5,10,15,20-Tetra­kis(1-methyl­pyridinium-4-yl)porphyrin tetra­iodide tetra­hydrate

Lourenço, L.M.O.; Fernandes, J.A.; Neves, M.G.P.M.S.; Cavaleiro, J.A.S.; Tomé, J.P.C.; Almeida Paz, F.A.

doi:10.1107/S1600536811043844

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages o3157-o3158

https://doi.org/10.1107/S1600536811043844

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5,10,15,20-Tetrakis(1-methylpyridinium-4-yl)porphyrin tetraiodide tetrahydrate

Leandro M. O. Lourenço,^a José A. Fernandes,^b Maria G. P. M. S. Neves,^a José A. S. Cavaleiro,^a João P. C. Tomé ^a and Filipe A. Almeida Paz ^b ^*

^aDepartment of Chemistry, University of Aveiro, QOPNA, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 19 October 2011; accepted 21 October 2011; online 2 November 2011)

The asymmetric unit of the title compound, C₄₄H₃₈N₈²⁺·4I⁻·4H₂O, comprises two halves of non-equivalent cations of 5,10,15,20-tetrakis(1-methylpyridinium)porphyrin (with the full molecule of each completed by the application of inversion symmetry), four charge balancing iodide anions and four water molecules of crystallization (two water molecules are fully occupied and four molecules have a site occupancy of 50%). The porphyrin cations are arranged into supramolecular columns parallel to the b axis, mediated by π–π [centroid–centroid distance = 3.762 (4) Å] and C—H⋯π supramolecular interactions [C⋯centroid distance = 3.522 (7) Å, C—H⋯centroid = 128°], leading to the formation of columns parallel to the b axis. The close packing leads to the presence of a one-dimensional channel filled with partially occupied water molecules engaged in O—H⋯O and O—H⋯I hydrogen bonds

Related literature

For general background on the search for alternative treatments for microbial infections, see: Gomes et al. (2011 ); Alves et al. (2008 ); Carvalho et al. (2009 ). For the use of porphyrins as photosensitizers, see: Alves et al. (2009 ); Banfi et al. (2006 ); Merchat et al. (1996 ); Tomé et al. (2004 ); Yu et al. (2009 ). For general background on the work carried out by our group, see: Paz et al. (2002 ); Paz & Klinowski (2003 ); Shi et al. (2008 ).

Experimental

Crystal data

C₄₄H₃₈N₈²⁺·4I⁻·4H₂O
M_r = 1258.49
Monoclinic, P 2₁ /n
a = 24.3331 (4) Å
b = 6.5209 (1) Å
c = 30.5663 (5) Å
β = 95.025 (1)°
V = 4831.43 (13) Å³
Z = 4
Cu Kα radiation
μ = 20.65 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.08 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.104, T_max = 0.289
47661 measured reflections
7346 independent reflections
7013 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.110
S = 1.09
7346 reflections
563 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 2.73 e Å⁻³
Δρ_min = −2.79 e Å⁻³

Table 1
Selected interatomic distances (Å)

O2W⋯O4Wⁱ	2.781 (15)
O2W⋯O6Wⁱⁱ	2.793 (15)
O3W⋯O5Wⁱⁱ	2.730 (19)
O3W⋯O6W	2.56 (2)
O4W⋯O5W	2.721 (19)
O5W⋯O6Wⁱⁱ	2.73 (2)
O1W⋯I2ⁱⁱⁱ	3.565 (5)
O1W⋯I3ⁱⁱⁱ	3.594 (5)
O2W⋯I3	3.684 (9)
O6W⋯I4^iv	3.299 (18)
C13⋯I1	3.691 (6)
C14⋯I2^iv	3.760 (6)
C44⋯I2	3.844 (7)
C22⋯I3ⁱ	3.882 (7)
C36⋯I4^v	3.566 (5)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2005 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811043844/tk5003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811043844/tk5003Isup2.hkl

checkCIF report

Comment top

With the increasing number of antibiotic-resistant strains of microorganisms it is imperative to find alternative treatments for microbial infections (Alves et al., 2008). Photodynamic therapy is a promising non-antibiotic approach to photoinactivate antibiotic-multi-resistant pathogenic microorganisms. The photodynamic destruction of microorganisms is based on the ability of certain photosensitizers, when activated by light, generate reactive oxygen species that are able to destroy or affect bacterial membranes (Carvalho et al., 2009). For example, studies using cationic meso-substituted porphyrins acting as photosensitizers revealed interesting results in the destruction of Gram-positive and Gram-negative bacteria (Alves et al., 2009; Banfi et al., 2006; Merchat et al., 1996). The compound 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin (Gomes et al., 2011) is one of the most used photosensitizers in the photo-inactivation studies of microorganisms. Results have shown that the cationic conjugates are able to efficiently photosensitize different types of microorganisms (Gomes et al., 2011; Tomé et al., 2004; Alves et al., 2008; Yu et al., 2009). Following our on-going interest on organic crystals (Paz et al., 2002; Paz & Klinowski, 2003) and in water clusters confined in organic/hybrid matrices (Shi et al., 2008), here we wish to describe the crystal structure of the title compound.

