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Crystals of bis­(pyridine-3-carboxyl­ato)[tetra­kis­(4-iodo­phenyl)porphyrin­ato]tin(IV) di­methyl­formamide sesqui­solvate, [Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NO, (I), and bis­(pyri­midine-5-carboxyl­ato)[tetra­kis­(4-iodo­phenyl)porphyrin­ato]tin(IV) di­methyl­formamide sesquisolvate, [Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NO, (II), exhibit inter­porphyrin iodine–iodine halogen bonds, which direct the supra­molecular assembly of the porphyrin entities into halogen-bonded layers. Each mol­ecule inter­acts with its four nearest neighbours within the layer via eight I...I inter­actions at approximately 3.8 and 4.0 Å. The two structures are isomorphous and isometric, with the metalloporphyrin complexes located on centres of crystallographic inversion.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113020209/fg3302sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020209/fg3302Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020209/fg3302IIsup3.hkl
Contains datablock II

CCDC references: 964758; 964759

Introduction top

Halogen bonds are attractive noncovalent supra­molecular inter­actions that have been found useful in crystal engineering of new crystalline materials and in diverse applications (Desiraju & Parthasarathy, 1989; Metrangolo et al., 2005; Parisini et al., 2011; Erdelyi, 2012; Beale et al., 2013). They involve the positive electrostatic potential of the polarizable halogen atom and an electron-rich atom that acts as a Lewis base. Direct halogen–halogen inter­actions represent one type of halogen bond, and among these I···I inter­actions are the strongest and most readily expressed in different crystalline environments (Bosch & Barnes, 2002; Awwadi et al., 2006). We have described previously the structural patterns of a large variety of tetra­(4-halogeno­phenyl)­porphyrin materials with F, Cl, Br and I atoms as the halogen substituents (Krupitsky et al., 1995; Dastidar et al., 1996; Lipstman et al., 2007). The observed inter­porphyrin architectures of the chloro, bromo and iodo (but not the fluoro) derivatives were found to be affected by directional Cl···Cl, Br···Br and I···I inter­actions. In the context of the present study, Fig. 1 illustrates the charge distribution around the I atom in an iodo­phenyl fragment (Ibrahimi, 2011). It shows that the I atom is positively polarized at its cap, while being negatively polarized around the equatorial periphery. These polarizability features are responsible for the involvement of the halogens (in particular iodine and bromine) in attractive inter­actions with other electron-rich atoms (Gavezzotti, 2008).

As part of our continuing investigation of porphyrin assemblies involving halogen bonds (Krupitsky et al., 1995; Dastidar et al., 1996; Lipstman et al., 2007, 2008; Muniappan et al., 2008; Titi et al., 2011), we present here additional examples of porphyrin structures exhibiting inter­porphyrin halogen bonding, namely bis­(pyridine-3-carboxyl­ato)[tetra­kis(4-iodo­phenyl)­porphyrinato]tin(IV), (I), and bis­(pyrimidine-5-carboxyl­ato)[tetra­kis(4-iodo­phenyl)­porphyrinato]tin(IV), (II) (Fig. 2).

Experimental top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Synthesis and crystallization top

All chemicals for the syntheses were commercially available reagents of analytical grade and were used without further purification. The meso-tetra­kis(4-iodo­phenyl)­porphyrin was prepared via common procedures of porphyrin synthesis, by condensing iodo­benzaldehyde with hot propionic acid. In the next stage, tin insertion into the porphyrin macrocycle was achieved by reacting the corresponding porphyrin derivative with tin dichloride dissolved in pyridine. The dichloride was then converted to the di­hydroxide derivative by reacting it with an aqueous solution of sodium hydroxide (Patra et al., 2013). In the subsequent steps, the syntheses of complexes (I) and (II) were carried out by reacting the corresponding tin(di­hydroxide)porphyrin (5 mg, 0.004 ml) with a stoichiometric excess of the axial ligand L [3 mg, 0.024 mmol, of either nicotinic acid for (I) or pyrimidine-5-carb­oxy­lic acid for (II)] dissolved in di­methyl­formamide (DMF, 1 ml). The reaction mixtures were heated in a bath reactor at 363 K for 3 h, and then allowed to cool slowly to ambient temperature. Chloro­form (2 ml), followed by two drops of nitro­benzene, were added in order to facilitate crystallization. In both cases, red crystals were obtained after about 4 d. The resulting products were cooled to room temperature, washed and left for crystallization.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All the H atoms in the structure were located in calculated positions and constrained to ride on their parent C atoms, with Csp2—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The intensities of two reflections (100 and 110) in (I) and a single reflection (100) in (II), which were affected by the inter­fering beam-stop, could not be estimated reliably and were omitted in the refinement calculations. In the two isomorphous structures, the DMF crystallization solvent was trapped in the lattice near centres of inversion at (1/2,0,1) in (I) and at (1/2,0,1/2) in (II). It was severely disordered and could not be reliably modelled as discrete atoms, although six significant electron-density peaks 1.7–2.7 e Å-3 high in (I) and 1.8–3.2 e Å-3 high in (II) were present in the solvent-accessible voids of the asymmetric unit. The solvent contribution to the diffraction pattern was thus subtracted by the SQUEEZE technique using PLATON (Spek, 2009). 122 electrons per unit cell were removed in this procedure in each of the two structures, which corresponds to about 1.5 molecules of DMF per porphyrin unit.

