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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\overline{1}. 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107063524/gd3172sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107063524/gd3172Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107063524/gd3172IIsup3.hkl
Contains datablock II

CCDC references: 677162; 677163

Comment top

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 top

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).

Experimental top

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.

Refinement top

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 Uiso(H) values of 1.2 or 1.5 times Ueq(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 Uiso(H) values of 1.2 or 1.5 times Ueq(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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. Schematic representations of the different hydrogen-bonding synthons between the carboxylic acid substituents. (a) The R22(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 R33(10) pattern observed in (I). (c) The solvation pattern of the carboxylic acid groups in (II) (see text).
[Figure 3] 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.
[Figure 4] 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.
[Figure 5] 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.
[Figure 6] 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 top
Crystal data top
[Pd(C48H28N4O8)]·CH4OF(000) = 3776
Mr = 927.21Dx = 1.354 Mg m3
Orthorhombic, CmcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2Cell parameters from 4588 reflections
a = 31.0347 (6) Åθ = 2.6–25.6°
b = 15.9441 (11) ŵ = 0.47 mm1
c = 18.3824 (7) ÅT = 110 K
V = 9096.0 (7) Å3Rhomb, red
Z = 80.30 × 0.10 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer
2688 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.098
Graphite monochromatorθmax = 25.6°, θmin = 2.6°
Detector resolution: 12.8 pixels mm-1h = 037
0.5 deg. ϕ scansk = 019
20365 measured reflectionsl = 220
4344 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0724P)2 + 2.4049P]
where P = (Fo2 + 2Fc2)/3
4344 reflections(Δ/σ)max = 0.008
291 parametersΔρmax = 0.50 e Å3
12 restraintsΔρmin = 0.77 e Å3
Crystal data top
[Pd(C48H28N4O8)]·CH4OV = 9096.0 (7) Å3
Mr = 927.21Z = 8
Orthorhombic, CmcaMo Kα radiation
a = 31.0347 (6) ŵ = 0.47 mm1
b = 15.9441 (11) ÅT = 110 K
c = 18.3824 (7) Å0.30 × 0.10 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer
2688 reflections with I > 2σ(I)
20365 measured reflectionsRint = 0.098
4344 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07012 restraints
wR(F2) = 0.160H-atom parameters constrained
S = 1.00Δρmax = 0.50 e Å3
4344 reflectionsΔρmin = 0.77 e Å3
291 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.00000.03589 (4)0.35956 (3)0.0237 (2)
C20.02189 (18)0.1673 (4)0.5582 (3)0.0309 (14)
H20.04010.18760.59580.037*
C30.03551 (18)0.1305 (4)0.4903 (3)0.0293 (14)
C40.07828 (17)0.1262 (4)0.4667 (3)0.0255 (13)