The asymmetric unit (Fig. 1) of the title compound, (C₄₄H₃₈N₈)I₄^.4H₂O, comprises two distinct halves of centrosymmetric tetracationic porphyrin molecules, whose charge is balanced by four iodide anions, plus four water molecules of crystallization. The porphyrin rings are planar (with deviations from planarity smaller than ca 0.16 Å) subtending angles with the substituent pyridinium rings which range from ca 56 to ca 68°. The crystal structure is rich in weak supramolecular interactions such as π–π stacking and C—H···π interactions: there are two π–π stacking interactions between adjacent pyrrole rings [Cg···Cg distances of 3.762 (4) and 4.108 (4) Å], and there is a single C35—H35···π interaction [C···Cg of 3.522 (7) Å] between a hydrogen from the pyridinium ring and a pyrrole ring (interactions not shown). These supramolecular interactions contribute to the formation of columns of porphyrin molecules which are parallel to the b axis as depicted in Fig. 2. These columnar arrangements close pack in the ac plane leading to the formation of one-dimensional channels which, due to the need of close proximity of the iodide anions with the pyridinium rings, are instead filled with disordered water molecules of crystallization engaged in hydrogen bonding interactions (Table 1 and Figs 2 and 3). We note that a sole water molecule (O1W) is located between two iodide anions (I2 and I3) and outside the aforementioned channel, deeply embedded into the hydrophobic portion of the crystal structure. The remaining three water molecules are distributed among five independent crystallographic sites which may be involved in several O—H···O hydrogen bonding interactions as depicted in Fig. 3 (see Table 1 for geometric details). It is also interesting to note that only one iodide anion (I1) is not close to water molecules, participating instead in several short contacts with the porphyrin cations, among which a C—H···I^- weak hydrogen interaction (d_D···A = 3.691 (6) Å) arises as the strongest and more directional one (green dashed lines in Fig. 2). I2 to I4 are also involved in such type of interactions (not shown) as summarized in Table 1.

Related literature top

For general background on the search for alternative treatments for microbial infections, see: Gomes et al. (2011); Alves et al. (2008); Carvalho et al. (2009). For the use of porphyrins as photosensitizers, see: Alves et al. (2009); Banfi et al. (2006); Merchat et al. (1996); Tomé et al. (2004); Yu et al. (2009). For general background on the work carried out by our group, see: Paz et al. (2002); Paz & Klinowski (2003); Shi et al. (2008).

Experimental top

Crystals of the title compound have been isolated using the synthetic procedure described in detail by Gomes et al. (2011).

Structure description top

For general background on the search for alternative treatments for microbial infections, see: Gomes et al. (2011); Alves et al. (2008); Carvalho et al. (2009). For the use of porphyrins as photosensitizers, see: Alves et al. (2009); Banfi et al. (2006); Merchat et al. (1996); Tomé et al. (2004); Yu et al. (2009). For general background on the work carried out by our group, see: Paz et al. (2002); Paz & Klinowski (2003); Shi et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular units comprising the asymmetric unit of the title compound. The porphyrin molecules have been completed (through inversion symmetry) for clarity. Displacement ellipsoids are drawn at the 50% probability level and the atomic labeling is provided for all non-hydrogen atoms comprising the asymmetric unit. Hydrogen atoms are represented as small spheres with arbitrary radius.
	Fig. 2. Crystal packing of the title compound viewed in perspective along the [010] direction of the unit cell. Hydrogen bonds involving only water molecules are depicted as dashed bright green lines and those involving water molecules and iodide anions are depicted as dashed pink lines. The C—H···I^- weak hydrogen bond is depicted as a dashed green line.
	Fig. 3. Portion of the hydrogen bonded zigzag chain involving iodide anions and water molecules of crystallization present in the crystal structure of the title compound. For clarity, the site occupancy of each water molecule is represented next to the label, and the symmetry codes used to generate equivalent atoms are omitted. For geometric details on the represented supramolecular interactions see Table 1.

5,10,15,20-Tetrakis(1-methylpyridinium-4-yl)porphyrin tetraiodide tetrahydrate top

Crystal data top

C₄₄H₃₈N₈²⁺·4I⁻·4H₂O	F(000) = 2440
M_r = 1258.49	D_x = 1.730 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 8573 reflections
a = 24.3331 (4) Å	θ = 3.7–62.2°
b = 6.5209 (1) Å	µ = 20.65 mm⁻¹
c = 30.5663 (5) Å	T = 100 K
β = 95.025 (1)°	Block, brown
V = 4831.43 (13) Å³	0.20 × 0.15 × 0.08 mm
Z = 4

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	7346 independent reflections
Radiation source: fine-focus sealed tube	7013 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω and φ scans	θ_max = 62.7°, θ_min = 7.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −27→27
T_min = 0.104, T_max = 0.289	k = −7→7
47661 measured reflections	l = −22→34

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0481P)² + 42.1978P] where P = (F_o² + 2F_c²)/3
7346 reflections	(Δ/σ)_max = 0.001
563 parameters	Δρ_max = 2.73 e Å⁻³
6 restraints	Δρ_min = −2.79 e Å⁻³

Crystal data top

C₄₄H₃₈N₈²⁺·4I⁻·4H₂O	V = 4831.43 (13) Å³
M_r = 1258.49	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 24.3331 (4) Å	µ = 20.65 mm⁻¹
b = 6.5209 (1) Å	T = 100 K
c = 30.5663 (5) Å	0.20 × 0.15 × 0.08 mm
β = 95.025 (1)°

