Crystal structure of bis­(tetra­phenyl­phospho­nium) bis­(cyanido-κC)(29H,31H-tetra­benzo[b,g,l,q]porphinato-κ4N29,N30,N31,N32)ferrate(II) acetone disolvate

Nishi, M.; Matsuda, M.; Hoshino, N.; Akutagawa, T.

doi:10.1107/S2056989015001735

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages m48-m49

doi:10.1107/S2056989015001735

Open

access

Crystal structure of bis(tetraphenylphosphonium) bis(cyanido-κC)(29H,31H-tetrabenzo[b,g,l,q]porphinato-κ⁴N²⁹,N³⁰,N³¹,N³²)ferrate(II) acetone disolvate

Miki Nishi,^a Masaki Matsuda,^a ^* Norihisa Hoshino ^b and Tomoyuki Akutagawa ^b

^aDepartment of Chemistry, Kumamoto University, Kurokami 2-39-1, Chuo-ku, Kumamoto 860-8555, Japan, and ^bInstitute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan
^*Correspondence e-mail: masaki@sci.kumamoto-u.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 January 2015; accepted 27 January 2015; online 31 January 2015)

The crystal structure of the title compound, (C₂₄H₂₀P)₂[Fe(C₃₆H₂₀N₄)(CN)₂]·2C₃H₆O, is constructed from a tetrahedral Ph₄P⁺ (tetraphenylphosphonium) cation, one [Fe(tbp)(CN)₂]²⁻ anion (tbp = tetrabenzoporphyrin in its doubly deprotonated form), located on a centre of inversion, and an acetone molecule as crystallization solvent. Since the molecular structure of the M(tbp) moiety is insensitive to the kind of metal ion and its oxidation state, bond lengths and angles in the [Fe(tbp)(CN)₂]²⁻ anion are similar to those in other M(tbp) compounds. The Fe²⁺ ion, located on a centre of inversion, is coordinated by four N atoms of tpb in the equatorial plane and by two C atoms of the cyanide anion at axial positions in a slightly distorted octahedral configuration. The packing is stabilized by C—H⋯N interactions between the Ph₄P⁺ cation and the CN⁻ ligand of the [Fe(tbp)(CN)₂]²⁻ anion, and by C—H⋯π interactions between the Ph₄P⁺ cation, acetone solvent molecules and the [Fe(tbp)(CN)₂]²⁻ anion.

Keywords: crystal structure; tetrabenzoporphine; iron(II) complex; C—H⋯N interactions; C—H⋯π interactions.

CCDC reference: 1045739

1. Related literature

For [Fe(tbp)(CN)₂]⁻ and [Co(tbp)(CN)₂]⁻ complexes, see: Matsuda et al. (2011 , 2014 ); Nishi et al. (2015 ). The crystal structure of metal-free tbp was reported by Aramaki & Mizuguchi (2003 ).

2. Experimental

2.1. Crystal data

(C₂₄H₂₀P)₂[Fe(C₃₆H₂₀N₄)(CN)₂]·2C₃H₆O
M_r = 1411.35
Triclinic, $[P \overline 1]$
a = 11.8412 (3) Å
b = 12.7764 (3) Å
c = 13.8298 (3) Å
α = 67.217 (1)°
β = 66.915 (1)°
γ = 85.510 (1)°
V = 1767.88 (7) Å³
Z = 1
Cu Kα radiation
μ = 2.59 mm⁻¹
T = 120 K
0.20 × 0.10 × 0.05 mm

2.2. Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ) T_min = 0.764, T_max = 1.000
20279 measured reflections
6348 independent reflections
3518 reflections with I > 2σ(I)
R_int = 0.065

2.3. Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.198
S = 0.98
6348 reflections
469 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the N2/C11/C12/C17/C18, C12–C17, C26–C31 and N1/C2/C3/C8/C9 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C34—H22⋯N3ⁱ	0.95	2.57	3.292 (7)	133
C41—H28⋯N3ⁱⁱ	0.95	2.45	3.181 (7)	134
C28—H17⋯Cg1ⁱⁱⁱ	0.95	2.63	3.446 (4)	145
C29—H18⋯Cg2ⁱⁱⁱ	0.95	2.76	3.582 (4)	145
C33—H21⋯Cg3^iv	0.95	2.90	3.729 (5)	147
C35—H23⋯Cg4ⁱ	0.95	2.92	3.733 (4)	145
C45—H32⋯Cg2^v	0.98	2.99	3.798 (6)	141
C45—H33⋯Cg1^v	0.98	2.87	3.469 (5)	120
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y, -z; (iii) x, y, z+1; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1999 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: Yadokari-XG (Wakita, 2001 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1045739

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015001735/wm5120sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015001735/wm5120Isup2.hkl

checkCIF report

Synthesis and crystallization top

Fe(tbp) and (Ph₄P)[Fe(tbp)(CN)₂] were synthesized by the procedure reported by Nishi et al. (2015). Electroreduction of (Ph₄P)[Fe(tbp)(CN)₂] in acetone gave black single crystals of the title compound (Ph₄P)₂[Fe(tbp)(CN)₂].

