Tris[4-(2-pyridylmethyl­eneamino)phenol]iron(II) bis­(perchlorate)

Şerb, M.-D.; Calmuschi-Cula, B.; Dumitru, F.; Englert, U.; Guran, C.

doi:10.1107/S1600536807066688

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m212-m213

https://doi.org/10.1107/S1600536807066688

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Tris[4-(2-pyridylmethyleneamino)phenol]iron(II) bis(perchlorate)

Mihaela-Diana Şerb,^a Beatrice Calmuschi-Cula,^b ^* Florina Dumitru,^a Ulli Englert ^b and Cornelia Guran ^a

^aDepartment of Inorganic Chemistry, University "Politehnica" of Bucharest, Polizu 1, 011061 Bucharest, Romania, and ^bInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
^*Correspondence e-mail: beatrice.calmuschi@ac.rwth-aachen.de

(Received 10 December 2007; accepted 12 December 2007; online 18 December 2007)

In the title compound, [Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂, the metal center is coordinated by six N atoms from the three bidentate chelating ligands in a distorted octahedral coordination geometry, with overall formation of the meridional (OC-6-21) isomer. Intermolecular O—H⋯O hydrogen bonds between the hydroxyl groups of the cation and the counter-anions form an infinite one-dimensional chain in the c-axis direction.

Related literature

For related literature, see: Cloete & Mapolie (2006 ); Osman (2006 ); Sharma & Dubey (1994 ); Thankarajan & Mohanan (1986 ); Dash et al. (1983 ); Dhar et al. (2005 ); Golcu et al. (2005 ); Lacroxin et al. (2004 ); Shaker et al. (2003 ).

Experimental

Crystal data

[Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂
M_r = 849.41
Monoclinic, P 2₁ /c
a = 16.201 (3) Å
b = 9.1222 (15) Å
c = 23.787 (4) Å
β = 91.089 (5)°
V = 3514.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 130 (2) K
0.55 × 0.07 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.714, T_max = 0.974
20409 measured reflections
7879 independent reflections
4431 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.115
S = 1.01
7879 reflections
505 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—N4	1.963 (3)
Fe1—N6	1.971 (3)
Fe1—N1	1.974 (3)
Fe1—N3	1.997 (3)
Fe1—N2	2.002 (3)
Fe1—N5	2.015 (3)

N4—Fe1—N6	173.00 (12)
N4—Fe1—N1	89.66 (11)
N6—Fe1—N1	96.85 (12)
N4—Fe1—N3	81.32 (12)
N6—Fe1—N3	95.72 (11)
N1—Fe1—N3	92.83 (12)
N4—Fe1—N2	93.54 (11)
N6—Fe1—N2	90.05 (11)
N1—Fe1—N2	81.04 (12)
N3—Fe1—N2	172.06 (12)
N4—Fe1—N5	93.27 (11)
N6—Fe1—N5	80.00 (12)
N1—Fe1—N5	173.71 (12)
N3—Fe1—N5	82.12 (11)
N2—Fe1—N5	104.31 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O7ⁱ	0.82	2.05	2.815 (4)	155
O2—H2⋯O4ⁱⁱ	0.82	1.92	2.733 (4)	174
O3—H3⋯O9ⁱⁱⁱ	0.82	1.96	2.772 (4)	172
Symmetry codes: (i) $[-x+1, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 1999 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066688/wn2231sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066688/wn2231Isup2.hkl

checkCIF report

Comment top

A large number of Schiff bases and their complexes have been studied for their interesting and important properties, such as their ability to reversibly bind oxygen, their catalytic activity in the hydrogenation of olefins and their photochromic properties (Osman, 2006). The synthesis of new Schiff bases and their metal complexes are the subject of ongoing research (Golcu et al., 2005; Lacroxin et al., 2004; Dhar et al., 2005). Similar to the ligands 2,2'-bipyridine and 1,10-phenanthroline, Schiff bases derived from 2-pyridinecarboxaldehyde provide the π-acidic α,α'-diimine fragment for metal coordination.

Very little effort has been spent in the preparation of Fe(II) Schiff base complexes (Thankarajan & Mohanan, 1986; Sharma & Dubey, 1994), despite their importance as complexes containing a metal in a low and potentially unstable oxidation state, as well as involving relatively unstable ligands, the Schiff bases (Shaker et al., 2003). Such ligands are hydrolytically unstable but the metal ions stabilize the aldimine linkage to hydrolytic splitting (Dash et al., 1983).