Results and discussion top

Structures (I) and (II) are isomorphous and isometric, the two compounds (positioned on centres of inversion) crystallizing as di­methyl­formamide (DMF) solvates. The electrostatic polarization of the electron shell around the I nuclei shown in Fig. 1 is well expressed by halogen bonding between the perperdicularly oriented I atoms of neighbouring porphyrin entities, where the electrophilic (δ+) region (termed σ-hole) of one I atom points towards the nucleophilic (δ-) equatorial shell around an adjacent I-atom site (Fig. 3). All four I-atom substituents of a given porphyrin entity are involved in such inter­actions, inducing a layered assembly of halogen-bonded porphyrins that are aligned parallel to the ac plane of the crystal structure. In this arrangement, each porphyrin unit is engaged in eight I···I contacts to four surrounding species. The corresponding crystallographically independent I···I inter­action distances in (I) and (II) are near 3.8 and 4.0 Å (Tables 2 and 3), shorter than the sum of the van der Waals radii of I atoms (>4.2 Å; Awwadi et al., 2006; Bondi, 1964). The inter­molecular inter­action synthon involves four I atoms of four different porphyrin entities which converge in the tetra­iodo-connected re­cta­ngle (Fig. 3). In such a re­cta­ngular setting, the electrostatic inter­actions between any pair of I atoms are optimized (by a nearly perpendicular approach of the inter­acting I atoms in the re­cta­ngle) in accordance with the polarized charge distribution described in Fig. 1.

The topology of the porphyrin network thus formed has been analysed with the TOPOS software, reducing the structure to a simpler node-and-linker net (Blatov, 2012). Accordingly, the network depicted in Fig. 3 is best described as a uninodal sql tetra­gonal plane net (when the entire porphyrin complex is considered as a 4-connected site). The layered-type arrangement of the porphyrin species in (I) and (II), with intra­layer sovent-accessible voids described above, is similar to that observed in the structure of the free base tetra­kis(4-iodo­phenyl)­porphyrin chloro­form 0.85-solvate (Lipstman et al., 2007). The latter structure is characterized by a tighter porphyrin organization within the layers, the inter­porphyrin binding nodes exhibiting two I···I halogen bonds and two I···π inter­actions. The structure of the flat porphyrin pattern in (I) and (II) is affected by the need to optimize the crystal packing of six-coordinate (rather than flat free base) porphyrin entities and the inclusion of a larger amount of the crystallization solvent (1.5 molecules of DMF, instead of 0.85 molecules of chloro­form, per porphyrin). This is reflected in a slight expansion of the porphyrin layers (to allow larger inter­porphyrin voids), which is in turn associated with the expression of the weaker set of secondary I···I inter­actions (at 4.0 Å), instead of the I···π contacts at 3.6 Å in the structure of tetra­kis(4-iodo­phenyl)­porphyrin. Against our original expe­cta­tions, the electron-rich N atoms of the axial ligands are not involved in halogen bonds with the I atoms of neighbouring entities.

The crystal structures of (I) and (II) contain two independent halogen-bonded layers which stack one on top of the other along the normal direction in an offset manner, so that the Sn-bound axial ligands of one layer protrude into the inter­porphyrin voids of adjacent layers above and below. In addition, three molecules per unit-cell of the disordered DMF crystallization solvent are included in the crystal lattice at (1/2,0,0) and (1/2,1/2,1/2) in (I), and at (1/2,1/2,0) and (1/2,0,1/2) in (II).

Conclusions top

The expression of directional but relatively weak halogen bonding in the crystalline self-assembly of organic species in common reaction environments is not straightforward, in view of competing inter­molecular binding forces of similar strength such as hydrogen bonds or ππ inter­actions. The latter, along with molecular-shape considerations, are of particular significance in systems with extended aromatic cores such as tetra­aryl porphyrins. The observed inter­molecular arrangement in (I) and (II) accommodates the general tendency of such porphyrins to aggregate preferentially in three-dimensional crystal structures in a body-centred-type packing (Cambridge Structural Database; Allen, 2002), while simultaneously optimizing a unique I···I inter­action pattern. This is consistent with earlier observations in related porphyrin compounds with halogenated peripheries (Lipstman et al., 2007; Krupitsky et al., 1995; Dastidar et al., 1996). One may conclude that, although specific halogen bonds present only a small contribution to the total enthalphy of the inter­molecular packing, and are not a major cohesive factor (Gavezzotti, 2008), they can influence the supra­molecular organization of molecular scaffolds with preorganized and sterically unhindered molecular recognition functions.

Related literature top

For related literature, see: Allen (2002); Awwadi et al. (2006); Beale et al. (2013); Blatov (2012); Bondi (1964); Bosch & Barnes (2002); Dastidar et al. (1996); Desiraju & Parthasarathy (1989); Erdelyi (2012); Gavezzotti (2008); Ibrahimi (2011); Krupitsky et al. (1995); Lipstman et al. (2007, 2008); Metrangolo et al. (2005); Muniappan et al. (2008); Parisini et al. (2011); Patra et al. (2013); Spek (2009); Titi et al. (2011).

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I); APEX2 (Bruker, 2007) for (II). Cell refinement: DENZO (Otwinowski & Minor, 1997) for (I); SAINT (Bruker, 2007) for (II). Data reduction: DENZO (Otwinowski & Minor, 1997) for (I); SAINT (Bruker, 2007) for (II). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SHELXS2012 (Sheldrick, 2008) for (II). For both compounds, program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2012 (Sheldrick, 2008).

Figures top
Fig. 1. Illustration of the molecular electrostatic potential surface of iodobenzene (Ibrahimi, 2011). (In the electronic version of the paper, positive potential is depicted in blue and negative potential in red.)

