Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113020209/fg3302sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020209/fg3302Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113020209/fg3302IIsup3.hkl |
CCDC references: 964758; 964759
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).
Crystal data, data collection and structure refinement details are summarized in Table 1.
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.
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.
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).
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 π–π 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.
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).
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).
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. |
[Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NO | F(000) = 1528 |
Mr = 1558.81 | Dx = 1.922 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0594 (3) Å | Cell parameters from 4946 reflections |
b = 17.1924 (3) Å | θ = 2.2–27.9° |
c = 11.4740 (2) Å | µ = 2.77 mm−1 |
β = 98.1460 (7)° | T = 110 K |
V = 2745.45 (9) Å3 | Plate, red |
Z = 2 | 0.30 × 0.25 × 0.12 mm |
Nonius KappaCCD diffractometer | 6485 independent reflections |
Radiation source: fine-focus sealed tube | 4946 reflections with I > 2σ(I) |
Detector resolution: 12.8 pixels mm-1 | Rint = 0.041 |
1° ϕ and ω scans | θmax = 27.9°, θmin = 2.2° |
Absorption correction: multi-scan (Blessing, 1995) | h = −18→18 |
Tmin = 0.491, Tmax = 0.733 | k = −22→22 |
11339 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-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 parameters | Δρmax = 1.84 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
[Sn(C44H24I4N4)(C6H4NO2)2]·1.5C3H7NO | V = 2745.45 (9) Å3 |
Mr = 1558.81 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0594 (3) Å | µ = 2.77 mm−1 |
b = 17.1924 (3) Å | T = 110 K |
c = 11.4740 (2) Å | 0.30 × 0.25 × 0.12 mm |
β = 98.1460 (7)° |
Nonius KappaCCD diffractometer | 6485 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 4946 reflections with I > 2σ(I) |
Tmin = 0.491, Tmax = 0.733 | Rint = 0.041 |
11339 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.84 e Å−3 |
6485 reflections | Δρmin = −0.88 e Å−3 |
322 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn | 0.0000 | 0.5000 | 0.0000 | 0.02279 (10) | |
C1 | 0.1882 (3) | 0.3807 (2) | 0.1151 (3) | 0.0266 (8) | |
C2 | 0.1113 (3) | 0.3454 (2) | 0.0432 (4) | 0.0264 (8) | |
C3 | −0.1067 (3) | 0.7351 (2) | −0.0065 (4) | 0.0290 (8) | |
H3 | −0.1539 | 0.7738 | −0.0294 | 0.035* | |
C4 | −0.0233 (3) | 0.7455 (2) | 0.0661 (4) | 0.0310 (9) | |
H4 | −0.0021 | 0.7927 | 0.1046 | 0.037* | |
C5 | 0.0275 (3) | 0.6733 (2) | 0.0751 (3) | 0.0269 (8) | |
C6 | 0.1197 (3) | 0.6589 (2) | 0.1399 (3) | 0.0261 (8) | |
C7 | 0.1686 (3) | 0.5878 (2) | 0.1501 (3) | 0.0253 (8) | |
C8 | 0.2597 (3) | 0.5728 (2) | 0.2198 (3) | 0.0289 (8) | |
H8 | 0.2998 | 0.6105 | 0.2629 | 0.035* | |
C9 | 0.2786 (3) | 0.4957 (2) | 0.2136 (4) | 0.0300 (9) | |
H9 | 0.3343 | 0.4697 | 0.2509 | 0.036* | |
C10 | 0.2000 (3) | 0.4609 (2) | 0.1412 (3) | 0.0256 (8) | |
