Crystal structure of di­chlorido­{2-[(2-hy­droxyeth­yl)(pyridin-2-ylmeth­yl)amino]­ethano­lato-κ4N,N′,O,O′}iron(III) dihydrate from synchrotron data

Shin, J.W.; Kim, D.-W.; Moon, D.

doi:10.1107/S1600536814022089

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Volume 70| Part 11| November 2014| Pages 334-336

doi:10.1107/S1600536814022089

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Crystal structure of dichlorido{2-[(2-hydroxyethyl)(pyridin-2-ylmethyl)amino]ethanolato-κ⁴N,N′,O,O′}iron(III) dihydrate from synchrotron data

Jong Won Shin,^a Dae-Woong Kim ^a and Dohyun Moon ^a ^*

^aBeamline Department, Pohang Accelerator Laboratory/POSTECH 80, Pohang 790-784, Republic of Korea
^*Correspondence e-mail: dmoon@postech.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 September 2014; accepted 7 October 2014; online 11 October 2014)

In the title compound, [Fe(C₁₀H₁₅N₂O₂)Cl₂]·2H₂O, the Fe^III ion is coordinated by two N and two O atoms of the tetradentate 2-{(2-hydroxyethyl)(pyridin-2-ylmethyl)amino}ethanolate ligand and by two chloride anions, resulting in a distorted octahedral coordination sphere. The average Fe—X (X = ligand N and O atoms) and Fe—Cl bond lengths are 2.10 and 2.32 Å, respectively. In the crystal, duplex O—H⋯O hydrogen bonds between the hydroxyl and ethoxy groups of two neighbouring complexes give rise to a dimeric unit. The dimers are connected to the lattice water molecules (one of which is equally disordered over two sets of sites) through O—H⋯Cl hydrogen bonds, forming undulating sheets parallel to (010). Weak C—H⋯Cl hydrogen bonds are also observed.

Keywords: crystal structure; tetradentate ligand; Fe^III high-spin complex.

CCDC reference: 1027864

1. Chemical context

Tetradentate ligands including pyridine and hydroxyl groups have attracted considerable attention in chemistry and materials science (Paz et al., 2012 ; Li et al., 2007 ). These ligands are able to form multinuclear complexes with various transition metal ions, leading to dimeric, trimeric, tetrameric or polymeric structures through the deprotonation of hydroxyl groups (Shin et al., 2010 ; Han et al., 2009 ). Such multinuclear complexes have potential applications in catalysis and magnetic materials. For example, Fe^III and Co^II/III complexes with aminoethanol moieties have been studied as oxidation catalysts of various olefins and investigated due to their magnetic properties (Shin et al., 2011 , 2014 ). Moreover, Mn^II/III complexes containing hydroxyl substituents exhibit excellent single-molecular magnetic properties due to magnetic spin-orbit anisotropy (Wu et al., 2010 ).

Here, we report the synthesis and crystal structure of a complex with six-coordinate Fe^III constructed from the tetradentate ligand 2-[(2-hydroxyethyl)(pyridin-2-ylmethyl)amino]ethanol (H₂pmide; C₁₀H₁₇N₂O₂) and chloride anions, [Fe(Hpmide)Cl₂]·2H₂O, (I).

2. Structural commentary

A view of the molecular structure of compound (I) is shown in Fig. 1. The coordination sphere of the Fe^III ion can be described as distorted octahedral, consisting of the two N atoms and two O atoms from the Hpmide ligand, and two chloride anions. The chloride anions are trans to the deprotonated ethoxy O atom and the N atom of the pyridine group of the Hpmide ligand, respectively, and coordinate in cis position to each other. The average Fe—X_Hpmide (X = N, O) bond length is 2.10 Å and the Fe—Cl bond lengths are 2.2773 (5) (equatorial) and 2.3581 (7) (axial) Å. Both the average Fe—N (2.182 Å) and Fe—O (2.010 Å) distances in (I) are comparable to those found in related N₂O₂-chelated high-spin Fe^III complexes (Shin et al., 2014; Cappillino et al., 2012 ). The bite angles of the five-membered chelate rings in (I) range from 76.59 (5) to 81.45 (4)°.

Figure 1
View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms and lattice water molecules are omitted for clarity except for the H atom of the hydroxyl group.

