Chlorido{5,10,15,20-tetra­kis­[2-(2,2-dimethyl­propanamido)­phen­yl]porphyrinato-κ4N,N′,N′′,N′′′}iron(III) chloro­benzene hemisolvate monohydrate

Dhifet, M.; Belkhiria, M.S.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536811009299

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages m460-m461

doi:10.1107/S1600536811009299

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Chlorido{5,10,15,20-tetrakis[2-(2,2-dimethylpropanamido)phenyl]porphyrinato-κ⁴N,N′,N′′,N′′′}iron(III) chlorobenzene hemisolvate monohydrate

Mondher Dhifet,^a Mohamed Salah Belkhiria,^a Jean-Claude Daran ^b and Habib Nasri ^a ^*

^aDépartement de Chimie, Faculté des Sciences de Monastir, Université de Monastir, Avenue de l'environnement, 5019 Monastir, Tunisia, and ^bLaboratoire de Chimie de Coordination, CNRS UPR 8241, 205 route de Norbonne, 31077 Toulouse, Cedex 04, France
^*Correspondence e-mail: hnasri1@gmail.com

(Received 15 February 2011; accepted 10 March 2011; online 15 March 2011)

In the title complex, [Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O, the equatorial iron–pyrrole N atom distance (Fe—N_p) is 2.065 (2) Å and the axial Fe—Cl distance is 2.207 (2) Å. The iron cation is displaced by 0.420 (4) Å from the 24-atom mean plane of the porphyrin core. The asymmetric unit contains a quarter of an [Fe^III(C₆₄H₆₄N₈O₄)Cl] complex molecule, with a fourfold rotation axis passing through the central metal cation and the Cl ligand, along with disordered molecules of chlorobenzene and water of solvation; the solvent molecules were excluded from the refinement.

Related literature

For a review of porphyrin complexes, see: Scheidt (2000 ). For synthetic procedures, see: Gismelseed et al. (1990 ). For structural features of porphyrins, see: Schappacher et al. (1983 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O
M_r = 1206.84
Tetragonal, P 4/n c c
a = 18.069 (3) Å
c = 18.919 (4) Å
V = 6177 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 180 K
0.22 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.842, T_max = 0.937
43373 measured reflections
3021 independent reflections
2089 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.180
S = 1.07
3021 reflections
178 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009299/pv2389sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009299/pv2389Isup2.hkl

checkCIF report

Comment top

In the Cambridge Structural Database (CSD, Version 5.32; Allen, 2002) there are more than sixty structures of iron(III) chloride with many types of porphyrins. This large number of structures reflects the importance of this type of complex which is used as starting material in the synthesis of iron(III) and iron(II) porphyrin species.

A formula unit of the title complex contains a amolecule of [Fe^III(C₆₄H₆₄N₈O₄)Cl] (Fig. 1), a half molecule of chlorobenzene and a molecule of water of solvation; the solvent molecules were disordered and were therefore, excluded from the refinement. The most important feature of the structure is the fact that the chloride ion is coordinated to the Fe(III) from the open side face of the picket fence porphyrin for which anionic axial ligands are known to be bound to the metal ion from the protected side of this porphyrin (Schappacher et al., 1983). The square-pyramidal coordination of the central atom, with an equatorial iron-pyrrole nitrogen atom distance (Fe–N_p) of 2.065 (2) Å and 2.207 (2) Å for the axial Fe–Cl distance, is typical for penta-coodined iron(III) high-spin (S = 5/2) chloride porphyrin species (Scheidt, 2000). The iron atom is displaced by 0.420 (4) Å from the 24 atom mean plane.

Related literature top

For a review of porphyrin complexes, see: Scheidt (2000). For synthetic procedures, see: Gismelseed et al. (1990). For structural features of porphyrins, see: Schappacher et al. (1983). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The reaction of the [Fe^III(TpivPP)(SO₃CF₃)(H₂O)] complex (Gismelseed et al., 1990) (100 mg, 0.081 mmol) with an excess of potassium chlorite, KClO₃ (198 mg, 1.62 mmol) and 18-crown-6 (214 mg, 0.81 mmol) in chlorobenzene (5 ml) yields a reddish-brown solution. Crystals of the title complex were obtained as impurities by diffusion of hexanes through the chlorobenzene solution.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of ion complex [Fe^III(C₆₄H₆₄N₈O₄)Cl] showing the atom numbering schem. Displacement ellipsoids are drawn at 50%. The H atoms have been omitted for clarity. Symmetry codes: (i) -y + 1/2, x, z; (ii) y, -x + 1/2, z; (iii) -x + 1/2, -y + 1/2, z.
	Fig. 2. A unit cell packing of the title complex viewed down the c-axis, solvents have been excluded.

