074*	0.460 (4)
H42C	0.3380	0.6018	0.5477	0.074*	0.460 (4)
C43A	0.2634 (12)	0.4953 (7)	0.3669 (3)	0.056 (2)	0.460 (4)
H43A	0.2463	0.4236	0.3622	0.083*	0.460 (4)
H43B	0.3785	0.5139	0.3408	0.083*	0.460 (4)
H43C	0.1744	0.5385	0.3324	0.083*	0.460 (4)
O39B	0.2072 (7)	0.4754 (3)	0.5985 (3)	0.0615 (15)	0.540 (4)
C40B	0.2490 (8)	0.5360 (4)	0.5288 (3)	0.0508 (18)	0.540 (4)
H40B	0.2614	0.6052	0.5363	0.061*	0.540 (4)
N41B	0.2782 (6)	0.5108 (3)	0.4432 (3)	0.0421 (14)	0.540 (4)
C42B	0.2411 (10)	0.4087 (4)	0.4259 (5)	0.059 (2)	0.540 (4)
H42D	0.2022	0.3678	0.4841	0.089*	0.540 (4)
H42E	0.3464	0.3762	0.4013	0.089*	0.540 (4)
H42F	0.1499	0.4136	0.3808	0.089*	0.540 (4)
C43B	0.3229 (10)	0.5875 (5)	0.3643 (4)	0.058 (2)	0.540 (4)
H43D	0.3278	0.6541	0.3852	0.086*	0.540 (4)
H43E	0.2347	0.5912	0.3176	0.086*	0.540 (4)
H43F	0.4363	0.5687	0.3371	0.086*	0.540 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01361 (14)	0.01625 (14)	0.01373 (15)	−0.00118 (10)	−0.00450 (10)	−0.00173 (10)
C2	0.0125 (11)	0.0180 (12)	0.0172 (13)	−0.0010 (10)	−0.0021 (10)	−0.0035 (10)
C3	0.0148 (11)	0.0214 (12)	0.0178 (13)	−0.0043 (10)	−0.0055 (10)	−0.0025 (10)
C4	0.0160 (12)	0.0226 (13)	0.0177 (13)	−0.0027 (10)	−0.0068 (10)	−0.0032 (10)
C5	0.0107 (10)	0.0182 (12)	0.0132 (12)	−0.0002 (9)	−0.0028 (9)	−0.0035 (9)
C6	0.0128 (11)	0.0201 (12)	0.0128 (12)	0.0008 (10)	−0.0031 (9)	−0.0034 (9)
C7	0.0121 (11)	0.0174 (12)	0.0144 (12)	0.0015 (9)	−0.0010 (9)	−0.0023 (9)
C8	0.0153 (11)	0.0184 (12)	0.0148 (12)	0.0006 (10)	−0.0039 (10)	−0.0003 (10)
C9	0.0130 (11)	0.0181 (12)	0.0160 (12)	−0.0019 (10)	−0.0021 (9)	−0.0015 (10)
C10	0.0136 (11)	0.0179 (12)	0.0139 (12)	−0.0007 (10)	0.0002 (9)	−0.0039 (9)
C11	0.0129 (11)	0.0153 (11)	0.0178 (13)	0.0011 (9)	−0.0041 (10)	−0.0043 (9)
N12	0.0151 (9)	0.0156 (10)	0.0136 (10)	0.0008 (8)	−0.0031 (8)	−0.0019 (8)
N13	0.0127 (9)	0.0155 (10)	0.0119 (10)	−0.0005 (8)	−0.0031 (8)	−0.0027 (8)
C14	0.0172 (11)	0.0141 (11)	0.0155 (12)	−0.0009 (10)	−0.0043 (10)	−0.0020 (9)
C15	0.0176 (12)	0.0296 (14)	0.0145 (13)	0.0021 (11)	−0.0014 (10)	−0.0042 (11)
C16	0.0148 (12)	0.0299 (14)	0.0203 (13)	0.0039 (11)	−0.0047 (10)	−0.0044 (11)
C17	0.0175 (12)	0.0192 (12)	0.0161 (13)	−0.0010 (10)	−0.0066 (10)	0.0003 (10)
C18	0.0199 (12)	0.0232 (13)	0.0161 (13)	0.0010 (11)	−0.0016 (10)	−0.0017 (10)