In this context, the title complex of Fe(II) with 2-pyridinecarboxaldehyde(p-hydroxyphenylimine) has been prepared and its crystal structure is reported here. The central Fe atom is coordinated by three ligand molecules through the nitrogen atoms in a bidentate manner. The coordination geometry is distorted octahedral. The complex crystallizes as the meridional isomer in the monoclinic centrosymmetric space group P2₁/c. The meridional isomer is associated with two different orientations of the bidentate ligands in a 2:1 distribution. These two different types of geometry are reflected in different dihedral angles between the aromatic and heteroaromatic rings. For the ligands which have the same orientation (N1···N2 and N3···N4 bidentate ligands) the dihedral angles are similar, viz. 36.72 (16) and 34.21 (16)°, respectively, whereas for the bidentate ligand N5···N6 with different orientation the angle is 50.30 (17)°. The Fe(II)—N(pyridine) distances are shorter than the Fe(II)—N(imine) bonds (see Table 1). Classical intermolecular O—H···O hydrogen bonds between the OH groups of the cation and the anions form an infinite one-dimensional chain in the c direction.

Related literature top

For related literature, see: Cloete & Mapolie (2006); Osman (2006); Sharma & Dubey (1994); Thankarajan & Mohanan (1986); Dash et al. (1983); Dhar et al. (2005); Golcu et al. (2005); Lacroxin et al. (2004); Shaker et al. (2003).

Experimental top

Attempts to synthesize Fe(II) complexes with the Schiff base ligand 2-pyridinecarboxaldehyde(p-hydroxyphenylimine) in a molar ratio M:L 1:1 or 1:2 resulted in the same crystalline complex [Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂, independent of reactant stoichiometry. The ligand 2-pyridinecarboxaldehyde(p-hydroxyphenylimine) was prepared following the procedure developed in the literature (Cloete & Mapolie, 2006). Stoichiometric amounts of Fe(ClO₄)₂.xH₂O (0.255 g, 1 mmol) and 2-pyridinecarboxaldehyde(p-hydroxyphenylimine) (0.198 g, 1 mmol respectively 0.296 g, 2 mmol) were dissolved in acetonitrile (40 ml) and stirred under reflux to promote the complete formation of the purple complex, [Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂. Single crystals suitable for X-ray diffraction were obtained by slow diffusion of diisopropyl ether into an acetonitrile solution of the complex at room temperature.

Structure description top

For related literature, see: Cloete & Mapolie (2006); Osman (2006); Sharma & Dubey (1994); Thankarajan & Mohanan (1986); Dash et al. (1983); Dhar et al. (2005); Golcu et al. (2005); Lacroxin et al. (2004); Shaker et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. Displacement ellipsoid plots (30% probability) of the cation. Hydrogen atoms and the anions have been omitted for clarity.
	Fig. 2. The packing of the structure in the unit cell. Hydrogen bonds are indicated by dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted.

Tris[4-(2-pyridylmethyleneamino)phenol]iron(II) bis(perchlorate) top

Crystal data top

[Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂	F(000) = 1744
M_r = 849.41	D_x = 1.605 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.201 (3) Å	Cell parameters from 8096 reflections
b = 9.1222 (15) Å	θ = 2.1–27.4°
c = 23.787 (4) Å	µ = 0.66 mm⁻¹
β = 91.089 (5)°	T = 130 K
V = 3514.8 (10) Å³	Rod, dark brown
Z = 4	0.55 × 0.07 × 0.04 mm

Data collection top

Bruker SMART APEX CCD diffractometer	7879 independent reflections
Radiation source: fine-focus sealed tube	4431 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ω scans	θ_max = 27.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→21
T_min = 0.714, T_max = 0.974	k = −11→11
20409 measured reflections	l = −26→30

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.034P)²] where P = (F_o² + 2F_c²)/3
7879 reflections	(Δ/σ)_max < 0.001
505 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂	V = 3514.8 (10) Å³
M_r = 849.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.201 (3) Å	µ = 0.66 mm⁻¹
b = 9.1222 (15) Å	T = 130 K
c = 23.787 (4) Å	0.55 × 0.07 × 0.04 mm
β = 91.089 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	7879 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4431 reflections with I > 2σ(I)
T_min = 0.714, T_max = 0.974	R_int = 0.081
20409 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.01	Δρ_max = 0.60 e Å⁻³
7879 reflections	Δρ_min = −0.53 e Å⁻³
505 parameters

Special details top

Experimental. The values of Tmin and Tmax are 0.764276 and 1.000000 from SADABS.