Chlorido{5,10,15,20-tetrakis[2-(2,2-dimethylpropanamido)phenyl]porphyrinato- κ⁴N,N',N'',N'''}iron(III) chlorobenzene hemisolvate monohydrate top

Crystal data top

[Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O	D_x = 1.298 Mg m⁻³
M_r = 1206.84	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/ncc	Cell parameters from 43373 reflections
Hall symbol: -P 4a 2ac	θ = 2.7–26.0°
a = 18.069 (3) Å	µ = 0.34 mm⁻¹
c = 18.919 (4) Å	T = 180 K
V = 6177 (2) Å³	Prism, dark purple
Z = 4	0.22 × 0.18 × 0.16 mm
F(000) = 2536

Data collection top

Bruker APEXII CCD area-detector diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	2089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −22→22
T_min = 0.842, T_max = 0.937	k = −20→22
43373 measured reflections	l = −23→23

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.115P)² + 0.6251P] where P = (F_o² + 2F_c²)/3
3021 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

[Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O	Z = 4
M_r = 1206.84	Mo Kα radiation
Tetragonal, P4/ncc	µ = 0.34 mm⁻¹
a = 18.069 (3) Å	T = 180 K
c = 18.919 (4) Å	0.22 × 0.18 × 0.16 mm
V = 6177 (2) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3021 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2089 reflections with I > 2σ(I)
T_min = 0.842, T_max = 0.937	R_int = 0.064
43373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.180	H-atom parameters constrained
S = 1.07	Δρ_max = 0.81 e Å⁻³
3021 reflections	Δρ_min = −1.34 e Å⁻³
178 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Fe	0.2500	0.2500	0.12373 (4)	0.0222 (3)
Cl	0.2500	0.2500	0.24040 (7)	0.0335 (4)
O1	0.56932 (17)	0.3807 (2)	−0.12040 (12)	0.0677 (10)
N1	0.35198 (11)	0.20458 (11)	0.10034 (11)	0.0163 (5)
N2	0.49310 (14)	0.35229 (16)	−0.03138 (13)	0.0371 (7)
HN2	0.4488	0.3373	−0.0231	0.045*
C1	0.36920 (14)	0.13070 (14)	0.09954 (14)	0.0187 (6)
C2	0.44818 (15)	0.12135 (16)	0.09858 (15)	0.0250 (6)
H2	0.4735	0.0766	0.0981	0.030*
C3	0.47859 (15)	0.18914 (15)	0.09854 (15)	0.0249 (6)
H3	0.5289	0.2001	0.0980	0.030*
C4	0.41823 (14)	0.24197 (14)	0.09945 (14)	0.0190 (6)
C5	0.42756 (14)	0.31872 (14)	0.09900 (13)	0.0183 (6)
C6	0.50541 (14)	0.34772 (14)	0.09465 (14)	0.0200 (6)
C7	0.54726 (15)	0.35788 (16)	0.15514 (15)	0.0262 (7)
H7	0.5264	0.3482	0.1991	0.031*
C8	0.61929 (17)	0.38216 (18)	0.15117 (16)	0.0333 (7)
H8	0.6466	0.3890	0.1923	0.040*
C9	0.65061 (18)	0.3961 (2)	0.08699 (18)	0.0433 (9)
H9	0.6995	0.4120	0.0845	0.052*
C10	0.61015 (18)	0.3869 (2)	0.02555 (17)	0.0412 (9)
H10	0.6316	0.3969	−0.0181	0.049*
C11	0.53757 (16)	0.36263 (17)	0.02937 (15)	0.0286 (7)
C12	0.50947 (19)	0.36235 (17)	−0.10004 (16)	0.0327 (7)
C13	0.44577 (19)	0.34785 (17)	−0.15323 (16)	0.0342 (8)
C14	0.4681 (2)	0.2800 (2)	−0.19598 (18)	0.0431 (8)
