Bis(1H-imidazole-κN3){2,2′-[propane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4O,N,N′,O′}iron(III) perchlorate

Kojima, Y.; Kato, K.; Yamamoto, Y.; Inoue, K.; Hayami, S.

doi:10.1107/S1600536810004010

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m302-m303

doi:10.1107/S1600536810004010

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Bis(1H-imidazole-κN³){2,2′-[propane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}iron(III) perchlorate

Yoshihiro Kojima,^a Kazuya Kato,^b Yuuki Yamamoto,^b Katsuya Inoue ^a and Shinya Hayami ^b ^*

^aDepartment of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan, and ^bDepartment of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto, 860-8555, Japan
^*Correspondence e-mail: hayami@sci.kumamoto-u.ac.jp

(Received 22 December 2009; accepted 1 February 2010; online 17 February 2010)

The title compound, [Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄, consists of monomeric [Fe(salmen)(HIm)₂]⁺ cations {salmen is the 2,2′-[propane-1,2-diylbis(nitrilomethylidyne)]diphenolate dianion and HIm is 1H-imiazole} and perchlorate anions. In the cation, the Fe³⁺ ion is octahedrally coordinated by two N atoms and two O atoms from a tetradentate salmen anion and two N atoms from two Him molecules. These ligands are coordinated to the iron ion in a direction perpendicular to the [Fe(salmen)]⁺ coordination plane. The benzene ring planes in the salmen ligands are oriented nearly parallel to one another intermolecularly [dihedral angle = 6.36 (3)°]. The dihedral angle between the mean planes through the imidazole rings in the cation is 76.9 (2)°. In the crystal, N—H⋯O interactions link the molecules into a one-dimensional double chain running along [101] and C—H⋯O interactions link the double chains into a two-dimensional network, running parallel to the ac plane.

Related literature

For salen–metal complexes with spin crossover properties, see: Brendan et al. (1984 , 1987 ); Hernández-Molina et al. (1998 ).

Experimental

Crystal data

[Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄
M_r = 571.78
Monoclinic, P 2₁ /c
a = 10.4898 (8) Å
b = 16.4312 (9) Å
c = 14.7729 (8) Å
β = 105.5081 (17)°
V = 2453.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 113 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ) T_min = 0.860, T_max = 0.860
20794 measured reflections
5615 independent reflections
3529 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.179
S = 0.99
5615 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—O1	1.879 (2)
Fe1—O2	1.914 (3)
Fe1—N1	2.119 (3)
Fe1—N2	2.108 (3)
Fe1—N3	2.161 (3)
Fe1—N5	2.161 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O6ⁱ	0.95	2.53	3.436 (6)	161
C16—H16⋯O5	0.95	2.53	3.325 (6)	142
N4—H4A⋯O2ⁱⁱ	0.88	2.48	3.063 (4)	125
N4—H4A⋯O6ⁱⁱ	0.88	2.36	3.031 (4)	133
N6—H6A⋯O4ⁱⁱⁱ	0.88	2.03	2.892 (4)	167
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x+2, -y, -z+2; (iii) -x+1, -y, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalClear (Molecular Structure Corporation and Rigaku, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG (Wakita, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004010/kj2139sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004010/kj2139Isup2.hkl

checkCIF report

Comment top

A number of spin-crossover compounds have been studied. The salen molecule (salen = N,N'-ethylenebis(salicylideneiminato) dianion) has often been used as ligand in spin-crossover complexes (Brendan et al., 1984, Hernández-Molina et al., 1998). Brendan et al. reported Fe(III)-salen complexes [Fe(salen)(L)₂](Y) (L = imidazole series, Y = counter anion) and showed that the spin state can be tuned by using different imidazole series and counter anions (Brendan et al., 1987). They also showed that [Fe(salen)(HIm)₂](ClO₄)₂ has spin-crossover properties. In this study, the crystal stucture of the derivative [Fe(salmen)(HIm)₂](ClO₄)₂ is reported.