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	0.25204 (3)	0.69147 (6)	0.15599 (2)	0.02052 (14)
O1	0.44356 (17)	1.3193 (3)	0.27185 (11)	0.0430 (7)
H1	0.4309	1.3514	0.3027	0.065*
O2	0.30912 (16)	0.2248 (3)	−0.07599 (10)	0.0376 (7)
H2	0.3384	0.1595	−0.0628	0.056*
O3	0.03875 (16)	1.2193 (3)	0.01116 (10)	0.0379 (7)
H3	0.0218	1.2735	0.0359	0.057*
N1	0.22735 (17)	0.5285 (3)	0.20764 (12)	0.0243 (7)
N2	0.29799 (17)	0.7776 (3)	0.22739 (12)	0.0230 (7)
N3	0.19351 (18)	0.5951 (3)	0.09126 (11)	0.0221 (7)
N4	0.14110 (17)	0.7711 (3)	0.16764 (11)	0.0210 (7)
N5	0.27866 (17)	0.8410 (3)	0.09666 (11)	0.0211 (7)
N6	0.36340 (17)	0.6253 (3)	0.13568 (11)	0.0199 (7)
C1	0.2528 (2)	0.5509 (4)	0.26149 (15)	0.0238 (9)
C2	0.2939 (2)	0.6898 (4)	0.27008 (15)	0.0255 (8)
H2A	0.3165	0.7153	0.3049	0.031*
C3	0.3315 (2)	0.9198 (4)	0.23806 (14)	0.0225 (8)
C4	0.3158 (2)	0.9923 (4)	0.28827 (14)	0.0259 (9)
H4	0.2804	0.9502	0.3141	0.031*
C5	0.3519 (2)	1.1253 (4)	0.30015 (15)	0.0288 (9)
H5	0.3412	1.1723	0.3339	0.035*
C6	0.4038 (2)	1.1889 (4)	0.26232 (15)	0.0272 (9)
C7	0.4177 (2)	1.1200 (4)	0.21192 (15)	0.0317 (10)
H7	0.4516	1.1643	0.1858	0.038*
C8	0.3822 (2)	0.9875 (4)	0.19971 (15)	0.0277 (9)
H8	0.3922	0.9425	0.1654	0.033*
C9	0.2382 (2)	0.4512 (4)	0.30424 (15)	0.0284 (9)
H9	0.2572	0.4695	0.3407	0.034*
C10	0.1950 (2)	0.3248 (4)	0.29190 (16)	0.0335 (10)
H10	0.1854	0.2553	0.3196	0.040*
C11	0.1661 (2)	0.3035 (4)	0.23742 (16)	0.0333 (10)
H11	0.1354	0.2207	0.2280	0.040*
C12	0.1839 (2)	0.4077 (4)	0.19731 (15)	0.0282 (9)
H12	0.1642	0.3923	0.1608	0.034*
C13	0.2266 (2)	0.5021 (4)	0.04826 (14)	0.0228 (8)
C14	0.2054 (2)	0.5242 (4)	−0.00785 (14)	0.0278 (9)
H14	0.1714	0.6024	−0.0180	0.033*
C15	0.2342 (2)	0.4314 (4)	−0.04842 (15)	0.0323 (10)
H15	0.2198	0.4474	−0.0860	0.039*
C16	0.2843 (2)	0.3144 (4)	−0.03397 (15)	0.0290 (9)
C17	0.3091 (2)	0.2942 (4)	0.02191 (15)	0.0250 (9)
H17	0.3453	0.2189	0.0317	0.030*
C18	0.2791 (2)	0.3878 (4)	0.06279 (15)	0.0244 (9)
H18	0.2945	0.3736	0.1003	0.029*
C19	0.1181 (2)	0.6377 (4)	0.08495 (15)	0.0248 (9)
H19	0.0854	0.6040	0.0551	0.030*
C20	0.0859 (2)	0.7398 (4)	0.12569 (14)	0.0229 (8)
C21	0.1159 (2)	0.8625 (4)	0.20802 (14)	0.0247 (9)
H21	0.1509	0.8799	0.2387	0.030*
C22	0.0397 (2)	0.9321 (4)	0.20587 (15)	0.0280 (9)
H22	0.0245	0.9958	0.2344	0.034*
C23	−0.0129 (2)	0.9057 (4)	0.16097 (16)	0.0328 (10)
H23	−0.0628	0.9559	0.1576	0.039*
C24	0.0089 (2)	0.8037 (4)	0.12084 (15)	0.0304 (9)
H24	−0.0272	0.7790	0.0915	0.037*
C25	0.2220 (2)	0.9464 (4)	0.07386 (14)	0.0221 (8)
C26	0.1963 (2)	0.9394 (4)	0.01779 (14)	0.0271 (9)
H26	0.2202	0.8713	−0.0060	0.032*
C27	0.1365 (2)	1.0312 (4)	−0.00281 (15)	0.0297 (9)