H14A	0.5152	0.2886	−0.2179	0.065*
H14B	0.4316	0.2707	−0.2317	0.065*
H14C	0.4715	0.2379	−0.1652	0.065*
C15	0.3714 (2)	0.3359 (3)	−0.11812 (18)	0.0494 (10)
H15A	0.3582	0.3791	−0.0915	0.074*
H15B	0.3742	0.2940	−0.0870	0.074*
H15C	0.3345	0.3268	−0.1536	0.074*
C16	0.4413 (3)	0.4155 (2)	−0.2017 (2)	0.0747 (15)
H16A	0.4271	0.4581	−0.1745	0.112*
H16B	0.4052	0.4068	−0.2380	0.112*
H16C	0.4887	0.4242	−0.2229	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.0228 (3)	0.0228 (3)	0.0211 (4)	0.000	0.000	0.000
Cl	0.0409 (6)	0.0409 (6)	0.0188 (7)	0.000	0.000	0.000
O1	0.0669 (19)	0.111 (3)	0.0255 (13)	−0.0554 (19)	0.0096 (12)	−0.0067 (13)
N1	0.0157 (11)	0.0160 (11)	0.0171 (10)	0.0016 (9)	0.0025 (9)	−0.0008 (9)
N2	0.0264 (14)	0.0630 (19)	0.0220 (13)	−0.0182 (13)	−0.0021 (11)	0.0079 (12)
C1	0.0199 (14)	0.0203 (14)	0.0158 (12)	0.0021 (10)	0.0008 (10)	−0.0001 (10)
C2	0.0189 (14)	0.0226 (15)	0.0336 (15)	0.0052 (11)	0.0024 (12)	0.0002 (12)
C3	0.0167 (14)	0.0257 (15)	0.0323 (15)	0.0024 (11)	0.0038 (12)	−0.0042 (12)
C4	0.0172 (13)	0.0239 (15)	0.0158 (12)	0.0012 (10)	0.0018 (10)	−0.0014 (10)
C5	0.0184 (13)	0.0210 (14)	0.0155 (12)	−0.0026 (10)	0.0028 (10)	0.0009 (11)
C6	0.0166 (14)	0.0202 (14)	0.0232 (14)	−0.0010 (10)	0.0007 (11)	0.0002 (11)
C7	0.0244 (16)	0.0324 (17)	0.0219 (14)	−0.0009 (12)	0.0017 (12)	−0.0027 (12)
C8	0.0258 (16)	0.047 (2)	0.0271 (15)	−0.0057 (14)	−0.0049 (13)	−0.0102 (14)
C9	0.0231 (17)	0.063 (2)	0.0435 (19)	−0.0194 (16)	0.0014 (14)	−0.0035 (18)
C10	0.0304 (18)	0.067 (2)	0.0265 (16)	−0.0233 (16)	0.0047 (13)	0.0042 (15)
C11	0.0267 (16)	0.0364 (17)	0.0226 (15)	−0.0084 (12)	−0.0010 (12)	0.0025 (12)
C12	0.047 (2)	0.0288 (16)	0.0224 (15)	−0.0122 (14)	0.0016 (14)	0.0017 (13)
C13	0.052 (2)	0.0302 (17)	0.0209 (15)	−0.0009 (14)	−0.0103 (14)	0.0017 (12)
C14	0.047 (2)	0.048 (2)	0.0350 (18)	0.0001 (16)	−0.0096 (16)	−0.0104 (16)
C15	0.039 (2)	0.071 (3)	0.0376 (19)	0.0059 (18)	−0.0167 (16)	−0.0144 (18)
C16	0.132 (4)	0.046 (2)	0.046 (2)	0.013 (3)	−0.022 (3)	0.015 (2)

Geometric parameters (Å, º) top

Fe—N1ⁱ	2.065 (2)	C7—C8	1.376 (4)
Fe—N1ⁱⁱ	2.065 (2)	C7—H7	0.9300
Fe—N1	2.065 (2)	C8—C9	1.363 (5)
Fe—N1ⁱⁱⁱ	2.065 (2)	C8—H8	0.9300
Fe—Cl	2.2073 (16)	C9—C10	1.383 (4)
O1—C12	1.195 (4)	C9—H9	0.9300
N1—C1	1.371 (3)	C10—C11	1.385 (4)
N1—C4	1.375 (3)	C10—H10	0.9300
N2—C12	1.345 (4)	C12—C13	1.551 (4)
N2—C11	1.415 (4)	C13—C15	1.515 (5)
N2—HN2	0.8600	C13—C14	1.523 (5)
C1—C5ⁱⁱ	1.393 (4)	C13—C16	1.530 (5)
C1—C2	1.437 (4)	C14—H14A	0.9600
C2—C3	1.343 (4)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.449 (4)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.397 (4)	C15—H15C	0.9600
C5—C1ⁱ	1.393 (4)	C16—H16A	0.9600
C5—C6	1.503 (4)	C16—H16B	0.9600
C6—C7	1.384 (4)	C16—H16C	0.9600
C6—C11	1.391 (4)