The title compound consists of a cation whose iron ion is coordinated by a salmen anion and two imidazole ligands. The structure further contains a perchlorate anion. The molecular planes of the benzene rings of all salmen ligands in the crystal are oriented essentially parallel to one another. The two imidazoles coordinated to the Fe³⁺ ion aren't coplanar; the dihedral angle between their mean planes is 76.9 (2)°. Imidazole ligands are coordinated to iron ion in a direction perpendicular to [Fe(salmen)]⁺, with the angle around iron ion O1— Fe1— N3 = 88.40 (12)°, O2—Fe1—N3 = 90.95 (12)°, O1—Fe1—N5 = 93.19 (12)° and O2—Fe1—N5 = 87.99 (12)°. The two benzene rings in a salmen ligand are nearly coplanar, but the bridging carbon atoms are not located in this plane. C2 is displaced 0.1057 (2)Å from the C5–C12 benzene plane and C3 is displaced 0.1785 (2)Å from the C12–C17 benzene plane. The torsion angle N1—C2—C3—N2 is 41.1 (5)°.

In addition, many intermolecular interactions are observed in the crystal structure. Intermolecular C—H···O hydrogen bonds link the benzene hydrogens H7 and H16 with the anion oxygens O6 and O5, respectively. N—H···O hydrogen bonds link the imidazole hydrogen H6A to anionic oxygen O4 and link the imidazole H4A in a bifurcated bond to the ring oxygen O2 and the anion oxygen O6. The N—H···O interactions link the molecules into a one-dimensional double chain (step ladder) running in the [1 0 1] direction, with N4—H4A···O2 acting as the rungs in the ladder. The C—H···O interactions link the double chains into a two-dimensional network, running parallel to the ac plane.

Related literature top

For salen–metal complexes with spin crossover properties, see: Brendan et al. (1984, 1987); Hernández-Molina et al. (1998).

Experimental top

The salmen ligand was prepared by the reaction of 1, 2-diaminopropane (2 mmol) and salicylaldehyde (4 mmol) in ethanol. The title compound was synthesized in accordance with the procedure reported in the literature (Brendan et al., 1987).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalClear (Molecular Structure Corporation and Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG (Wakita, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound drawn with 50% probability displacement ellipsoids.

Bis(1H-imidazole-κN³){2,2'-[propane-1,2- diylbis(nitrilomethylidyne)]diphenolato- κ⁴O,N,N',O'}iron(III) perchlorate top

Crystal data top

[Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄	F(000) = 1180
M_r = 571.78	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
a = 10.4898 (8) Å	Cell parameters from 18352 reflections
b = 16.4312 (9) Å	θ = 2.5–27.5°
c = 14.7729 (8) Å	µ = 0.78 mm⁻¹
β = 105.5081 (17)°	T = 113 K
V = 2453.6 (3) Å³	Block, black
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku R-AXIS RAPID Imaging Plate diffractometer	5615 independent reflections
Radiation source: fine-focus sealed tube	3529 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	h = −13→11
T_min = 0.860, T_max = 0.860	k = −21→21
20794 measured reflections	l = −19→19

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
5615 reflections	(Δ/σ)_max = 0.001
335 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄	V = 2453.6 (3) Å³
M_r = 571.78	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4898 (8) Å	µ = 0.78 mm⁻¹
b = 16.4312 (9) Å	T = 113 K
c = 14.7729 (8) Å	0.20 × 0.20 × 0.20 mm
β = 105.5081 (17)°