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	7346 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	7013 reflections with I > 2σ(I)
T_min = 0.104, T_max = 0.289	R_int = 0.039
47661 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	6 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0481P)² + 42.1978P] where P = (F_o² + 2F_c²)/3
7346 reflections	Δρ_max = 2.73 e Å⁻³
563 parameters	Δρ_min = −2.79 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.46552 (19)	0.1385 (8)	0.05010 (16)	0.0156 (11)
N2	0.43689 (19)	−0.2216 (8)	−0.00352 (16)	0.0161 (11)
H2	0.4640	−0.1320	−0.0009	0.019*
N3	0.24687 (19)	−0.1678 (8)	0.12933 (15)	0.0145 (11)
N4	0.6006 (2)	0.7920 (9)	0.17192 (18)	0.0247 (12)
C1	0.4873 (2)	0.2957 (9)	0.0757 (2)	0.0160 (13)
C2	0.4553 (2)	0.3298 (10)	0.1131 (2)	0.0178 (13)
H2A	0.4630	0.4267	0.1360	0.021*
C3	0.4128 (2)	0.1972 (10)	0.1089 (2)	0.0172 (13)
H3	0.3839	0.1849	0.1278	0.021*
C4	0.4196 (2)	0.0765 (9)	0.06957 (19)	0.0146 (12)
C5	0.3859 (2)	−0.0908 (9)	0.05650 (19)	0.0137 (12)
C6	0.3943 (2)	−0.2300 (9)	0.02283 (19)	0.0153 (13)
C7	0.3613 (2)	−0.4026 (10)	0.0091 (2)	0.0173 (13)
H7	0.3295	−0.4488	0.0222	0.021*
C8	0.3828 (2)	−0.4894 (10)	−0.0258 (2)	0.0192 (14)
H8	0.3687	−0.6060	−0.0417	0.023*
C9	0.4311 (2)	−0.3731 (9)	−0.0346 (2)	0.0174 (13)
C10	0.5360 (2)	0.4044 (9)	0.0686 (2)	0.0161 (13)
C11	0.3363 (2)	−0.1240 (9)	0.08095 (19)	0.0133 (12)
C12	0.2939 (2)	0.0224 (9)	0.07885 (19)	0.0139 (12)
H12	0.2955	0.1386	0.0603	0.017*
C13	0.2500 (2)	−0.0028 (9)	0.1039 (2)	0.0171 (13)
H13	0.2217	0.0980	0.1030	0.021*
C14	0.2850 (2)	−0.3158 (9)	0.13028 (19)	0.0155 (12)
H14	0.2808	−0.4357	0.1473	0.019*
C15	0.3306 (2)	−0.2950 (9)	0.10647 (19)	0.0165 (13)
H15	0.3579	−0.3992	0.1078	0.020*
C16	0.1992 (2)	−0.1914 (10)	0.1559 (2)	0.0211 (14)
H16A	0.1680	−0.2503	0.1376	0.032*
H16B	0.1888	−0.0569	0.1668	0.032*
H16C	0.2093	−0.2825	0.1808	0.032*
C17	0.5575 (2)	0.5474 (9)	0.1041 (2)	0.0155 (12)
C18	0.6056 (2)	0.4934 (10)	0.1296 (2)	0.0201 (14)
H18	0.6243	0.3703	0.1234	0.024*
C19	0.6261 (3)	0.6164 (10)	0.1634 (2)	0.0229 (14)
H19	0.6585	0.5771	0.1809	0.027*
C20	0.5550 (3)	0.8516 (10)	0.1477 (2)	0.0249 (15)
H20	0.5381	0.9781	0.1540	0.030*
C21	0.5323 (3)	0.7323 (10)	0.1136 (2)	0.0212 (14)
H21	0.4996	0.7753	0.0968	0.025*
C22	0.6256 (3)	0.9247 (14)	0.2076 (3)	0.045 (2)
H22A	0.6552	1.0066	0.1967	0.068*
H22B	0.6407	0.8391	0.2322	0.068*
H22C	0.5973	1.0162	0.2177	0.068*
N5	0.51171 (18)	0.1474 (7)	0.44291 (15)	0.0119 (10)
N6	0.54933 (18)	0.2175 (7)	0.53522 (15)	0.0120 (10)
H6	0.5312	0.1189	0.5205	0.014*
N7	0.6882 (2)	0.8716 (8)	0.43573 (17)	0.0179 (11)
N8	0.4068 (2)	−0.1873 (8)	0.25635 (16)	0.0205 (12)
C23	0.4912 (2)	0.0947 (9)	0.40114 (18)	0.0139 (12)
C24	0.5102 (3)	0.2350 (10)	0.3689 (2)	0.0201 (14)
H24	0.5004	0.2334	0.3381	0.024*
C25	0.5444 (3)	0.3681 (9)	0.3913 (2)	0.0182 (13)
H25	0.5647	0.4756	0.3793	0.022*
C26	0.5441 (2)	0.3150 (9)	0.43721 (19)	0.0126 (12)
C27	0.5742 (2)	0.4198 (9)	0.47193 (19)	0.0130 (12)
C28	0.5731 (2)	0.3828 (9)	0.51656 (19)	0.0115 (12)
C29	0.5950 (2)	0.5102 (9)	0.5519 (2)	0.0145 (13)
H29	0.6135	0.6372	0.5490	0.017*
C30	0.5850 (2)	0.4185 (9)	0.59024 (19)	0.0138 (12)
H30	0.5943	0.4717	0.6189	0.017*
C31	0.5579 (2)	0.2279 (9)	0.57998 (19)	0.0138 (12)
C32	0.4584 (2)	−0.0811 (9)	0.39060 (19)	0.0131 (12)
C33	0.6133 (2)	0.5840 (9)	0.45991 (18)	0.0131 (12)
C34	0.5960 (2)	0.7561 (9)	0.4354 (2)	0.0170 (13)
H34	0.5578	0.7760	0.4270	0.020*
C35	0.6340 (3)	0.8974 (10)	0.4233 (2)	0.0191 (13)
H35	0.6220	1.0132	0.4062	0.023*
C36	0.7057 (2)	0.7111 (10)	0.4609 (2)	0.0198 (14)
H36	0.7438	0.6983	0.4704	0.024*
C37	0.6690 (2)	0.5647 (9)	0.4733 (2)	0.0160 (12)
H37	0.6819	0.4514	0.4909	0.019*
C38	0.7285 (3)	1.0258 (11)	0.4241 (2)	0.0287 (16)
H38A	0.7390	1.1123	0.4496	0.043*
H38B	0.7121	1.1112	0.4000	0.043*
H38C	0.7613	0.9567	0.4148	0.043*
C39	0.4407 (2)	−0.1190 (9)	0.34373 (19)	0.0141 (12)
C40	0.3846 (2)	−0.1374 (9)	0.3289 (2)	0.0165 (13)
H40	0.3575	−0.1257	0.3493	0.020*
C41	0.3686 (3)	−0.1720 (9)	0.2855 (2)	0.0194 (13)
H41	0.3306	−0.1852	0.2760	0.023*
C42	0.4608 (3)	−0.1704 (10)	0.2694 (2)	0.0212 (14)
H42	0.4871	−0.1805	0.2483	0.025*
C43	0.4784 (3)	−0.1387 (9)	0.3127 (2)	0.0197 (14)
H43	0.5168	−0.1302	0.3214	0.024*
C44	0.3891 (3)	−0.2322 (11)	0.2096 (2)	0.0309 (17)
H44A	0.4215	−0.2368	0.1927	0.046*
H44B	0.3639	−0.1246	0.1978	0.046*
H44C	0.3701	−0.3650	0.2075	0.046*
I1	0.195450 (15)	0.46659 (6)	0.048331 (12)	0.01785 (12)
I2	0.294854 (17)	0.24104 (7)	0.209298 (13)	0.02653 (13)
I3	0.52507 (2)	0.35907 (8)	0.235129 (16)	0.04044 (15)
