meso-5,10,15,20-Tetra­kis(4-hy­droxy-3-meth­oxy­phen­yl)porphyrin propionic acid monosolvate

Leonarska, A.; Zubko, M.; Kuś, P.; Kusz, J.; Ratuszna, A.

doi:10.1107/S1600536812036495

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages o2797-o2798

doi:10.1107/S1600536812036495

Open

access

meso-5,10,15,20-Tetrakis(4-hydroxy-3-methoxyphenyl)porphyrin propionic acid monosolvate

Agnieszka Leonarska,^a Maciej Zubko,^b Piotr Kuś,^c Joachim Kusz ^a ^* and Alicja Ratuszna ^a

^aInstitute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland, ^bInstitute of Materials Science, University of Silesia, Bankowa 12, 40-007 Katowice, Poland, and ^cInstitute of Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice, Poland
^*Correspondence e-mail: joachim.kusz@us.edu.pl

(Received 10 August 2012; accepted 21 August 2012; online 25 August 2012)

In the title compound, C₄₈H₃₈N₄O₈·C₃H₆O₂, the porphyrin molecule is centrosymmetric. The propionic acid solvent molecule is disordered over two sets of sites with equal occupancy factors. The porphyrin central core is almost planar, with an r.m.s. deviation of the fitted atoms of 0.045 Å. The substituent benzene rings make dihedral angles of 70.37 (4) and 66.95 (4)° with respect to the porphyrin core plane. The crystal structure is stabilized by an interesting network of hydrogen bonds. Porphyrin molecules are connected by O—H⋯O hydrogen bonds creating ribbons running along the [101] direction. Weak C—H⋯O hydrogen bonds connect separate molecular ribbons in the [110] direction, creating (-111) layers. Intramolecular N—H⋯N hydrogen bonds also occur. The propionic acid molecules are connected by pairs of —H⋯O hydrogen bonds, creating dimers.

Related literature

For the biological activity and potential applications of porphyrin molecules, see: Allison et al. (2004 ); Dougherty et al. (1998 ); Agostinis et al. (2011 ); Szurko et al. (2009 ). For spectroscopic data, see Bonar-Law (1996 ).

Experimental

Crystal data

C₄₈H₃₈N₄O₈·C₃H₆O₂
M_r = 872.90
Triclinic, $[P \overline 1]$
a = 6.8715 (5) Å
b = 12.0783 (7) Å
c = 14.3772 (10) Å
α = 112.850 (6)°
β = 98.560 (5)°
γ = 97.480 (5)°
V = 1063.97 (12) Å³
Z = 1
Cu Kα radiation
μ = 0.78 mm⁻¹
T = 100 K
0.10 × 0.03 × 0.02 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.926, T_max = 0.985
9919 measured reflections
3688 independent reflections
3098 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.104
S = 1.03
3688 reflections
339 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2	0.85 (2)	2.392 (19)	2.9286 (19)	121.4 (15)
N1—H1N⋯N2ⁱ	0.85 (2)	2.377 (19)	2.9121 (19)	121.2 (15)
O1—H1O⋯O3	0.84 (2)	2.17 (2)	2.6655 (17)	117.4 (19)
O2—H2O⋯O4	0.90 (2)	2.18 (2)	2.6726 (16)	113.8 (18)
O2—H2O⋯O1ⁱⁱ	0.90 (2)	2.03 (2)	2.8588 (17)	151 (2)
C10—H10⋯O3ⁱⁱⁱ	0.98 (2)	2.46 (2)	3.4085 (19)	162.0 (16)
C23—H23B⋯O3ⁱⁱ	0.99 (3)	2.51 (3)	3.383 (2)	147.3 (19)
C23—H23C⋯O5ⁱⁱ	1.00 (3)	2.43 (3)	3.189 (5)	132.3 (19)
O5—H5A⋯O6ⁱⁱ	0.84	1.77	2.608 (9)	173
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z+1; (iii) -x-1, -y, -z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812036495/bt5999sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036495/bt5999Isup2.hkl

checkCIF report

Comment top

Photodynamic therapy (PDT) for cancer treatment is still developed method. PDT process is result of the photochemistry reactions, where the photosensitizers are activated by the light and during the deactivation their energy is used to excite molecular O₂ to the singlet state ¹O₂*. The excited oxygen as well as the other species (ROS) are highly toxic and oxidize organic substrates found within tumour cells, leading to its destruction. Effectiveness of this technique is determined by the properties exhibited by the photosensitizers. For this reason we try to obtain a well defined compounds, which should have among the others: chemical purity, stability, good solubility in water or fat, lack of aggregation, optimal quantum yield of fluorescence and long lifetime of triplet states [Allison et al., 2004; Dougherty et al., 1998; Agostinis et al., 2011; Szurko et al., 2009]. Promising compounds for application in PDT are the porhyrins, due to their photosensibilization properties.