Data collection top

Rigaku R-AXIS RAPID Imaging Plate diffractometer	5615 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	3529 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.860	R_int = 0.086
20794 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 0.99	Δρ_max = 0.77 e Å⁻³
5615 reflections	Δρ_min = −0.65 e Å⁻³
335 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.79757 (6)	0.13608 (3)	0.88002 (3)	0.02225 (18)
Cl1	0.69936 (10)	−0.13827 (6)	0.61401 (6)	0.0306 (2)
O1	0.7346 (3)	0.06289 (15)	0.95574 (17)	0.0267 (6)
O2	0.8686 (3)	0.06897 (16)	0.79939 (17)	0.0268 (6)
O3	0.6186 (3)	−0.20419 (19)	0.5683 (2)	0.0464 (9)
O4	0.6768 (4)	−0.06891 (19)	0.5516 (2)	0.0506 (9)
O5	0.8363 (3)	−0.1597 (2)	0.6359 (3)	0.0530 (10)
O6	0.6683 (4)	−0.1151 (3)	0.6984 (2)	0.0633 (11)
N1	0.7220 (3)	0.23386 (19)	0.9436 (2)	0.0283 (8)
N2	0.8607 (3)	0.23941 (19)	0.8192 (2)	0.0258 (7)
N3	0.9857 (3)	0.13642 (19)	0.9853 (2)	0.0266 (7)
N4	1.1404 (4)	0.0971 (2)	1.1086 (2)	0.0386 (9)
H4A	1.1795	0.0723	1.1615	0.046*
N5	0.6125 (3)	0.1369 (2)	0.7717 (2)	0.0276 (8)
N6	0.4654 (4)	0.1116 (2)	0.6386 (2)	0.0400 (10)
H6A	0.4292	0.0916	0.5823	0.048*
C1	0.7007 (5)	0.3882 (3)	0.9504 (3)	0.0436 (12)
H1A	0.6109	0.3875	0.9584	0.065*
H1B	0.7123	0.4370	0.9153	0.065*
H1C	0.7651	0.3887	1.0122	0.065*
C2	0.7217 (5)	0.3135 (3)	0.8970 (3)	0.0437 (12)
H2	0.6444	0.3116	0.8401	0.052*
C3	0.8397 (5)	0.3177 (3)	0.8607 (4)	0.0465 (13)
H3A	0.8276	0.3610	0.8125	0.056*
H3B	0.9183	0.3314	0.9125	0.056*
C4	0.6667 (4)	0.2260 (2)	1.0119 (3)	0.0292 (9)
H4	0.6375	0.2744	1.0354	0.035*
C5	0.6456 (4)	0.1508 (3)	1.0550 (3)	0.0289 (9)
C6	0.5831 (5)	0.1545 (3)	1.1286 (3)	0.0368 (11)
H6	0.5582	0.2062	1.1472	0.044*
C7	0.5574 (5)	0.0875 (3)	1.1733 (3)	0.0429 (12)
H7	0.5132	0.0920	1.2214	0.051*
C8	0.5962 (5)	0.0116 (3)	1.1484 (3)	0.0420 (12)
H8	0.5811	−0.0357	1.1811	0.050*
C9	0.6569 (5)	0.0047 (3)	1.0759 (3)	0.0347 (10)
H9	0.6829	−0.0474	1.0595	0.042*
C10	0.6801 (4)	0.0724 (2)	1.0274 (2)	0.0270 (9)
C11	0.9182 (4)	0.2386 (3)	0.7521 (3)	0.0283 (9)
H11	0.9369	0.2898	0.7285	0.034*
C12	0.9565 (4)	0.1668 (3)	0.7100 (3)	0.0278 (9)
C13	1.0235 (4)	0.1789 (3)	0.6396 (3)	0.0335 (10)
H13	1.0400	0.2329	0.6226	0.040*
C14	1.0649 (5)	0.1152 (3)	0.5955 (3)	0.0375 (11)
H14	1.1102	0.1247	0.5487	0.045*
C15	1.0401 (4)	0.0360 (3)	0.6199 (3)	0.0363 (11)
H15	1.0677	−0.0087	0.5890	0.044*
C16	0.9763 (4)	0.0220 (3)	0.6880 (3)	0.0340 (10)
H16	0.9611	−0.0325	0.7039	0.041*
C17	0.9327 (4)	0.0864 (3)	0.7351 (3)	0.0277 (9)
C18	1.0139 (5)	0.0901 (3)	1.0620 (3)	0.0320 (10)
H18	0.9518	0.0566	1.0808	0.038*
C19	1.1997 (5)	0.1494 (3)	1.0607 (3)	0.0355 (10)
H19	1.2899	0.1658	1.0774	0.043*
C20	1.1030 (4)	0.1732 (2)	0.9839 (3)	0.0286 (9)
H20	1.1147	0.2095	0.9368	0.034*
C21	0.5883 (4)	0.0979 (3)	0.6904 (3)	0.0327 (10)
H21	0.6506	0.0645	0.6715	0.039*