Fig. 2. Views of the asymmetric unit in (a) (I) and (b) (II), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level at 110 (2) K. The molecules (the Sn ions) are located on centres of crystallographic inversion.

Fig. 3. A view of the halogen-bonded sql layer observed in (I) and (II). The I···I contacts are indicated by dashed lines: (i) is 3.8 Å and (ii) is 4.0 Å (Tables 2 and 3). Note the rectangular arrangement of the four mutually perpendicular C—I bonds around centres of inversion.
(I) bis(pyridine-3-carboxylato)[tetrakis(4-iodophenyl)porphyrinato]tin(IV) dimethylformamide sesquisolvate top
Crystal data top
[Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NOF(000) = 1528
Mr = 1558.81Dx = 1.922 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.0594 (3) ÅCell parameters from 4946 reflections
b = 17.1924 (3) Åθ = 2.2–27.9°
c = 11.4740 (2) ŵ = 2.77 mm1
β = 98.1460 (7)°T = 110 K
V = 2745.45 (9) Å3Plate, red
Z = 20.30 × 0.25 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
6485 independent reflections
Radiation source: fine-focus sealed tube4946 reflections with I > 2σ(I)
Detector resolution: 12.8 pixels mm-1Rint = 0.041
ϕ and ω scansθmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1818
Tmin = 0.491, Tmax = 0.733k = 2222
11339 measured reflectionsl = 1515
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.069P)2 + 0.2949P]
where P = (Fo2 + 2Fc2)/3
6485 reflections(Δ/σ)max = 0.001
322 parametersΔρmax = 1.84 e Å3
0 restraintsΔρmin = 0.88 e Å3
Crystal data top
[Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NOV = 2745.45 (9) Å3
Mr = 1558.81Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.0594 (3) ŵ = 2.77 mm1
b = 17.1924 (3) ÅT = 110 K
c = 11.4740 (2) Å0.30 × 0.25 × 0.12 mm
β = 98.1460 (7)°
Data collection top
Nonius KappaCCD
diffractometer
6485 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
4946 reflections with I > 2σ(I)
Tmin = 0.491, Tmax = 0.733Rint = 0.041
11339 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.03Δρmax = 1.84 e Å3
6485 reflectionsΔρmin = 0.88 e Å3
322 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn0.00000.50000.00000.02279 (10)
C10.1882 (3)0.3807 (2)0.1151 (3)0.0266 (8)
C20.1113 (3)0.3454 (2)0.0432 (4)0.0264 (8)
C30.1067 (3)0.7351 (2)0.0065 (4)0.0290 (8)
H30.15390.77380.02940.035*
C40.0233 (3)0.7455 (2)0.0661 (4)0.0310 (9)
H40.00210.79270.10460.037*
C50.0275 (3)0.6733 (2)0.0751 (3)0.0269 (8)
C60.1197 (3)0.6589 (2)0.1399 (3)0.0261 (8)
C70.1686 (3)0.5878 (2)0.1501 (3)0.0253 (8)
C80.2597 (3)0.5728 (2)0.2198 (3)0.0289 (8)
H80.29980.61050.26290.035*
C90.2786 (3)0.4957 (2)0.2136 (4)0.0300 (9)
H90.33430.46970.25090.036*
C100.2000 (3)0.4609 (2)0.1412 (3)0.0256 (8)
N110.1341 (2)0.51760 (18)0.1017 (3)0.0242 (6)
N120.0278 (2)0.61913 (17)0.0089 (3)0.0243 (6)
C130.2640 (3)0.3270 (2)0.1748 (4)0.0267 (8)
C140.3579 (3)0.3288 (2)0.1511 (4)0.0339 (9)
H140.37540.36470.09490.041*
C150.4268 (3)0.2786 (3)0.2084 (4)0.0384 (10)
H150.49120.28030.19220.046*
C160.4000 (3)0.2261 (2)0.2897 (4)0.0311 (9)
C170.3068 (3)0.2232 (2)0.3141 (4)0.0329 (9)
H170.28960.18710.37020.039*
C180.2384 (3)0.2731 (2)0.2566 (4)0.0322 (9)
H180.17390.27090.27260.039*
I190.50357 (2)0.15077 (2)0.37978 (3)0.03780 (10)
C200.1731 (3)0.7283 (2)0.1986 (3)0.0265 (8)
C210.1447 (3)0.7635 (2)0.2967 (4)0.0314 (9)
H210.09160.74330.32980.038*
C220.1937 (3)0.8283 (2)0.3468 (4)0.0359 (10)
H220.17340.85290.41320.043*