Refinement top

All hydrogen atoms were positioned geometrically with C—H = 0.95 Å for aromatic and C—H = 0.98 Å for methyl, and they were constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) for aromatic and U_iso(H) = 1.5 U_eq(C) for methyl. Reflection 6 12 0 was obstructed from the beam stop and was omitted from the refinement.

Related literature top

For [Fe(tbp)(CN)₂]^- and [Co(tbp)(CN)₂]^- complexes, see: Matsuda et al. (2011, 2014); Nishi et al. (2015). The crystal structure of metal-free tbp was reported by Aramaki & Mizuguchi (2003).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1999); cell refinement: RAPID-AUTO (Rigaku, 1999); data reduction: RAPID-AUTO (Rigaku, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: Yadokari-XG (Wakita, 2001) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The Ph₄P⁺, [Fe(tbp)(CN)₂]^2- and acetone molecular units in the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: i) -x, -y, -z.]
	Fig. 2. The packing of the title compound viewed down [010].

Bis(tetraphenylphosphonium) bis(cyanido-κC)(29H,31H-tetrabenzo[b,g,l,q]porphinato-κ⁴N²⁹,N³⁰,N³¹,N³²)ferrate(II) acetone disolvate top

Crystal data top

(C₂₄H₂₀P)₂[Fe(C₃₆H₂₀N₄)(CN)₂]·2C₃H₆O	Z = 1
M_r = 1411.35	F(000) = 738
Triclinic, P1	D_x = 1.326 Mg m⁻³
a = 11.8412 (3) Å	Cu Kα radiation, λ = 1.54187 Å
b = 12.7764 (3) Å	Cell parameters from 9659 reflections
c = 13.8298 (3) Å	θ = 3.8–68.1°
α = 67.217 (1)°	µ = 2.59 mm⁻¹
β = 66.915 (1)°	T = 120 K
γ = 85.510 (1)°	Block, black
V = 1767.88 (7) Å³	0.20 × 0.10 × 0.05 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	6348 independent reflections
Radiation source: fine-focus sealed tube	3518 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ω scans	θ_max = 68.2°, θ_min = 3.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	h = −14→14
T_min = 0.764, T_max = 1.000	k = −14→14
20279 measured reflections	l = −16→16

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)] = 0.068	H-atom parameters constrained
wR(F²) = 0.198	w = 1/[σ²(F_o²) + (0.0991P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
6348 reflections	Δρ_max = 0.71 e Å⁻³
469 parameters	Δρ_min = −0.36 e Å⁻³
0 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: 0.0038 (5)