3. Supramolecular features

The hydroxyl substituent of the Hpmide ligand forms a strong hydrogen bond with the O atom of the deprotonated ethoxy group of a neighbouring molecule. These duplex interactions lead to a dinuclear dimeric unit. The dimers are linked through O—H⋯Cl interactions to the lattice water molecules, that are likewise connected to each other through O—H⋯O hydrogen bonds. All these hydrogen-bonding interactions (Steed & Atwood, 2009 ) lead to the formation of undulating sheets parallel to (010). Further weak hydrogen bonding between pyridine and methyl H atoms and chloride anions stabilizes this arrangement (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W1—H1W1⋯Cl1	0.84 (1)	2.51 (3)	3.279 (4)	152 (5)
O1W2—H2W2⋯Cl1	0.84 (1)	2.91 (5)	3.470 (4)	125 (5)
O2—H1O2⋯O1ⁱ	0.83 (2)	1.69 (2)	2.5196 (14)	177 (2)
O1W1—H2W1⋯O2Wⁱⁱ	0.84 (1)	2.15 (4)	2.876 (7)	144 (7)
O1W2—H1W2⋯O2Wⁱⁱ	0.84 (1)	2.06 (5)	2.647 (8)	126 (5)
O1W2—H1W2⋯O2Wⁱⁱⁱ	0.84 (1)	2.06 (3)	2.836 (8)	153 (6)
C4—H4⋯Cl1^iv	0.95	2.76	3.5962 (16)	147
C9—H9A⋯Cl1^v	0.99	2.78	3.6371 (15)	145
C3—H3⋯Cl2^vi	0.95	2.80	3.5721 (16)	139
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z-1; (iii) -x, -y+1, -z+1; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
View of the crystal packing of the title compound, with intermolecular O—H⋯O hydrogen bonds between Fe^III complex molecules drawn as blue dashed lines. C—H⋯Cl hydrogen bonds are indicated as red dashed lines; water molecules and chloride anions are also connected through O—H⋯O hydrogen bonds (black dashed lines).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, November 2013 with three updates; Groom & Allen, 2014 ) indicated that five complexes derived from the H₂pmide ligand have been reported. These include Ni^II and Mn^II/III; Fe^III complexes have been studied for their magnetic properties and catalytic effects (Saalfrank et al., 2001 ; Wu et al., 2010; Shin et al., 2014).

5. Synthesis and crystallization

The H₂pmide ligand was prepared following a previously reported method (Wu et al., 2010). Compound (I) was prepared as follows: to a MeOH solution (4 ml) of FeCl₂·4H₂O (81 mg, 0.408 mmol) was added dropwise a MeOH solution (3 ml) of H₂pmide (80 mg, 0.408 mmol). The colour became yellow, and then the solution was stirred for 30 min at room temperature. Yellow crystals of (I) were obtained by diffusion of diethyl ether into the yellow solution for several days, and were collected by filtration and washed with diethyl ether and dried in air. Yield: 67 mg (46%). Elemental analysis calculated for C₁₀H₁₅Cl₂FeN₂O₂: C 37.30, H 4.70, N 8.70%; found: C 37.19, H 4.58, N 8.78%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms attached to C atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (aromatic H atoms) and 0.99 Å (open-chain H atoms) and with U_iso(H) values of 1.2U_eq(C) of the parent atoms. One lattice water molecule (OW1) was found to be equally disordered over two positions. The H atoms of this disordered water molecule (H1W1 and H1W2) were located from difference Fourier maps and refined with restraints and a fixed O—H distances of 0.84 Å, with U_iso(H) values of 1.2U_eq(O). Moreover, the second water molecule (O2W) was modelled without hydrogen atoms because difference Fourier maps did not suggest suitable H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Fe(C₁₀H₁₅N₂O₂)Cl₂]·2H₂O
M_r	358.02
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.2690 (15), 14.497 (3), 14.094 (3)
β (°)	95.86 (3)
V (Å³)	1477.4 (5)
Z	4
Radiation type	Synchrotron, λ = 0.62998 Å
μ (mm⁻¹)	0.99
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	ADSC Q210 CCD area-detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.907, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	14975, 4056, 3866
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.04
No. of reflections	4056
No. of parameters	197
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.51, −0.84
Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXS2013/1 and SHELXL2014/7 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1027864

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814022089/wm5071sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022089/wm5071Isup2.hkl

checkCIF report

Chemical context top

Tetradentate ligands including pyridine and hydroxyl groups have attracted considerable attention in chemistry and materials science (Paz et al., 2012; Li et al., 2007). These ligands are able to form multinuclear complexes with various transition metal ions, leading to dimeric, trimeric, tetrameric or polymeric structures through the deprotonation of hydroxyl groups (Shin et al., 2010; Han et al., 2009). Such multinuclear complexes have potential applications in catalysis and magnetic materials. For example, Fe^III and Co^II/III complexes with aminoethanol moieties have been studied as oxidation catalysts of various olefins and investigated due to their magnetic properties (Shin et al., 2011, 2014). Moreover, Mn^II/III complexes containing hydroxyl substituents exhibit excellent single-molecular magnetic properties due to magnetic spin orbit anisotropy (Wu et al., 2010).