C50.09124 (18)0.0853 (4)0.4028 (3)0.0265 (13)
C60.13500 (17)0.0824 (4)0.3773 (3)0.0309 (15)
H60.15910.10990.39830.037*
C70.13524 (17)0.0327 (4)0.3172 (3)0.0311 (14)
H70.15980.01780.28910.037*
C80.09142 (18)0.0067 (4)0.3040 (3)0.0283 (14)
C90.07875 (17)0.0460 (4)0.2478 (3)0.0278 (13)
C100.03559 (18)0.0646 (4)0.2321 (3)0.0294 (14)
C110.02210 (18)0.1147 (4)0.1706 (3)0.0334 (15)
H110.04030.14230.13670.040*
N120.00000.1062 (5)0.4506 (3)0.0271 (16)
N130.06496 (13)0.0403 (3)0.3576 (2)0.0258 (10)
N140.00000.0358 (5)0.2700 (3)0.0264 (15)
C150.11126 (17)0.1686 (4)0.5126 (3)0.0281 (14)
C160.11155 (18)0.2557 (4)0.5201 (3)0.0327 (15)
H160.09150.28870.49350.039*
C170.14104 (19)0.2949 (5)0.5662 (3)0.0405 (17)
H170.14200.35430.56950.049*
C180.16916 (18)0.2456 (5)0.6075 (3)0.0360 (15)
C190.1693 (2)0.1591 (5)0.6009 (3)0.0436 (18)
H190.18890.12620.62850.052*
C200.14048 (19)0.1207 (5)0.5534 (3)0.0380 (16)
H200.14060.06140.54860.046*
C210.1996 (2)0.2884 (5)0.6601 (3)0.0395 (17)
O220.19883 (16)0.3654 (4)0.6649 (4)0.091 (2)
H220.21560.39290.69260.109*0.50
O230.22375 (15)0.2398 (4)0.6969 (2)0.0738 (19)
H230.24220.26240.72370.089*0.50
C240.11290 (17)0.0826 (4)0.2009 (3)0.0300 (14)
C250.1340 (2)0.0354 (5)0.1482 (3)0.0462 (16)
H250.12680.02200.14160.055*
C260.1659 (2)0.0728 (5)0.1048 (4)0.0461 (19)
H260.18030.04000.06910.055*
C270.17659 (19)0.1556 (5)0.1130 (4)0.0385 (16)
C280.1563 (2)0.2028 (5)0.1647 (4)0.0445 (17)
H280.16370.26020.17060.053*
C290.12447 (19)0.1666 (5)0.2095 (3)0.0388 (17)
H290.11080.19960.24580.047*
C300.2105 (2)0.1966 (5)0.0644 (3)0.0391 (16)
O310.23083 (13)0.1452 (3)0.0237 (2)0.0509 (13)
H310.24870.17230.00630.061*
O320.21594 (14)0.2735 (3)0.0659 (2)0.0475 (13)
C330.25000.0366 (8)0.25000.077 (4)
H33A0.27970.05710.25300.116*0.50
H33B0.23670.05710.20510.116*0.50
H33C0.23360.05710.29200.116*0.50
O340.25000.0498 (6)0.25000.124 (4)
H340.26770.07870.27950.149*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0213 (3)0.0260 (4)0.0238 (3)0.0000.0000.0054 (3)
C20.033 (3)0.030 (4)0.030 (3)0.008 (3)0.007 (2)0.003 (3)
C30.034 (3)0.035 (4)0.019 (3)0.006 (3)0.006 (3)0.003 (3)
C40.027 (3)0.028 (4)0.021 (3)0.001 (3)0.003 (2)0.006 (2)
C50.028 (3)0.024 (4)0.027 (3)0.001 (3)0.000 (2)0.000 (3)
C60.021 (3)0.031 (4)0.040 (4)0.003 (3)0.002 (3)0.000 (3)
C70.023 (3)0.037 (4)0.033 (3)0.001 (3)0.012 (2)0.004 (3)
C80.028 (3)0.027 (4)0.030 (3)0.002 (3)0.006 (3)0.002 (3)
C90.033 (3)0.024 (4)0.027 (3)0.003 (3)0.003 (2)0.000 (3)
C100.032 (3)0.032 (4)0.025 (3)0.005 (3)0.007 (3)0.005 (3)
C110.035 (3)0.036 (4)0.029 (3)0.004 (3)0.003 (3)0.013 (3)
N120.024 (3)0.029 (4)0.029 (4)0.0000.0000.008 (3)
N130.028 (2)0.025 (3)0.025 (2)0.002 (2)0.004 (2)0.011 (2)
N140.027 (3)0.026 (4)0.027 (3)0.0000.0000.002 (3)
C150.026 (3)0.035 (4)0.023 (3)0.006 (3)0.001 (2)0.004 (3)
C160.025 (3)0.035 (4)0.038 (3)0.001 (3)0.002 (3)0.004 (3)
C170.034 (3)0.038 (5)0.049 (4)0.008 (3)0.001 (3)0.010 (3)
C180.029 (3)0.050 (5)0.029 (3)0.002 (3)0.001 (3)0.012 (3)
C190.042 (4)0.053 (5)0.036 (4)0.004 (4)0.008 (3)0.007 (3)