I4	0.68215 (2)	0.99182 (7)	0.09052 (2)	0.04330 (16)
O1W	0.09764 (19)	0.8556 (8)	0.20744 (16)	0.0320 (11)
O2W	0.6112 (3)	0.6675 (15)	0.3155 (3)	0.088 (3)
O3W	0.7269 (5)	0.367 (2)	0.2106 (6)	0.075 (4)	0.50
O4W	0.6235 (5)	0.0915 (17)	0.3155 (3)	0.040 (3)	0.50
O5W	0.7152 (6)	0.225 (2)	0.2792 (6)	0.074 (4)	0.50
O6W	0.7762 (5)	0.078 (2)	0.1729 (7)	0.093 (6)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.010 (2)	0.020 (3)	0.017 (3)	−0.001 (2)	0.0031 (19)	0.001 (2)
N2	0.010 (2)	0.021 (3)	0.018 (3)	−0.003 (2)	0.006 (2)	−0.002 (2)
N3	0.010 (2)	0.022 (3)	0.012 (2)	−0.001 (2)	0.0000 (19)	−0.002 (2)
N4	0.019 (3)	0.033 (3)	0.023 (3)	−0.008 (2)	0.004 (2)	−0.008 (3)
C1	0.012 (3)	0.018 (3)	0.018 (3)	0.004 (2)	0.005 (2)	−0.002 (3)
C2	0.019 (3)	0.018 (3)	0.017 (3)	0.001 (3)	0.007 (2)	−0.005 (3)
C3	0.013 (3)	0.021 (3)	0.018 (3)	0.000 (3)	0.006 (2)	0.001 (3)
C4	0.011 (3)	0.016 (3)	0.017 (3)	0.001 (2)	0.003 (2)	0.002 (3)
C5	0.010 (3)	0.016 (3)	0.015 (3)	0.004 (2)	0.005 (2)	0.004 (3)
C6	0.010 (3)	0.021 (3)	0.016 (3)	0.002 (2)	0.004 (2)	0.003 (3)
C7	0.010 (3)	0.023 (3)	0.019 (3)	−0.003 (3)	0.005 (2)	−0.002 (3)
C8	0.014 (3)	0.023 (3)	0.021 (3)	−0.004 (3)	0.002 (2)	−0.002 (3)
C9	0.014 (3)	0.019 (3)	0.019 (3)	0.000 (2)	−0.002 (2)	0.000 (3)
C10	0.009 (3)	0.018 (3)	0.022 (3)	0.001 (2)	0.004 (2)	0.003 (3)
C11	0.008 (3)	0.019 (3)	0.013 (3)	−0.004 (2)	0.001 (2)	−0.004 (2)
C12	0.012 (3)	0.015 (3)	0.014 (3)	0.000 (2)	0.003 (2)	0.004 (2)
C13	0.012 (3)	0.017 (3)	0.022 (3)	0.003 (2)	0.001 (2)	0.002 (3)
C14	0.017 (3)	0.017 (3)	0.012 (3)	−0.003 (3)	0.000 (2)	0.001 (2)
C15	0.012 (3)	0.019 (3)	0.018 (3)	0.003 (2)	−0.001 (2)	−0.002 (3)
C16	0.017 (3)	0.026 (4)	0.021 (3)	−0.004 (3)	0.008 (3)	0.002 (3)
C17	0.012 (3)	0.016 (3)	0.019 (3)	−0.003 (2)	0.006 (2)	0.000 (3)
C18	0.015 (3)	0.022 (3)	0.024 (3)	0.003 (3)	0.006 (3)	0.000 (3)
C19	0.019 (3)	0.029 (4)	0.020 (3)	0.002 (3)	−0.001 (3)	−0.006 (3)
C20	0.024 (3)	0.019 (3)	0.033 (4)	0.002 (3)	0.012 (3)	−0.006 (3)
C21	0.016 (3)	0.023 (3)	0.026 (4)	0.002 (3)	0.004 (3)	0.000 (3)
C22	0.040 (5)	0.048 (5)	0.046 (5)	−0.003 (4)	−0.001 (4)	−0.028 (4)
N5	0.010 (2)	0.012 (2)	0.014 (3)	−0.0003 (19)	0.0006 (19)	0.000 (2)
N6	0.010 (2)	0.015 (3)	0.010 (2)	−0.006 (2)	−0.0029 (18)	−0.001 (2)
N7	0.016 (3)	0.015 (3)	0.024 (3)	−0.006 (2)	0.007 (2)	−0.001 (2)
N8	0.031 (3)	0.017 (3)	0.011 (3)	−0.002 (2)	−0.007 (2)	−0.002 (2)
C23	0.014 (3)	0.015 (3)	0.012 (3)	0.000 (2)	0.000 (2)	0.000 (2)
C24	0.025 (3)	0.021 (3)	0.014 (3)	−0.004 (3)	0.000 (3)	0.001 (3)
C25	0.022 (3)	0.015 (3)	0.018 (3)	−0.005 (3)	0.000 (3)	0.002 (3)
C26	0.010 (3)	0.013 (3)	0.015 (3)	0.002 (2)	0.001 (2)	0.001 (2)
C27	0.012 (3)	0.010 (3)	0.017 (3)	−0.001 (2)	0.000 (2)	0.001 (2)
C28	0.006 (2)	0.012 (3)	0.016 (3)	0.000 (2)	−0.001 (2)	0.002 (2)
C29	0.010 (3)	0.015 (3)	0.019 (3)	0.000 (2)	0.000 (2)	−0.001 (2)
C30	0.014 (3)	0.013 (3)	0.014 (3)	0.000 (2)	−0.004 (2)	−0.001 (2)
C31	0.008 (3)	0.017 (3)	0.017 (3)	0.001 (2)	0.001 (2)	0.001 (2)
C32	0.013 (3)	0.014 (3)	0.012 (3)	0.002 (2)	0.001 (2)	−0.002 (2)
C33	0.012 (3)	0.014 (3)	0.013 (3)	−0.002 (2)	0.002 (2)	−0.005 (2)
C34	0.014 (3)	0.016 (3)	0.022 (3)	0.000 (2)	0.001 (2)	0.000 (3)
C35	0.021 (3)	0.014 (3)	0.023 (3)	0.001 (3)	0.003 (3)	0.000 (3)
C36	0.013 (3)	0.021 (3)	0.025 (3)	0.001 (3)	0.003 (3)	−0.003 (3)
C37	0.016 (3)	0.013 (3)	0.018 (3)	0.000 (2)	0.003 (2)	−0.003 (3)
C38	0.024 (4)	0.027 (4)	0.036 (4)	−0.009 (3)	0.009 (3)	0.002 (3)
C39	0.020 (3)	0.009 (3)	0.012 (3)	−0.001 (2)	−0.002 (2)	0.001 (2)
C40	0.017 (3)	0.014 (3)	0.017 (3)	−0.001 (2)	−0.005 (2)	0.005 (2)
C41	0.022 (3)	0.016 (3)	0.020 (3)	−0.001 (3)	−0.006 (3)	0.000 (3)
C42	0.030 (4)	0.018 (3)	0.016 (3)	−0.001 (3)	0.005 (3)	0.002 (3)
C43	0.020 (3)	0.017 (3)	0.021 (3)	−0.004 (3)	−0.003 (3)	0.000 (3)
C44	0.044 (4)	0.031 (4)	0.016 (3)	0.002 (3)	−0.006 (3)	−0.005 (3)
I1	0.0156 (2)	0.0166 (2)	0.0208 (2)	−0.00044 (15)	−0.00111 (15)	0.00148 (15)
I2	0.0291 (2)	0.0267 (2)	0.0232 (2)	−0.00046 (18)	−0.00126 (17)	0.00460 (17)
I3	0.0449 (3)	0.0435 (3)	0.0363 (3)	0.0162 (2)	0.0227 (2)	0.0111 (2)
I4	0.0381 (3)	0.0211 (2)	0.0761 (4)	0.0003 (2)	0.0356 (3)	0.0008 (2)
O1W	0.028 (3)	0.035 (3)	0.033 (3)	0.001 (2)	0.005 (2)	−0.006 (2)
O2W	0.060 (5)	0.111 (7)	0.094 (6)	0.011 (5)	0.015 (4)	0.032 (5)
O3W	0.026 (5)	0.054 (6)	0.141 (9)	0.004 (5)	−0.019 (6)	0.042 (7)
O4W	0.051 (6)	0.040 (6)	0.029 (6)	0.011 (5)	0.004 (5)	0.001 (5)
O5W	0.051 (8)	0.045 (8)	0.125 (13)	−0.007 (6)	0.004 (8)	−0.009 (8)
O6W	0.038 (7)	0.067 (10)	0.164 (17)	−0.012 (7)	−0.054 (9)	0.029 (10)