This paper presents the crystal structure of meso-tetra(4-hydroxy-3-methoxyphenyl)porphyrin (I), which is good a candidate as a starting material for synthesis of a new potential anticancer photosensitizer. Compound (I) crystallizes in triclinic system with one porphyrin molecule in the unit cell. Crystal structure contains also one propionic acid solvent molecule per one porphyrin molecule (Fig.1). The solvent molecule is disordered and can occupy two positions in the unit cell with equal occupancy factors. Porphyrin molecule is centrosymmetric with two sets of benzene rings orientations. Central core of porphyrin molecule is approximately planar with r.m.s. deviation of fitted atoms equal to 0.045 Å. The largest distance from one atom (N1) to the average plane is 0.1057 (13) Å. The angles of substituent benzene rings with the porphyrin core plane are 70.37 (4)° and 66.95 (4)°. Porphyrin molecules occupy (596) planes creating π-π stacking structure. The distance between centroids of two pyrrolide ring and pyrrole rings is 4.232 Å. Two sets of methylene groups are almost coplanar with benzene rings with largest distance to average plane equal to 0.0982 (34) Å and 0.1053 (31) Å for atoms C23 and C24 respectively. The two torsion angles are as follows: C5—C6—O3—C24 = -4.5 (2)° and C22—C21—O4—C23 = 4.4 (2)°.

Propionic acid molecules are connected by two O5—H5A···O6ⁱⁱ [symmetry codes: (ii) 1 - x,1 - y,1 - z] hydrogen bonds creating dimmers along [100] direction. Porphyrin molecules are connected by O2—H2O···O1ⁱⁱ hydrogen bonds creating ribbons running along [101] directions. Weak C10—H10···O3ⁱⁱⁱ [symmetry codes: (iii) -1 - x, -y,-z] hydrogen bonds connect separated molecular ribbons in [110] direction creating (111) layers. Ribbons of porphyrin molecules are intersecting with direction of propionic acid molecules dimmers and additional C23—H23B···O3ⁱⁱ and C23—H23C···O5ⁱⁱ hydrogen bonds are created (Fig.2). π-π stacking and interactions with propionic acid molecules stabilize the crystal structure of presented compound. Two types of intramolecular hydrogen bonds O1—H1O···O3 and O2—H2O···O4 are present connecting methylene group and oxygen atom connected to benzene rings. Detailed information regarding hydrogen bonds in the compound are stated in Table 1.

Related literature top

For the biological activity and potential applications of porphyrin molecules, see: Allison et al. (2004); Dougherty et al. (1998); Agostinis et al. (2011); Szurko et al. (2009). For spectroscopic data, see Bonar-Law, (1996).

Experimental top

Chemicals and solvents were purchased from commercial sources and used as received. Synthesis of meso-tetra(4-hydroxy-3-methoxyphenyl)porphyrin (I) was performed as fallows. 8.8 g (0.072 m) of vanillin was added into 300 ml of propionic acid. The mixture was boiled until the all aldehyde was dissolved. After this 5 ml (0.072 m) of pyrrole was added and the solution was boiled for 1.5 h. Then about 200 ml of propionic acid was distilled off, the residue was cooled to ambient temperature and neutralized with saturated solution of NaHCO₃. The precipitate was filtered and washed with chloroform until the filtrate was colourless. The product of the reaction was purified by column chromatography (silica gel/chloroform:ethyl acetate).

The single crystals of (I) were obtained directly from precipitate after reaction procedure (before column chromatography purification).

All spectroscopic data were in accordance with literature [Bonar-Law, 1996].

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of compound (I), showing atom-labelling scheme. The molecule is centrosymmetric and only the unique atoms of the asymmetric unit are labelled. Ellipsoids representing displacement parameters are drown at the 50% probability level.