C22	0.4052 (5)	0.1619 (3)	0.6876 (3)	0.0414 (12)
H22	0.3171	0.1819	0.6678	0.050*
C23	0.4955 (4)	0.1780 (3)	0.7700 (3)	0.0336 (10)
H23	0.4814	0.2117	0.8186	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0297 (3)	0.0202 (3)	0.0168 (3)	−0.0031 (3)	0.0062 (2)	0.0003 (2)
Cl1	0.0300 (6)	0.0369 (6)	0.0223 (5)	−0.0017 (5)	0.0027 (4)	−0.0049 (4)
O1	0.0457 (18)	0.0202 (14)	0.0196 (13)	−0.0033 (12)	0.0179 (12)	−0.0002 (11)
O2	0.0360 (17)	0.0266 (15)	0.0207 (13)	−0.0046 (12)	0.0125 (12)	−0.0028 (11)
O3	0.046 (2)	0.0410 (19)	0.0427 (18)	−0.0176 (16)	−0.0051 (15)	0.0030 (15)
O4	0.068 (3)	0.0364 (19)	0.0353 (17)	−0.0089 (17)	−0.0065 (16)	0.0077 (15)
O5	0.032 (2)	0.0399 (19)	0.081 (3)	0.0024 (16)	0.0046 (18)	−0.0156 (18)
O6	0.062 (3)	0.102 (3)	0.0309 (17)	0.008 (2)	0.0201 (17)	−0.0083 (19)
N1	0.038 (2)	0.0223 (18)	0.0258 (17)	−0.0004 (15)	0.0100 (15)	0.0028 (14)
N2	0.033 (2)	0.0216 (17)	0.0227 (16)	−0.0018 (14)	0.0071 (15)	0.0003 (14)
N3	0.034 (2)	0.0221 (17)	0.0214 (16)	0.0028 (15)	0.0039 (14)	−0.0011 (14)
N4	0.044 (2)	0.041 (2)	0.0259 (18)	0.0210 (19)	0.0008 (17)	0.0019 (17)
N5	0.029 (2)	0.0269 (18)	0.0247 (16)	−0.0055 (16)	0.0032 (14)	0.0011 (15)
N6	0.045 (3)	0.040 (2)	0.0264 (18)	−0.0146 (19)	−0.0063 (17)	0.0028 (17)
C1	0.042 (3)	0.036 (3)	0.054 (3)	0.001 (2)	0.015 (2)	0.001 (2)
C2	0.066 (4)	0.023 (2)	0.048 (3)	0.000 (2)	0.026 (3)	−0.001 (2)
C3	0.067 (4)	0.025 (2)	0.057 (3)	0.001 (2)	0.032 (3)	0.006 (2)
C4	0.034 (3)	0.029 (2)	0.024 (2)	0.0023 (18)	0.0075 (18)	−0.0048 (18)
C5	0.032 (2)	0.032 (2)	0.0224 (19)	−0.0017 (18)	0.0078 (17)	−0.0033 (17)
C6	0.050 (3)	0.039 (3)	0.029 (2)	0.002 (2)	0.021 (2)	−0.0055 (19)
C7	0.054 (3)	0.047 (3)	0.037 (2)	−0.007 (2)	0.028 (2)	−0.008 (2)
C8	0.063 (3)	0.037 (3)	0.033 (2)	−0.013 (2)	0.024 (2)	−0.001 (2)
C9	0.050 (3)	0.025 (2)	0.033 (2)	−0.007 (2)	0.017 (2)	−0.0014 (18)
C10	0.032 (2)	0.029 (2)	0.0188 (18)	−0.0061 (18)	0.0054 (17)	−0.0024 (17)
C11	0.032 (2)	0.028 (2)	0.0238 (19)	−0.0055 (18)	0.0044 (17)	0.0065 (17)
C12	0.027 (2)	0.034 (2)	0.0217 (19)	−0.0025 (18)	0.0056 (17)	−0.0007 (17)
C13	0.033 (3)	0.041 (3)	0.027 (2)	−0.008 (2)	0.0077 (19)	0.0062 (19)
C14	0.036 (3)	0.057 (3)	0.020 (2)	−0.004 (2)	0.0084 (19)	−0.002 (2)
C15	0.031 (3)	0.052 (3)	0.025 (2)	−0.003 (2)	0.0057 (19)	−0.006 (2)
C16	0.040 (3)	0.038 (3)	0.027 (2)	−0.006 (2)	0.0136 (19)	−0.0025 (19)
C17	0.027 (2)	0.035 (2)	0.0208 (19)	−0.0059 (18)	0.0045 (17)	0.0019 (17)
C18	0.045 (3)	0.028 (2)	0.023 (2)	0.010 (2)	0.0078 (19)	0.0044 (17)
C19	0.032 (3)	0.039 (3)	0.034 (2)	0.008 (2)	0.008 (2)	−0.005 (2)
C20	0.030 (2)	0.025 (2)	0.028 (2)	0.0017 (18)	0.0046 (18)	−0.0047 (17)
C21	0.039 (3)	0.031 (2)	0.024 (2)	−0.007 (2)	0.0010 (19)	0.0026 (18)
C22	0.030 (3)	0.041 (3)	0.045 (3)	−0.011 (2)	−0.003 (2)	0.014 (2)
C23	0.031 (3)	0.028 (2)	0.041 (2)	−0.0066 (19)	0.009 (2)	0.0048 (19)