C230.2709 (3)0.8564 (2)0.3004 (4)0.0327 (9)
C240.3012 (3)0.8226 (2)0.2035 (4)0.0387 (10)
H240.35490.84270.17150.046*
C250.2511 (3)0.7579 (2)0.1531 (4)0.0360 (10)
H250.27120.73390.08610.043*
I260.34345 (2)0.95691 (2)0.37241 (3)0.04500 (11)
O270.0681 (2)0.49441 (15)0.1482 (2)0.0293 (6)
O280.0162 (2)0.40739 (17)0.2652 (3)0.0457 (8)
C290.0442 (3)0.4593 (2)0.2475 (4)0.0350 (10)
C300.0969 (3)0.4890 (2)0.3440 (4)0.0378 (10)
C310.1468 (4)0.5595 (3)0.3346 (5)0.0444 (11)
H310.14980.58820.26350.053*
N320.1901 (3)0.5881 (2)0.4209 (4)0.0540 (11)
C330.1848 (4)0.5456 (3)0.5185 (5)0.0540 (14)
H330.21320.56670.58190.065*
C340.1421 (4)0.4743 (3)0.5359 (5)0.0563 (14)
H340.14520.44570.60610.068*
C350.0952 (4)0.4459 (3)0.4498 (5)0.0505 (13)
H350.06170.39780.46010.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.0225 (2)0.02082 (18)0.0242 (2)0.00167 (12)0.00014 (14)0.00078 (13)
C10.0227 (19)0.0314 (19)0.026 (2)0.0045 (15)0.0047 (15)0.0061 (16)
C20.024 (2)0.0247 (19)0.030 (2)0.0014 (14)0.0030 (16)0.0019 (15)
C30.030 (2)0.0244 (18)0.031 (2)0.0030 (15)0.0002 (17)0.0010 (16)
C40.030 (2)0.0249 (19)0.038 (2)0.0007 (15)0.0018 (18)0.0048 (16)
C50.030 (2)0.0245 (18)0.027 (2)0.0003 (15)0.0060 (16)0.0032 (15)
C60.027 (2)0.0257 (18)0.026 (2)0.0010 (14)0.0048 (16)0.0011 (15)
C70.0222 (19)0.0286 (19)0.024 (2)0.0017 (14)0.0008 (15)0.0000 (15)
C80.027 (2)0.034 (2)0.024 (2)0.0026 (16)0.0003 (16)0.0030 (16)
C90.024 (2)0.032 (2)0.034 (2)0.0022 (15)0.0046 (17)0.0049 (16)
C100.023 (2)0.0280 (19)0.025 (2)0.0014 (14)0.0024 (16)0.0057 (15)
N110.0215 (16)0.0254 (15)0.0260 (17)0.0025 (12)0.0040 (13)0.0022 (13)
N120.0246 (16)0.0238 (15)0.0234 (17)0.0004 (12)0.0009 (13)0.0013 (12)
C130.025 (2)0.0228 (17)0.031 (2)0.0032 (14)0.0013 (16)0.0002 (15)
C140.028 (2)0.033 (2)0.040 (3)0.0053 (16)0.0049 (19)0.0098 (18)
C150.023 (2)0.040 (2)0.053 (3)0.0025 (17)0.009 (2)0.008 (2)
C160.024 (2)0.0262 (19)0.041 (2)0.0057 (15)0.0009 (18)0.0061 (17)
C170.032 (2)0.033 (2)0.034 (2)0.0021 (16)0.0051 (18)0.0089 (17)
C180.024 (2)0.036 (2)0.037 (2)0.0030 (16)0.0060 (18)0.0068 (18)
I190.02733 (16)0.03408 (17)0.0505 (2)0.00775 (10)0.00021 (13)0.01019 (12)
C200.028 (2)0.0210 (17)0.029 (2)0.0004 (14)0.0016 (17)0.0019 (15)
C210.030 (2)0.034 (2)0.030 (2)0.0006 (16)0.0034 (17)0.0022 (17)
C220.043 (3)0.031 (2)0.033 (2)0.0051 (17)0.0012 (19)0.0114 (17)
C230.032 (2)0.0243 (19)0.038 (2)0.0042 (15)0.0093 (18)0.0013 (16)
C240.033 (2)0.035 (2)0.046 (3)0.0063 (18)0.000 (2)0.0030 (19)
C250.030 (2)0.034 (2)0.044 (3)0.0036 (17)0.0059 (19)0.0066 (19)
I260.04290 (19)0.02718 (16)0.0578 (2)0.00030 (11)0.01763 (15)0.00542 (12)
O270.0298 (15)0.0329 (14)0.0250 (15)0.0001 (11)0.0034 (12)0.0017 (11)
O280.050 (2)0.0415 (17)0.045 (2)0.0082 (15)0.0079 (16)0.0087 (15)
C290.036 (2)0.032 (2)0.036 (3)0.0010 (17)0.0055 (19)0.0023 (17)
C300.039 (3)0.039 (2)0.036 (3)0.0084 (18)0.006 (2)0.0023 (19)
C310.050 (3)0.040 (2)0.043 (3)0.001 (2)0.009 (2)0.007 (2)
N320.070 (3)0.047 (2)0.048 (3)0.001 (2)0.021 (2)0.003 (2)
C330.068 (4)0.061 (3)0.035 (3)0.004 (3)0.018 (3)0.010 (2)
C340.073 (4)0.060 (3)0.040 (3)0.012 (3)0.022 (3)0.009 (2)
C350.064 (3)0.048 (3)0.041 (3)0.008 (2)0.013 (3)0.006 (2)
Geometric parameters (Å, º) top
Sn—O27i2.069 (3)C15—H150.9500
Sn—O272.069 (3)C16—C171.379 (6)
Sn—N12i2.090 (3)C16—I192.106 (4)
Sn—N122.090 (3)C17—C181.385 (5)
Sn—N112.094 (3)C17—H170.9500
Sn—N11i2.094 (3)C18—H180.9500
C1—C21.402 (5)C20—C251.377 (5)
C1—C101.415 (5)C20—C211.386 (6)