C200.037 (3)0.036 (4)0.041 (4)0.008 (3)0.009 (3)0.006 (3)
C210.027 (3)0.054 (5)0.037 (4)0.006 (3)0.001 (3)0.011 (3)
O220.047 (3)0.089 (5)0.136 (6)0.005 (3)0.027 (3)0.080 (5)
O230.046 (3)0.139 (6)0.036 (3)0.028 (3)0.016 (2)0.004 (3)
C240.023 (3)0.032 (4)0.034 (3)0.001 (3)0.003 (3)0.005 (3)
C250.049 (4)0.045 (4)0.045 (4)0.004 (4)0.011 (3)0.004 (4)
C260.044 (4)0.060 (5)0.034 (4)0.009 (4)0.020 (3)0.003 (3)
C270.028 (3)0.041 (5)0.046 (4)0.002 (3)0.001 (3)0.008 (3)
C280.042 (4)0.043 (5)0.048 (4)0.006 (3)0.005 (3)0.002 (3)
C290.034 (3)0.048 (5)0.035 (3)0.003 (3)0.009 (3)0.011 (3)
C300.035 (3)0.044 (5)0.039 (4)0.001 (3)0.001 (3)0.008 (3)
O310.035 (2)0.066 (4)0.052 (3)0.002 (3)0.014 (2)0.011 (3)
O320.043 (3)0.045 (4)0.055 (3)0.005 (2)0.004 (2)0.011 (2)
C330.065 (7)0.038 (8)0.129 (11)0.0000.022 (7)0.000
O340.113 (8)0.049 (7)0.211 (12)0.0000.104 (8)0.000
Geometric parameters (Å, º) top
Pd1—N142.004 (7)C17—C181.398 (9)
Pd1—N122.015 (6)C17—H170.9500
Pd1—N132.018 (4)C18—C191.386 (10)
Pd1—N13i2.018 (4)C18—C211.515 (9)
C2—C2i1.359 (11)C19—C201.391 (9)
C2—C31.442 (8)C19—H190.9500
C2—H20.9500C20—H200.9500
C3—N121.377 (6)C21—O221.230 (9)
C3—C41.398 (7)C21—O231.272 (8)
C4—C51.402 (7)O22—H220.8506
C4—C151.489 (7)O23—H230.8359
C5—N131.368 (7)C24—C251.390 (9)
C5—C61.438 (8)C24—C291.396 (9)
C6—C71.359 (8)C25—C261.405 (9)
C6—H60.9500C25—H250.9500
C7—C81.442 (8)C26—C271.370 (10)
C7—H70.9500C26—H260.9500
C8—C91.389 (8)C27—C281.367 (9)
C8—N131.390 (7)C27—C301.528 (9)
C9—C101.402 (8)C28—C291.410 (8)
C9—C241.485 (8)C28—H280.9500
C10—N141.385 (7)C29—H290.9500
C10—C111.446 (8)C30—O321.238 (8)
C11—C11i1.372 (11)C30—O311.274 (8)
C11—H110.9500O31—H310.8945
N12—C3i1.377 (6)C33—O341.378 (14)
N14—C10i1.385 (6)C33—H33A0.9800
C15—C161.396 (9)C33—H33B0.9800
C15—C201.403 (8)C33—H33C0.9800
C16—C171.395 (8)O34—H340.8984
C16—H160.9500
N14—Pd1—N12179.1 (3)C15—C16—H16119.7
N14—Pd1—N1390.30 (13)C17—C16—H16119.7
N12—Pd1—N1389.73 (13)C16—C17—C18119.2 (7)
N14—Pd1—N13i90.30 (13)C16—C17—H17120.4
N12—Pd1—N13i89.73 (13)C18—C17—H17120.4
N13—Pd1—N13i175.5 (3)C19—C18—C17120.9 (6)
C2i—C2—C3107.0 (3)C19—C18—C21120.1 (6)
C2i—C2—H2126.5C17—C18—C21118.9 (7)
C3—C2—H2126.5C18—C19—C20119.4 (6)
N12—C3—C4125.6 (5)C18—C19—H19120.3
N12—C3—C2109.7 (5)C20—C19—H19120.3
C4—C3—C2124.5 (5)C19—C20—C15120.7 (7)
C3—C4—C5123.7 (5)C19—C20—H20119.6
C3—C4—C15117.1 (5)C15—C20—H20119.6
C5—C4—C15119.2 (5)O22—C21—O23125.5 (7)
N13—C5—C4125.6 (5)O22—C21—C18118.8 (7)
N13—C5—C6110.3 (5)O23—C21—C18115.7 (7)
C4—C5—C6124.0 (5)C21—O22—H22123.1
C7—C6—C5106.8 (5)C21—O23—H23117.0
C7—C6—H6126.6C25—C24—C29118.5 (6)
C5—C6—H6126.6C25—C24—C9121.9 (6)
C6—C7—C8107.4 (5)C29—C24—C9119.6 (5)
C6—C7—H7126.3C24—C25—C26120.0 (7)
C8—C7—H7126.3C24—C25—H25120.0
C9—C8—N13126.4 (5)C26—C25—H25120.0
C9—C8—C7124.4 (5)C27—C26—C25121.1 (7)
N13—C8—C7109.1 (5)C27—C26—H26119.5
C8—C9—C10123.5 (5)C25—C26—H26119.5
C8—C9—C24117.9 (5)C28—C27—C26119.8 (6)
C10—C9—C24118.6 (5)C28—C27—C30119.3 (7)
N14—C10—C9126.0 (5)C26—C27—C30120.9 (6)
N14—C10—C11110.2 (5)C27—C28—C29120.2 (7)