H27	0.1200	1.0261	−0.0404	0.036*
C28	0.1004 (2)	1.1321 (4)	0.03266 (15)	0.0260 (9)
C29	0.1265 (2)	1.1410 (4)	0.08820 (14)	0.0238 (9)
H29	0.1029	1.2097	0.1119	0.029*
C30	0.1869 (2)	1.0497 (4)	0.10853 (15)	0.0241 (9)
H30	0.2044	1.0570	0.1459	0.029*
C31	0.3439 (2)	0.8096 (4)	0.06834 (14)	0.0248 (8)
H31	0.3575	0.8609	0.0360	0.030*
C32	0.3945 (2)	0.6907 (4)	0.08974 (14)	0.0223 (8)
C33	0.4093 (2)	0.5220 (4)	0.16004 (15)	0.0241 (9)
H33	0.3901	0.4780	0.1925	0.029*
C34	0.4844 (2)	0.4767 (4)	0.13958 (16)	0.0304 (9)
H34	0.5146	0.4042	0.1582	0.036*
C35	0.5140 (2)	0.5396 (4)	0.09150 (17)	0.0330 (10)
H35	0.5632	0.5079	0.0762	0.040*
C36	0.4691 (2)	0.6504 (4)	0.06662 (16)	0.0306 (9)
H36	0.4884	0.6975	0.0348	0.037*
Cl1	0.56386 (6)	0.08454 (11)	0.08604 (4)	0.0336 (3)
O4	0.59056 (18)	−0.0018 (3)	0.03976 (10)	0.0498 (8)
O5	0.48010 (18)	0.1187 (4)	0.08003 (13)	0.0798 (12)
O6	0.6107 (3)	0.2155 (4)	0.08746 (18)	0.1029 (14)
O7	0.58053 (19)	0.0088 (4)	0.13652 (11)	0.0648 (10)
Cl2	0.07519 (6)	0.85572 (12)	0.36151 (4)	0.0384 (3)
O8	0.10983 (19)	0.9829 (3)	0.33517 (11)	0.0603 (10)
O9	0.03283 (17)	0.9033 (3)	0.41089 (11)	0.0498 (8)
O10	0.1390 (2)	0.7602 (4)	0.37764 (16)	0.0819 (12)
O11	0.0186 (2)	0.7834 (4)	0.32467 (12)	0.0663 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0234 (3)	0.0188 (3)	0.0193 (3)	0.0015 (2)	−0.0003 (2)	−0.0005 (2)
O1	0.062 (2)	0.0289 (17)	0.0377 (16)	−0.0113 (15)	−0.0031 (14)	−0.0074 (14)
O2	0.0576 (19)	0.0300 (17)	0.0254 (15)	0.0163 (14)	0.0023 (13)	−0.0022 (12)
O3	0.0444 (17)	0.0399 (18)	0.0290 (15)	0.0151 (14)	−0.0073 (13)	−0.0052 (13)
N1	0.0273 (17)	0.0210 (18)	0.0245 (17)	0.0019 (14)	−0.0037 (14)	−0.0032 (14)
N2	0.0220 (16)	0.0204 (19)	0.0265 (17)	0.0042 (14)	−0.0002 (13)	0.0000 (14)
N3	0.0285 (18)	0.0171 (17)	0.0209 (16)	0.0005 (14)	0.0035 (13)	0.0002 (13)
N4	0.0256 (17)	0.0206 (18)	0.0167 (16)	−0.0016 (14)	0.0009 (13)	0.0017 (13)
N5	0.0257 (17)	0.0153 (17)	0.0221 (16)	−0.0029 (13)	−0.0021 (14)	−0.0002 (13)
N6	0.0227 (16)	0.0181 (17)	0.0189 (16)	−0.0026 (14)	−0.0018 (13)	−0.0004 (13)
C1	0.020 (2)	0.023 (2)	0.027 (2)	0.0055 (17)	−0.0035 (16)	0.0019 (18)
C2	0.029 (2)	0.025 (2)	0.022 (2)	−0.0014 (18)	−0.0028 (16)	0.0033 (18)
C3	0.022 (2)	0.019 (2)	0.026 (2)	0.0014 (17)	−0.0037 (16)	−0.0051 (17)
C4	0.030 (2)	0.026 (2)	0.022 (2)	0.0002 (18)	−0.0019 (17)	0.0018 (17)
C5	0.033 (2)	0.031 (2)	0.022 (2)	0.0036 (19)	−0.0038 (18)	−0.0052 (18)
C6	0.032 (2)	0.015 (2)	0.034 (2)	0.0023 (19)	−0.0095 (18)	−0.0030 (19)
C7	0.044 (3)	0.026 (2)	0.025 (2)	−0.008 (2)	0.0053 (19)	−0.0007 (18)
C8	0.033 (2)	0.026 (2)	0.025 (2)	0.0032 (19)	0.0020 (18)	−0.0030 (18)
C9	0.030 (2)	0.031 (2)	0.024 (2)	0.0003 (19)	−0.0033 (17)	0.0047 (18)