C1—C131.501 (5)C21—C221.391 (6)
C2—N12i1.381 (5)C21—H210.9500
C2—C3i1.445 (5)C22—C231.362 (6)
C3—C41.351 (6)C22—H220.9500
C3—C2i1.445 (5)C23—C241.376 (6)
C3—H30.9500C23—I262.114 (4)
C4—C51.429 (5)C24—C251.397 (6)
C4—H40.9500C24—H240.9500
C5—N121.371 (5)C25—H250.9500
C5—C61.422 (6)O27—C291.291 (5)
C6—C71.399 (5)O28—C291.229 (5)
C6—C201.516 (5)C29—C301.506 (6)
C7—N111.387 (5)C30—C311.397 (6)
C7—C81.433 (5)C30—C351.420 (7)
C8—C91.357 (6)C31—N321.328 (6)
C8—H80.9500C31—H310.9500
C9—C101.416 (6)N32—C331.330 (7)
C9—H90.9500C33—C341.366 (8)
C10—N111.377 (5)C33—H330.9500
N12—C2i1.381 (5)C34—C351.354 (7)
C13—C141.385 (6)C34—H340.9500
C13—C181.401 (5)C35—H350.9500
C14—C151.391 (6)I19—I26ii3.7955 (4)
C14—H140.9500I19—I26iii4.0162 (4)
C15—C161.388 (6)
O27i—Sn—O27180.0C13—C14—C15120.8 (4)
O27i—Sn—N12i83.90 (11)C13—C14—H14119.6
O27—Sn—N12i96.10 (11)C15—C14—H14119.6
O27i—Sn—N1296.10 (11)C16—C15—C14119.0 (4)
O27—Sn—N1283.90 (11)C16—C15—H15120.5
N12i—Sn—N12180.0C14—C15—H15120.5
O27i—Sn—N1188.05 (11)C17—C16—C15121.0 (4)
O27—Sn—N1191.95 (11)C17—C16—I19119.3 (3)
N12i—Sn—N1190.51 (12)C15—C16—I19119.7 (3)
N12—Sn—N1189.49 (12)C16—C17—C18119.8 (4)
O27i—Sn—N11i91.95 (11)C16—C17—H17120.1
O27—Sn—N11i88.05 (11)C18—C17—H17120.1
N12i—Sn—N11i89.49 (12)C17—C18—C13120.1 (4)
N12—Sn—N11i90.51 (12)C17—C18—H18120.0
N11—Sn—N11i180.0C13—C18—H18120.0
C2—C1—C10127.2 (3)C25—C20—C21118.8 (4)
C2—C1—C13116.1 (3)C25—C20—C6119.6 (4)
C10—C1—C13116.7 (3)C21—C20—C6121.6 (3)
N12i—C2—C1126.9 (3)C22—C21—C20120.2 (4)
N12i—C2—C3i107.2 (3)C22—C21—H21119.9
C1—C2—C3i125.8 (3)C20—C21—H21119.9
C4—C3—C2i107.8 (3)C23—C22—C21119.9 (4)
C4—C3—H3126.1C23—C22—H22120.1
C2i—C3—H3126.1C21—C22—H22120.1
C3—C4—C5108.0 (3)C22—C23—C24121.4 (4)
C3—C4—H4126.0C22—C23—I26120.3 (3)
C5—C4—H4126.0C24—C23—I26118.3 (3)
N12—C5—C6125.1 (3)C23—C24—C25118.3 (4)
N12—C5—C4108.2 (3)C23—C24—H24120.8
C6—C5—C4126.7 (3)C25—C24—H24120.8
C7—C6—C5126.6 (3)C20—C25—C24121.4 (4)
C7—C6—C20116.4 (3)C20—C25—H25119.3
C5—C6—C20116.9 (3)C24—C25—H25119.3
N11—C7—C6125.9 (3)C29—O27—Sn130.8 (3)
N11—C7—C8107.6 (3)O28—C29—O27125.0 (4)
C6—C7—C8126.3 (4)O28—C29—C30121.6 (4)
C9—C8—C7108.2 (4)O27—C29—C30113.4 (4)
C9—C8—H8125.9C31—C30—C35117.8 (4)
C7—C8—H8125.9C31—C30—C29122.0 (4)
C8—C9—C10107.5 (4)C35—C30—C29120.2 (4)
C8—C9—H9126.2N32—C31—C30122.8 (5)
C10—C9—H9126.2N32—C31—H31118.6
N11—C10—C1124.5 (4)C30—C31—H31118.6
N11—C10—C9109.1 (3)C31—N32—C33116.6 (5)
C1—C10—C9126.4 (4)N32—C33—C34125.9 (5)
C10—N11—C7107.6 (3)N32—C33—H33117.0
C10—N11—Sn126.3 (3)C34—C33—H33117.0
C7—N11—Sn125.8 (2)C35—C34—C33117.8 (5)
C5—N12—C2i108.7 (3)C35—C34—H34121.1
C5—N12—Sn126.7 (3)C33—C34—H34121.1
C2i—N12—Sn124.4 (2)C34—C35—C30119.0 (5)
C14—C13—C18119.3 (3)C34—C35—H35120.5
C14—C13—C1122.1 (3)C30—C35—H35120.5
C18—C13—C1118.6 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z+1; (iii) x, y1, z.
(II) Bis(pyrimidine-5-carboxylato)[tetrakis(4-iodophenyl)porphyrinato]tin(IV) dimethylformamide sesquisolvate top
Crystal data top
[Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NOF(000) = 1528
Mr = 1590.79Dx = 1.948 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.0712 (2) ÅCell parameters from 5509 reflections
b = 17.2283 (3) Åθ = 1.9–28.4°
c = 11.3198 (2) ŵ = 2.81 mm1
β = 98.742 (1)°T = 110 K
V = 2712.30 (8) Å3Prism, red
Z = 20.20 × 0.15 × 0.15 mm
Data collection top
Bruker APEX DUO
diffractometer
6728 independent reflections