C9—C10—C11123.7 (5)C27—C28—H28119.9
C11i—C11—C10106.8 (3)C29—C28—H28119.9
C11i—C11—H11126.6C24—C29—C28120.5 (6)
C10—C11—H11126.6C24—C29—H29119.7
C3i—N12—C3106.3 (6)C28—C29—H29119.7
C3i—N12—Pd1126.6 (3)O32—C30—O31125.6 (6)
C3—N12—Pd1126.6 (3)O32—C30—C27120.2 (6)
C5—N13—C8106.3 (4)O31—C30—C27114.1 (7)
C5—N13—Pd1127.1 (4)C30—O31—H31111.0
C8—N13—Pd1126.1 (4)O34—C33—H33A109.5
C10—N14—C10i105.8 (6)O34—C33—H33B109.5
C10—N14—Pd1127.1 (3)H33A—C33—H33B109.5
C10i—N14—Pd1127.1 (3)O34—C33—H33C109.5
C16—C15—C20119.0 (5)H33A—C33—H33C109.5
C16—C15—C4120.8 (5)H33B—C33—H33C109.5
C20—C15—C4119.9 (6)C33—O34—H34120.8
C15—C16—C17120.6 (6)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O23—H23···O23ii0.841.842.542 (9)141
O31—H31···O32iii0.891.772.669 (6)180
O34—H34···O22iv0.901.712.608 (7)179
Symmetry codes: (ii) x+1/2, y, z+3/2; (iii) x+1/2, y1/2, 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) top
Crystal data top
[Pd(C48H28N4O8)]·4C3H7NO·4H2OZ = 1
Mr = 1259.61F(000) = 654
Triclinic, P1Dx = 1.418 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7243 (2) ÅCell parameters from 5044 reflections
b = 13.2668 (4) Åθ = 1.4–25.7°
c = 14.5878 (5) ŵ = 0.39 mm1
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) Å3
Data collection top
Nonius KappaCCD
diffractometer
4868 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 25.7°, θmin = 2.3°
Detector resolution: 12.8 pixels mm-1h = 99
1 deg. ϕ and ω scansk = 1516
12855 measured reflectionsl = 1717
5498 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycleSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0221P)2 + 1.3991P]
where P = (Fo2 + 2Fc2)/3
5498 reflections(Δ/σ)max = 0.049
437 parametersΔρmax = 0.31 e Å3
8 restraintsΔρmin = 0.72 e Å3
Crystal data top
[Pd(C48H28N4O8)]·4C3H7NO·4H2Oγ = 87.0384 (17)°
Mr = 1259.61V = 1474.91 (8) Å3
Triclinic, P1Z = 1
a = 7.7243 (2) ÅMo Kα radiation
b = 13.2668 (4) ŵ = 0.39 mm1
c = 14.5878 (5) ÅT = 110 K
α = 81.3820 (16)°0.60 × 0.10 × 0.10 mm
β = 87.3282 (17)°
Data collection top
Nonius KappaCCD
diffractometer
4868 reflections with I > 2σ(I)
12855 measured reflectionsRint = 0.045
5498 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0378 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.02Δρmax = 0.31 e Å3
5498 reflectionsΔρmin = 0.72 e Å3
437 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.00000.00001.00000.01444 (8)
C20.2902 (3)0.13339 (18)0.96293 (17)0.0157 (5)
C30.4005 (3)0.15028 (18)0.89005 (17)0.0178 (5)
H30.47840.20380.89250.021*
C40.3726 (3)0.07618 (18)0.81786 (17)0.0185 (5)
H40.42690.06800.75990.022*
C50.2451 (3)0.01155 (17)0.84459 (16)0.0138 (5)
C60.1837 (3)0.07443 (18)0.78745 (16)0.0151 (5)
C70.0485 (3)0.13108 (17)0.80966 (16)0.0147 (5)
C80.0216 (3)0.21695 (18)0.75038 (17)0.0163 (5)
H80.01690.24540.69070.020*
C90.1524 (3)0.24978 (18)0.79508 (16)0.0157 (5)
H90.22380.30500.77230.019*
C100.1635 (3)0.18551 (18)0.88381 (16)0.0150 (5)
C110.2818 (3)0.19532 (17)0.95141 (17)0.0151 (5)
N120.1937 (2)0.04911 (14)0.93278 (13)0.0148 (4)