Crystal data top

(C₂₄H₂₀P)₂[Fe(C₃₆H₂₀N₄)(CN)₂]·2C₃H₆O	γ = 85.510 (1)°
M_r = 1411.35	V = 1767.88 (7) Å³
Triclinic, P1	Z = 1
a = 11.8412 (3) Å	Cu Kα radiation
b = 12.7764 (3) Å	µ = 2.59 mm⁻¹
c = 13.8298 (3) Å	T = 120 K
α = 67.217 (1)°	0.20 × 0.10 × 0.05 mm
β = 66.915 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	6348 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	3518 reflections with I > 2σ(I)
T_min = 0.764, T_max = 1.000	R_int = 0.065
20279 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.198	H-atom parameters constrained
S = 0.98	Δρ_max = 0.71 e Å⁻³
6348 reflections	Δρ_min = −0.36 e Å⁻³
469 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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
Fe1	0.0000	0.0000	0.0000	0.0631 (3)
N1	−0.0906 (3)	0.1372 (3)	0.0160 (2)	0.0632 (8)
N2	0.1223 (3)	0.0411 (3)	0.0499 (2)	0.0607 (8)
N3	0.1490 (3)	0.1625 (3)	−0.2526 (3)	0.0708 (9)
C1	−0.2519 (3)	0.1171 (3)	−0.0458 (3)	0.0642 (10)
H1	−0.3217	0.1499	−0.0597	0.077*
C2	−0.1919 (4)	0.1733 (3)	−0.0101 (3)	0.0633 (10)
C3	−0.2255 (4)	0.2805 (3)	0.0038 (3)	0.0626 (10)
C4	−0.3147 (4)	0.3540 (3)	−0.0154 (3)	0.0700 (11)
H2	−0.3725	0.3357	−0.0397	0.084*
C5	−0.3175 (4)	0.4548 (3)	0.0017 (3)	0.0727 (11)
H3	−0.3770	0.5064	−0.0119	0.087*
C6	−0.2325 (4)	0.4806 (3)	0.0392 (3)	0.0708 (11)
H4	−0.2353	0.5498	0.0501	0.085*
C7	−0.1459 (4)	0.4077 (3)	0.0602 (3)	0.0647 (10)
H5	−0.0904	0.4247	0.0876	0.078*
C8	−0.1409 (3)	0.3070 (3)	0.0403 (3)	0.0614 (10)
C9	−0.0590 (4)	0.2171 (3)	0.0474 (3)	0.0633 (10)
C10	0.0401 (4)	0.2143 (3)	0.0756 (3)	0.0652 (10)
H6	0.0517	0.2740	0.0965	0.078*
C11	0.1248 (3)	0.1345 (3)	0.0770 (3)	0.0641 (10)
C12	0.2283 (4)	0.1355 (3)	0.1073 (3)	0.0659 (10)
C13	0.2707 (4)	0.2092 (4)	0.1409 (3)	0.0710 (11)
H7	0.2286	0.2739	0.1484	0.085*
C14	0.3761 (4)	0.1848 (4)	0.1630 (3)	0.0770 (12)
H8	0.4072	0.2346	0.1847	0.092*
C15	0.4377 (4)	0.0903 (4)	0.1544 (3)	0.0743 (11)
H9	0.5101	0.0762	0.1699	0.089*
C16	0.3938 (4)	0.0151 (4)	0.1230 (3)	0.0713 (11)
H10	0.4346	−0.0508	0.1180	0.086*
C17	0.2886 (4)	0.0396 (3)	0.0992 (3)	0.0663 (10)
C18	0.2207 (4)	−0.0179 (3)	0.0635 (3)	0.0628 (10)
C19	0.0970 (3)	0.0993 (3)	−0.1600 (3)	0.0612 (10)
P1	0.58963 (9)	0.29255 (9)	0.46006 (8)	0.0668 (3)
C20	0.4674 (4)	0.3415 (3)	0.4124 (3)	0.0688 (11)
C21	0.4919 (4)	0.3757 (4)	0.2970 (4)	0.0797 (12)
H11	0.5736	0.3774	0.2446	0.096*
C22	0.3987 (5)	0.4070 (4)	0.2584 (4)	0.0918 (14)
H12	0.4169	0.4307	0.1794	0.110*
C23	0.2798 (5)	0.4047 (4)	0.3323 (4)	0.0914 (14)
H13	0.2159	0.4245	0.3047	0.110*
C24	0.2530 (4)	0.3735 (4)	0.4472 (4)	0.0896 (14)
H14	0.1712	0.3732	0.4986	0.107*
C25	0.3463 (4)	0.3429 (3)	0.4864 (4)	0.0777 (12)
H15	0.3281	0.3224	0.5650	0.093*