N11 | 0.1341 (2) | 0.51760 (18) | 0.1017 (3) | 0.0242 (6) | |
N12 | −0.0278 (2) | 0.61913 (17) | 0.0089 (3) | 0.0243 (6) | |
C13 | 0.2640 (3) | 0.3270 (2) | 0.1748 (4) | 0.0267 (8) | |
C14 | 0.3579 (3) | 0.3288 (2) | 0.1511 (4) | 0.0339 (9) | |
H14 | 0.3754 | 0.3647 | 0.0949 | 0.041* | |
C15 | 0.4268 (3) | 0.2786 (3) | 0.2084 (4) | 0.0384 (10) | |
H15 | 0.4912 | 0.2803 | 0.1922 | 0.046* | |
C16 | 0.4000 (3) | 0.2261 (2) | 0.2897 (4) | 0.0311 (9) | |
C17 | 0.3068 (3) | 0.2232 (2) | 0.3141 (4) | 0.0329 (9) | |
H17 | 0.2896 | 0.1871 | 0.3702 | 0.039* | |
C18 | 0.2384 (3) | 0.2731 (2) | 0.2566 (4) | 0.0322 (9) | |
H18 | 0.1739 | 0.2709 | 0.2726 | 0.039* | |
I19 | 0.50357 (2) | 0.15077 (2) | 0.37978 (3) | 0.03780 (10) | |
C20 | 0.1731 (3) | 0.7283 (2) | 0.1986 (3) | 0.0265 (8) | |
C21 | 0.1447 (3) | 0.7635 (2) | 0.2967 (4) | 0.0314 (9) | |
H21 | 0.0916 | 0.7433 | 0.3298 | 0.038* | |
C22 | 0.1937 (3) | 0.8283 (2) | 0.3468 (4) | 0.0359 (10) | |
H22 | 0.1734 | 0.8529 | 0.4132 | 0.043* | |
C23 | 0.2709 (3) | 0.8564 (2) | 0.3004 (4) | 0.0327 (9) | |
C24 | 0.3012 (3) | 0.8226 (2) | 0.2035 (4) | 0.0387 (10) | |
H24 | 0.3549 | 0.8427 | 0.1715 | 0.046* | |
C25 | 0.2511 (3) | 0.7579 (2) | 0.1531 (4) | 0.0360 (10) | |
H25 | 0.2712 | 0.7339 | 0.0861 | 0.043* | |
I26 | 0.34345 (2) | 0.95691 (2) | 0.37241 (3) | 0.04500 (11) | |
O27 | −0.0681 (2) | 0.49441 (15) | 0.1482 (2) | 0.0293 (6) | |
O28 | 0.0162 (2) | 0.40739 (17) | 0.2652 (3) | 0.0457 (8) | |
C29 | −0.0442 (3) | 0.4593 (2) | 0.2475 (4) | 0.0350 (10) | |
C30 | −0.0969 (3) | 0.4890 (2) | 0.3440 (4) | 0.0378 (10) | |
C31 | −0.1468 (4) | 0.5595 (3) | 0.3346 (5) | 0.0444 (11) | |
H31 | −0.1498 | 0.5882 | 0.2635 | 0.053* | |
N32 | −0.1901 (3) | 0.5881 (2) | 0.4209 (4) | 0.0540 (11) | |
C33 | −0.1848 (4) | 0.5456 (3) | 0.5185 (5) | 0.0540 (14) | |
H33 | −0.2132 | 0.5667 | 0.5819 | 0.065* | |
C34 | −0.1421 (4) | 0.4743 (3) | 0.5359 (5) | 0.0563 (14) | |
H34 | −0.1452 | 0.4457 | 0.6061 | 0.068* | |
C35 | −0.0952 (4) | 0.4459 (3) | 0.4498 (5) | 0.0505 (13) | |
H35 | −0.0617 | 0.3978 | 0.4601 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.0225 (2) | 0.02082 (18) | 0.0242 (2) | 0.00167 (12) | 0.00014 (14) | 0.00078 (13) |
C1 | 0.0227 (19) | 0.0314 (19) | 0.026 (2) | 0.0045 (15) | 0.0047 (15) | 0.0061 (16) |
C2 | 0.024 (2) | 0.0247 (19) | 0.030 (2) | 0.0014 (14) | 0.0030 (16) | 0.0019 (15) |
C3 | 0.030 (2) | 0.0244 (18) | 0.031 (2) | 0.0030 (15) | 0.0002 (17) | −0.0010 (16) |
C4 | 0.030 (2) | 0.0249 (19) | 0.038 (2) | −0.0007 (15) | 0.0018 (18) | −0.0048 (16) |
C5 | 0.030 (2) | 0.0245 (18) | 0.027 (2) | −0.0003 (15) | 0.0060 (16) | −0.0032 (15) |
C6 | 0.027 (2) | 0.0257 (18) | 0.026 (2) | −0.0010 (14) | 0.0048 (16) | −0.0011 (15) |
C7 | 0.0222 (19) | 0.0286 (19) | 0.024 (2) | −0.0017 (14) | 0.0008 (15) | 0.0000 (15) |
C8 | 0.027 (2) | 0.034 (2) | 0.024 (2) | −0.0026 (16) | −0.0003 (16) | 0.0030 (16) |
C9 | 0.024 (2) | 0.032 (2) | 0.034 (2) | 0.0022 (15) | 0.0046 (17) | 0.0049 (16) |
C10 | 0.023 (2) | 0.0280 (19) | 0.025 (2) | 0.0014 (14) | 0.0024 (16) | 0.0057 (15) |
N11 | 0.0215 (16) | 0.0254 (15) | 0.0260 (17) | 0.0025 (12) | 0.0040 (13) | 0.0022 (13) |