Radiation source: Iµ micro-focus5505 reflections with I > 2σ(I)
Detector resolution: 1.75 pixels mm-1Rint = 0.030
0.5° ϕ and ω scansθmax = 28.4°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1818
Tmin = 0.604, Tmax = 0.679k = 1823
25067 measured reflectionsl = 1515
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0314P)2 + 1.267P]
where P = (Fo2 + 2Fc2)/3
6728 reflections(Δ/σ)max = 0.007
322 parametersΔρmax = 1.63 e Å3
0 restraintsΔρmin = 1.06 e Å3
Crystal data top
[Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NOV = 2712.30 (8) Å3
Mr = 1590.79Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.0712 (2) ŵ = 2.81 mm1
b = 17.2283 (3) ÅT = 110 K
c = 11.3198 (2) Å0.20 × 0.15 × 0.15 mm
β = 98.742 (1)°
Data collection top
Bruker APEX DUO
diffractometer
6728 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
5505 reflections with I > 2σ(I)
Tmin = 0.604, Tmax = 0.679Rint = 0.030
25067 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.05Δρmax = 1.63 e Å3
6728 reflectionsΔρmin = 1.06 e Å3
322 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn0.00000.00000.00000.01209 (7)
C10.19062 (18)0.11819 (18)0.1126 (2)0.0153 (6)
C20.11298 (19)0.15403 (18)0.0393 (2)0.0156 (6)
C30.1091 (2)0.23296 (18)0.0010 (3)0.0188 (6)
H30.15700.27120.02330.023*
C40.02515 (19)0.24379 (19)0.0726 (3)0.0189 (6)
H40.00400.29080.11200.023*
C50.02616 (19)0.17174 (18)0.0806 (2)0.0159 (6)
C60.11889 (19)0.15795 (18)0.1451 (2)0.0148 (6)
C70.16746 (19)0.08728 (18)0.1553 (2)0.0145 (6)
C80.26036 (19)0.07250 (19)0.2256 (3)0.0185 (6)
H80.30040.11000.27020.022*
C90.28004 (19)0.00302 (18)0.2170 (3)0.0179 (6)
H90.33660.02840.25440.021*
C100.20100 (18)0.03927 (18)0.1414 (2)0.0150 (6)
N110.13426 (15)0.01800 (14)0.1039 (2)0.0137 (5)
N120.02914 (15)0.11796 (15)0.0120 (2)0.0149 (5)
C130.26645 (19)0.17238 (18)0.1725 (2)0.0163 (6)
C140.24235 (19)0.2265 (2)0.2534 (3)0.0228 (7)
H140.17820.22840.27000.027*
C150.3101 (2)0.2779 (2)0.3107 (3)0.0249 (7)
H150.29280.31490.36590.030*
C160.40267 (19)0.27422 (19)0.2860 (3)0.0213 (7)
C170.4292 (2)0.2207 (2)0.2052 (3)0.0251 (7)
H170.49330.21920.18840.030*
C180.3608 (2)0.16939 (19)0.1496 (3)0.0216 (7)
H180.37850.13190.09530.026*
I190.50609 (2)0.35059 (2)0.37523 (2)0.02806 (7)
C200.17169 (19)0.22700 (18)0.2036 (3)0.0173 (6)
C210.1449 (2)0.2629 (2)0.3023 (3)0.0228 (7)
H210.09250.24290.33670.027*
C220.1937 (2)0.3281 (2)0.3521 (3)0.0245 (7)
H220.17490.35240.42030.029*
C230.2701 (2)0.35737 (19)0.3016 (3)0.0230 (7)
C240.2982 (2)0.3225 (2)0.2042 (3)0.0274 (8)
H240.35100.34250.17050.033*
C250.2488 (2)0.2571 (2)0.1549 (3)0.0262 (7)
H250.26810.23290.08710.031*
I260.34061 (2)0.45907 (2)0.37056 (2)0.03287 (7)
O270.06651 (13)0.00730 (13)0.15244 (17)0.0199 (5)
O280.01780 (15)0.09563 (14)0.26804 (19)0.0262 (5)
C290.0413 (2)0.04314 (19)0.2497 (3)0.0208 (7)
C300.0926 (2)0.01485 (19)0.3491 (3)0.0219 (7)
C310.0973 (3)0.0590 (2)0.4513 (3)0.0319 (8)
H310.06860.10900.45690.038*
N320.1399 (2)0.03431 (19)0.5411 (3)0.0382 (8)
C330.1763 (3)0.0372 (2)0.5281 (3)0.0344 (9)
H330.20430.05670.59340.041*
N340.1782 (2)0.08464 (19)0.4354 (3)0.0349 (7)
C350.1365 (2)0.0583 (2)0.3455 (3)0.0283 (8)
H350.13640.08990.27680.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.01272 (12)0.01133 (16)0.01224 (12)0.00200 (10)0.00197 (9)0.00042 (10)
C10.0141 (12)0.0187 (18)0.0139 (13)0.0019 (11)0.0047 (10)0.0022 (12)
C20.0183 (13)0.0143 (17)0.0148 (13)0.0044 (11)0.0044 (10)0.0030 (12)