N130.0397 (2)0.11294 (14)0.89106 (13)0.0132 (4)
C140.2772 (3)0.10618 (17)0.69914 (16)0.0155 (5)
C150.4538 (3)0.13467 (19)0.70647 (17)0.0206 (5)
H150.50570.14240.76550.025*
C160.5538 (3)0.1517 (2)0.62900 (18)0.0216 (5)
H160.67380.17000.63520.026*
C170.4786 (3)0.14203 (18)0.54186 (17)0.0177 (5)
C180.3008 (3)0.11919 (18)0.53311 (18)0.0199 (5)
H180.24760.11640.47340.024*
C190.2012 (3)0.10041 (18)0.61135 (17)0.0180 (5)
H190.08060.08350.60500.022*
C200.5879 (3)0.15329 (18)0.45888 (18)0.0206 (5)
O210.5271 (2)0.15510 (14)0.37971 (12)0.0257 (4)
O220.7552 (2)0.15908 (16)0.47920 (13)0.0335 (5)
H220.83580.15840.43230.040*
C230.4094 (3)0.27708 (18)0.93129 (16)0.0158 (5)
C240.3565 (3)0.38050 (18)0.91880 (17)0.0182 (5)
H240.23680.39980.92450.022*
C250.4772 (3)0.45474 (18)0.89815 (17)0.0192 (5)
H250.43980.52470.88990.023*
C260.6540 (3)0.42765 (18)0.88928 (17)0.0170 (5)
C270.7077 (3)0.32493 (18)0.90345 (17)0.0165 (5)
H270.82770.30580.89870.020*
C280.5871 (3)0.25063 (18)0.92442 (17)0.0167 (5)
H280.62510.18070.93430.020*
C290.7804 (3)0.50806 (19)0.85813 (18)0.0200 (5)
O300.9438 (2)0.47405 (13)0.85937 (14)0.0265 (4)
H301.01880.52450.82200.032*
O310.7367 (2)0.59738 (13)0.83154 (14)0.0283 (4)
O320.8576 (2)0.42381 (14)0.25966 (14)0.0307 (4)
H32A0.82450.46130.30520.037*
H32B0.75510.38600.25480.037*
O330.5663 (2)0.32050 (14)0.25003 (15)0.0343 (5)
H33A0.53820.26120.28700.041*
H33B0.46390.35200.23230.041*
O341.0397 (2)0.14458 (14)0.35328 (12)0.0263 (4)
C351.0357 (3)0.19679 (19)0.27469 (18)0.0206 (5)
H351.11190.25150.26050.025*
N360.9309 (3)0.17978 (15)0.21023 (14)0.0191 (4)
C370.9205 (3)0.2473 (2)0.12174 (18)0.0255 (6)
H37A0.80850.28580.11940.038*
H37B0.93130.20660.07080.038*
H37C1.01460.29500.11560.038*
C380.8107 (3)0.0975 (2)0.2296 (2)0.0246 (6)
H38A0.85560.04540.27870.037*
H38B0.79830.06690.17330.037*
H38C0.69740.12480.24990.037*
O39A0.1977 (8)0.4360 (4)0.6152 (3)0.0574 (17)0.460 (4)
C40A0.2154 (10)0.4309 (4)0.5312 (3)0.0418 (18)0.460 (4)
H40A0.20390.36610.51240.050*0.460 (4)
N41A0.2497 (6)0.5099 (3)0.4642 (3)0.0285 (13)0.460 (4)
C42A0.2842 (11)0.6100 (4)0.4874 (5)0.050 (2)0.460 (4)
H42A0.17490.65060.49030.074*0.460 (4)
H42B0.36270.64500.43970.074*0.460 (4)
H42C0.33800.60180.54770.074*0.460 (4)
C43A0.2634 (12)0.4953 (7)0.3669 (3)0.056 (2)0.460 (4)
H43A0.24630.42360.36220.083*0.460 (4)
H43B0.37850.51390.34080.083*0.460 (4)
H43C0.17440.53850.33240.083*0.460 (4)
O39B0.2072 (7)0.4754 (3)0.5985 (3)0.0615 (15)0.540 (4)
C40B0.2490 (8)0.5360 (4)0.5288 (3)0.0508 (18)0.540 (4)
H40B0.26140.60520.53630.061*0.540 (4)
N41B0.2782 (6)0.5108 (3)0.4432 (3)0.0421 (14)0.540 (4)
C42B0.2411 (10)0.4087 (4)0.4259 (5)0.059 (2)0.540 (4)
H42D0.20220.36780.48410.089*0.540 (4)
H42E0.34640.37620.40130.089*0.540 (4)
H42F0.14990.41360.38080.089*0.540 (4)
C43B0.3229 (10)0.5875 (5)0.3643 (4)0.058 (2)0.540 (4)
H43D0.32780.65410.38520.086*0.540 (4)
H43E0.23470.59120.31760.086*0.540 (4)
H43F0.43630.56870.33710.086*0.540 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01361 (14)0.01625 (14)0.01373 (15)0.00118 (10)0.00450 (10)0.00173 (10)