Fig. 2. Scheme of network of hydrogen bonds in (I). O2—H2O···O1ⁱⁱ [symmetry codes: (ii) 1 - x,1 - y,1 - z] hydrogen bonds are marked by blue lines connecting separated molecules into molecular ribbons. Magenta lines indicate C23—H23B···O3ⁱⁱ and C23—H23C···O5ⁱⁱ hydrogen bonds and green lines indicate O5—H5A···O6ⁱⁱ hydrogen bond connecting propionic acid molecules.

meso-5,10,15,20-Tetrakis(4-hydroxy-3-methoxyphenyl)porphyrin propionic acid monosolvate top

Crystal data top

C₄₈H₃₈N₄O₈·C₃H₆O₂	Z = 1
M_r = 872.90	F(000) = 458
Triclinic, P1	D_x = 1.362 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.8715 (5) Å	Cell parameters from 4163 reflections
b = 12.0783 (7) Å	θ = 3.4–65.9°
c = 14.3772 (10) Å	µ = 0.78 mm⁻¹
α = 112.850 (6)°	T = 100 K
β = 98.560 (5)°	Polyhedron, black
γ = 97.480 (5)°	0.10 × 0.03 × 0.02 mm
V = 1063.97 (12) Å³

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3688 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3098 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4498 pixels mm^-1	θ_max = 66.0°, θ_min = 3.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→14
T_min = 0.926, T_max = 0.985	l = −15→17
9919 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0536P)² + 0.3935P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3688 reflections	Δρ_max = 0.22 e Å⁻³
339 parameters	Δρ_min = −0.25 e Å⁻³
12 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0040 (5)