N12 | 0.0246 (16) | 0.0238 (15) | 0.0234 (17) | 0.0004 (12) | −0.0009 (13) | 0.0013 (12) |
C13 | 0.025 (2) | 0.0228 (17) | 0.031 (2) | 0.0032 (14) | −0.0013 (16) | −0.0002 (15) |
C14 | 0.028 (2) | 0.033 (2) | 0.040 (3) | 0.0053 (16) | 0.0049 (19) | 0.0098 (18) |
C15 | 0.023 (2) | 0.040 (2) | 0.053 (3) | 0.0025 (17) | 0.009 (2) | 0.008 (2) |
C16 | 0.024 (2) | 0.0262 (19) | 0.041 (2) | 0.0057 (15) | −0.0009 (18) | 0.0061 (17) |
C17 | 0.032 (2) | 0.033 (2) | 0.034 (2) | 0.0021 (16) | 0.0051 (18) | 0.0089 (17) |
C18 | 0.024 (2) | 0.036 (2) | 0.037 (2) | 0.0030 (16) | 0.0060 (18) | 0.0068 (18) |
I19 | 0.02733 (16) | 0.03408 (17) | 0.0505 (2) | 0.00775 (10) | 0.00021 (13) | 0.01019 (12) |
C20 | 0.028 (2) | 0.0210 (17) | 0.029 (2) | −0.0004 (14) | −0.0016 (17) | 0.0019 (15) |
C21 | 0.030 (2) | 0.034 (2) | 0.030 (2) | −0.0006 (16) | 0.0034 (17) | −0.0022 (17) |
C22 | 0.043 (3) | 0.031 (2) | 0.033 (2) | 0.0051 (17) | 0.0012 (19) | −0.0114 (17) |
C23 | 0.032 (2) | 0.0243 (19) | 0.038 (2) | 0.0042 (15) | −0.0093 (18) | −0.0013 (16) |
C24 | 0.033 (2) | 0.035 (2) | 0.046 (3) | −0.0063 (18) | 0.000 (2) | 0.0030 (19) |
C25 | 0.030 (2) | 0.034 (2) | 0.044 (3) | −0.0036 (17) | 0.0059 (19) | −0.0066 (19) |
I26 | 0.04290 (19) | 0.02718 (16) | 0.0578 (2) | 0.00030 (11) | −0.01763 (15) | −0.00542 (12) |
O27 | 0.0298 (15) | 0.0329 (14) | 0.0250 (15) | 0.0001 (11) | 0.0034 (12) | 0.0017 (11) |
O28 | 0.050 (2) | 0.0415 (17) | 0.045 (2) | 0.0082 (15) | 0.0079 (16) | 0.0087 (15) |
C29 | 0.036 (2) | 0.032 (2) | 0.036 (3) | −0.0010 (17) | 0.0055 (19) | 0.0023 (17) |
C30 | 0.039 (3) | 0.039 (2) | 0.036 (3) | −0.0084 (18) | 0.006 (2) | −0.0023 (19) |
C31 | 0.050 (3) | 0.040 (2) | 0.043 (3) | 0.001 (2) | 0.009 (2) | −0.007 (2) |
N32 | 0.070 (3) | 0.047 (2) | 0.048 (3) | 0.001 (2) | 0.021 (2) | −0.003 (2) |
C33 | 0.068 (4) | 0.061 (3) | 0.035 (3) | −0.004 (3) | 0.018 (3) | −0.010 (2) |
C34 | 0.073 (4) | 0.060 (3) | 0.040 (3) | 0.012 (3) | 0.022 (3) | 0.009 (2) |
C35 | 0.064 (3) | 0.048 (3) | 0.041 (3) | 0.008 (2) | 0.013 (3) | 0.006 (2) |
Sn—O27i | 2.069 (3) | C15—H15 | 0.9500 |
Sn—O27 | 2.069 (3) | C16—C17 | 1.379 (6) |
Sn—N12i | 2.090 (3) | C16—I19 | 2.106 (4) |
Sn—N12 | 2.090 (3) | C17—C18 | 1.385 (5) |
Sn—N11 | 2.094 (3) | C17—H17 | 0.9500 |
Sn—N11i | 2.094 (3) | C18—H18 | 0.9500 |
C1—C2 | 1.402 (5) | C20—C25 | 1.377 (5) |
C1—C10 | 1.415 (5) | C20—C21 | 1.386 (6) |
C1—C13 | 1.501 (5) | C21—C22 | 1.391 (6) |
C2—N12i | 1.381 (5) | C21—H21 | 0.9500 |
C2—C3i | 1.445 (5) | C22—C23 | 1.362 (6) |
C3—C4 | 1.351 (6) | C22—H22 | 0.9500 |
C3—C2i | 1.445 (5) | C23—C24 | 1.376 (6) |
C3—H3 | 0.9500 | C23—I26 | 2.114 (4) |
C4—C5 | 1.429 (5) | C24—C25 | 1.397 (6) |
C4—H4 | 0.9500 | C24—H24 | 0.9500 |
C5—N12 | 1.371 (5) | C25—H25 | 0.9500 |
C5—C6 | 1.422 (6) | O27—C29 | 1.291 (5) |
C6—C7 | 1.399 (5) | O28—C29 | 1.229 (5) |
C6—C20 | 1.516 (5) | C29—C30 | 1.506 (6) |
C7—N11 | 1.387 (5) | C30—C31 | 1.397 (6) |
C7—C8 | 1.433 (5) | C30—C35 | 1.420 (7) |
C8—C9 | 1.357 (6) | C31—N32 | 1.328 (6) |
C8—H8 | 0.9500 | C31—H31 | 0.9500 |
C9—C10 | 1.416 (6) | N32—C33 | 1.330 (7) |
C9—H9 | 0.9500 | C33—C34 | 1.366 (8) |
C10—N11 | 1.377 (5) | C33—H33 | 0.9500 |