C20.0125 (11)0.0180 (12)0.0172 (13)0.0010 (10)0.0021 (10)0.0035 (10)
C30.0148 (11)0.0214 (12)0.0178 (13)0.0043 (10)0.0055 (10)0.0025 (10)
C40.0160 (12)0.0226 (13)0.0177 (13)0.0027 (10)0.0068 (10)0.0032 (10)
C50.0107 (10)0.0182 (12)0.0132 (12)0.0002 (9)0.0028 (9)0.0035 (9)
C60.0128 (11)0.0201 (12)0.0128 (12)0.0008 (10)0.0031 (9)0.0034 (9)
C70.0121 (11)0.0174 (12)0.0144 (12)0.0015 (9)0.0010 (9)0.0023 (9)
C80.0153 (11)0.0184 (12)0.0148 (12)0.0006 (10)0.0039 (10)0.0003 (10)
C90.0130 (11)0.0181 (12)0.0160 (12)0.0019 (10)0.0021 (9)0.0015 (10)
C100.0136 (11)0.0179 (12)0.0139 (12)0.0007 (10)0.0002 (9)0.0039 (9)
C110.0129 (11)0.0153 (11)0.0178 (13)0.0011 (9)0.0041 (10)0.0043 (9)
N120.0151 (9)0.0156 (10)0.0136 (10)0.0008 (8)0.0031 (8)0.0019 (8)
N130.0127 (9)0.0155 (10)0.0119 (10)0.0005 (8)0.0031 (8)0.0027 (8)
C140.0172 (11)0.0141 (11)0.0155 (12)0.0009 (10)0.0043 (10)0.0020 (9)
C150.0176 (12)0.0296 (14)0.0145 (13)0.0021 (11)0.0014 (10)0.0042 (11)
C160.0148 (12)0.0299 (14)0.0203 (13)0.0039 (11)0.0047 (10)0.0044 (11)
C170.0175 (12)0.0192 (12)0.0161 (13)0.0010 (10)0.0066 (10)0.0003 (10)
C180.0199 (12)0.0232 (13)0.0161 (13)0.0010 (11)0.0016 (10)0.0017 (10)
C190.0139 (11)0.0207 (12)0.0193 (13)0.0004 (10)0.0024 (10)0.0021 (10)
C200.0230 (13)0.0207 (13)0.0183 (14)0.0008 (11)0.0060 (11)0.0026 (10)
O210.0280 (10)0.0348 (10)0.0143 (10)0.0031 (8)0.0066 (8)0.0012 (8)
O220.0182 (9)0.0632 (14)0.0209 (10)0.0054 (9)0.0107 (8)0.0114 (9)
C230.0167 (11)0.0189 (12)0.0124 (12)0.0030 (10)0.0027 (9)0.0032 (9)
C240.0137 (11)0.0204 (12)0.0208 (13)0.0012 (10)0.0037 (10)0.0029 (10)
C250.0186 (12)0.0165 (12)0.0220 (14)0.0001 (10)0.0028 (10)0.0011 (10)
C260.0163 (12)0.0196 (12)0.0157 (12)0.0036 (10)0.0031 (10)0.0031 (10)
C270.0113 (11)0.0206 (12)0.0176 (13)0.0010 (10)0.0028 (9)0.0027 (10)
C280.0158 (11)0.0160 (12)0.0184 (13)0.0017 (10)0.0023 (10)0.0014 (10)
C290.0167 (12)0.0228 (13)0.0214 (14)0.0023 (10)0.0033 (10)0.0046 (11)
O300.0142 (8)0.0218 (9)0.0412 (12)0.0041 (7)0.0015 (8)0.0038 (8)
O310.0202 (9)0.0183 (9)0.0446 (12)0.0030 (8)0.0003 (9)0.0017 (8)
O320.0243 (10)0.0319 (10)0.0369 (12)0.0093 (8)0.0050 (9)0.0074 (9)
O330.0214 (9)0.0251 (10)0.0524 (14)0.0019 (8)0.0012 (9)0.0081 (9)
O340.0232 (9)0.0346 (10)0.0210 (10)0.0015 (8)0.0104 (8)0.0010 (8)
C350.0133 (11)0.0248 (13)0.0248 (14)0.0010 (10)0.0066 (10)0.0062 (11)
N360.0160 (10)0.0215 (11)0.0201 (11)0.0018 (9)0.0051 (9)0.0033 (9)
C370.0256 (13)0.0294 (14)0.0210 (14)0.0046 (12)0.0055 (11)0.0027 (11)
C380.0183 (12)0.0260 (14)0.0314 (16)0.0009 (11)0.0051 (11)0.0089 (12)
O39A0.102 (5)0.032 (3)0.036 (3)0.006 (3)0.008 (3)0.001 (2)
C40A0.059 (5)0.032 (4)0.037 (4)0.006 (3)0.002 (3)0.013 (3)
N41A0.034 (3)0.027 (3)0.024 (3)0.001 (2)0.005 (2)0.006 (2)
C42A0.086 (6)0.028 (4)0.034 (4)0.017 (4)0.002 (4)0.006 (3)
C43A0.076 (6)0.068 (5)0.024 (4)0.004 (5)0.001 (4)0.010 (4)
O39B0.095 (4)0.062 (3)0.030 (3)0.022 (3)0.018 (2)0.016 (2)
C40B0.055 (4)0.048 (4)0.057 (5)0.005 (3)0.009 (3)0.030 (3)