Crystal data top

C₄₈H₃₈N₄O₈·C₃H₆O₂	γ = 97.480 (5)°
M_r = 872.90	V = 1063.97 (12) Å³
Triclinic, P1	Z = 1
a = 6.8715 (5) Å	Cu Kα radiation
b = 12.0783 (7) Å	µ = 0.78 mm⁻¹
c = 14.3772 (10) Å	T = 100 K
α = 112.850 (6)°	0.10 × 0.03 × 0.02 mm
β = 98.560 (5)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3688 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3098 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.985	R_int = 0.028
9919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	12 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
3688 reflections	Δρ_min = −0.25 e Å⁻³
339 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.19 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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)
O1	−0.28230 (18)	0.01112 (11)	0.33140 (9)	0.0254 (3)
H1O	−0.211 (3)	−0.042 (2)	0.3180 (17)	0.038*
O2	1.21357 (17)	0.83439 (12)	0.45275 (9)	0.0294 (3)
H2O	1.190 (3)	0.882 (2)	0.5143 (19)	0.044*
O3	−0.00783 (17)	−0.03851 (10)	0.21636 (8)	0.0237 (3)
O4	0.87195 (16)	0.87779 (11)	0.51416 (8)	0.0256 (3)
N1	0.1653 (2)	0.46061 (12)	0.11394 (10)	0.0188 (3)
H1N	0.101 (3)	0.4735 (17)	0.0650 (15)	0.023*
N2	−0.24395 (19)	0.37519 (11)	−0.01361 (10)	0.0186 (3)
C1	−0.2385 (2)	0.08075 (14)	0.27810 (12)	0.0216 (4)
C2	−0.3381 (3)	0.17440 (15)	0.28535 (13)	0.0256 (4)
H2	−0.4365	0.1896	0.3262	0.031*
C3	−0.2950 (2)	0.24694 (15)	0.23292 (13)	0.0241 (4)
H3	−0.3647	0.3114	0.2381	0.029*
C4	−0.1513 (2)	0.22622 (14)	0.17301 (12)	0.0198 (3)
C5	−0.0510 (2)	0.13016 (14)	0.16546 (12)	0.0205 (3)
H5	0.0473	0.1147	0.1246	0.025*
C6	−0.0946 (2)	0.05773 (14)	0.21729 (12)	0.0201 (3)
C7	−0.1047 (2)	0.30658 (14)	0.11882 (11)	0.0188 (3)
C8	−0.2574 (2)	0.30429 (14)	0.04101 (12)	0.0194 (3)
C9	−0.4521 (2)	0.22058 (15)	0.00422 (12)	0.0228 (4)
H9	−0.4984	0.1625	0.0297	0.027*
C10	−0.5542 (2)	0.24117 (15)	−0.07284 (12)	0.0224 (4)
H10	−0.689 (3)	0.1991 (18)	−0.1155 (15)	0.027*
C11	−0.4238 (2)	0.33809 (14)	−0.08348 (12)	0.0193 (3)
C12	0.4759 (2)	0.61748 (14)	0.15889 (12)	0.0188 (3)
C13	0.3540 (2)	0.52417 (14)	0.17144 (12)	0.0189 (3)
C14	0.3994 (2)	0.48061 (14)	0.24959 (12)	0.0225 (4)
H14	0.5208	0.5076	0.3007	0.027*
C15	0.2393 (2)	0.39374 (14)	0.23837 (12)	0.0228 (4)
H15	0.2294	0.3494	0.2800	0.027*
C16	0.0885 (2)	0.38112 (14)	0.15268 (12)	0.0195 (3)
C17	0.6721 (2)	0.67684 (14)	0.23575 (12)	0.0191 (3)
C18	0.8540 (2)	0.65879 (15)	0.20740 (13)	0.0247 (4)
H18	0.8553	0.6091	0.1377	0.030*
C19	1.0343 (2)	0.71304 (15)	0.28061 (13)	0.0260 (4)
H19	1.1579	0.7003	0.2604	0.031*
C20	1.0351 (2)	0.78502 (14)	0.38213 (12)	0.0217 (3)
C21	0.8527 (2)	0.80458 (14)	0.41172 (12)	0.0194 (3)
C22	0.6726 (2)	0.75083 (14)	0.33878 (12)	0.0192 (3)
H22	0.5490	0.7643	0.3589	0.023*
C23	0.6888 (3)	0.8927 (2)	0.54936 (14)	0.0344 (5)
H23A	0.600 (4)	0.933 (2)	0.5120 (19)	0.052*
H23B	0.729 (4)	0.944 (2)	0.624 (2)	0.052*
H23C	0.608 (4)	0.811 (2)	0.5363 (19)	0.052*
C24	0.1311 (3)	−0.07391 (17)	0.15062 (14)	0.0321 (4)
H24A	0.2460	−0.0054	0.1724	0.048*
H24B	0.0641	−0.0956	0.0789	0.048*