Geometric parameters (Å, º) top

N1—C1	1.368 (8)	N5—C26	1.367 (8)
N1—C4	1.373 (8)	N5—C23	1.373 (7)
N2—C6	1.367 (8)	N6—C31	1.367 (8)
N2—C9	1.370 (8)	N6—C28	1.371 (8)
N2—H2	0.8800	N6—H6	0.8800
N3—C13	1.334 (8)	N7—C36	1.347 (8)
N3—C14	1.337 (8)	N7—C35	1.350 (8)
N3—C16	1.480 (8)	N7—C38	1.471 (8)
N4—C20	1.337 (9)	N8—C42	1.344 (8)
N4—C19	1.339 (9)	N8—C41	1.347 (9)
N4—C22	1.481 (9)	N8—C44	1.484 (8)
C1—C10	1.414 (8)	C23—C32	1.417 (8)
C1—C2	1.454 (8)	C23—C24	1.450 (9)
C2—C3	1.347 (9)	C24—C25	1.348 (9)
C2—H2A	0.9500	C24—H24	0.9500
C3—C4	1.458 (9)	C25—C26	1.446 (9)
C3—H3	0.9500	C25—H25	0.9500
C4—C5	1.401 (9)	C26—C27	1.413 (8)
C5—C6	1.401 (9)	C27—C28	1.388 (8)
C5—C11	1.490 (8)	C27—C33	1.499 (8)
C6—C7	1.426 (9)	C28—C29	1.428 (8)
C7—C8	1.353 (9)	C29—C30	1.358 (9)
C7—H7	0.9500	C29—H29	0.9500
C8—C9	1.442 (9)	C30—C31	1.429 (8)
C8—H8	0.9500	C30—H30	0.9500
C9—C10ⁱ	1.384 (9)	C31—C32ⁱⁱ	1.394 (9)
C10—C9ⁱ	1.384 (9)	C32—C31ⁱⁱ	1.394 (9)
C10—C17	1.489 (9)	C32—C39	1.480 (8)
C11—C15	1.375 (9)	C33—C37	1.386 (8)
C11—C12	1.402 (8)	C33—C34	1.394 (9)
C12—C13	1.378 (9)	C34—C35	1.379 (9)
C12—H12	0.9500	C34—H34	0.9500
C13—H13	0.9500	C35—H35	0.9500
C14—C15	1.385 (9)	C36—C37	1.382 (9)
C14—H14	0.9500	C36—H36	0.9500
C15—H15	0.9500	C37—H37	0.9500
C16—H16A	0.9800	C38—H38A	0.9800
C16—H16B	0.9800	C38—H38B	0.9800
C16—H16C	0.9800	C38—H38C	0.9800
C17—C18	1.393 (9)	C39—C43	1.383 (9)
C17—C21	1.395 (9)	C39—C40	1.404 (8)
C18—C19	1.367 (9)	C40—C41	1.368 (9)
C18—H18	0.9500	C40—H40	0.9500
C19—H19	0.9500	C41—H41	0.9500
C20—C21	1.376 (10)	C42—C43	1.372 (9)
C20—H20	0.9500	C42—H42	0.9500
C21—H21	0.9500	C43—H43	0.9500
C22—H22A	0.9800	C44—H44A	0.9800
C22—H22B	0.9800	C44—H44B	0.9800
C22—H22C	0.9800	C44—H44C	0.9800