N41B0.044 (3)0.047 (3)0.037 (3)0.011 (2)0.002 (2)0.017 (2)
C42B0.088 (5)0.046 (4)0.048 (4)0.009 (4)0.005 (4)0.023 (3)
C43B0.076 (5)0.051 (4)0.042 (4)0.008 (4)0.001 (4)0.001 (3)
Geometric parameters (Å, º) top
Pd1—N122.0133 (19)C26—C271.392 (3)
Pd1—N12i2.0133 (19)C26—C291.490 (3)
Pd1—N132.0379 (19)C27—C281.383 (3)
Pd1—N13i2.0379 (19)C27—H270.9500
C2—N121.381 (3)C28—H280.9500
C2—C11i1.391 (3)C29—O311.225 (3)
C2—C31.443 (3)C29—O301.318 (3)
C3—C41.346 (3)O30—H300.9905
C3—H30.9500O32—H32A0.9084
C4—C51.442 (3)O32—H32B0.9694
C4—H40.9500O33—H33A0.9147
C5—N121.377 (3)O33—H33B0.9056
C5—C61.398 (3)O34—C351.248 (3)
C6—C71.395 (3)C35—N361.321 (3)
C6—C141.500 (3)C35—H350.9500
C7—N131.380 (3)N36—C381.456 (3)
C7—C81.437 (3)N36—C371.460 (3)
C8—C91.352 (3)C37—H37A0.9800
C8—H80.9500C37—H37B0.9800
C9—C101.443 (3)C37—H37C0.9800
C9—H90.9500C38—H38A0.9800
C10—N131.381 (3)C38—H38B0.9800
C10—C111.400 (3)C38—H38C0.9800
C11—C2i1.391 (3)O39A—C40A1.239 (3)
C11—C231.491 (3)C40A—N41A1.349 (3)
C14—C191.395 (3)C40A—H40A0.9500
C14—C151.400 (3)N41A—C42A1.460 (3)
C15—C161.382 (3)N41A—C43A1.460 (3)
C15—H150.9500C42A—H42A0.9800
C16—C171.394 (4)C42A—H42B0.9800
C16—H160.9500C42A—H42C0.9800
C17—C181.395 (3)C43A—H43A0.9800
C17—C201.493 (3)C43A—H43B0.9800
C18—C191.391 (3)C43A—H43C0.9800
C18—H180.9500O39B—C40B1.240 (3)
C19—H190.9500C40B—N41B1.347 (3)
C20—O211.224 (3)C40B—H40B0.9500
C20—O221.313 (3)N41B—C42B1.458 (3)
O22—H220.9473N41B—C43B1.459 (3)
C23—C241.399 (3)C42B—H42D0.9800
C23—C281.401 (3)C42B—H42E0.9800
C24—C251.382 (3)C42B—H42F0.9800
C24—H240.9500C43B—H43D0.9800
C25—C261.399 (3)C43B—H43E0.9800
C25—H250.9500C43B—H43F0.9800
N12—Pd1—N12i180.0C24—C23—C11121.6 (2)
N12—Pd1—N1389.59 (8)C28—C23—C11119.7 (2)
N12i—Pd1—N1390.41 (8)C25—C24—C23120.4 (2)
N12—Pd1—N13i90.41 (8)C25—C24—H24119.8
N12i—Pd1—N13i89.59 (8)C23—C24—H24119.8
N13—Pd1—N13i180.0C24—C25—C26120.5 (2)
N12—C2—C11i126.5 (2)C24—C25—H25119.7
N12—C2—C3109.3 (2)C26—C25—H25119.7
C11i—C2—C3124.2 (2)C27—C26—C25119.3 (2)
C4—C3—C2107.4 (2)C27—C26—C29120.8 (2)
C4—C3—H3126.3C25—C26—C29119.8 (2)
C2—C3—H3126.3C28—C27—C26120.2 (2)
C3—C4—C5107.4 (2)C28—C27—H27119.9
C3—C4—H4126.3C26—C27—H27119.9
C5—C4—H4126.3C27—C28—C23120.9 (2)
N12—C5—C6126.5 (2)C27—C28—H28119.6
N12—C5—C4109.4 (2)C23—C28—H28119.6
C6—C5—C4124.0 (2)O31—C29—O30122.8 (2)
C7—C6—C5124.0 (2)O31—C29—C26123.2 (2)
C7—C6—C14120.4 (2)O30—C29—C26114.0 (2)
C5—C6—C14115.6 (2)C29—O30—H30110.5
N13—C7—C6125.5 (2)H32A—O32—H32B102.2
N13—C7—C8109.5 (2)H33A—O33—H33B105.5
C6—C7—C8125.0 (2)O34—C35—N36123.2 (2)
C9—C8—C7107.4 (2)O34—C35—H35118.4
C9—C8—H8126.3N36—C35—H35118.4
C7—C8—H8126.3C35—N36—C38120.0 (2)
C8—C9—C10107.3 (2)C35—N36—C37121.6 (2)
C8—C9—H9126.3C38—N36—C37118.2 (2)
C10—C9—H9126.3N36—C37—H37A109.5
N13—C10—C11125.6 (2)N36—C37—H37B109.5
N13—C10—C9109.23 (19)H37A—C37—H37B109.5
C11—C10—C9125.1 (2)N36—C37—H37C109.5
C2i—C11—C10124.6 (2)H37A—C37—H37C109.5
C2i—C11—C23116.8 (2)H37B—C37—H37C109.5
C10—C11—C23118.6 (2)N36—C38—H38A109.5
C5—N12—C2106.44 (19)N36—C38—H38B109.5
C5—N12—Pd1126.95 (16)H38A—C38—H38B109.5