N12—C2i | 1.381 (5) | C34—C35 | 1.354 (7) |
C13—C14 | 1.385 (6) | C34—H34 | 0.9500 |
C13—C18 | 1.401 (5) | C35—H35 | 0.9500 |
C14—C15 | 1.391 (6) | I19—I26ii | 3.7955 (4) |
C14—H14 | 0.9500 | I19—I26iii | 4.0162 (4) |
C15—C16 | 1.388 (6) | ||
O27i—Sn—O27 | 180.0 | C13—C14—C15 | 120.8 (4) |
O27i—Sn—N12i | 83.90 (11) | C13—C14—H14 | 119.6 |
O27—Sn—N12i | 96.10 (11) | C15—C14—H14 | 119.6 |
O27i—Sn—N12 | 96.10 (11) | C16—C15—C14 | 119.0 (4) |
O27—Sn—N12 | 83.90 (11) | C16—C15—H15 | 120.5 |
N12i—Sn—N12 | 180.0 | C14—C15—H15 | 120.5 |
O27i—Sn—N11 | 88.05 (11) | C17—C16—C15 | 121.0 (4) |
O27—Sn—N11 | 91.95 (11) | C17—C16—I19 | 119.3 (3) |
N12i—Sn—N11 | 90.51 (12) | C15—C16—I19 | 119.7 (3) |
N12—Sn—N11 | 89.49 (12) | C16—C17—C18 | 119.8 (4) |
O27i—Sn—N11i | 91.95 (11) | C16—C17—H17 | 120.1 |
O27—Sn—N11i | 88.05 (11) | C18—C17—H17 | 120.1 |
N12i—Sn—N11i | 89.49 (12) | C17—C18—C13 | 120.1 (4) |
N12—Sn—N11i | 90.51 (12) | C17—C18—H18 | 120.0 |
N11—Sn—N11i | 180.0 | C13—C18—H18 | 120.0 |
C2—C1—C10 | 127.2 (3) | C25—C20—C21 | 118.8 (4) |
C2—C1—C13 | 116.1 (3) | C25—C20—C6 | 119.6 (4) |
C10—C1—C13 | 116.7 (3) | C21—C20—C6 | 121.6 (3) |
N12i—C2—C1 | 126.9 (3) | C22—C21—C20 | 120.2 (4) |
N12i—C2—C3i | 107.2 (3) | C22—C21—H21 | 119.9 |
C1—C2—C3i | 125.8 (3) | C20—C21—H21 | 119.9 |
C4—C3—C2i | 107.8 (3) | C23—C22—C21 | 119.9 (4) |
C4—C3—H3 | 126.1 | C23—C22—H22 | 120.1 |
C2i—C3—H3 | 126.1 | C21—C22—H22 | 120.1 |
C3—C4—C5 | 108.0 (3) | C22—C23—C24 | 121.4 (4) |
C3—C4—H4 | 126.0 | C22—C23—I26 | 120.3 (3) |
C5—C4—H4 | 126.0 | C24—C23—I26 | 118.3 (3) |
N12—C5—C6 | 125.1 (3) | C23—C24—C25 | 118.3 (4) |
N12—C5—C4 | 108.2 (3) | C23—C24—H24 | 120.8 |
C6—C5—C4 | 126.7 (3) | C25—C24—H24 | 120.8 |
C7—C6—C5 | 126.6 (3) | C20—C25—C24 | 121.4 (4) |
C7—C6—C20 | 116.4 (3) | C20—C25—H25 | 119.3 |
C5—C6—C20 | 116.9 (3) | C24—C25—H25 | 119.3 |
N11—C7—C6 | 125.9 (3) | C29—O27—Sn | 130.8 (3) |
N11—C7—C8 | 107.6 (3) | O28—C29—O27 | 125.0 (4) |
C6—C7—C8 | 126.3 (4) | O28—C29—C30 | 121.6 (4) |
C9—C8—C7 | 108.2 (4) | O27—C29—C30 | 113.4 (4) |
C9—C8—H8 | 125.9 | C31—C30—C35 | 117.8 (4) |
C7—C8—H8 | 125.9 | C31—C30—C29 | 122.0 (4) |
C8—C9—C10 | 107.5 (4) | C35—C30—C29 | 120.2 (4) |
C8—C9—H9 | 126.2 | N32—C31—C30 | 122.8 (5) |
C10—C9—H9 | 126.2 | N32—C31—H31 | 118.6 |
N11—C10—C1 | 124.5 (4) | C30—C31—H31 | 118.6 |
N11—C10—C9 | 109.1 (3) | C31—N32—C33 | 116.6 (5) |
C1—C10—C9 | 126.4 (4) | N32—C33—C34 | 125.9 (5) |
C10—N11—C7 | 107.6 (3) | N32—C33—H33 | 117.0 |
C10—N11—Sn | 126.3 (3) | C34—C33—H33 | 117.0 |
C7—N11—Sn | 125.8 (2) | C35—C34—C33 | 117.8 (5) |
C5—N12—C2i | 108.7 (3) | C35—C34—H34 | 121.1 |
C5—N12—Sn | 126.7 (3) | C33—C34—H34 | 121.1 |
C2i—N12—Sn | 124.4 (2) | C34—C35—C30 | 119.0 (5) |
C14—C13—C18 | 119.3 (3) | C34—C35—H35 | 120.5 |
C14—C13—C1 | 122.1 (3) | C30—C35—H35 | 120.5 |
C18—C13—C1 | 118.6 (3) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z. |
[Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NO | F(000) = 1528 |
Mr = 1590.79 | Dx = 1.948 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0712 (2) Å | Cell parameters from 5509 reflections |
b = 17.2283 (3) Å | θ = 1.9–28.4° |