C10	0.037 (2)	0.024 (2)	0.039 (2)	0.004 (2)	0.000 (2)	0.0086 (19)
C11	0.036 (2)	0.022 (2)	0.042 (2)	−0.0021 (19)	0.0037 (19)	0.000 (2)
C12	0.035 (2)	0.021 (2)	0.029 (2)	−0.0057 (19)	−0.0014 (18)	0.0003 (18)
C13	0.029 (2)	0.015 (2)	0.024 (2)	−0.0001 (17)	−0.0013 (17)	−0.0008 (16)
C14	0.038 (2)	0.021 (2)	0.024 (2)	0.0073 (19)	−0.0034 (18)	0.0003 (17)
C15	0.046 (3)	0.034 (3)	0.017 (2)	0.011 (2)	−0.0044 (18)	−0.0031 (18)
C16	0.040 (2)	0.023 (2)	0.024 (2)	0.005 (2)	0.0053 (18)	−0.0031 (18)
C17	0.026 (2)	0.017 (2)	0.031 (2)	0.0009 (17)	−0.0008 (17)	0.0012 (18)
C18	0.033 (2)	0.020 (2)	0.020 (2)	−0.0081 (18)	−0.0031 (17)	0.0005 (17)
C19	0.026 (2)	0.023 (2)	0.025 (2)	−0.0071 (18)	−0.0004 (17)	0.0001 (17)
C20	0.026 (2)	0.019 (2)	0.024 (2)	−0.0005 (17)	0.0029 (17)	0.0037 (16)
C21	0.031 (2)	0.027 (2)	0.0156 (19)	0.0036 (18)	0.0017 (16)	0.0018 (17)
C22	0.032 (2)	0.030 (2)	0.022 (2)	0.0020 (19)	0.0089 (18)	−0.0002 (18)
C23	0.026 (2)	0.039 (3)	0.034 (2)	0.011 (2)	0.0085 (19)	0.007 (2)
C24	0.027 (2)	0.039 (3)	0.025 (2)	0.001 (2)	−0.0051 (17)	0.000 (2)
C25	0.026 (2)	0.014 (2)	0.026 (2)	−0.0007 (16)	−0.0010 (17)	0.0020 (16)
C26	0.037 (2)	0.020 (2)	0.024 (2)	0.0028 (18)	0.0030 (18)	0.0002 (17)
C27	0.040 (2)	0.026 (2)	0.023 (2)	0.0027 (19)	−0.0034 (18)	−0.0015 (18)
C28	0.027 (2)	0.021 (2)	0.029 (2)	0.0016 (18)	−0.0024 (17)	0.0016 (18)
C29	0.027 (2)	0.018 (2)	0.027 (2)	−0.0040 (17)	0.0034 (17)	−0.0047 (17)
C30	0.027 (2)	0.021 (2)	0.024 (2)	−0.0014 (17)	−0.0031 (17)	−0.0017 (17)
C31	0.029 (2)	0.024 (2)	0.0212 (19)	−0.0061 (19)	0.0044 (17)	−0.0025 (18)
C32	0.0245 (19)	0.017 (2)	0.025 (2)	0.0007 (17)	−0.0034 (16)	−0.0037 (17)
C33	0.026 (2)	0.019 (2)	0.027 (2)	0.0009 (17)	−0.0038 (17)	0.0027 (17)
C34	0.027 (2)	0.019 (2)	0.045 (3)	0.0058 (18)	−0.0073 (19)	0.0015 (19)
C35	0.025 (2)	0.024 (2)	0.051 (3)	0.0050 (19)	0.0047 (19)	−0.004 (2)
C36	0.031 (2)	0.029 (2)	0.032 (2)	−0.0013 (19)	0.0080 (18)	−0.0022 (19)
Cl1	0.0392 (6)	0.0342 (6)	0.0273 (5)	0.0127 (5)	0.0016 (4)	−0.0004 (5)
O4	0.078 (2)	0.0455 (19)	0.0267 (16)	0.0280 (17)	0.0097 (15)	−0.0017 (14)
O5	0.046 (2)	0.139 (4)	0.054 (2)	0.047 (2)	−0.0139 (17)	−0.024 (2)
O6	0.124 (4)	0.036 (2)	0.149 (4)	−0.007 (2)	0.015 (3)	−0.023 (2)
O7	0.074 (2)	0.089 (3)	0.0317 (18)	0.036 (2)	0.0095 (16)	0.0198 (18)
Cl2	0.0365 (6)	0.0503 (7)	0.0283 (6)	−0.0131 (5)	−0.0019 (5)	−0.0016 (5)
O8	0.078 (2)	0.069 (2)	0.0346 (17)	−0.0477 (19)	0.0098 (16)	−0.0038 (16)
O9	0.056 (2)	0.048 (2)	0.0459 (18)	−0.0090 (16)	0.0241 (16)	0.0002 (15)
O10	0.064 (2)	0.084 (3)	0.097 (3)	0.037 (2)	−0.015 (2)	−0.024 (2)
O11	0.077 (2)	0.083 (3)	0.0391 (18)	−0.052 (2)	−0.0175 (16)	0.0084 (17)