Geometric parameters (Å, º) top

Fe1—O1	1.879 (2)	C3—H3B	0.9900
Fe1—O2	1.914 (3)	C4—C5	1.434 (6)
Fe1—N1	2.119 (3)	C4—H4	0.9500
Fe1—N2	2.108 (3)	C5—C6	1.412 (5)
Fe1—N3	2.161 (3)	C5—C10	1.428 (6)
Fe1—N5	2.161 (3)	C6—C7	1.348 (6)
Cl1—O3	1.428 (3)	C6—H6	0.9500
Cl1—O4	1.445 (3)	C7—C8	1.392 (6)
Cl1—O5	1.429 (3)	C7—H7	0.9500
Cl1—O6	1.422 (3)	C8—C9	1.389 (6)
O1—C10	1.339 (4)	C8—H8	0.9500
O2—C17	1.333 (4)	C9—C10	1.380 (6)
N1—C2	1.478 (5)	C9—H9	0.9500
N1—C4	1.297 (5)	C11—C12	1.441 (6)
N2—C3	1.466 (5)	C11—H11	0.9500
N2—C11	1.291 (5)	C12—C13	1.416 (5)
N3—C18	1.331 (5)	C12—C17	1.413 (6)
N3—C20	1.376 (5)	C13—C14	1.364 (6)
N4—C18	1.327 (5)	C13—H13	0.9500
N4—C19	1.364 (6)	C14—C15	1.394 (6)
N4—H4A	0.8800	C14—H14	0.9500
N5—C21	1.325 (5)	C15—C16	1.368 (6)
N5—C23	1.395 (5)	C15—H15	0.9500
N6—C21	1.331 (5)	C16—C17	1.408 (6)
N6—C22	1.360 (6)	C16—H16	0.9500
N6—H6A	0.8800	C18—H18	0.9500
C1—C2	1.507 (6)	C19—C20	1.361 (6)
C1—H1A	0.9800	C19—H19	0.9500
C1—H1B	0.9800	C20—H20	0.9500
C1—H1C	0.9800	C21—H21	0.9500
C2—C3	1.476 (7)	C22—C23	1.353 (6)
C2—H2	1.0000	C22—H22	0.9500
C3—H3A	0.9900	C23—H23	0.9500