c = 11.3198 (2) Å | µ = 2.81 mm−1 |
β = 98.742 (1)° | T = 110 K |
V = 2712.30 (8) Å3 | Prism, red |
Z = 2 | 0.20 × 0.15 × 0.15 mm |
Bruker APEX DUO diffractometer | 6728 independent reflections |
Radiation source: Iµ micro-focus | 5505 reflections with I > 2σ(I) |
Detector resolution: 1.75 pixels mm-1 | Rint = 0.030 |
0.5° ϕ and ω scans | θmax = 28.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −18→18 |
Tmin = 0.604, Tmax = 0.679 | k = −18→23 |
25067 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-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 parameters | Δρmax = 1.63 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
[Sn(C44H24I4N4)(C5H3N2O2)2]·1.5C3H7NO | V = 2712.30 (8) Å3 |
Mr = 1590.79 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0712 (2) Å | µ = 2.81 mm−1 |
b = 17.2283 (3) Å | T = 110 K |
c = 11.3198 (2) Å | 0.20 × 0.15 × 0.15 mm |
β = 98.742 (1)° |
Bruker APEX DUO diffractometer | 6728 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 5505 reflections with I > 2σ(I) |
Tmin = 0.604, Tmax = 0.679 | Rint = 0.030 |
25067 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.63 e Å−3 |
6728 reflections | Δρmin = −1.06 e Å−3 |
322 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn | 0.0000 | 0.0000 | 0.0000 | 0.01209 (7) | |
C1 | −0.19062 (18) | 0.11819 (18) | −0.1126 (2) | 0.0153 (6) | |
C2 | 0.11298 (19) | −0.15403 (18) | 0.0393 (2) | 0.0156 (6) | |
C3 | 0.1091 (2) | −0.23296 (18) | 0.0010 (3) | 0.0188 (6) | |
H3 | 0.1570 | −0.2712 | 0.0233 | 0.023* | |
C4 | 0.02515 (19) | −0.24379 (19) | −0.0726 (3) | 0.0189 (6) | |
H4 | 0.0040 | −0.2908 | −0.1120 | 0.023* | |
C5 | −0.02616 (19) | −0.17174 (18) | −0.0806 (2) | 0.0159 (6) | |
C6 | −0.11889 (19) | −0.15795 (18) | −0.1451 (2) | 0.0148 (6) | |
C7 | −0.16746 (19) | −0.08728 (18) | −0.1553 (2) | 0.0145 (6) | |
C8 | −0.26036 (19) | −0.07250 (19) | −0.2256 (3) | 0.0185 (6) | |
H8 | −0.3004 | −0.1100 | −0.2702 | 0.022* | |
C9 | −0.28004 (19) | 0.00302 (18) | −0.2170 (3) | 0.0179 (6) | |
H9 | −0.3366 | 0.0284 | −0.2544 | 0.021* | |
C10 | −0.20100 (18) | 0.03927 (18) | −0.1414 (2) | 0.0150 (6) | |
N11 | −0.13426 (15) | −0.01800 (14) | −0.1039 (2) | 0.0137 (5) | |
N12 | 0.02914 (15) | −0.11796 (15) | −0.0120 (2) | 0.0149 (5) | |
C13 | −0.26645 (19) | 0.17238 (18) | −0.1725 (2) | 0.0163 (6) | |
C14 | −0.24235 (19) | 0.2265 (2) | −0.2534 (3) | 0.0228 (7) | |
H14 | −0.1782 | 0.2284 | −0.2700 | 0.027* | |
C15 | −0.3101 (2) | 0.2779 (2) | −0.3107 (3) | 0.0249 (7) | |
H15 | −0.2928 | 0.3149 | −0.3659 | 0.030* | |
C16 | −0.40267 (19) | 0.27422 (19) | −0.2860 (3) | 0.0213 (7) | |
C17 | −0.4292 (2) | 0.2207 (2) | −0.2052 (3) | 0.0251 (7) | |
H17 | −0.4933 | 0.2192 | −0.1884 | 0.030* | |
C18 | −0.3608 (2) | 0.16939 (19) | −0.1496 (3) | 0.0216 (7) | |
H18 | −0.3785 | 0.1319 | −0.0953 | 0.026* | |
I19 | −0.50609 (2) | 0.35059 (2) | −0.37523 (2) | 0.02806 (7) | |
C20 | −0.17169 (19) | −0.22700 (18) | −0.2036 (3) | 0.0173 (6) | |
C21 | −0.1449 (2) | −0.2629 (2) | −0.3023 (3) | 0.0228 (7) | |
H21 | −0.0925 | −0.2429 | −0.3367 | 0.027* | |
C22 | −0.1937 (2) | −0.3281 (2) | −0.3521 (3) | 0.0245 (7) | |
H22 | −0.1749 | −0.3524 | −0.4203 | 0.029* | |