C19	0.0139 (11)	0.0207 (12)	0.0193 (13)	−0.0004 (10)	−0.0024 (10)	−0.0021 (10)
C20	0.0230 (13)	0.0207 (13)	0.0183 (14)	−0.0008 (11)	−0.0060 (11)	−0.0026 (10)
O21	0.0280 (10)	0.0348 (10)	0.0143 (10)	−0.0031 (8)	−0.0066 (8)	−0.0012 (8)
O22	0.0182 (9)	0.0632 (14)	0.0209 (10)	0.0054 (9)	−0.0107 (8)	−0.0114 (9)
C23	0.0167 (11)	0.0189 (12)	0.0124 (12)	−0.0030 (10)	−0.0027 (9)	−0.0032 (9)
C24	0.0137 (11)	0.0204 (12)	0.0208 (13)	−0.0012 (10)	−0.0037 (10)	−0.0029 (10)
C25	0.0186 (12)	0.0165 (12)	0.0220 (14)	0.0001 (10)	−0.0028 (10)	−0.0011 (10)
C26	0.0163 (12)	0.0196 (12)	0.0157 (12)	−0.0036 (10)	−0.0031 (10)	−0.0031 (10)
C27	0.0113 (11)	0.0206 (12)	0.0176 (13)	0.0010 (10)	−0.0028 (9)	−0.0027 (10)
C28	0.0158 (11)	0.0160 (12)	0.0184 (13)	−0.0017 (10)	−0.0023 (10)	−0.0014 (10)
C29	0.0167 (12)	0.0228 (13)	0.0214 (14)	−0.0023 (10)	−0.0033 (10)	−0.0046 (11)
O30	0.0142 (8)	0.0218 (9)	0.0412 (12)	−0.0041 (7)	−0.0015 (8)	0.0038 (8)
O31	0.0202 (9)	0.0183 (9)	0.0446 (12)	−0.0030 (8)	−0.0003 (9)	0.0017 (8)
O32	0.0243 (10)	0.0319 (10)	0.0369 (12)	−0.0093 (8)	0.0050 (9)	−0.0074 (9)
O33	0.0214 (9)	0.0251 (10)	0.0524 (14)	−0.0019 (8)	−0.0012 (9)	0.0081 (9)
O34	0.0232 (9)	0.0346 (10)	0.0210 (10)	−0.0015 (8)	−0.0104 (8)	−0.0010 (8)
C35	0.0133 (11)	0.0248 (13)	0.0248 (14)	0.0010 (10)	−0.0066 (10)	−0.0062 (11)
N36	0.0160 (10)	0.0215 (11)	0.0201 (11)	0.0018 (9)	−0.0051 (9)	−0.0033 (9)
C37	0.0256 (13)	0.0294 (14)	0.0210 (14)	0.0046 (12)	−0.0055 (11)	−0.0027 (11)
C38	0.0183 (12)	0.0260 (14)	0.0314 (16)	−0.0009 (11)	−0.0051 (11)	−0.0089 (12)
O39A	0.102 (5)	0.032 (3)	0.036 (3)	−0.006 (3)	0.008 (3)	0.001 (2)
C40A	0.059 (5)	0.032 (4)	0.037 (4)	−0.006 (3)	0.002 (3)	−0.013 (3)
N41A	0.034 (3)	0.027 (3)	0.024 (3)	0.001 (2)	0.005 (2)	−0.006 (2)
C42A	0.086 (6)	0.028 (4)	0.034 (4)	−0.017 (4)	−0.002 (4)	0.006 (3)
C43A	0.076 (6)	0.068 (5)	0.024 (4)	0.004 (5)	−0.001 (4)	−0.010 (4)
O39B	0.095 (4)	0.062 (3)	0.030 (3)	−0.022 (3)	0.018 (2)	−0.016 (2)
C40B	0.055 (4)	0.048 (4)	0.057 (5)	0.005 (3)	−0.009 (3)	−0.030 (3)
N41B	0.044 (3)	0.047 (3)	0.037 (3)	0.011 (2)	0.002 (2)	−0.017 (2)
C42B	0.088 (5)	0.046 (4)	0.048 (4)	0.009 (4)	−0.005 (4)	−0.023 (3)
C43B	0.076 (5)	0.051 (4)	0.042 (4)	0.008 (4)	0.001 (4)	0.001 (3)

Geometric parameters (Å, º)

Pd1—N12	2.0133 (19)	C26—C27	1.392 (3)