Geometric parameters (Å, º) top

Fe1—N4	1.963 (3)	C14—C15	1.372 (5)
Fe1—N6	1.971 (3)	C14—H14	0.9300
Fe1—N1	1.974 (3)	C15—C16	1.380 (5)
Fe1—N3	1.997 (3)	C15—H15	0.9300
Fe1—N2	2.002 (3)	C16—C17	1.394 (5)
Fe1—N5	2.015 (3)	C17—C18	1.388 (5)
O1—C6	1.370 (4)	C17—H17	0.9300
O1—H1	0.8200	C18—H18	0.9300
O2—C16	1.358 (4)	C19—C20	1.449 (5)
O2—H2	0.8200	C19—H19	0.9300
O3—C28	1.369 (4)	C20—C24	1.378 (5)
O3—H3	0.8200	C21—C22	1.388 (5)
N1—C12	1.328 (4)	C21—H21	0.9300
N1—C1	1.354 (4)	C22—C23	1.375 (5)
N2—C2	1.296 (4)	C22—H22	0.9300
N2—C3	1.426 (4)	C23—C24	1.384 (5)
N3—C19	1.288 (4)	C23—H23	0.9300
N3—C13	1.440 (4)	C24—H24	0.9300
N4—C21	1.341 (4)	C25—C30	1.382 (5)
N4—C20	1.358 (4)	C25—C26	1.391 (5)
N5—C31	1.296 (4)	C26—C27	1.365 (5)
N5—C25	1.429 (4)	C26—H26	0.9300
N6—C33	1.327 (4)	C27—C28	1.385 (5)
N6—C32	1.351 (4)	C27—H27	0.9300
C1—C9	1.388 (5)	C28—C29	1.382 (5)
C1—C2	1.444 (5)	C29—C30	1.366 (5)
C2—H2A	0.9300	C29—H29	0.9300
C3—C8	1.385 (5)	C30—H30	0.9300
C3—C4	1.393 (5)	C31—C32	1.446 (5)
C4—C5	1.374 (5)	C31—H31	0.9300
C4—H4	0.9300	C32—C36	1.387 (5)
C5—C6	1.371 (5)	C33—C34	1.382 (5)
C5—H5	0.9300	C33—H33	0.9300
C6—C7	1.376 (5)	C34—C35	1.374 (5)
C7—C8	1.368 (5)	C34—H34	0.9300
C7—H7	0.9300	C35—C36	1.372 (5)
C8—H8	0.9300	C35—H35	0.9300
C9—C10	1.378 (5)	C36—H36	0.9300
C9—H9	0.9300	Cl1—O5	1.397 (3)
C10—C11	1.383 (5)	Cl1—O7	1.407 (3)
C10—H10	0.9300	Cl1—O6	1.416 (4)
C11—C12	1.381 (5)	Cl1—O4	1.427 (3)
C11—H11	0.9300	Cl2—O10	1.400 (3)
C12—H12	0.9300	Cl2—O11	1.418 (3)
C13—C18	1.385 (5)	Cl2—O8	1.438 (3)
C13—C14	1.387 (5)	Cl2—O9	1.439 (3)