O1—Fe1—O2	105.02 (11)	N1—C4—H4	117.1
O1—Fe1—N1	89.34 (12)	C5—C4—H4	117.1
O1—Fe1—N2	165.83 (12)	C4—C5—C6	117.6 (4)
O1—Fe1—N3	88.40 (12)	C4—C5—C10	124.7 (3)
O1—Fe1—N5	93.19 (12)	C6—C5—C10	117.7 (4)
O2—Fe1—N1	165.15 (12)	C5—C6—C7	122.4 (4)
O2—Fe1—N2	88.86 (12)	C5—C6—H6	118.8
O2—Fe1—N3	90.95 (12)	C7—C6—H6	118.8
O2—Fe1—N5	87.99 (12)	C6—C7—C8	119.5 (4)
N1—Fe1—N2	77.04 (12)	C6—C7—H7	120.3
N1—Fe1—N3	93.25 (13)	C8—C7—H7	120.3
N1—Fe1—N5	87.44 (13)	C7—C8—C9	120.2 (4)
N2—Fe1—N3	88.51 (12)	C7—C8—H8	119.9
N2—Fe1—N5	90.10 (12)	C9—C8—H8	119.9
N3—Fe1—N5	178.27 (12)	C8—C9—C10	121.1 (4)
O3—Cl1—O4	108.75 (19)	C8—C9—H9	119.5
O3—Cl1—O5	110.6 (2)	C10—C9—H9	119.5
O3—Cl1—O6	111.8 (2)	O1—C10—C9	119.3 (4)
O4—Cl1—O5	108.8 (2)	O1—C10—C5	121.7 (3)
O4—Cl1—O6	108.2 (2)	C5—C10—C9	119.0 (4)
O5—Cl1—O6	108.6 (2)	N2—C11—C12	125.6 (4)
Fe1—O1—C10	133.5 (2)	N2—C11—H11	117.2
Fe1—O2—C17	132.4 (3)	C12—C11—H11	117.2
Fe1—N1—C2	114.7 (2)	C11—C12—C13	116.9 (4)
Fe1—N1—C4	124.6 (3)	C11—C12—C17	124.3 (3)
C2—N1—C4	120.3 (3)	C13—C12—C17	118.8 (4)
Fe1—N2—C3	115.4 (3)	C12—C13—C14	121.8 (4)
Fe1—N2—C11	125.7 (3)	C12—C13—H13	119.1
C3—N2—C11	118.9 (3)	C14—C13—H13	119.1
Fe1—N3—C18	124.3 (3)	C13—C14—C15	119.2 (4)
Fe1—N3—C20	129.7 (3)	C13—C14—H14	120.4
C18—N3—C20	105.5 (4)	C15—C14—H14	120.4
C18—N4—C19	108.5 (4)	C14—C15—C16	120.6 (4)
C18—N4—H4A	125.8	C14—C15—H15	119.7
C19—N4—H4A	125.8	C16—C15—H15	119.7
Fe1—N5—C21	125.8 (3)	C15—C16—C17	121.6 (4)
Fe1—N5—C23	128.9 (3)	C15—C16—H16	119.2
C21—N5—C23	105.3 (4)	C17—C16—H16	119.2
C21—N6—C22	108.3 (4)	O2—C17—C12	123.1 (4)
C21—N6—H6A	125.9	O2—C17—C16	118.9 (4)
C22—N6—H6A	125.9	C12—C17—C16	118.0 (3)
C2—C1—H1A	109.5	N3—C18—N4	110.9 (4)
C2—C1—H1B	109.5	N3—C18—H18	124.6
C2—C1—H1C	109.5	N4—C18—H18	124.6
H1A—C1—H1B	109.5	N4—C19—C20	105.7 (4)
H1A—C1—H1C	109.5	N4—C19—H19	127.1
H1B—C1—H1C	109.5	C20—C19—H19	127.1
N1—C2—C1	117.3 (4)	N3—C20—C19	109.4 (4)
N1—C2—C3	108.2 (4)	N3—C20—H20	125.3
N1—C2—H2	105.4	C19—C20—H20	125.3
C1—C2—C3	114.0 (4)	N5—C21—N6	111.1 (4)
C1—C2—H2	105.4	N5—C21—H21	124.4
C3—C2—H2	105.4	N6—C21—H21	124.4
N2—C3—C2	110.2 (4)	N6—C22—C23	106.5 (4)
N2—C3—H3A	109.6	N6—C22—H22	126.7
N2—C3—H3B	109.6	C23—C22—H22	126.7
C2—C3—H3A	109.6	N5—C23—C23	108.8 (4)
C2—C3—H3B	109.6	N5—C23—H23	125.6
H3A—C3—H3B	108.1	C22—C23—H23	125.6
N1—C4—C5	125.8 (4)