H24C	0.1785	−0.1450	0.1556	0.048*
O6	0.3201 (9)	0.5783 (3)	0.5140 (3)	0.1001 (17)	0.50
O5	0.2982 (10)	0.3840 (4)	0.4875 (3)	0.0992 (17)	0.50
H5A	0.4195	0.4002	0.4851	0.149*	0.50
C25	0.2215 (14)	0.4812 (6)	0.5036 (4)	0.078 (2)	0.50
C26	0.0013 (18)	0.4670 (7)	0.5103 (7)	0.086 (3)	0.50
H26A	−0.0735	0.3851	0.4583	0.103*	0.50
H26B	−0.0093	0.4716	0.5796	0.103*	0.50
C27	−0.0933 (19)	0.5642 (10)	0.4919 (9)	0.099 (4)	0.50
H27A	−0.2359	0.5497	0.4941	0.148*	0.50
H27B	−0.0808	0.5611	0.4240	0.148*	0.50
H27C	−0.0250	0.6452	0.5458	0.148*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0275 (6)	0.0259 (6)	0.0237 (6)	0.0023 (5)	0.0049 (5)	0.0125 (5)
O2	0.0141 (6)	0.0390 (7)	0.0221 (6)	0.0023 (5)	−0.0026 (5)	0.0022 (5)
O3	0.0252 (6)	0.0214 (6)	0.0243 (6)	0.0060 (5)	0.0046 (5)	0.0092 (5)
O4	0.0159 (6)	0.0363 (7)	0.0161 (5)	0.0004 (5)	0.0021 (4)	0.0039 (5)
N1	0.0152 (6)	0.0196 (7)	0.0180 (7)	0.0012 (5)	−0.0007 (5)	0.0065 (5)
N2	0.0166 (6)	0.0187 (6)	0.0171 (6)	0.0030 (5)	0.0012 (5)	0.0051 (5)
C1	0.0211 (8)	0.0212 (8)	0.0180 (8)	−0.0023 (6)	−0.0003 (6)	0.0070 (6)
C2	0.0223 (8)	0.0285 (9)	0.0253 (8)	0.0037 (7)	0.0071 (7)	0.0102 (7)
C3	0.0226 (8)	0.0243 (8)	0.0260 (8)	0.0060 (7)	0.0053 (7)	0.0107 (7)
C4	0.0176 (8)	0.0195 (8)	0.0172 (7)	−0.0008 (6)	−0.0016 (6)	0.0055 (6)
C5	0.0177 (8)	0.0214 (8)	0.0176 (7)	0.0004 (6)	0.0010 (6)	0.0051 (6)
C6	0.0191 (8)	0.0179 (7)	0.0171 (7)	0.0001 (6)	−0.0024 (6)	0.0043 (6)
C7	0.0181 (8)	0.0184 (7)	0.0172 (7)	0.0026 (6)	0.0030 (6)	0.0053 (6)
C8	0.0188 (8)	0.0179 (7)	0.0178 (7)	0.0017 (6)	0.0032 (6)	0.0044 (6)
C9	0.0203 (8)	0.0226 (8)	0.0221 (8)	−0.0012 (6)	0.0018 (6)	0.0086 (7)
C10	0.0168 (8)	0.0235 (8)	0.0212 (8)	−0.0011 (6)	−0.0001 (6)	0.0064 (7)
C11	0.0163 (7)	0.0186 (8)	0.0176 (7)	0.0018 (6)	0.0020 (6)	0.0032 (6)
C12	0.0158 (8)	0.0180 (7)	0.0176 (7)	0.0035 (6)	0.0019 (6)	0.0028 (6)
C13	0.0161 (7)	0.0179 (7)	0.0178 (7)	0.0029 (6)	0.0012 (6)	0.0035 (6)
C14	0.0177 (8)	0.0216 (8)	0.0219 (8)	0.0017 (6)	−0.0038 (6)	0.0062 (7)
C15	0.0225 (8)	0.0218 (8)	0.0220 (8)	0.0028 (6)	−0.0001 (6)	0.0094 (7)
C16	0.0190 (8)	0.0183 (7)	0.0185 (7)	0.0033 (6)	0.0023 (6)	0.0057 (6)
C17	0.0164 (8)	0.0169 (7)	0.0208 (8)	0.0005 (6)	0.0001 (6)	0.0069 (6)
C18	0.0195 (8)	0.0273 (9)	0.0192 (8)	0.0046 (7)	0.0017 (6)	0.0023 (7)
C19	0.0167 (8)	0.0298 (9)	0.0255 (9)	0.0061 (7)	0.0038 (7)	0.0050 (7)
C20	0.0150 (8)	0.0233 (8)	0.0220 (8)	0.0008 (6)	−0.0013 (6)	0.0071 (7)
C21	0.0183 (8)	0.0199 (8)	0.0170 (7)	0.0011 (6)	0.0023 (6)	0.0059 (6)
C22	0.0145 (7)	0.0209 (8)	0.0203 (8)	0.0010 (6)	0.0018 (6)	0.0081 (6)
C23	0.0182 (9)	0.0506 (12)	0.0210 (9)	0.0000 (8)	0.0060 (7)	0.0027 (8)
C24	0.0372 (10)	0.0318 (9)	0.0324 (10)	0.0161 (8)	0.0136 (8)	0.0138 (8)
O6	0.192 (5)	0.039 (2)	0.067 (3)	0.009 (3)	0.050 (3)	0.0162 (18)
O5	0.165 (5)	0.054 (2)	0.073 (3)	0.006 (3)	−0.001 (3)	0.036 (2)
C25	0.157 (7)	0.038 (3)	0.025 (2)	0.001 (4)	−0.001 (3)	0.011 (2)
C26	0.153 (8)	0.037 (5)	0.050 (3)	0.002 (5)	−0.017 (5)	0.020 (3)
C27	0.138 (11)	0.053 (6)	0.092 (6)	0.010 (5)	−0.026 (6)	0.037 (4)