C26	0.5437 (3)	0.2790 (3)	0.6049 (3)	0.0636 (10)
C27	0.4390 (3)	0.2088 (3)	0.6914 (3)	0.0686 (10)
H16	0.3935	0.1653	0.6743	0.082*
C28	0.4017 (4)	0.2025 (3)	0.8011 (3)	0.0689 (10)
H17	0.3278	0.1582	0.8587	0.083*
C29	0.4711 (4)	0.2603 (3)	0.8277 (3)	0.0732 (11)
H18	0.4453	0.2547	0.9040	0.088*
C30	0.5782 (4)	0.3266 (3)	0.7441 (3)	0.0753 (11)
H19	0.6273	0.3644	0.7631	0.090*
C31	0.6130 (4)	0.3371 (3)	0.6319 (3)	0.0694 (11)
H20	0.6847	0.3844	0.5736	0.083*
C32	0.7236 (4)	0.3919 (3)	0.3697 (3)	0.0646 (10)
C33	0.7121 (4)	0.5078 (4)	0.3189 (3)	0.0752 (11)
H21	0.6330	0.5348	0.3281	0.090*
C34	0.8169 (4)	0.5832 (4)	0.2549 (3)	0.0814 (13)
H22	0.8098	0.6621	0.2191	0.098*
C35	0.9311 (4)	0.5443 (4)	0.2431 (3)	0.0826 (13)
H23	1.0023	0.5969	0.2004	0.099*
C36	0.9432 (4)	0.4301 (4)	0.2925 (3)	0.0857 (13)
H24	1.0225	0.4035	0.2831	0.103*
C37	0.8384 (4)	0.3537 (4)	0.3563 (3)	0.0746 (11)
H25	0.8462	0.2747	0.3909	0.090*
C38	0.6318 (4)	0.1582 (3)	0.4509 (3)	0.0679 (10)
C39	0.6386 (4)	0.0666 (4)	0.5426 (3)	0.0843 (13)
H26	0.6145	0.0719	0.6146	0.101*
C40	0.6812 (4)	−0.0337 (4)	0.5290 (4)	0.0928 (14)
H27	0.6843	−0.0975	0.5925	0.111*
C41	0.7186 (4)	−0.0409 (4)	0.4251 (3)	0.0811 (12)
H28	0.7492	−0.1091	0.4164	0.097*
C42	0.7123 (4)	0.0496 (4)	0.3336 (4)	0.0839 (13)
H29	0.7381	0.0439	0.2617	0.101*
C43	0.6688 (4)	0.1485 (4)	0.3452 (3)	0.0785 (12)
H30	0.6637	0.2107	0.2816	0.094*
C44	0.9787 (5)	0.1696 (6)	0.5651 (5)	0.119 (2)
C45	0.9684 (5)	0.0429 (5)	0.6275 (4)	0.129 (2)
H31	1.0248	0.0088	0.5762	0.193*
H32	0.8837	0.0120	0.6538	0.193*
H33	0.9901	0.0251	0.6933	0.193*
C46	0.9225 (5)	0.2432 (6)	0.6308 (5)	0.141 (2)
H34	0.9285	0.3222	0.5776	0.212*
H35	0.9665	0.2393	0.6790	0.212*
H36	0.8356	0.2163	0.6789	0.212*
O1	1.0386 (3)	0.2122 (3)	0.4591 (3)	0.1390 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0676 (6)	0.0566 (6)	0.0485 (5)	−0.0194 (4)	−0.0090 (4)	−0.0133 (4)
N1	0.071 (2)	0.0558 (19)	0.0446 (16)	−0.0205 (16)	−0.0090 (15)	−0.0100 (14)
N2	0.0626 (19)	0.0485 (18)	0.0501 (16)	−0.0144 (15)	−0.0066 (15)	−0.0106 (14)
N3	0.077 (2)	0.062 (2)	0.0551 (18)	−0.0193 (17)	−0.0078 (17)	−0.0175 (16)
C1	0.066 (2)	0.059 (2)	0.059 (2)	−0.0122 (19)	−0.0180 (19)	−0.0174 (19)
C2	0.070 (2)	0.058 (2)	0.0459 (19)	−0.013 (2)	−0.0130 (18)	−0.0115 (18)
C3	0.071 (2)	0.053 (2)	0.0461 (19)	−0.017 (2)	−0.0084 (18)	−0.0117 (17)
C4	0.079 (3)	0.063 (3)	0.057 (2)	−0.008 (2)	−0.020 (2)	−0.016 (2)
C5	0.081 (3)	0.061 (3)	0.065 (2)	−0.004 (2)	−0.021 (2)	−0.021 (2)
C6	0.085 (3)	0.059 (3)	0.056 (2)	−0.013 (2)	−0.016 (2)	−0.0188 (19)
C7	0.074 (2)	0.059 (2)	0.047 (2)	−0.018 (2)	−0.0132 (18)	−0.0128 (18)
C8	0.067 (2)	0.052 (2)	0.0452 (19)	−0.0191 (19)	−0.0066 (17)	−0.0106 (17)
C9	0.068 (2)	0.058 (2)	0.048 (2)	−0.021 (2)	−0.0099 (18)	−0.0124 (18)