O2—Fe1—O1—C10	176.7 (3)	Fe1—N1—C2—C3	−35.1 (5)
N1—Fe1—O1—C10	−7.2 (4)	C4—N1—C2—C1	21.0 (6)
N2—Fe1—O1—C10	8.6 (8)	C4—N1—C2—C3	151.7 (4)
N3—Fe1—O1—C10	86.1 (4)	Fe1—N1—C4—C5	−0.8 (6)
N5—Fe1—O1—C10	−94.6 (4)	C2—N1—C4—C5	171.8 (4)
O1—Fe1—O2—C17	−175.8 (3)	Fe1—N2—C3—C2	−30.6 (5)
N1—Fe1—O2—C17	19.3 (7)	C11—N2—C3—C2	151.3 (4)
N2—Fe1—O2—C17	1.3 (3)	Fe1—N2—C11—C12	−3.7 (6)
N3—Fe1—O2—C17	−87.2 (3)	C3—N2—C11—C12	174.2 (4)
N5—Fe1—O2—C17	91.4 (3)	Fe1—N3—C18—N4	173.6 (3)
O1—Fe1—N1—C2	−169.1 (3)	C20—N3—C18—N4	1.0 (4)
O1—Fe1—N1—C4	3.9 (3)	Fe1—N3—C20—C19	−173.0 (3)
O2—Fe1—N1—C2	−3.6 (7)	C18—N3—C20—C19	−0.9 (4)
O2—Fe1—N1—C4	169.3 (4)	Fe1—N5—C23—C22	179.1 (3)
N2—Fe1—N1—C2	14.9 (3)	C19—N4—C18—N3	−0.8 (5)
N2—Fe1—N1—C4	−172.2 (4)	C18—N4—C19—C20	0.2 (5)
N3—Fe1—N1—C2	102.6 (3)	C21—N5—C23—C22	0.1 (5)
N3—Fe1—N1—C4	−84.5 (3)	Fe1—N5—C21—N6	−179.1 (3)
N5—Fe1—N1—C4	97.1 (3)	C23—N5—C21—N6	0.0 (4)
N5—Fe1—N1—C2	−75.8 (3)	C22—N6—C21—N5	0.0 (5)
O1—Fe1—N2—C3	−7.4 (7)	C21—N6—C22—C23	0.1 (5)
O1—Fe1—N2—C11	170.5 (4)	N1—C2—C3—N2	41.1 (5)
O2—Fe1—N2—C3	−175.8 (3)	C1—C2—C3—N2	173.6 (4)
O2—Fe1—N2—C11	2.1 (3)	N1—C4—C5—C6	−179.8 (4)
N1—Fe1—N2—C3	8.8 (3)	N1—C4—C5—C10	−1.6 (7)
N1—Fe1—N2—C11	−173.2 (4)	C4—C5—C6—C7	179.4 (4)
N3—Fe1—N2—C3	−84.9 (3)	C10—C5—C6—C7	1.0 (7)
N3—Fe1—N2—C11	93.1 (3)	C4—C5—C10—O1	−1.1 (6)
N5—Fe1—N2—C3	96.2 (3)	C4—C5—C10—C9	178.8 (4)
N5—Fe1—N2—C11	−85.9 (3)	C6—C5—C10—O1	177.1 (4)
O1—Fe1—N3—C18	4.1 (3)	C6—C5—C10—C9	−3.0 (6)
O1—Fe1—N3—C20	174.8 (3)	C5—C6—C7—C8	1.6 (8)
O2—Fe1—N3—C18	−100.9 (3)	C6—C7—C8—C9	−2.1 (8)
O2—Fe1—N3—C20	69.8 (3)	C7—C8—C9—C10	0.0 (7)
N1—Fe1—N3—C18	93.3 (3)	C8—C9—C10—O1	−177.6 (4)
N1—Fe1—N3—C20	−95.9 (3)	C8—C9—C10—C5	2.5 (7)
N2—Fe1—N3—C18	170.3 (3)	N2—C11—C12—C13	−177.5 (4)
N2—Fe1—N3—C20	−19.0 (3)	N2—C11—C12—C17	1.8 (6)
O1—Fe1—N5—C21	−103.2 (3)	C11—C12—C13—C14	179.6 (4)
O1—Fe1—N5—C23	77.9 (3)	C17—C12—C13—C14	0.2 (6)
O2—Fe1—N5—C21	1.8 (3)	C11—C12—C17—O2	1.8 (6)
O2—Fe1—N5—C23	−177.1 (3)	C11—C12—C17—C16	−179.7 (4)
N1—Fe1—N5—C21	167.6 (3)	C13—C12—C17—O2	−178.9 (4)
N1—Fe1—N5—C23	−11.3 (3)	C13—C12—C17—C16	−0.4 (6)
N2—Fe1—N5—C21	90.6 (3)	C12—C13—C14—C15	0.4 (7)
N2—Fe1—N5—C23	−88.3 (3)	C13—C14—C15—C16	−0.7 (7)
Fe1—O1—C10—C5	7.0 (6)	C14—C15—C16—C17	0.5 (7)
Fe1—O1—C10—C9	−172.9 (3)	C15—C16—C17—O2	178.6 (4)
Fe1—O2—C17—C12	−3.2 (6)	C15—C16—C17—C12	0.1 (6)
Fe1—O2—C17—C16	178.4 (3)	N4—C19—C20—N3	0.5 (5)
Fe1—N1—C2—C1	−165.7 (3)	N6—C22—C23—N5	−0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O6ⁱ	0.95	2.53	3.436 (6)	161
C16—H16···O5	0.95	2.53	3.325 (6)	142
N4—H4A···O2ⁱⁱ	0.88	2.48	3.063 (4)	125
N4—H4A···O6ⁱⁱ	0.88	2.36	3.031 (4)	133
N6—H6A···O4ⁱⁱⁱ	0.88	2.03	2.892 (4)	167