Here, we report the synthesis and crystal structure of a complex with six-coordinate Fe^III constructed from the tetradentate ligand [2-{(2-hydroxyethyl)(pyridin-2-ylmethyl)amino}ethanol (H₂pmide; C₁₀H₁₇N₂O₂) and chloride anions, [Fe(Hpmide)Cl₂]·2H₂O, (I).

Structural commentary top

A view of the molecular structure of compound (I) is shown in Fig. 1. The coordination sphere of the Fe^III ion can be described as distorted octahedral, consisting of the two N atoms and two O atoms from the Hpmide ligand, and two chloride anions. The chloride anions are trans to the deprotonated ethoxy O atom and the N atom of the pyridine group of the Hpmide ligand, respectively, and coordinate in cis position to each other. The average Fe—X_Hpmide (X = N, O) bond length is 2.10 Å and the Fe—Cl bond lengths are 2.2773 (5) (equatorial) and 2.3581 (7) (axial) Å. Both the average Fe—N (2.182 Å) and Fe—O (2.010 Å) distances in (I) are comparable to those found in related N₂O₂-chelated high-spin Fe^III complexes (Shin et al., 2014; Cappillino et al., 2012). The bite angles of the five-membered chelate rings in (I) range from 76.59 (5) to 81.45 (4)°.

Supramolecular features top

The hydroxyl substituent of the Hpmide ligand forms a strong hydrogen bond with the O atom of the deprotonated ethoxy group of a neighbouring molecule. These duplex interactions lead to a dinuclear dimeric unit. The dimers are linked through O—H···Cl interactions to the lattice water molecules, that are likewise connected to each other through O—H···O hydrogen bonds. All these hydrogen-bonding interactions (Steed & Atwood, 2009) lead to the formation of undulating sheets parallel to (010). Further weak hydrogen bonding between pyridine and methyl H atoms and chloride anions stabilizes this arrangement (Fig. 2 and Table 2).

Database survey top

A search of the Cambridge Structural Database (Version 5.35, November 2013 with three updates; Groom & Allen, 2014) indicated that five complexes derived from the H₂pmide ligand have been reported. These include Ni^II and Mn^II/III; Fe^III complexes have been studied for their magnetic properties and catalytic effects (Saalfrank et al., 2001; Wu et al., 2010; Shin et al., 2014).

Synthesis and crystallization top

The H₂pmide ligand was prepared following a previously reported method (Wu et al., 2010). Compound (I) was prepared as follows: To a MeOH solution (4 ml) of FeCl₂·4H₂O (81 mg, 0.408 mmol) was added dropwise a MeOH solution (3 ml) of H₂pmide (80 mg, 0.408 mmol). The colour became yellow, and then the solution was stirred for 30 min at room temperature. Yellow crystals of (I) were obtained by diffusion of diethyl ether into the yellow solution for several days, and were collected by filtration and washed with diethyl ether and dried in air. Yield: 67 mg (46%). Analysis: calculated for C₁₀H₁₅Cl₂FeN₂O₂: C, 37.30; H, 4.70; N, 8.70; found: C, 37.19; H, 4.58; N, 8.78.

Refinement top

Related literature top

For related literature, see: Groon & Allen (2014); Cappillino et al. (2012); Han et al. (2009); Li et al. (2007); Paz et al. (2012); Saalfrank et al. (2001); Shin et al. (2010, 2011, 2014); Steed & Atwood (2009); Wu et al. (2010).

Computing details top

Data collection: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms and lattice water molecules are omitted for clarity except for the H atom of the hydroxyl group.

View of the crystal packing of the title compound, with intermolecular O—H···O hydrogen bonds between Fe^III complex molecules drawn as blue dashed lines. C—H···Cl hydrogen bonds are indicated as red dashed lines; water molecules and chloride anions are also connected through O—H···O hydrogen bonds (black dashed lines).