C10	0.072 (3)	0.056 (2)	0.054 (2)	−0.017 (2)	−0.0136 (19)	−0.0151 (18)
C11	0.062 (2)	0.060 (2)	0.054 (2)	−0.017 (2)	−0.0110 (18)	−0.0135 (19)
C12	0.070 (2)	0.061 (3)	0.049 (2)	−0.019 (2)	−0.0112 (18)	−0.0125 (19)
C13	0.078 (3)	0.067 (3)	0.057 (2)	−0.013 (2)	−0.019 (2)	−0.017 (2)
C14	0.092 (3)	0.063 (3)	0.065 (2)	−0.019 (2)	−0.022 (2)	−0.018 (2)
C15	0.082 (3)	0.070 (3)	0.061 (2)	−0.018 (2)	−0.023 (2)	−0.016 (2)
C16	0.079 (3)	0.063 (3)	0.060 (2)	−0.013 (2)	−0.019 (2)	−0.017 (2)
C17	0.070 (3)	0.059 (2)	0.052 (2)	−0.017 (2)	−0.0132 (19)	−0.0105 (18)
C18	0.071 (2)	0.055 (2)	0.048 (2)	−0.016 (2)	−0.0112 (18)	−0.0154 (18)
C19	0.065 (2)	0.055 (2)	0.057 (2)	−0.0157 (18)	−0.0117 (19)	−0.0239 (19)
P1	0.0737 (7)	0.0586 (6)	0.0496 (6)	−0.0164 (5)	−0.0083 (5)	−0.0145 (5)
C20	0.074 (3)	0.058 (2)	0.057 (2)	−0.011 (2)	−0.014 (2)	−0.0137 (19)
C21	0.088 (3)	0.074 (3)	0.069 (3)	−0.006 (2)	−0.025 (2)	−0.024 (2)
C22	0.111 (4)	0.083 (3)	0.079 (3)	−0.010 (3)	−0.040 (3)	−0.024 (3)
C23	0.097 (4)	0.074 (3)	0.093 (4)	−0.018 (3)	−0.042 (3)	−0.013 (3)
C24	0.081 (3)	0.071 (3)	0.093 (3)	−0.017 (2)	−0.028 (3)	−0.010 (3)
C25	0.078 (3)	0.065 (3)	0.067 (3)	−0.021 (2)	−0.015 (2)	−0.010 (2)
C26	0.069 (2)	0.057 (2)	0.051 (2)	−0.0120 (19)	−0.0112 (18)	−0.0165 (17)
C27	0.075 (2)	0.062 (2)	0.055 (2)	−0.017 (2)	−0.0120 (19)	−0.0177 (19)
C28	0.072 (2)	0.062 (2)	0.053 (2)	−0.008 (2)	−0.0110 (19)	−0.0146 (19)
C29	0.087 (3)	0.062 (3)	0.057 (2)	−0.010 (2)	−0.017 (2)	−0.0183 (19)
C30	0.086 (3)	0.069 (3)	0.061 (2)	−0.016 (2)	−0.018 (2)	−0.022 (2)
C31	0.071 (2)	0.062 (2)	0.058 (2)	−0.014 (2)	−0.0109 (19)	−0.0171 (19)
C32	0.069 (2)	0.061 (2)	0.050 (2)	−0.016 (2)	−0.0108 (19)	−0.0164 (18)
C33	0.081 (3)	0.067 (3)	0.060 (2)	−0.018 (2)	−0.008 (2)	−0.022 (2)
C34	0.099 (3)	0.062 (3)	0.061 (2)	−0.026 (3)	−0.008 (2)	−0.019 (2)
C35	0.079 (3)	0.085 (3)	0.055 (2)	−0.035 (3)	−0.004 (2)	−0.015 (2)
C36	0.075 (3)	0.095 (4)	0.064 (3)	−0.019 (3)	−0.013 (2)	−0.017 (2)
C37	0.076 (3)	0.071 (3)	0.060 (2)	−0.011 (2)	−0.020 (2)	−0.012 (2)
C38	0.075 (2)	0.052 (2)	0.056 (2)	−0.0189 (19)	−0.0066 (19)	−0.0147 (19)
C39	0.110 (4)	0.068 (3)	0.057 (2)	−0.002 (3)	−0.017 (2)	−0.020 (2)
C40	0.124 (4)	0.062 (3)	0.063 (3)	−0.001 (3)	−0.014 (3)	−0.016 (2)
C41	0.089 (3)	0.065 (3)	0.061 (3)	−0.015 (2)	−0.004 (2)	−0.018 (2)
C42	0.098 (3)	0.071 (3)	0.069 (3)	−0.005 (3)	−0.016 (2)	−0.028 (2)
C43	0.096 (3)	0.066 (3)	0.058 (2)	−0.006 (2)	−0.016 (2)	−0.019 (2)
C44	0.086 (4)	0.147 (6)	0.086 (4)	−0.038 (4)	−0.034 (3)	0.004 (4)
C45	0.128 (4)	0.127 (5)	0.088 (4)	−0.052 (4)	−0.033 (3)	0.004 (3)
C46	0.096 (4)	0.177 (6)	0.107 (5)	0.018 (4)	−0.020 (4)	−0.033 (5)
O1	0.124 (3)	0.157 (4)	0.083 (3)	−0.039 (3)	−0.029 (2)	0.004 (2)