C23 | −0.2701 (2) | −0.35737 (19) | −0.3016 (3) | 0.0230 (7) | |
C24 | −0.2982 (2) | −0.3225 (2) | −0.2042 (3) | 0.0274 (8) | |
H24 | −0.3510 | −0.3425 | −0.1705 | 0.033* | |
C25 | −0.2488 (2) | −0.2571 (2) | −0.1549 (3) | 0.0262 (7) | |
H25 | −0.2681 | −0.2329 | −0.0871 | 0.031* | |
I26 | −0.34061 (2) | −0.45907 (2) | −0.37056 (2) | 0.03287 (7) | |
O27 | −0.06651 (13) | −0.00730 (13) | 0.15244 (17) | 0.0199 (5) | |
O28 | 0.01780 (15) | −0.09563 (14) | 0.26804 (19) | 0.0262 (5) | |
C29 | −0.0413 (2) | −0.04314 (19) | 0.2497 (3) | 0.0208 (7) | |
C30 | −0.0926 (2) | −0.01485 (19) | 0.3491 (3) | 0.0219 (7) | |
C31 | −0.0973 (3) | −0.0590 (2) | 0.4513 (3) | 0.0319 (8) | |
H31 | −0.0686 | −0.1090 | 0.4569 | 0.038* | |
N32 | −0.1399 (2) | −0.03431 (19) | 0.5411 (3) | 0.0382 (8) | |
C33 | −0.1763 (3) | 0.0372 (2) | 0.5281 (3) | 0.0344 (9) | |
H33 | −0.2043 | 0.0567 | 0.5934 | 0.041* | |
N34 | −0.1782 (2) | 0.08464 (19) | 0.4354 (3) | 0.0349 (7) | |
C35 | −0.1365 (2) | 0.0583 (2) | 0.3455 (3) | 0.0283 (8) | |
H35 | −0.1364 | 0.0899 | 0.2768 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.01272 (12) | 0.01133 (16) | 0.01224 (12) | 0.00200 (10) | 0.00197 (9) | 0.00042 (10) |
C1 | 0.0141 (12) | 0.0187 (18) | 0.0139 (13) | 0.0019 (11) | 0.0047 (10) | 0.0022 (12) |
C2 | 0.0183 (13) | 0.0143 (17) | 0.0148 (13) | 0.0044 (11) | 0.0044 (10) | 0.0030 (12) |
C3 | 0.0206 (14) | 0.0139 (17) | 0.0213 (15) | 0.0055 (11) | 0.0020 (11) | 0.0022 (12) |
C4 | 0.0199 (14) | 0.0156 (18) | 0.0209 (14) | 0.0001 (11) | 0.0027 (11) | −0.0008 (12) |
C5 | 0.0184 (13) | 0.0150 (17) | 0.0152 (13) | 0.0016 (11) | 0.0054 (10) | 0.0003 (12) |
C6 | 0.0190 (13) | 0.0141 (17) | 0.0117 (13) | −0.0010 (11) | 0.0041 (10) | −0.0011 (11) |
C7 | 0.0174 (13) | 0.0148 (17) | 0.0119 (12) | −0.0018 (11) | 0.0045 (10) | 0.0023 (11) |
C8 | 0.0144 (13) | 0.0218 (19) | 0.0188 (14) | 0.0003 (11) | 0.0011 (11) | 0.0003 (13) |
C9 | 0.0138 (13) | 0.0196 (19) | 0.0199 (14) | 0.0010 (11) | 0.0010 (11) | 0.0011 (12) |
C10 | 0.0137 (12) | 0.0151 (17) | 0.0167 (14) | 0.0011 (11) | 0.0037 (10) | 0.0028 (12) |
N11 | 0.0144 (11) | 0.0106 (14) | 0.0160 (11) | 0.0014 (9) | 0.0025 (9) | 0.0021 (10) |
N12 | 0.0160 (11) | 0.0125 (14) | 0.0161 (12) | 0.0019 (9) | 0.0024 (9) | −0.0005 (10) |
C13 | 0.0168 (13) | 0.0159 (18) | 0.0157 (13) | 0.0029 (11) | 0.0013 (10) | 0.0005 (12) |
C14 | 0.0117 (13) | 0.034 (2) | 0.0229 (15) | 0.0037 (12) | 0.0044 (11) | 0.0058 (14) |
C15 | 0.0175 (14) | 0.028 (2) | 0.0291 (17) | 0.0030 (12) | 0.0038 (12) | 0.0099 (15) |
C16 | 0.0166 (13) | 0.0205 (19) | 0.0256 (16) | 0.0069 (12) | −0.0012 (11) | 0.0035 (13) |
C17 | 0.0129 (13) | 0.029 (2) | 0.0346 (18) | 0.0044 (12) | 0.0070 (12) | 0.0058 (15) |
C18 | 0.0180 (14) | 0.0189 (19) | 0.0283 (16) | 0.0036 (12) | 0.0047 (12) | 0.0070 (13) |
I19 | 0.01761 (10) | 0.02708 (14) | 0.03879 (13) | 0.00826 (8) | 0.00198 (8) | 0.01082 (10) |
C20 | 0.0170 (13) | 0.0149 (17) | 0.0194 (14) | 0.0025 (11) | 0.0007 (11) | −0.0006 (12) |
C21 | 0.0245 (15) | 0.026 (2) | 0.0183 (15) | −0.0007 (13) | 0.0045 (12) | 0.0028 (13) |
C22 | 0.0318 (16) | 0.021 (2) | 0.0188 (15) | 0.0016 (13) | −0.0006 (12) | −0.0048 (13) |