N4—Fe1—N6	173.00 (12)	C14—C15—C16	120.6 (3)
N4—Fe1—N1	89.66 (11)	C14—C15—H15	119.7
N6—Fe1—N1	96.85 (12)	C16—C15—H15	119.7
N4—Fe1—N3	81.32 (12)	O2—C16—C15	117.6 (3)
N6—Fe1—N3	95.72 (11)	O2—C16—C17	122.6 (3)
N1—Fe1—N3	92.83 (12)	C15—C16—C17	119.8 (3)
N4—Fe1—N2	93.54 (11)	C18—C17—C16	119.2 (3)
N6—Fe1—N2	90.05 (11)	C18—C17—H17	120.4
N1—Fe1—N2	81.04 (12)	C16—C17—H17	120.4
N3—Fe1—N2	172.06 (12)	C13—C18—C17	120.6 (3)
N4—Fe1—N5	93.27 (11)	C13—C18—H18	119.7
N6—Fe1—N5	80.00 (12)	C17—C18—H18	119.7
N1—Fe1—N5	173.71 (12)	N3—C19—C20	118.0 (3)
N3—Fe1—N5	82.12 (11)	N3—C19—H19	121.0
N2—Fe1—N5	104.31 (12)	C20—C19—H19	121.0
C6—O1—H1	109.5	N4—C20—C24	123.7 (3)
C16—O2—H2	109.5	N4—C20—C19	112.7 (3)
C28—O3—H3	109.5	C24—C20—C19	123.6 (3)
C12—N1—C1	116.8 (3)	N4—C21—C22	122.7 (3)
C12—N1—Fe1	128.5 (2)	N4—C21—H21	118.6
C1—N1—Fe1	114.4 (2)	C22—C21—H21	118.6
C2—N2—C3	116.6 (3)	C23—C22—C21	119.1 (3)
C2—N2—Fe1	113.5 (2)	C23—C22—H22	120.4
C3—N2—Fe1	129.9 (2)	C21—C22—H22	120.4
C19—N3—C13	117.4 (3)	C22—C23—C24	119.3 (3)
C19—N3—Fe1	113.1 (2)	C22—C23—H23	120.3
C13—N3—Fe1	129.0 (2)	C24—C23—H23	120.3
C21—N4—C20	116.8 (3)	C20—C24—C23	118.0 (3)
C21—N4—Fe1	128.5 (2)	C20—C24—H24	121.0
C20—N4—Fe1	114.3 (2)	C23—C24—H24	121.0
C31—N5—C25	118.4 (3)	C30—C25—C26	118.9 (3)
C31—N5—Fe1	113.7 (2)	C30—C25—N5	120.1 (3)
C25—N5—Fe1	125.2 (2)	C26—C25—N5	120.8 (3)
C33—N6—C32	116.9 (3)	C27—C26—C25	120.9 (3)
C33—N6—Fe1	128.2 (2)	C27—C26—H26	119.5
C32—N6—Fe1	114.9 (2)	C25—C26—H26	119.5
N1—C1—C9	122.8 (3)	C26—C27—C28	119.6 (3)
N1—C1—C2	113.4 (3)	C26—C27—H27	120.2
C9—C1—C2	123.8 (3)	C28—C27—H27	120.2
N2—C2—C1	117.5 (3)	O3—C28—C29	122.1 (3)
N2—C2—H2A	121.2	O3—C28—C27	118.2 (3)
C1—C2—H2A	121.2	C29—C28—C27	119.8 (3)
C8—C3—C4	118.2 (3)	C30—C29—C28	120.4 (3)
C8—C3—N2	121.1 (3)	C30—C29—H29	119.8
C4—C3—N2	120.6 (3)	C28—C29—H29	119.8
C5—C4—C3	120.8 (4)	C29—C30—C25	120.3 (3)
C5—C4—H4	119.6	C29—C30—H30	119.8
C3—C4—H4	119.6	C25—C30—H30	119.8
C6—C5—C4	120.1 (4)	N5—C31—C32	116.4 (3)
C6—C5—H5	119.9	N5—C31—H31	121.8
C4—C5—H5	119.9	C32—C31—H31	121.8
O1—C6—C5	123.4 (3)	N6—C32—C36	123.0 (3)
O1—C6—C7	117.2 (3)	N6—C32—C31	113.5 (3)
C5—C6—C7	119.4 (4)	C36—C32—C31	123.5 (3)
C8—C7—C6	120.9 (4)	N6—C33—C34	123.3 (3)
C8—C7—H7	119.5	N6—C33—H33	118.4
C6—C7—H7	119.5	C34—C33—H33	118.4
C7—C8—C3	120.4 (3)	C35—C34—C33	119.4 (4)
C7—C8—H8	119.8	C35—C34—H34	120.3
C3—C8—H8	119.8	C33—C34—H34	120.3
C10—C9—C1	119.0 (3)	C36—C35—C34	118.5 (4)
C10—C9—H9	120.5	C36—C35—H35	120.8
C1—C9—H9	120.5	C34—C35—H35	120.8
C9—C10—C11	118.6 (4)	C35—C36—C32	118.9 (4)
C9—C10—H10	120.7	C35—C36—H36	120.6
C11—C10—H10	120.7	C32—C36—H36	120.6
C12—C11—C10	118.7 (4)	O5—Cl1—O7	111.5 (2)
C12—C11—H11	120.7	O5—Cl1—O6	109.5 (2)
C10—C11—H11	120.7	O7—Cl1—O6	107.4 (2)
N1—C12—C11	124.1 (4)	O5—Cl1—O4	110.62 (19)
N1—C12—H12	118.0	O7—Cl1—O4	109.36 (17)
C11—C12—H12	118.0	O6—Cl1—O4	108.3 (2)
C18—C13—C14	119.3 (3)	O10—Cl2—O11	110.2 (2)
C18—C13—N3	120.1 (3)	O10—Cl2—O8	109.2 (2)
C14—C13—N3	120.6 (3)	O11—Cl2—O8	111.05 (18)
C15—C14—C13	120.4 (3)	O10—Cl2—O9	109.0 (2)
C15—C14—H14	119.8	O11—Cl2—O9	109.40 (19)
C13—C14—H14	119.8	O8—Cl2—O9	107.96 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7ⁱ	0.82	2.05	2.815 (4)	155
O2—H2···O4ⁱⁱ	0.82	1.92	2.733 (4)	174
O3—H3···O9ⁱⁱⁱ	0.82	1.96	2.772 (4)	172