C30.0206 (14)0.0139 (17)0.0213 (15)0.0055 (11)0.0020 (11)0.0022 (12)
C40.0199 (14)0.0156 (18)0.0209 (14)0.0001 (11)0.0027 (11)0.0008 (12)
C50.0184 (13)0.0150 (17)0.0152 (13)0.0016 (11)0.0054 (10)0.0003 (12)
C60.0190 (13)0.0141 (17)0.0117 (13)0.0010 (11)0.0041 (10)0.0011 (11)
C70.0174 (13)0.0148 (17)0.0119 (12)0.0018 (11)0.0045 (10)0.0023 (11)
C80.0144 (13)0.0218 (19)0.0188 (14)0.0003 (11)0.0011 (11)0.0003 (13)
C90.0138 (13)0.0196 (19)0.0199 (14)0.0010 (11)0.0010 (11)0.0011 (12)
C100.0137 (12)0.0151 (17)0.0167 (14)0.0011 (11)0.0037 (10)0.0028 (12)
N110.0144 (11)0.0106 (14)0.0160 (11)0.0014 (9)0.0025 (9)0.0021 (10)
N120.0160 (11)0.0125 (14)0.0161 (12)0.0019 (9)0.0024 (9)0.0005 (10)
C130.0168 (13)0.0159 (18)0.0157 (13)0.0029 (11)0.0013 (10)0.0005 (12)
C140.0117 (13)0.034 (2)0.0229 (15)0.0037 (12)0.0044 (11)0.0058 (14)
C150.0175 (14)0.028 (2)0.0291 (17)0.0030 (12)0.0038 (12)0.0099 (15)
C160.0166 (13)0.0205 (19)0.0256 (16)0.0069 (12)0.0012 (11)0.0035 (13)
C170.0129 (13)0.029 (2)0.0346 (18)0.0044 (12)0.0070 (12)0.0058 (15)
C180.0180 (14)0.0189 (19)0.0283 (16)0.0036 (12)0.0047 (12)0.0070 (13)
I190.01761 (10)0.02708 (14)0.03879 (13)0.00826 (8)0.00198 (8)0.01082 (10)
C200.0170 (13)0.0149 (17)0.0194 (14)0.0025 (11)0.0007 (11)0.0006 (12)
C210.0245 (15)0.026 (2)0.0183 (15)0.0007 (13)0.0045 (12)0.0028 (13)
C220.0318 (16)0.021 (2)0.0188 (15)0.0016 (13)0.0006 (12)0.0048 (13)
C230.0211 (14)0.0177 (19)0.0261 (16)0.0036 (12)0.0096 (12)0.0034 (13)
C240.0211 (15)0.028 (2)0.0342 (18)0.0049 (13)0.0065 (13)0.0022 (15)
C250.0244 (15)0.026 (2)0.0294 (17)0.0025 (13)0.0078 (13)0.0101 (14)
I260.03110 (12)0.01852 (14)0.04232 (14)0.00022 (9)0.01585 (9)0.00524 (10)
O270.0183 (10)0.0257 (14)0.0166 (10)0.0003 (8)0.0056 (8)0.0015 (9)
O280.0287 (11)0.0243 (14)0.0261 (12)0.0042 (10)0.0053 (9)0.0044 (10)
C290.0179 (14)0.0149 (18)0.0297 (17)0.0053 (12)0.0041 (12)0.0002 (13)
C300.0244 (15)0.0199 (19)0.0219 (15)0.0045 (12)0.0048 (12)0.0002 (13)
C310.045 (2)0.027 (2)0.0246 (17)0.0015 (16)0.0088 (15)0.0020 (15)
N320.0543 (19)0.033 (2)0.0324 (17)0.0018 (15)0.0226 (14)0.0057 (14)
C330.044 (2)0.036 (3)0.0279 (18)0.0037 (17)0.0184 (15)0.0078 (16)
N340.0458 (17)0.030 (2)0.0311 (16)0.0011 (14)0.0142 (13)0.0042 (14)
C350.0337 (17)0.031 (2)0.0219 (16)0.0042 (14)0.0089 (13)0.0043 (14)
Geometric parameters (Å, º) top
Sn—N12i2.082 (3)C15—H150.9500
Sn—N122.082 (3)C16—C171.390 (4)
Sn—O27i2.0881 (19)C16—I192.103 (3)
Sn—O272.0881 (19)C17—C181.385 (4)
Sn—N11i2.091 (2)C17—H170.9500
Sn—N112.091 (2)C18—H180.9500
C1—C101.401 (4)C20—C211.379 (4)
C1—C2i1.410 (4)C20—C251.390 (4)
C1—C131.500 (4)C21—C221.390 (4)
C2—N121.381 (3)C21—H210.9500
C2—C1i1.410 (4)C22—C231.386 (5)
C2—C31.426 (4)C22—H220.9500
C3—C41.351 (4)C23—C241.366 (5)
C3—H30.9500C23—I262.104 (3)
C4—C51.432 (4)C24—C251.394 (4)
C4—H40.9500C24—H240.9500
C5—N121.373 (4)C25—H250.9500
C5—C61.415 (4)O27—C291.265 (4)
C6—C71.392 (4)O28—C291.225 (4)
C6—C201.502 (4)C29—C301.507 (4)
C7—N111.378 (4)C30—C311.394 (5)
C7—C81.446 (4)C30—C351.401 (5)
C8—C91.337 (4)C31—N321.327 (4)
C8—H80.9500C31—H310.9500
C9—C101.439 (4)N32—C331.334 (5)
C9—H90.9500C33—N341.327 (5)
C10—N111.384 (3)C33—H330.9500
C13—C141.384 (4)N34—C351.330 (4)
C13—C181.392 (4)C35—H350.9500
C14—C151.388 (4)I19—I26ii3.8131 (3)
C14—H140.9500I19—I26iii4.0175 (3)
C15—C161.375 (4)
N12i—Sn—N12180.00 (16)C18—C13—C1121.7 (3)
N12i—Sn—O27i96.45 (9)C13—C14—C15121.3 (3)
N12—Sn—O27i83.55 (9)C13—C14—H14119.4