Geometric parameters (Å, º) top

O1—C1	1.3742 (19)	C12—C11ⁱ	1.406 (2)
O1—H1O	0.84 (2)	C12—C17	1.497 (2)
O2—C20	1.3637 (19)	C13—C14	1.426 (2)
O2—H2O	0.90 (2)	C14—C15	1.361 (2)
O3—C6	1.3704 (19)	C14—H14	0.9500
O3—C24	1.431 (2)	C15—C16	1.431 (2)
O4—C21	1.3670 (19)	C15—H15	0.9500
O4—C23	1.432 (2)	C17—C18	1.389 (2)
N1—C16	1.372 (2)	C17—C22	1.401 (2)
N1—C13	1.372 (2)	C18—C19	1.392 (2)
N1—H1N	0.85 (2)	C18—H18	0.9500
N2—C11	1.369 (2)	C19—C20	1.377 (2)
N2—C8	1.372 (2)	C19—H19	0.9500
C1—C2	1.375 (2)	C20—C21	1.402 (2)
C1—C6	1.400 (2)	C21—C22	1.389 (2)
C2—C3	1.391 (2)	C22—H22	0.9500
C2—H2	0.9500	C23—H23A	1.04 (3)
C3—C4	1.389 (2)	C23—H23B	0.99 (3)
C3—H3	0.9500	C23—H23C	1.00 (3)
C4—C5	1.402 (2)	C24—H24A	0.9800
C4—C7	1.494 (2)	C24—H24B	0.9800
C5—C6	1.384 (2)	C24—H24C	0.9800
C5—H5	0.9500	O6—C25	1.218 (8)
C7—C16	1.402 (2)	O5—C25	1.303 (9)
C7—C8	1.405 (2)	O5—H5A	0.8400
C8—C9	1.454 (2)	C25—C26	1.522 (16)
C9—C10	1.345 (2)	C26—C27	1.503 (13)
C9—H9	0.9500	C26—H26A	0.9900
C10—C11	1.450 (2)	C26—H26B	0.9900
C10—H10	0.98 (2)	C27—H27A	0.9800
C11—C12ⁱ	1.406 (2)	C27—H27B	0.9800
C12—C13	1.401 (2)	C27—H27C	0.9800

C1—O1—H1O	107.0 (15)	C14—C15—H15	126.1
C20—O2—H2O	108.6 (15)	C16—C15—H15	126.1
C6—O3—C24	117.77 (13)	N1—C16—C7	126.76 (14)
C21—O4—C23	116.35 (12)	N1—C16—C15	106.89 (13)
C16—N1—C13	110.09 (13)	C7—C16—C15	126.26 (14)
C16—N1—H1N	124.7 (13)	C18—C17—C22	119.17 (14)
C13—N1—H1N	124.9 (13)	C18—C17—C12	121.39 (14)
C11—N2—C8	105.46 (12)	C22—C17—C12	119.44 (14)
O1—C1—C2	118.99 (15)	C17—C18—C19	120.38 (15)
O1—C1—C6	121.02 (15)	C17—C18—H18	119.8
C2—C1—C6	119.99 (15)	C19—C18—H18	119.8
C1—C2—C3	120.07 (15)	C20—C19—C18	120.56 (15)
C1—C2—H2	120.0	C20—C19—H19	119.7
C3—C2—H2	120.0	C18—C19—H19	119.7
C4—C3—C2	120.75 (15)	O2—C20—C19	119.30 (15)
C4—C3—H3	119.6	O2—C20—C21	121.01 (14)
C2—C3—H3	119.6	C19—C20—C21	119.68 (14)
C3—C4—C5	118.91 (15)	O4—C21—C22	125.60 (14)
C3—C4—C7	119.91 (14)	O4—C21—C20	114.51 (13)
C5—C4—C7	121.18 (14)	C22—C21—C20	119.88 (14)
C6—C5—C4	120.30 (15)	C21—C22—C17	120.32 (15)
C6—C5—H5	119.9	C21—C22—H22	119.8
C4—C5—H5	119.9	C17—C22—H22	119.8
O3—C6—C5	126.06 (14)	O4—C23—H23A	112.4 (14)
O3—C6—C1	113.96 (13)	O4—C23—H23B	105.9 (14)
C5—C6—C1	119.98 (15)	H23A—C23—H23B	111.4 (19)
C16—C7—C8	125.43 (14)	O4—C23—H23C	109.9 (14)
C16—C7—C4	116.49 (14)	H23A—C23—H23C	108 (2)
C8—C7—C4	118.05 (13)	H23B—C23—H23C	109 (2)
N2—C8—C7	125.96 (14)	O3—C24—H24A	109.5
N2—C8—C9	110.38 (13)	O3—C24—H24B	109.5
C7—C8—C9	123.62 (14)	H24A—C24—H24B	109.5
C10—C9—C8	106.76 (14)	O3—C24—H24C	109.5
C10—C9—H9	126.6	H24A—C24—H24C	109.5
C8—C9—H9	126.6	H24B—C24—H24C	109.5
C9—C10—C11	106.70 (14)	C25—O5—H5A	109.5
C9—C10—H10	128.0 (11)	O6—C25—O5	122.2 (9)
C11—C10—H10	125.3 (11)	O6—C25—C26	121.8 (7)
N2—C11—C12ⁱ	125.73 (14)	O5—C25—C26	116.0 (7)
N2—C11—C10	110.70 (14)	C27—C26—C25	112.1 (6)
C12ⁱ—C11—C10	123.52 (14)	C27—C26—H26A	109.2
C13—C12—C11ⁱ	125.08 (14)	C25—C26—H26A	109.2
C13—C12—C17	116.23 (14)	C27—C26—H26B	109.2
C11ⁱ—C12—C17	118.62 (13)	C25—C26—H26B	109.2
N1—C13—C12	126.83 (14)	H26A—C26—H26B	107.9
N1—C13—C14	106.81 (13)	C26—C27—H27A	109.5
C12—C13—C14	126.31 (14)	C26—C27—H27B	109.5
C15—C14—C13	108.34 (14)	H27A—C27—H27B	109.5
C15—C14—H14	125.8	C26—C27—H27C	109.5
C13—C14—H14	125.8	H27A—C27—H27C	109.5
C14—C15—C16	107.86 (14)	H27B—C27—H27C	109.5