Pd1—N12^i	2.0133 (19)	C26—C29	1.490 (3)
Pd1—N13	2.0379 (19)	C27—C28	1.383 (3)
Pd1—N13^i	2.0379 (19)	C27—H27	0.9500
C2—N12	1.381 (3)	C28—H28	0.9500
C2—C11^i	1.391 (3)	C29—O31	1.225 (3)
C2—C3	1.443 (3)	C29—O30	1.318 (3)
C3—C4	1.346 (3)	O30—H30	0.9905
C3—H3	0.9500	O32—H32A	0.9084
C4—C5	1.442 (3)	O32—H32B	0.9694
C4—H4	0.9500	O33—H33A	0.9147
C5—N12	1.377 (3)	O33—H33B	0.9056
C5—C6	1.398 (3)	O34—C35	1.248 (3)
C6—C7	1.395 (3)	C35—N36	1.321 (3)
C6—C14	1.500 (3)	C35—H35	0.9500
C7—N13	1.380 (3)	N36—C38	1.456 (3)
C7—C8	1.437 (3)	N36—C37	1.460 (3)
C8—C9	1.352 (3)	C37—H37A	0.9800
C8—H8	0.9500	C37—H37B	0.9800
C9—C10	1.443 (3)	C37—H37C	0.9800
C9—H9	0.9500	C38—H38A	0.9800
C10—N13	1.381 (3)	C38—H38B	0.9800
C10—C11	1.400 (3)	C38—H38C	0.9800
C11—C2^i	1.391 (3)	O39A—C40A	1.239 (3)
C11—C23	1.491 (3)	C40A—N41A	1.349 (3)
C14—C19	1.395 (3)	C40A—H40A	0.9500
C14—C15	1.400 (3)	N41A—C42A	1.460 (3)
C15—C16	1.382 (3)	N41A—C43A	1.460 (3)
C15—H15	0.9500	C42A—H42A	0.9800
C16—C17	1.394 (4)	C42A—H42B	0.9800
C16—H16	0.9500	C42A—H42C	0.9800
C17—C18	1.395 (3)	C43A—H43A	0.9800
C17—C20	1.493 (3)	C43A—H43B	0.9800
C18—C19	1.391 (3)	C43A—H43C	0.9800
C18—H18	0.9500	O39B—C40B	1.240 (3)
C19—H19	0.9500	C40B—N41B	1.347 (3)
C20—O21	1.224 (3)	C40B—H40B	0.9500
C20—O22	1.313 (3)	N41B—C42B	1.458 (3)
O22—H22	0.9473	N41B—C43B	1.459 (3)
C23—C24	1.399 (3)	C42B—H42D	0.9800
C23—C28	1.401 (3)	C42B—H42E	0.9800
C24—C25	1.382 (3)	C42B—H42F	0.9800
C24—H24	0.9500	C43B—H43D	0.9800
C25—C26	1.399 (3)	C43B—H43E	0.9800
C25—H25	0.9500	C43B—H43F	0.9800
N12—Pd1—N12^i	180.0	C24—C23—C11	121.6 (2)
N12—Pd1—N13	89.59 (8)	C28—C23—C11	119.7 (2)
N12^i—Pd1—N13	90.41 (8)	C25—C24—C23	120.4 (2)
N12—Pd1—N13^i	90.41 (8)	C25—C24—H24	119.8
N12^i—Pd1—N13^i	89.59 (8)	C23—C24—H24	119.8
N13—Pd1—N13^i	180.0	C24—C25—C26	120.5 (2)
N12—C2—C11^i	126.5 (2)	C24—C25—H25	119.7
N12—C2—C3	109.3 (2)	C26—C25—H25	119.7
C11^i—C2—C3	124.2 (2)	C27—C26—C25	119.3 (2)
C4—C3—C2	107.4 (2)	C27—C26—C29	120.8 (2)
C4—C3—H3	126.3	C25—C26—C29	119.8 (2)
C2—C3—H3	126.3	C28—C27—C26	120.2 (2)
C3—C4—C5	107.4 (2)	C28—C27—H27	119.9
C3—C4—H4	126.3	C26—C27—H27	119.9
C5—C4—H4	126.3	C27—C28—C23	120.9 (2)
N12—C5—C6	126.5 (2)	C27—C28—H28	119.6
N12—C5—C4	109.4 (2)	C23—C28—H28	119.6
C6—C5—C4	124.0 (2)	O31—C29—O30	122.8 (2)
C7—C6—C5	124.0 (2)	O31—C29—C26	123.2 (2)
C7—C6—C14	120.4 (2)	O30—C29—C26	114.0 (2)