Geometric parameters (Å, º) top

Fe1—C19ⁱ	1.971 (4)	C22—C23	1.372 (6)
Fe1—C19	1.971 (4)	C22—H12	0.9500
Fe1—N2	2.008 (3)	C23—C24	1.386 (6)
Fe1—N2ⁱ	2.008 (3)	C23—H13	0.9500
Fe1—N1ⁱ	2.023 (3)	C24—C25	1.380 (6)
Fe1—N1	2.023 (3)	C24—H14	0.9500
N1—C9	1.380 (4)	C25—H15	0.9500
N1—C2	1.380 (5)	C26—C31	1.384 (5)
N2—C18	1.373 (5)	C26—C27	1.397 (4)
N2—C11	1.387 (4)	C27—C28	1.375 (5)
N3—C19	1.154 (4)	C27—H16	0.9500
C1—C2	1.377 (5)	C28—C29	1.378 (5)
C1—C18ⁱ	1.378 (5)	C28—H17	0.9500
C1—H1	0.9500	C29—C30	1.387 (5)
C2—C3	1.460 (5)	C29—H18	0.9500
C3—C4	1.392 (5)	C30—C31	1.394 (5)
C3—C8	1.398 (5)	C30—H19	0.9500
C4—C5	1.392 (5)	C31—H20	0.9500
C4—H2	0.9500	C32—C37	1.374 (5)
C5—C6	1.408 (5)	C32—C33	1.393 (5)
C5—H3	0.9500	C33—C34	1.385 (5)
C6—C7	1.371 (5)	C33—H21	0.9500
C6—H4	0.9500	C34—C35	1.372 (6)
C7—C8	1.408 (5)	C34—H22	0.9500
C7—H5	0.9500	C35—C36	1.375 (6)
C8—C9	1.443 (5)	C35—H23	0.9500
C9—C10	1.368 (5)	C36—C37	1.391 (5)
C10—C11	1.373 (5)	C36—H24	0.9500
C10—H6	0.9500	C37—H25	0.9500
C11—C12	1.445 (5)	C38—C39	1.379 (5)
C12—C17	1.389 (5)	C38—C43	1.404 (5)
C12—C13	1.397 (5)	C39—C40	1.394 (5)
C13—C14	1.383 (5)	C39—H26	0.9500
C13—H7	0.9500	C40—C41	1.366 (5)
C14—C15	1.382 (6)	C40—H27	0.9500
C14—H8	0.9500	C41—C42	1.368 (6)
C15—C16	1.400 (5)	C41—H28	0.9500
C15—H9	0.9500	C42—C43	1.369 (5)
C16—C17	1.392 (5)	C42—H29	0.9500
C16—H10	0.9500	C43—H30	0.9500
C17—C18	1.454 (5)	C44—O1	1.255 (6)
C18—C1ⁱ	1.378 (5)	C44—C46	1.498 (8)
P1—C38	1.788 (4)	C44—C45	1.499 (8)
P1—C20	1.792 (4)	C45—H31	0.9800
P1—C32	1.795 (4)	C45—H32	0.9800
P1—C26	1.797 (4)	C45—H33	0.9800
C20—C21	1.392 (5)	C46—H34	0.9800
C20—C25	1.401 (5)	C46—H35	0.9800
C21—C22	1.376 (6)	C46—H36	0.9800
C21—H11	0.9500