O1—C1—C2—C3	179.38 (14)	C17—C12—C13—N1	176.90 (14)
C6—C1—C2—C3	−0.5 (2)	C11ⁱ—C12—C13—C14	−177.37 (15)
C1—C2—C3—C4	−0.1 (2)	C17—C12—C13—C14	−0.3 (2)
C2—C3—C4—C5	0.5 (2)	N1—C13—C14—C15	−0.45 (18)
C2—C3—C4—C7	−178.92 (14)	C12—C13—C14—C15	177.19 (15)
C3—C4—C5—C6	−0.2 (2)	C13—C14—C15—C16	−0.24 (18)
C7—C4—C5—C6	179.19 (14)	C13—N1—C16—C7	175.63 (15)
C24—O3—C6—C5	−4.5 (2)	C13—N1—C16—C15	−1.14 (17)
C24—O3—C6—C1	175.86 (14)	C8—C7—C16—N1	−2.8 (3)
C4—C5—C6—O3	−179.98 (13)	C4—C7—C16—N1	179.17 (14)
C4—C5—C6—C1	−0.4 (2)	C8—C7—C16—C15	173.42 (15)
O1—C1—C6—O3	0.5 (2)	C4—C7—C16—C15	−4.7 (2)
C2—C1—C6—O3	−179.61 (14)	C14—C15—C16—N1	0.84 (18)
O1—C1—C6—C5	−179.11 (13)	C14—C15—C16—C7	−175.96 (15)
C2—C1—C6—C5	0.8 (2)	C13—C12—C17—C18	110.22 (18)
C3—C4—C7—C16	113.71 (17)	C11ⁱ—C12—C17—C18	−72.5 (2)
C5—C4—C7—C16	−65.69 (19)	C13—C12—C17—C22	−68.89 (19)
C3—C4—C7—C8	−64.5 (2)	C11ⁱ—C12—C17—C22	108.39 (17)
C5—C4—C7—C8	116.09 (16)	C22—C17—C18—C19	0.3 (2)
C11—N2—C8—C7	177.38 (15)	C12—C17—C18—C19	−178.78 (15)
C11—N2—C8—C9	−0.18 (17)	C17—C18—C19—C20	0.2 (3)
C16—C7—C8—N2	−0.8 (3)	C18—C19—C20—O2	178.29 (16)
C4—C7—C8—N2	177.23 (14)	C18—C19—C20—C21	−0.5 (3)
C16—C7—C8—C9	176.43 (15)	C23—O4—C21—C22	4.4 (2)
C4—C7—C8—C9	−5.5 (2)	C23—O4—C21—C20	−175.46 (16)
N2—C8—C9—C10	0.38 (18)	O2—C20—C21—O4	1.4 (2)
C7—C8—C9—C10	−177.25 (15)	C19—C20—C21—O4	−179.76 (15)
C8—C9—C10—C11	−0.40 (18)	O2—C20—C21—C22	−178.45 (15)
C8—N2—C11—C12ⁱ	−177.59 (15)	C19—C20—C21—C22	0.4 (2)
C8—N2—C11—C10	−0.07 (17)	O4—C21—C22—C17	−179.70 (14)
C9—C10—C11—N2	0.31 (18)	C20—C21—C22—C17	0.2 (2)
C9—C10—C11—C12ⁱ	177.89 (15)	C18—C17—C22—C21	−0.5 (2)
C16—N1—C13—C12	−176.62 (15)	C12—C17—C22—C21	178.62 (14)
C16—N1—C13—C14	1.00 (17)	O6—C25—C26—C27	20.7 (8)
C11ⁱ—C12—C13—N1	−0.2 (3)	O5—C25—C26—C27	−160.2 (5)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.85 (2)	2.392 (19)	2.9286 (19)	121.4 (15)
N1—H1N···N2ⁱ	0.85 (2)	2.377 (19)	2.9121 (19)	121.2 (15)
O1—H1O···O3	0.84 (2)	2.17 (2)	2.6655 (17)	117.4 (19)
O2—H2O···O4	0.90 (2)	2.18 (2)	2.6726 (16)	113.8 (18)
O2—H2O···O1ⁱⁱ	0.90 (2)	2.03 (2)	2.8588 (17)	151 (2)
C10—H10···O3ⁱⁱⁱ	0.98 (2)	2.46 (2)	3.4085 (19)	162.0 (16)
C23—H23B···O3ⁱⁱ	0.99 (3)	2.51 (3)	3.383 (2)	147.3 (19)
C23—H23C···O5ⁱⁱ	1.00 (3)	2.43 (3)	3.189 (5)	132.3 (19)
O5—H5A···O6ⁱⁱ	0.84	1.77	2.608 (9)	173