C5—C6—C14	115.6 (2)	C29—O30—H30	110.5
N13—C7—C6	125.5 (2)	H32A—O32—H32B	102.2
N13—C7—C8	109.5 (2)	H33A—O33—H33B	105.5
C6—C7—C8	125.0 (2)	O34—C35—N36	123.2 (2)
C9—C8—C7	107.4 (2)	O34—C35—H35	118.4
C9—C8—H8	126.3	N36—C35—H35	118.4
C7—C8—H8	126.3	C35—N36—C38	120.0 (2)
C8—C9—C10	107.3 (2)	C35—N36—C37	121.6 (2)
C8—C9—H9	126.3	C38—N36—C37	118.2 (2)
C10—C9—H9	126.3	N36—C37—H37A	109.5
N13—C10—C11	125.6 (2)	N36—C37—H37B	109.5
N13—C10—C9	109.23 (19)	H37A—C37—H37B	109.5
C11—C10—C9	125.1 (2)	N36—C37—H37C	109.5
C2^i—C11—C10	124.6 (2)	H37A—C37—H37C	109.5
C2^i—C11—C23	116.8 (2)	H37B—C37—H37C	109.5
C10—C11—C23	118.6 (2)	N36—C38—H38A	109.5
C5—N12—C2	106.44 (19)	N36—C38—H38B	109.5
C5—N12—Pd1	126.95 (16)	H38A—C38—H38B	109.5
C2—N12—Pd1	126.36 (15)	N36—C38—H38C	109.5
C7—N13—C10	106.49 (19)	H38A—C38—H38C	109.5
C7—N13—Pd1	127.17 (15)	H38B—C38—H38C	109.5
C10—N13—Pd1	126.33 (15)	O39A—C40A—N41A	125.2 (5)
C19—C14—C15	118.8 (2)	O39A—C40A—H40A	117.4
C19—C14—C6	123.4 (2)	N41A—C40A—H40A	117.4
C15—C14—C6	117.6 (2)	C40A—N41A—C42A	121.1 (5)
C16—C15—C14	120.9 (2)	C40A—N41A—C43A	120.4 (5)
C16—C15—H15	119.5	C42A—N41A—C43A	118.4 (5)
C14—C15—H15	119.5	O39B—C40B—N41B	124.6 (5)
C15—C16—C17	120.1 (2)	O39B—C40B—H40B	117.7
C15—C16—H16	120.0	N41B—C40B—H40B	117.7
C17—C16—H16	120.0	C40B—N41B—C42B	119.7 (5)
C16—C17—C18	119.5 (2)	C40B—N41B—C43B	121.1 (5)
C16—C17—C20	120.3 (2)	C42B—N41B—C43B	118.7 (5)
C18—C17—C20	120.2 (2)	N41B—C42B—H42D	109.5
C19—C18—C17	120.3 (2)	N41B—C42B—H42E	109.5
C19—C18—H18	119.9	H42D—C42B—H42E	109.5
C17—C18—H18	119.9	N41B—C42B—H42F	109.5
C18—C19—C14	120.4 (2)	H42D—C42B—H42F	109.5
C18—C19—H19	119.8	H42E—C42B—H42F	109.5
C14—C19—H19	119.8	N41B—C43B—H43D	109.5
O21—C20—O22	123.4 (2)	N41B—C43B—H43E	109.5
O21—C20—C17	123.0 (2)	H43D—C43B—H43E	109.5
O22—C20—C17	113.6 (2)	N41B—C43B—H43F	109.5
C20—O22—H22	120.1	H43D—C43B—H43F	109.5
C24—C23—C28	118.7 (2)	H43E—C43B—H43F	109.5

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O34^ii	0.95	1.57	2.516 (2)	173
O30—H30···O32^iii	0.99	1.59	2.543 (3)	161
O32—H32A···O39B^iv	0.91	1.74	2.642 (4)	170
O32—H32A···O39A^iv	0.91	1.91	2.799 (5)	164
O32—H32B···O33	0.97	1.75	2.714 (3)	177
O33—H33A···O21^v	0.91	1.87	2.776 (3)	169
O33—H33B···O31^iv	0.91	1.89	2.773 (3)	166

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