O2W···O4Wⁱⁱⁱ	2.781 (15)	O2W···I3	3.684 (9)
O2W···O6W^iv	2.793 (15)	O6W···I4^vi	3.299 (18)
O3W···O5W^iv	2.730 (19)	C13···I1	3.691 (6)
O3W···O6W	2.56 (2)	C14···I2^vi	3.760 (6)
O4W···O5W	2.721 (19)	C44···I2	3.844 (7)
O5W···O6W^iv	2.73 (2)	C22···I3ⁱⁱⁱ	3.882 (7)
O1W···I2^v	3.565 (5)	C36···I4^vii	3.566 (5)
O1W···I3^v	3.594 (5)

C1—N1—C4	105.2 (5)	C26—N5—C23	104.4 (5)
C6—N2—C9	110.0 (5)	C31—N6—C28	110.2 (5)
C6—N2—H2	125.0	C31—N6—H6	124.9
C9—N2—H2	125.0	C28—N6—H6	124.9
C13—N3—C14	121.3 (5)	C36—N7—C35	120.6 (5)
C13—N3—C16	119.4 (5)	C36—N7—C38	119.1 (5)
C14—N3—C16	119.2 (5)	C35—N7—C38	120.2 (5)
C20—N4—C19	121.1 (6)	C42—N8—C41	120.8 (5)
C20—N4—C22	120.4 (6)	C42—N8—C44	119.7 (6)
C19—N4—C22	118.5 (6)	C41—N8—C44	119.5 (5)
N1—C1—C10	125.1 (5)	N5—C23—C32	124.4 (5)
N1—C1—C2	111.0 (5)	N5—C23—C24	111.2 (5)
C10—C1—C2	123.8 (6)	C32—C23—C24	124.2 (5)
C3—C2—C1	106.6 (5)	C25—C24—C23	106.3 (5)
C3—C2—H2A	126.7	C25—C24—H24	126.8
C1—C2—H2A	126.7	C23—C24—H24	126.8
C2—C3—C4	106.5 (5)	C24—C25—C26	106.4 (5)
C2—C3—H3	126.7	C24—C25—H25	126.8
C4—C3—H3	126.7	C26—C25—H25	126.8
N1—C4—C5	125.8 (5)	N5—C26—C27	124.0 (5)
N1—C4—C3	110.7 (5)	N5—C26—C25	111.5 (5)
C5—C4—C3	123.3 (5)	C27—C26—C25	124.5 (5)
C6—C5—C4	126.4 (5)	C28—C27—C26	126.9 (5)
C6—C5—C11	116.9 (5)	C28—C27—C33	115.7 (5)
C4—C5—C11	116.7 (5)	C26—C27—C33	117.4 (5)
N2—C6—C5	125.1 (5)	N6—C28—C27	126.2 (5)
N2—C6—C7	107.1 (5)	N6—C28—C29	106.6 (5)
C5—C6—C7	127.8 (5)	C27—C28—C29	127.1 (5)
C8—C7—C6	108.4 (5)	C30—C29—C28	108.2 (5)
C8—C7—H7	125.8	C30—C29—H29	125.9
C6—C7—H7	125.8	C28—C29—H29	125.9
C7—C8—C9	107.7 (6)	C29—C30—C31	108.0 (5)
C7—C8—H8	126.1	C29—C30—H30	126.0
C9—C8—H8	126.1	C31—C30—H30	126.0
N2—C9—C10ⁱ	126.6 (6)	N6—C31—C32ⁱⁱ	125.8 (5)
N2—C9—C8	106.7 (5)	N6—C31—C30	106.8 (5)
C10ⁱ—C9—C8	126.7 (6)	C32ⁱⁱ—C31—C30	127.4 (5)
C9ⁱ—C10—C1	126.2 (6)	C31ⁱⁱ—C32—C23	126.5 (5)
C9ⁱ—C10—C17	116.7 (5)	C31ⁱⁱ—C32—C39	115.8 (5)
C1—C10—C17	116.7 (5)	C23—C32—C39	117.7 (5)
C15—C11—C12	117.9 (5)	C37—C33—C34	118.4 (5)
C15—C11—C5	122.0 (5)	C37—C33—C27	119.1 (5)
C12—C11—C5	120.1 (5)	C34—C33—C27	122.5 (5)
C13—C12—C11	119.8 (5)	C35—C34—C33	120.2 (5)
C13—C12—H12	120.1	C35—C34—H34	119.9
C11—C12—H12	120.1	C33—C34—H34	119.9
N3—C13—C12	120.4 (5)	N7—C35—C34	120.2 (6)
N3—C13—H13	119.8	N7—C35—H35	119.9
C12—C13—H13	119.8	C34—C35—H35	119.9
N3—C14—C15	120.2 (6)	N7—C36—C37	121.0 (5)
N3—C14—H14	119.9	N7—C36—H36	119.5
C15—C14—H14	119.9	C37—C36—H36	119.5
C11—C15—C14	120.2 (6)	C36—C37—C33	119.6 (6)
C11—C15—H15	119.9	C36—C37—H37	120.2
C14—C15—H15	119.9	C33—C37—H37	120.2
N3—C16—H16A	109.5	N7—C38—H38A	109.5
N3—C16—H16B	109.5	N7—C38—H38B	109.5
H16A—C16—H16B	109.5	H38A—C38—H38B	109.5
N3—C16—H16C	109.5	N7—C38—H38C	109.5
H16A—C16—H16C	109.5	H38A—C38—H38C	109.5
H16B—C16—H16C	109.5	H38B—C38—H38C	109.5
C18—C17—C21	117.7 (6)	C43—C39—C40	117.1 (5)
C18—C17—C10	118.3 (5)	C43—C39—C32	121.7 (5)
C21—C17—C10	124.0 (5)	C40—C39—C32	121.2 (5)
C19—C18—C17	120.4 (6)	C41—C40—C39	120.8 (6)
C19—C18—H18	119.8	C41—C40—H40	119.6
C17—C18—H18	119.8	C39—C40—H40	119.6
N4—C19—C18	120.4 (6)	N8—C41—C40	120.0 (6)
N4—C19—H19	119.8	N8—C41—H41	120.0
C18—C19—H19	119.8	C40—C41—H41	120.0
N4—C20—C21	121.0 (6)	N8—C42—C43	120.9 (6)
N4—C20—H20	119.5	N8—C42—H42	119.6
C21—C20—H20	119.5	C43—C42—H42	119.6
C20—C21—C17	119.4 (6)	C42—C43—C39	120.4 (6)
C20—C21—H21	120.3	C42—C43—H43	119.8
C17—C21—H21	120.3	C39—C43—H43	119.8
N4—C22—H22A	109.5	N8—C44—H44A	109.5
N4—C22—H22B	109.5	N8—C44—H44B	109.5
H22A—C22—H22B	109.5	H44A—C44—H44B	109.5
N4—C22—H22C	109.5	N8—C44—H44C	109.5
H22A—C22—H22C	109.5	H44A—C44—H44C	109.5
H22B—C22—H22C	109.5	H44B—C44—H44C	109.5