C19ⁱ—Fe1—C19	180.0	C22—C21—C20	120.4 (4)
C19ⁱ—Fe1—N2	89.10 (12)	C22—C21—H11	119.8
C19—Fe1—N2	90.90 (12)	C20—C21—H11	119.8
C19ⁱ—Fe1—N2ⁱ	90.90 (12)	C23—C22—C21	121.1 (4)
C19—Fe1—N2ⁱ	89.10 (12)	C23—C22—H12	119.5
N2—Fe1—N2ⁱ	180.0	C21—C22—H12	119.5
C19ⁱ—Fe1—N1ⁱ	87.27 (13)	C22—C23—C24	119.8 (5)
C19—Fe1—N1ⁱ	92.73 (13)	C22—C23—H13	120.1
N2—Fe1—N1ⁱ	90.33 (13)	C24—C23—H13	120.1
N2ⁱ—Fe1—N1ⁱ	89.67 (13)	C25—C24—C23	119.4 (5)
C19ⁱ—Fe1—N1	92.73 (13)	C25—C24—H14	120.3
C19—Fe1—N1	87.27 (13)	C23—C24—H14	120.3
N2—Fe1—N1	89.67 (13)	C24—C25—C20	121.2 (4)
N2ⁱ—Fe1—N1	90.33 (13)	C24—C25—H15	119.4
N1ⁱ—Fe1—N1	180.0	C20—C25—H15	119.4
C9—N1—C2	106.4 (3)	C31—C26—C27	119.4 (3)
C9—N1—Fe1	127.1 (3)	C31—C26—P1	120.1 (3)
C2—N1—Fe1	126.4 (3)	C27—C26—P1	120.5 (3)
C18—N2—C11	106.3 (3)	C28—C27—C26	120.1 (4)
C18—N2—Fe1	126.6 (2)	C28—C27—H16	119.9
C11—N2—Fe1	127.1 (3)	C26—C27—H16	119.9
C2—C1—C18ⁱ	126.4 (4)	C27—C28—C29	120.2 (4)
C2—C1—H1	116.8	C27—C28—H17	119.9
C18ⁱ—C1—H1	116.8	C29—C28—H17	119.9
C1—C2—N1	124.8 (4)	C28—C29—C30	120.5 (4)
C1—C2—C3	124.7 (4)	C28—C29—H18	119.7
N1—C2—C3	110.5 (3)	C30—C29—H18	119.7
C4—C3—C8	120.7 (4)	C29—C30—C31	119.2 (4)
C4—C3—C2	133.6 (4)	C29—C30—H19	120.4
C8—C3—C2	105.6 (4)	C31—C30—H19	120.4
C5—C4—C3	118.7 (4)	C26—C31—C30	120.4 (3)
C5—C4—H2	120.7	C26—C31—H20	119.8
C3—C4—H2	120.7	C30—C31—H20	119.8
C4—C5—C6	120.3 (4)	C37—C32—C33	119.9 (4)
C4—C5—H3	119.8	C37—C32—P1	119.3 (3)
C6—C5—H3	119.8	C33—C32—P1	120.7 (3)
C7—C6—C5	121.3 (4)	C34—C33—C32	119.4 (4)
C7—C6—H4	119.4	C34—C33—H21	120.3
C5—C6—H4	119.4	C32—C33—H21	120.3
C6—C7—C8	118.5 (4)	C35—C34—C33	120.3 (4)
C6—C7—H5	120.8	C35—C34—H22	119.9
C8—C7—H5	120.8	C33—C34—H22	119.9
C3—C8—C7	120.5 (4)	C34—C35—C36	120.6 (4)
C3—C8—C9	106.9 (3)	C34—C35—H23	119.7
C7—C8—C9	132.6 (4)	C36—C35—H23	119.7
C10—C9—N1	124.5 (4)	C35—C36—C37	119.5 (4)
C10—C9—C8	124.9 (4)	C35—C36—H24	120.3
N1—C9—C8	110.5 (3)	C37—C36—H24	120.3
C9—C10—C11	127.1 (4)	C32—C37—C36	120.4 (4)
C9—C10—H6	116.5	C32—C37—H25	119.8
C11—C10—H6	116.5	C36—C37—H25	119.8
C10—C11—N2	124.6 (4)	C39—C38—C43	119.1 (4)
C10—C11—C12	124.9 (4)	C39—C38—P1	121.5 (3)
N2—C11—C12	110.6 (4)	C43—C38—P1	119.2 (3)
C17—C12—C13	120.9 (4)	C38—C39—C40	119.5 (4)
C17—C12—C11	106.2 (4)	C38—C39—H26	120.2
C13—C12—C11	132.9 (4)	C40—C39—H26	120.2
C14—C13—C12	117.7 (4)	C41—C40—C39	120.5 (4)
C14—C13—H7	121.2	C41—C40—H27	119.8
C12—C13—H7	121.2	C39—C40—H27	119.8
C15—C14—C13	122.1 (4)	C40—C41—C42	120.3 (4)
C15—C14—H8	119.0	C40—C41—H28	119.8
C13—C14—H8	119.0	C42—C41—H28	119.8
C14—C15—C16	120.2 (4)	C41—C42—C43	120.3 (4)
C14—C15—H9	119.9	C41—C42—H29	119.8
C16—C15—H9	119.9	C43—C42—H29	119.8
C17—C16—C15	118.2 (4)	C42—C43—C38	120.3 (4)
C17—C16—H10	120.9	C42—C43—H30	119.9
C15—C16—H10	120.9	C38—C43—H30	119.9
C12—C17—C16	120.9 (4)	O1—C44—C46	121.3 (6)
C12—C17—C18	106.7 (4)	O1—C44—C45	119.2 (7)
C16—C17—C18	132.4 (4)	C46—C44—C45	119.5 (5)
N2—C18—C1ⁱ	125.4 (4)	C44—C45—H31	109.5
N2—C18—C17	110.2 (3)	C44—C45—H32	109.5
C1ⁱ—C18—C17	124.4 (4)	H31—C45—H32	109.5
N3—C19—Fe1	175.8 (3)	C44—C45—H33	109.5
C38—P1—C20	110.89 (19)	H31—C45—H33	109.5
C38—P1—C32	107.17 (18)	H32—C45—H33	109.5
C20—P1—C32	109.48 (18)	C44—C46—H34	109.5
C38—P1—C26	109.39 (18)	C44—C46—H35	109.5
C20—P1—C26	110.28 (18)	H34—C46—H35	109.5
C32—P1—C26	109.57 (17)	C44—C46—H36	109.5
C21—C20—C25	118.0 (4)	H34—C46—H36	109.5
C21—C20—P1	118.8 (3)	H35—C46—H36	109.5
C25—C20—P1	123.1 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the N2/C11/C12/C17/C18, C12–C17, C26–C31 and N1/C2/C3/C8/C9 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C25—H15···N3ⁱⁱ	0.95	2.74	3.404 (4)	127
C27—H16···N3ⁱⁱ	0.95	2.66	3.259 (5)	121
C34—H22···N3ⁱⁱⁱ	0.95	2.57	3.292 (7)	133
C41—H28···N3^iv	0.95	2.45	3.181 (7)	134
C28—H17···Cg1ⁱⁱ	0.95	2.63	3.446 (4)	145
C29—H18···Cg2ⁱⁱ	0.95	2.76	3.582 (4)	145
C33—H21···Cg3^v	0.95	2.90	3.729 (5)	147
C35—H23···Cg4ⁱⁱⁱ	0.95	2.92	3.733 (4)	145
C45—H32···Cg2^vi	0.98	2.99	3.798 (6)	141
C45—H33···Cg1^vi	0.98	2.87	3.469 (5)	120