C23 | 0.0211 (14) | 0.0177 (19) | 0.0261 (16) | 0.0036 (12) | −0.0096 (12) | −0.0034 (13) |
C24 | 0.0211 (15) | 0.028 (2) | 0.0342 (18) | −0.0049 (13) | 0.0065 (13) | −0.0022 (15) |
C25 | 0.0244 (15) | 0.026 (2) | 0.0294 (17) | −0.0025 (13) | 0.0078 (13) | −0.0101 (14) |
I26 | 0.03110 (12) | 0.01852 (14) | 0.04232 (14) | 0.00022 (9) | −0.01585 (9) | −0.00524 (10) |
O27 | 0.0183 (10) | 0.0257 (14) | 0.0166 (10) | 0.0003 (8) | 0.0056 (8) | −0.0015 (9) |
O28 | 0.0287 (11) | 0.0243 (14) | 0.0261 (12) | 0.0042 (10) | 0.0053 (9) | 0.0044 (10) |
C29 | 0.0179 (14) | 0.0149 (18) | 0.0297 (17) | −0.0053 (12) | 0.0041 (12) | −0.0002 (13) |
C30 | 0.0244 (15) | 0.0199 (19) | 0.0219 (15) | −0.0045 (12) | 0.0048 (12) | 0.0002 (13) |
C31 | 0.045 (2) | 0.027 (2) | 0.0246 (17) | 0.0015 (16) | 0.0088 (15) | 0.0020 (15) |
N32 | 0.0543 (19) | 0.033 (2) | 0.0324 (17) | 0.0018 (15) | 0.0226 (14) | 0.0057 (14) |
C33 | 0.044 (2) | 0.036 (3) | 0.0279 (18) | −0.0037 (17) | 0.0184 (15) | −0.0078 (16) |
N34 | 0.0458 (17) | 0.030 (2) | 0.0311 (16) | −0.0011 (14) | 0.0142 (13) | −0.0042 (14) |
C35 | 0.0337 (17) | 0.031 (2) | 0.0219 (16) | 0.0042 (14) | 0.0089 (13) | 0.0043 (14) |
Sn—N12i | 2.082 (3) | C15—H15 | 0.9500 |
Sn—N12 | 2.082 (3) | C16—C17 | 1.390 (4) |
Sn—O27i | 2.0881 (19) | C16—I19 | 2.103 (3) |
Sn—O27 | 2.0881 (19) | C17—C18 | 1.385 (4) |
Sn—N11i | 2.091 (2) | C17—H17 | 0.9500 |
Sn—N11 | 2.091 (2) | C18—H18 | 0.9500 |
C1—C10 | 1.401 (4) | C20—C21 | 1.379 (4) |
C1—C2i | 1.410 (4) | C20—C25 | 1.390 (4) |
C1—C13 | 1.500 (4) | C21—C22 | 1.390 (4) |
C2—N12 | 1.381 (3) | C21—H21 | 0.9500 |
C2—C1i | 1.410 (4) | C22—C23 | 1.386 (5) |
C2—C3 | 1.426 (4) | C22—H22 | 0.9500 |
C3—C4 | 1.351 (4) | C23—C24 | 1.366 (5) |
C3—H3 | 0.9500 | C23—I26 | 2.104 (3) |
C4—C5 | 1.432 (4) | C24—C25 | 1.394 (4) |
C4—H4 | 0.9500 | C24—H24 | 0.9500 |
C5—N12 | 1.373 (4) | C25—H25 | 0.9500 |
C5—C6 | 1.415 (4) | O27—C29 | 1.265 (4) |
C6—C7 | 1.392 (4) | O28—C29 | 1.225 (4) |
C6—C20 | 1.502 (4) | C29—C30 | 1.507 (4) |
C7—N11 | 1.378 (4) | C30—C31 | 1.394 (5) |
C7—C8 | 1.446 (4) | C30—C35 | 1.401 (5) |
C8—C9 | 1.337 (4) | C31—N32 | 1.327 (4) |
C8—H8 | 0.9500 | C31—H31 | 0.9500 |
C9—C10 | 1.439 (4) | N32—C33 | 1.334 (5) |
C9—H9 | 0.9500 | C33—N34 | 1.327 (5) |
C10—N11 | 1.384 (3) | C33—H33 | 0.9500 |
C13—C14 | 1.384 (4) | N34—C35 | 1.330 (4) |
C13—C18 | 1.392 (4) | C35—H35 | 0.9500 |
C14—C15 | 1.388 (4) | I19—I26ii | 3.8131 (3) |
C14—H14 | 0.9500 | I19—I26iii | 4.0175 (3) |
C15—C16 | 1.375 (4) | ||
N12i—Sn—N12 | 180.00 (16) | C18—C13—C1 | 121.7 (3) |
N12i—Sn—O27i | 96.45 (9) | C13—C14—C15 | 121.3 (3) |
N12—Sn—O27i | 83.55 (9) | C13—C14—H14 | 119.4 |
N12i—Sn—O27 | 83.55 (9) | C15—C14—H14 | 119.4 |
N12—Sn—O27 | 96.45 (9) | C16—C15—C14 | 118.7 (3) |
O27i—Sn—O27 | 180.00 (15) | C16—C15—H15 | 120.7 |
N12i—Sn—N11i | 89.35 (9) | C14—C15—H15 | 120.7 |
N12—Sn—N11i | 90.65 (9) | C15—C16—C17 | 121.5 (3) |
O27i—Sn—N11i | 88.61 (8) | C15—C16—I19 | 118.8 (2) |
O27—Sn—N11i | 91.39 (8) | C17—C16—I19 | 119.7 (2) |
N12i—Sn—N11 | 90.65 (9) | C18—C17—C16 | 119.0 (3) |
N12—Sn—N11 | 89.35 (9) | C18—C17—H17 | 120.5 |
O27i—Sn—N11 | 91.39 (8) | C16—C17—H17 | 120.5 |