C4—N1—C1—C10	178.6 (6)	C26—N5—C23—C32	175.1 (5)
C4—N1—C1—C2	1.9 (6)	C26—N5—C23—C24	−1.3 (6)
N1—C1—C2—C3	−2.4 (7)	N5—C23—C24—C25	2.6 (7)
C10—C1—C2—C3	−179.2 (6)	C32—C23—C24—C25	−173.8 (6)
C1—C2—C3—C4	1.9 (7)	C23—C24—C25—C26	−2.7 (7)
C1—N1—C4—C5	−175.4 (6)	C23—N5—C26—C27	−179.2 (5)
C1—N1—C4—C3	−0.6 (6)	C23—N5—C26—C25	−0.5 (6)
C2—C3—C4—N1	−0.9 (7)	C24—C25—C26—N5	2.1 (7)
C2—C3—C4—C5	174.0 (6)	C24—C25—C26—C27	−179.2 (6)
N1—C4—C5—C6	3.3 (10)	N5—C26—C27—C28	−5.3 (9)
C3—C4—C5—C6	−170.8 (6)	C25—C26—C27—C28	176.2 (6)
N1—C4—C5—C11	−176.9 (5)	N5—C26—C27—C33	172.4 (5)
C3—C4—C5—C11	9.0 (8)	C25—C26—C27—C33	−6.1 (8)
C9—N2—C6—C5	−176.4 (6)	C31—N6—C28—C27	177.9 (5)
C9—N2—C6—C7	3.0 (7)	C31—N6—C28—C29	−3.5 (6)
C4—C5—C6—N2	−1.5 (10)	C26—C27—C28—N6	11.1 (9)
C11—C5—C6—N2	178.8 (5)	C33—C27—C28—N6	−166.7 (5)
C4—C5—C6—C7	179.3 (6)	C26—C27—C28—C29	−167.3 (6)
C11—C5—C6—C7	−0.5 (9)	C33—C27—C28—C29	14.9 (8)
N2—C6—C7—C8	−2.3 (7)	N6—C28—C29—C30	1.0 (6)
C5—C6—C7—C8	177.1 (6)	C27—C28—C29—C30	179.6 (5)
C6—C7—C8—C9	0.7 (7)	C28—C29—C30—C31	1.7 (6)
C6—N2—C9—C10ⁱ	175.5 (6)	C28—N6—C31—C32ⁱⁱ	−177.0 (5)
C6—N2—C9—C8	−2.5 (7)	C28—N6—C31—C30	4.5 (6)
C7—C8—C9—N2	1.1 (7)	C29—C30—C31—N6	−3.8 (6)
C7—C8—C9—C10ⁱ	−177.0 (6)	C29—C30—C31—C32ⁱⁱ	177.7 (6)
N1—C1—C10—C9ⁱ	1.2 (10)	N5—C23—C32—C31ⁱⁱ	−0.5 (9)
C2—C1—C10—C9ⁱ	177.5 (6)	C24—C23—C32—C31ⁱⁱ	175.4 (6)
N1—C1—C10—C17	−170.6 (6)	N5—C23—C32—C39	−178.4 (5)
C2—C1—C10—C17	5.7 (9)	C24—C23—C32—C39	−2.5 (9)
C6—C5—C11—C15	65.1 (7)	C28—C27—C33—C37	58.3 (7)
C4—C5—C11—C15	−114.7 (6)	C26—C27—C33—C37	−119.7 (6)
C6—C5—C11—C12	−115.8 (6)	C28—C27—C33—C34	−122.1 (6)
C4—C5—C11—C12	64.4 (7)	C26—C27—C33—C34	59.9 (8)
C15—C11—C12—C13	3.5 (8)	C37—C33—C34—C35	2.9 (9)
C5—C11—C12—C13	−175.7 (5)	C27—C33—C34—C35	−176.7 (6)
C14—N3—C13—C12	−2.2 (8)	C36—N7—C35—C34	−1.7 (9)
C16—N3—C13—C12	−180.0 (5)	C38—N7—C35—C34	−178.0 (6)
C11—C12—C13—N3	−1.4 (9)	C33—C34—C35—N7	−1.0 (9)
C13—N3—C14—C15	3.7 (8)	C35—N7—C36—C37	2.5 (9)
C16—N3—C14—C15	−178.6 (5)	C38—N7—C36—C37	178.9 (6)
C12—C11—C15—C14	−2.1 (8)	N7—C36—C37—C33	−0.5 (9)
C5—C11—C15—C14	177.1 (5)	C34—C33—C37—C36	−2.1 (9)
N3—C14—C15—C11	−1.4 (9)	C27—C33—C37—C36	177.5 (5)
C9ⁱ—C10—C17—C18	−64.2 (8)	C31ⁱⁱ—C32—C39—C43	−120.9 (6)
C1—C10—C17—C18	108.5 (6)	C23—C32—C39—C43	57.2 (8)
C9ⁱ—C10—C17—C21	116.3 (7)	C31ⁱⁱ—C32—C39—C40	58.8 (7)
C1—C10—C17—C21	−71.0 (8)	C23—C32—C39—C40	−123.0 (6)
C21—C17—C18—C19	1.6 (9)	C43—C39—C40—C41	−0.4 (9)
C10—C17—C18—C19	−177.9 (6)	C32—C39—C40—C41	179.8 (6)
C20—N4—C19—C18	−0.3 (10)	C42—N8—C41—C40	0.5 (9)
C22—N4—C19—C18	−177.4 (7)	C44—N8—C41—C40	177.8 (6)
C17—C18—C19—N4	−1.1 (10)	C39—C40—C41—N8	−0.5 (9)
C19—N4—C20—C21	1.2 (10)	C41—N8—C42—C43	0.5 (9)
C22—N4—C20—C21	178.2 (7)	C44—N8—C42—C43	−176.9 (6)
N4—C20—C21—C17	−0.6 (10)	N8—C42—C43—C39	−1.4 (9)
C18—C17—C21—C20	−0.7 (9)	C40—C39—C43—C42	1.3 (9)
C10—C17—C21—C20	178.8 (6)	C32—C39—C43—C42	−178.9 (6)