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the N2/C11/C12/C17/C18, C12–C17, C26–C31 and N1/C2/C3/C8/C9 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C34—H22···N3ⁱ	0.95	2.57	3.292 (7)	133
C41—H28···N3ⁱⁱ	0.95	2.45	3.181 (7)	134
C28—H17···Cg1ⁱⁱⁱ	0.95	2.63	3.446 (4)	145
C29—H18···Cg2ⁱⁱⁱ	0.95	2.76	3.582 (4)	145
C33—H21···Cg3^iv	0.95	2.90	3.729 (5)	147
C35—H23···Cg4ⁱ	0.95	2.92	3.733 (4)	145
C45—H32···Cg2^v	0.98	2.99	3.798 (6)	141
C45—H33···Cg1^v	0.98	2.87	3.469 (5)	120

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

References

Aramaki, S. & Mizuguchi, J. (2003). Acta Cryst. E59, o1556–o1558. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (2001). ABSCOR. Rigaku Corporation, Tokyo, Japan. 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
Matsuda, M., Nishi, M., Koga, S., Fujishima, M., Hoshino, N., Akutagawa, T. & Hasegawa, H. (2014). Chem. Eur. J. 20, 11318–11321. Google Scholar
Matsuda, M., Ohishi, H., Tofuku, M., Muramoto, N. & Yamaura, J. (2011). Chem. Lett. 40, 1257–1259. Google Scholar
Nishi, M., Matsuda, M., Hoshino, N. & Akutagawa, T. (2015). Chem. Lett. 44. In the press. Google Scholar
Rigaku (1999). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wakita, K. (2001). Yadokari-XG. http://www.hat.hi-ho.ne.jp/k-wakita/yadokari 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 71| Part 2| February 2015| Pages m48-m49

doi:10.1107/S2056989015001735

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

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