N1ⁱ—Fe—N1ⁱⁱ	155.25 (12)	C9—C8—H8	120.0
N1ⁱ—Fe—N1	87.37 (3)	C7—C8—H8	120.0
N1ⁱⁱ—Fe—N1	87.37 (3)	C8—C9—C10	120.4 (3)
N1ⁱ—Fe—N1ⁱⁱⁱ	87.37 (3)	C8—C9—H9	119.8
N1ⁱⁱ—Fe—N1ⁱⁱⁱ	87.37 (3)	C10—C9—H9	119.8
N1—Fe—N1ⁱⁱⁱ	155.25 (12)	C9—C10—C11	119.7 (3)
N1ⁱ—Fe—Cl	102.38 (6)	C9—C10—H10	120.2
N1ⁱⁱ—Fe—Cl	102.38 (6)	C11—C10—H10	120.2
N1—Fe—Cl	102.38 (6)	C10—C11—C6	120.2 (3)
N1ⁱⁱⁱ—Fe—Cl	102.38 (6)	C10—C11—N2	122.5 (3)
C1—N1—C4	106.3 (2)	C6—C11—N2	117.3 (2)
C1—N1—Fe	126.29 (17)	O1—C12—N2	123.2 (3)
C4—N1—Fe	125.75 (17)	O1—C12—C13	120.6 (3)
C12—N2—C11	130.0 (3)	N2—C12—C13	116.2 (3)
C12—N2—HN2	115.0	C15—C13—C14	110.6 (3)
C11—N2—HN2	115.0	C15—C13—C16	109.3 (3)
N1—C1—C5ⁱⁱ	126.0 (2)	C14—C13—C16	109.8 (3)
N1—C1—C2	109.9 (2)	C15—C13—C12	113.5 (3)
C5ⁱⁱ—C1—C2	124.1 (2)	C14—C13—C12	106.5 (3)
C3—C2—C1	107.4 (2)	C16—C13—C12	107.0 (3)
C3—C2—H2	126.3	C13—C14—H14A	109.5
C1—C2—H2	126.3	C13—C14—H14B	109.5
C2—C3—C4	107.0 (2)	H14A—C14—H14B	109.5
C2—C3—H3	126.5	C13—C14—H14C	109.5
C4—C3—H3	126.5	H14A—C14—H14C	109.5
N1—C4—C5	126.4 (2)	H14B—C14—H14C	109.5
N1—C4—C3	109.4 (2)	C13—C15—H15A	109.5
C5—C4—C3	124.2 (2)	C13—C15—H15B	109.5
C1ⁱ—C5—C4	124.0 (2)	H15A—C15—H15B	109.5
C1ⁱ—C5—C6	118.6 (2)	C13—C15—H15C	109.5
C4—C5—C6	117.3 (2)	H15A—C15—H15C	109.5
C7—C6—C11	118.7 (2)	H15B—C15—H15C	109.5
C7—C6—C5	120.8 (2)	C13—C16—H16A	109.5
C11—C6—C5	120.5 (2)	C13—C16—H16B	109.5
C8—C7—C6	120.9 (3)	H16A—C16—H16B	109.5
C8—C7—H7	119.5	C13—C16—H16C	109.5
C6—C7—H7	119.5	H16A—C16—H16C	109.5
C9—C8—C7	120.0 (3)	H16B—C16—H16C	109.5

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

Experimental details

Crystal data
Chemical formula	[Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O
M_r	1206.84
Crystal system, space group	Tetragonal, P4/ncc
Temperature (K)	180
a, c (Å)	18.069 (3), 18.919 (4)
V (Å³)	6177 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.22 × 0.18 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.842, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	43373, 3021, 2089
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.180, 1.07
No. of reflections	3021
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −1.34

Computer programs: APEX2 (Bruker, 2007), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009).

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.

References

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