N12i—Sn—O2783.55 (9)C15—C14—H14119.4
N12—Sn—O2796.45 (9)C16—C15—C14118.7 (3)
O27i—Sn—O27180.00 (15)C16—C15—H15120.7
N12i—Sn—N11i89.35 (9)C14—C15—H15120.7
N12—Sn—N11i90.65 (9)C15—C16—C17121.5 (3)
O27i—Sn—N11i88.61 (8)C15—C16—I19118.8 (2)
O27—Sn—N11i91.39 (8)C17—C16—I19119.7 (2)
N12i—Sn—N1190.65 (9)C18—C17—C16119.0 (3)
N12—Sn—N1189.35 (9)C18—C17—H17120.5
O27i—Sn—N1191.39 (8)C16—C17—H17120.5
O27—Sn—N1188.61 (8)C17—C18—C13120.5 (3)
N11i—Sn—N11180.0 (2)C17—C18—H18119.7
C10—C1—C2i127.3 (3)C13—C18—H18119.7
C10—C1—C13117.2 (2)C21—C20—C25118.6 (3)
C2i—C1—C13115.3 (3)C21—C20—C6122.4 (3)
N12—C2—C1i125.9 (3)C25—C20—C6119.0 (3)
N12—C2—C3108.1 (2)C20—C21—C22120.8 (3)
C1i—C2—C3126.0 (3)C20—C21—H21119.6
C4—C3—C2108.0 (3)C22—C21—H21119.6
C4—C3—H3126.0C23—C22—C21119.5 (3)
C2—C3—H3126.0C23—C22—H22120.3
C3—C4—C5107.7 (3)C21—C22—H22120.3
C3—C4—H4126.1C24—C23—C22120.7 (3)
C5—C4—H4126.1C24—C23—I26119.2 (2)
N12—C5—C6125.3 (3)C22—C23—I26120.1 (2)
N12—C5—C4108.2 (2)C23—C24—C25119.3 (3)
C6—C5—C4126.5 (3)C23—C24—H24120.3
C7—C6—C5126.3 (3)C25—C24—H24120.3
C7—C6—C20116.9 (2)C20—C25—C24121.0 (3)
C5—C6—C20116.8 (3)C20—C25—H25119.5
N11—C7—C6126.3 (2)C24—C25—H25119.5
N11—C7—C8107.5 (3)C29—O27—Sn130.33 (19)
C6—C7—C8126.2 (3)O28—C29—O27126.9 (3)
C9—C8—C7108.1 (3)O28—C29—C30120.1 (3)
C9—C8—H8125.9O27—C29—C30112.9 (3)
C7—C8—H8125.9C31—C30—C35116.0 (3)
C8—C9—C10108.4 (2)C31—C30—C29122.1 (3)
C8—C9—H9125.8C35—C30—C29121.9 (3)
C10—C9—H9125.8N32—C31—C30123.0 (3)
N11—C10—C1125.4 (2)N32—C31—H31118.5
N11—C10—C9107.5 (3)C30—C31—H31118.5
C1—C10—C9127.1 (3)C31—N32—C33114.9 (3)
C7—N11—C10108.5 (2)N34—C33—N32128.1 (3)
C7—N11—Sn125.82 (18)N34—C33—H33115.9
C10—N11—Sn125.44 (19)N32—C33—H33115.9
C5—N12—C2108.0 (2)C33—N34—C35115.9 (3)
C5—N12—Sn126.55 (18)N34—C35—C30121.9 (3)
C2—N12—Sn125.19 (19)N34—C35—H35119.0
C14—C13—C18119.0 (3)C30—C35—H35119.0
C14—C13—C1119.3 (2)
Symmetry codes: (i) x, y, z; (ii) x1, y, z1; (iii) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NO[Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NO
Mr1558.811590.79
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)110110
a, b, c (Å)14.0594 (3), 17.1924 (3), 11.4740 (2)14.0712 (2), 17.2283 (3), 11.3198 (2)
β (°) 98.1460 (7) 98.742 (1)
V3)2745.45 (9)2712.30 (8)
Z22
Radiation typeMo KαMo Kα
µ (mm1)2.772.81
Crystal size (mm)0.30 × 0.25 × 0.120.20 × 0.15 × 0.15
Data collection
DiffractometerNonius KappaCCD
diffractometer
Bruker APEX DUO
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Multi-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.491, 0.7330.604, 0.679
No. of measured, independent and
observed [I > 2σ(I)] reflections
11339, 6485, 4946 25067, 6728, 5505
Rint0.0410.030
(sin θ/λ)max1)0.6570.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.110, 1.03 0.031, 0.069, 1.05
No. of reflections64856728
No. of parameters322322
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.84, 0.881.63, 1.06

Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2007), DENZO (Otwinowski & Minor, 1997), SAINT (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXS2012 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008).

Selected bond lengths (Å) for (I) top
I19—I26i3.7955 (4)I19—I26ii4.0162 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z.
Selected bond lengths (Å) for (II) top
I19—I26i3.8131 (3)I19—I26ii4.0175 (3)
Symmetry codes: (i) x1, y, z1; (ii) x, y+1, z.
 

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