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

Experimental details

Crystal data
Chemical formula	C₄₄H₃₈N₈²⁺·4I⁻·4H₂O
M_r	1258.49
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	24.3331 (4), 6.5209 (1), 30.5663 (5)
β (°)	95.025 (1)
V (Å³)	4831.43 (13)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	20.65
Crystal size (mm)	0.20 × 0.15 × 0.08

Data collection
Diffractometer	Bruker X8 KappaCCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.104, 0.289
No. of measured, independent and observed [I > 2σ(I)] reflections	47661, 7346, 7013
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.577

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.110, 1.09
No. of reflections	7346
No. of parameters	563
No. of restraints	6
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0481P)² + 42.1978P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.73, −2.79

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected interatomic distances (Å) top

O2W···O4Wⁱ	2.781 (15)	O2W···I3	3.684 (9)
O2W···O6Wⁱⁱ	2.793 (15)	O6W···I4^iv	3.299 (18)
O3W···O5Wⁱⁱ	2.730 (19)	C13···I1	3.691 (6)
O3W···O6W	2.56 (2)	C14···I2^iv	3.760 (6)
O4W···O5W	2.721 (19)	C44···I2	3.844 (7)
O5W···O6Wⁱⁱ	2.73 (2)	C22···I3ⁱ	3.882 (7)
O1W···I2ⁱⁱⁱ	3.565 (5)	C36···I4^v	3.566 (5)
O1W···I3ⁱⁱⁱ	3.594 (5)

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

Acknowledgements

We are grateful to Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support through the R&D project PTDC/QUI/65228/2006, for the PhD and postdoctoral research grants Nos. SFRH/BD/64526/2009 (to LMOL) and SFRH/BPD/63736/2009 (to JAF), and for specific funding toward the purchase of the single-crystal diffractometer.

References

Alves, E., Carvalho, C. M. B., Tomé, J. P. C., Faustino, M. A. F., Neves, M. G. P. M. S., Tomé, A. C., Cavaleiro, J. A. S., Cunha, A., Mendo, S. & Almeida, A. (2008). J. Ind. Microbiol. Biotechnol. 35, 1447–1454. Web of Science CrossRef PubMed CAS Google Scholar
Alves, E., Costa, L., Carvalho, C. M. B., Tomé, J. P. C., Faustino, M. A., Neves, M. G. P. M. S., Tomé, A. C., Cavaleiro, J. A. S., Cunha, A. & Almeida, A. (2009). BMC Microbiol. 9, 70. Google Scholar
Banfi, S., Caruso, E., Buccafurni, L., Battini, V., Zazzaron, S., Barbieri, P. & Orlandi, V. (2006). J. Photochem. Photobiol. B, 85, 28–38. Web of Science CrossRef PubMed CAS Google Scholar
Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carvalho, C. M. B., Tomé, J. P. C., Faustino, M. A. F., Neves, M. G. P. M. S., Tomé, A. C., Cavaleiro, J. A. S., Costa, L., Alves, E., Oliveira, A., Cunha, A. & Almeida, A. (2009). J. Porphyrins Phthalocyanines, 13, 574–577. CrossRef CAS Google Scholar
Gomes, M. C., Woranovicz-Barreira, S. M., Faustino, M. A. F., Fernandes, R., Neves, M. G. P. M. S., Tomé, A. C., Gomes, N. C. M., Almeida, A., Cavaleiro, J. A. S., Cunha, A. & Tomé, J. P. C. (2011). Photochem. Photobiol. Sci. doi:10.1039/c1pp05174a. Google Scholar
Merchat, M., Bertolini, G., Giacomini, P., Villanueva, A. & Jori, G. (1996). J. Photochem. Photobiol. B, 32, 153–157. CrossRef CAS PubMed Web of Science Google Scholar
Paz, F. A. A., Bond, A. D., Khimyak, Y. Z. & Klinowski, J. (2002). New J. Chem. 26, 381–383. Google Scholar
Paz, F. A. A. & Klinowski, J. (2003). CrystEngComm, 5, 238–244. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1997). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150–167. Web of Science CSD CrossRef PubMed CAS Google Scholar
Tomé, J. P. C., Neves, M. G. P. M. S., Tomé, A. C., Cavaleiro, J. A. S., Soncin, M., Magaraggia, M., Ferro, F. & Jori, G. (2004). J. Med. Chem. 47, 6649–6652. Web of Science PubMed Google Scholar
Yu, K. G., Li, D. H., Zhou, C. H. & Diao, J. L. (2009). Chin. Chem. Lett. 20, 411–414. Web of Science CrossRef CAS Google Scholar

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