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₇H₁₆N₂O₂)(C₃H₄N₂)₂]ClO₄
M_r	571.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	10.4898 (8), 16.4312 (9), 14.7729 (8)
β (°)	105.5081 (17)
V (Å³)	2453.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID Imaging Plate diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 2001)
T_min, T_max	0.860, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	20794, 5615, 3529
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.179, 0.99
No. of reflections	5615
No. of parameters	335
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.65

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalClear (Molecular Structure Corporation and Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Yadokari-XG (Wakita, 2000).

Selected bond lengths (Å) top

Fe1—O1	1.879 (2)	Fe1—N2	2.108 (3)
Fe1—O2	1.914 (3)	Fe1—N3	2.161 (3)
Fe1—N1	2.119 (3)	Fe1—N5	2.161 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O6ⁱ	0.95	2.526	3.436 (6)	161
C16—H16···O5	0.95	2.527	3.325 (6)	142
N4—H4A···O2ⁱⁱ	0.88	2.476	3.063 (4)	125
N4—H4A···O6ⁱⁱ	0.88	2.359	3.031 (4)	133
N6—H6A···O4ⁱⁱⁱ	0.88	2.028	2.892 (4)	167

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

Acknowledgements

This work was supported by `Development of Molecular Devices in Ferroelectric Metallomesogens' in 2006 of the New Energy and Industrial Technology Development Organization (NEDO) of Japan, and by Grants-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government (No. 20350028).

References

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