C2—N12—Pd1126.36 (15)N36—C38—H38C109.5
C7—N13—C10106.49 (19)H38A—C38—H38C109.5
C7—N13—Pd1127.17 (15)H38B—C38—H38C109.5
C10—N13—Pd1126.33 (15)O39A—C40A—N41A125.2 (5)
C19—C14—C15118.8 (2)O39A—C40A—H40A117.4
C19—C14—C6123.4 (2)N41A—C40A—H40A117.4
C15—C14—C6117.6 (2)C40A—N41A—C42A121.1 (5)
C16—C15—C14120.9 (2)C40A—N41A—C43A120.4 (5)
C16—C15—H15119.5C42A—N41A—C43A118.4 (5)
C14—C15—H15119.5O39B—C40B—N41B124.6 (5)
C15—C16—C17120.1 (2)O39B—C40B—H40B117.7
C15—C16—H16120.0N41B—C40B—H40B117.7
C17—C16—H16120.0C40B—N41B—C42B119.7 (5)
C16—C17—C18119.5 (2)C40B—N41B—C43B121.1 (5)
C16—C17—C20120.3 (2)C42B—N41B—C43B118.7 (5)
C18—C17—C20120.2 (2)N41B—C42B—H42D109.5
C19—C18—C17120.3 (2)N41B—C42B—H42E109.5
C19—C18—H18119.9H42D—C42B—H42E109.5
C17—C18—H18119.9N41B—C42B—H42F109.5
C18—C19—C14120.4 (2)H42D—C42B—H42F109.5
C18—C19—H19119.8H42E—C42B—H42F109.5
C14—C19—H19119.8N41B—C43B—H43D109.5
O21—C20—O22123.4 (2)N41B—C43B—H43E109.5
O21—C20—C17123.0 (2)H43D—C43B—H43E109.5
O22—C20—C17113.6 (2)N41B—C43B—H43F109.5
C20—O22—H22120.1H43D—C43B—H43F109.5
C24—C23—C28118.7 (2)H43E—C43B—H43F109.5
Symmetry code: (i) x, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O22—H22···O34ii0.951.572.516 (2)173
O30—H30···O32iii0.991.592.543 (3)161
O32—H32A···O39Biv0.911.742.642 (4)170
O32—H32A···O39Aiv0.911.912.799 (5)164
O32—H32B···O330.971.752.714 (3)177
O33—H33A···O21v0.911.872.776 (3)169
O33—H33B···O31iv0.911.892.773 (3)166
Symmetry codes: (ii) x2, y, z; (iii) x+2, y+1, z+1; (iv) x+1, y+1, z+1; (v) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Pd(C48H28N4O8)]·CH4O[Pd(C48H28N4O8)]·4C3H7NO·4H2O
Mr927.211259.61
Crystal system, space groupOrthorhombic, CmcaTriclinic, P1
Temperature (K)110110
a, b, c (Å)31.0347 (6), 15.9441 (11), 18.3824 (7)7.7243 (2), 13.2668 (4), 14.5878 (5)
α, β, γ (°)90, 90, 9081.3820 (16), 87.3282 (17), 87.0384 (17)
V3)9096.0 (7)1474.91 (8)
Z81
Radiation typeMo KαMo Kα
µ (mm1)0.470.39
Crystal size (mm)0.30 × 0.10 × 0.050.60 × 0.10 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
20365, 4344, 2688 12855, 5498, 4868
Rint0.0980.045
(sin θ/λ)max1)0.6080.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.160, 1.00 0.037, 0.083, 1.02
No. of reflections43445498
No. of parameters291437
No. of restraints128
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.770.31, 0.72

Computer programs: Collect (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O23—H23···O23i0.841.842.542 (9)141
O31—H31···O32ii0.891.772.669 (6)180
O34—H34···O22iii0.901.712.608 (7)179
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x+1/2, y1/2, z; (iii) x+1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O22—H22···O34i0.951.572.516 (2)173
O30—H30···O32ii0.991.592.543 (3)161
O32—H32A···O39Biii0.911.742.642 (4)170
O32—H32A···O39Aiii0.911.912.799 (5)164
O32—H32B···O330.971.752.714 (3)177
O33—H33A···O21iv0.911.872.776 (3)169
O33—H33B···O31iii0.911.892.773 (3)166
Symmetry codes: (i) x2, y, z; (ii) x+2, y+1, z+1; (iii) x+1, y+1, z+1; (iv) x+1, y, z.
 

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