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

Experimental details

Crystal data
Chemical formula	C₄₈H₃₈N₄O₈·C₃H₆O₂
M_r	872.90
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.8715 (5), 12.0783 (7), 14.3772 (10)
α, β, γ (°)	112.850 (6), 98.560 (5), 97.480 (5)
V (Å³)	1063.97 (12)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.10 × 0.03 × 0.02

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.926, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	9919, 3688, 3098
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.104, 1.03
No. of reflections	3688
No. of parameters	339
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.85 (2)	2.392 (19)	2.9286 (19)	121.4 (15)
N1—H1N···N2ⁱ	0.85 (2)	2.377 (19)	2.9121 (19)	121.2 (15)
O1—H1O···O3	0.84 (2)	2.17 (2)	2.6655 (17)	117.4 (19)
O2—H2O···O4	0.90 (2)	2.18 (2)	2.6726 (16)	113.8 (18)
O2—H2O···O1ⁱⁱ	0.90 (2)	2.03 (2)	2.8588 (17)	151 (2)
C10—H10···O3ⁱⁱⁱ	0.98 (2)	2.46 (2)	3.4085 (19)	162.0 (16)
C23—H23B···O3ⁱⁱ	0.99 (3)	2.51 (3)	3.383 (2)	147.3 (19)
C23—H23C···O5ⁱⁱ	1.00 (3)	2.43 (3)	3.189 (5)	132.3 (19)
O5—H5A···O6ⁱⁱ	0.84	1.77	2.608 (9)	173.4

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

Acknowledgements

The authors are grateful to Dr M. Rojkiewicz for his help during the synthesis of the samples.

References

Agilent (2011). CrysAlis PRO. Agilent Techniologies, Yarnton, England. Google Scholar
Agostinis, P., Berg, K., Cengel, K. A., Foster, T. H., Girotti, A. W., Gollnick, S. O., Hahn, S. M., Hamblin, M. R., Juzeniene, A., Kessel, D., Korbelik, M., Moan, J., Mroz, P., Nowis, D., Piette, J., Wilson, B. C. & Golab, J. (2011). CA Cancer J. Clin. 61, 250–284. Web of Science CrossRef PubMed Google Scholar
Allison, R. R., Downie, G. H., Cuenca, R., Hu, X., Childs, C. J. & Sibata, C. H. (2004). Photodiagn. Photodyn. Ther. 1, 27–42. Web of Science CrossRef CAS Google Scholar
Bonar-Law, R. P. (1996). J. Org. Chem. 61, 3623–3634. PubMed CAS Google Scholar
Dougherty, T. J., Henderson, B. W., Gomer, C. J., Jori, G., Kessel, D., Korbelik, M., Moan, J. & Peng, Q. (1998). J. Natl Cancer. Inst. 90, 889–905. Web of Science CrossRef CAS PubMed Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szurko, A., Rams, M., Sochanik, A., Sieron-Stoltny, K., Kozielec, A. M., Montforts, F. P., Wrzalik, R. & Ratuszna, A. (2009). Bioorg. Med. Chem. 17, 8197–8205. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages o2797-o2798

doi:10.1107/S1600536812036495

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

meso-5,10,15,20-Tetra­kis(4-hy­dr­oxy-3-meth­­oxy­phen­yl)porphyrin propionic acid monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

meso-5,10,15,20-Tetrakis(4-hydroxy-3-methoxyphenyl)porphyrin propionic acid monosolvate