O27—Sn—N11 | 88.61 (8) | C17—C18—C13 | 120.5 (3) |
N11i—Sn—N11 | 180.0 (2) | C17—C18—H18 | 119.7 |
C10—C1—C2i | 127.3 (3) | C13—C18—H18 | 119.7 |
C10—C1—C13 | 117.2 (2) | C21—C20—C25 | 118.6 (3) |
C2i—C1—C13 | 115.3 (3) | C21—C20—C6 | 122.4 (3) |
N12—C2—C1i | 125.9 (3) | C25—C20—C6 | 119.0 (3) |
N12—C2—C3 | 108.1 (2) | C20—C21—C22 | 120.8 (3) |
C1i—C2—C3 | 126.0 (3) | C20—C21—H21 | 119.6 |
C4—C3—C2 | 108.0 (3) | C22—C21—H21 | 119.6 |
C4—C3—H3 | 126.0 | C23—C22—C21 | 119.5 (3) |
C2—C3—H3 | 126.0 | C23—C22—H22 | 120.3 |
C3—C4—C5 | 107.7 (3) | C21—C22—H22 | 120.3 |
C3—C4—H4 | 126.1 | C24—C23—C22 | 120.7 (3) |
C5—C4—H4 | 126.1 | C24—C23—I26 | 119.2 (2) |
N12—C5—C6 | 125.3 (3) | C22—C23—I26 | 120.1 (2) |
N12—C5—C4 | 108.2 (2) | C23—C24—C25 | 119.3 (3) |
C6—C5—C4 | 126.5 (3) | C23—C24—H24 | 120.3 |
C7—C6—C5 | 126.3 (3) | C25—C24—H24 | 120.3 |
C7—C6—C20 | 116.9 (2) | C20—C25—C24 | 121.0 (3) |
C5—C6—C20 | 116.8 (3) | C20—C25—H25 | 119.5 |
N11—C7—C6 | 126.3 (2) | C24—C25—H25 | 119.5 |
N11—C7—C8 | 107.5 (3) | C29—O27—Sn | 130.33 (19) |
C6—C7—C8 | 126.2 (3) | O28—C29—O27 | 126.9 (3) |
C9—C8—C7 | 108.1 (3) | O28—C29—C30 | 120.1 (3) |
C9—C8—H8 | 125.9 | O27—C29—C30 | 112.9 (3) |
C7—C8—H8 | 125.9 | C31—C30—C35 | 116.0 (3) |
C8—C9—C10 | 108.4 (2) | C31—C30—C29 | 122.1 (3) |
C8—C9—H9 | 125.8 | C35—C30—C29 | 121.9 (3) |
C10—C9—H9 | 125.8 | N32—C31—C30 | 123.0 (3) |
N11—C10—C1 | 125.4 (2) | N32—C31—H31 | 118.5 |
N11—C10—C9 | 107.5 (3) | C30—C31—H31 | 118.5 |
C1—C10—C9 | 127.1 (3) | C31—N32—C33 | 114.9 (3) |
C7—N11—C10 | 108.5 (2) | N34—C33—N32 | 128.1 (3) |
C7—N11—Sn | 125.82 (18) | N34—C33—H33 | 115.9 |
C10—N11—Sn | 125.44 (19) | N32—C33—H33 | 115.9 |
C5—N12—C2 | 108.0 (2) | C33—N34—C35 | 115.9 (3) |
C5—N12—Sn | 126.55 (18) | N34—C35—C30 | 121.9 (3) |
C2—N12—Sn | 125.19 (19) | N34—C35—H35 | 119.0 |
C14—C13—C18 | 119.0 (3) | C30—C35—H35 | 119.0 |
C14—C13—C1 | 119.3 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1, −y, −z−1; (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 |
Mr | 1558.81 | 1590.79 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 110 | 110 |
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) |
V (Å3) | 2745.45 (9) | 2712.30 (8) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.77 | 2.81 |
Crystal size (mm) | 0.30 × 0.25 × 0.12 | 0.20 × 0.15 × 0.15 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Bruker APEX DUO diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.491, 0.733 | 0.604, 0.679 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11339, 6485, 4946 | 25067, 6728, 5505 |
Rint | 0.041 | 0.030 |
(sin θ/λ)max (Å−1) | 0.657 | 0.669 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.110, 1.03 | 0.031, 0.069, 1.05 |
No. of reflections | 6485 | 6728 |
No. of parameters | 322 | 322 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.84, −0.88 | 1.63, −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).
I19—I26i | 3.7955 (4) | I19—I26ii | 4.0162 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z. |
I19—I26i | 3.8131 (3) | I19—I26ii | 4.0175 (3) |
Symmetry codes: (i) −x−1, −y, −z−1; (ii) x, y+1, z. |
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