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₁₀N₂O)₃](ClO₄)₂
M_r	849.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	130
a, b, c (Å)	16.201 (3), 9.1222 (15), 23.787 (4)
β (°)	91.089 (5)
V (Å³)	3514.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.55 × 0.07 × 0.04

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.714, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	20409, 7879, 4431
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.115, 1.01
No. of reflections	7879
No. of parameters	505
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.53

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

Fe1—N4	1.963 (3)	Fe1—N3	1.997 (3)
Fe1—N6	1.971 (3)	Fe1—N2	2.002 (3)
Fe1—N1	1.974 (3)	Fe1—N5	2.015 (3)

N4—Fe1—N6	173.00 (12)	N1—Fe1—N2	81.04 (12)
N4—Fe1—N1	89.66 (11)	N3—Fe1—N2	172.06 (12)
N6—Fe1—N1	96.85 (12)	N4—Fe1—N5	93.27 (11)
N4—Fe1—N3	81.32 (12)	N6—Fe1—N5	80.00 (12)
N6—Fe1—N3	95.72 (11)	N1—Fe1—N5	173.71 (12)
N1—Fe1—N3	92.83 (12)	N3—Fe1—N5	82.12 (11)
N4—Fe1—N2	93.54 (11)	N2—Fe1—N5	104.31 (12)
N6—Fe1—N2	90.05 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7ⁱ	0.82	2.05	2.815 (4)	155
O2—H2···O4ⁱⁱ	0.82	1.92	2.733 (4)	174
O3—H3···O9ⁱⁱⁱ	0.82	1.96	2.772 (4)	172

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

Acknowledgements

M-DŞ gratefully acknowledges financial support from OMNIASIG SA Romania.

References

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