Dichlorido{2-[(2-hydroxyethyl)(pyridin-2-ylmethyl)amino]ethanolato-κ⁴N,N',O,O'}iron(III) dihydrate top

Crystal data top

[Fe(C₁₀H₁₅N₂O₂)Cl₂]·2H₂O	F(000) = 740
M_r = 358.02	D_x = 1.610 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.62998 Å
a = 7.2690 (15) Å	Cell parameters from 47717 reflections
b = 14.497 (3) Å	θ = 0.4–33.6°
c = 14.094 (3) Å	µ = 0.99 mm⁻¹
β = 95.86 (3)°	T = 100 K
V = 1477.4 (5) Å³	Block, yellow
Z = 4	0.10 × 0.10 × 0.08 mm

Data collection top

ADSC Q210 CCD area-detector diffractometer	3866 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.021
ω scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.907, T_max = 0.925	k = −19→19
14975 measured reflections	l = −19→19
4056 independent reflections

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0354P)² + 1.6679P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4056 reflections	Δρ_max = 1.51 e Å⁻³
197 parameters	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Fe(C₁₀H₁₅N₂O₂)Cl₂]·2H₂O	V = 1477.4 (5) Å³
M_r = 358.02	Z = 4
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.62998 Å
a = 7.2690 (15) Å	µ = 0.99 mm⁻¹
b = 14.497 (3) Å	T = 100 K
c = 14.094 (3) Å	0.10 × 0.10 × 0.08 mm
β = 95.86 (3)°

Data collection top

ADSC Q210 CCD area-detector diffractometer	4056 independent reflections
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	3866 reflections with I > 2σ(I)
T_min = 0.907, T_max = 0.925	R_int = 0.021
14975 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	7 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.51 e Å⁻³
4056 reflections	Δρ_min = −0.84 e Å⁻³
197 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.49921 (2)	0.59458 (2)	0.35450 (2)	0.00581 (6)
Cl1	0.66209 (5)	0.61966 (2)	0.22045 (2)	0.01181 (8)
Cl2	0.32215 (5)	0.47400 (2)	0.29547 (2)	0.01270 (8)
O1	0.70234 (13)	0.53542 (7)	0.42787 (7)	0.00933 (18)
O2	0.33434 (14)	0.60360 (7)	0.46844 (7)	0.00925 (18)
H1O2	0.322 (3)	0.5590 (12)	0.5041 (13)	0.011*
N1	0.32550 (15)	0.70945 (8)	0.30279 (8)	0.0085 (2)
N2	0.62789 (15)	0.71338 (8)	0.43157 (8)	0.0075 (2)
C1	0.15712 (19)	0.70132 (10)	0.25359 (10)	0.0117 (2)
H1	0.1099	0.6415	0.2383	0.014*
C2	0.05082 (19)	0.77769 (11)	0.22469 (10)	0.0143 (3)
H2	−0.0669	0.7703	0.1896	0.017*
C3	0.1193 (2)	0.86521 (11)	0.24795 (11)	0.0156 (3)
H3	0.0492	0.9185	0.2288	0.019*
C4	0.2913 (2)	0.87365 (10)	0.29950 (11)	0.0130 (3)
H4	0.3401	0.9328	0.3169	0.016*
C5	0.39138 (18)	0.79407 (9)	0.32537 (10)	0.0089 (2)
C6	0.58321 (19)	0.79876 (9)	0.37700 (10)	0.0107 (2)
H6A	0.6743	0.8079	0.3302	0.013*
H6B	0.5917	0.8522	0.4210	0.013*
C7	0.82796 (18)	0.69147 (9)	0.43890 (10)	0.0102 (2)
H7A	0.8958	0.7310	0.4879	0.012*
H7B	0.8770	0.7035	0.3771	0.012*
C8	0.85570 (19)	0.58946 (9)	0.46615 (11)	0.0125 (3)
H8A	0.9699	0.5663	0.4416	0.015*
H8B	0.8706	0.5835	0.5365	0.015*
C9	0.56136 (19)	0.71512 (10)	0.52794 (10)	0.0113 (2)
H9A	0.5759	0.7781	0.5548	0.014*
H9B	0.6373	0.6726	0.5708	0.014*
C10	0.35997 (19)	0.68663 (10)	0.52331 (10)	0.0117 (2)
H10A	0.3250	0.6762	0.5885	0.014*
H10B	0.2804	0.7362	0.4932	0.014*
O1W1	0.4145 (8)	0.5368 (3)	0.0321 (3)	0.0527 (11)	0.5
H1W1	0.444 (8)	0.551 (5)	0.0896 (16)	0.063*	0.5
H2W1	0.300 (3)	0.526 (6)	0.025 (4)	0.063*	0.5
O1W2	0.3007 (7)	0.5629 (4)	0.0504 (3)	0.0549 (11)	0.5
H1W2	0.190 (3)	0.546 (5)	0.041 (4)	0.066*	0.5
H2W2	0.314 (8)	0.593 (4)	0.101 (3)	0.066*	0.5
O2W	0.0911 (9)	0.4335 (4)	0.9619 (4)	0.182 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.00713 (10)	0.00133 (10)	0.00853 (10)	−0.00039 (6)	−0.00140 (6)	0.00067 (6)
Cl1	0.01740 (15)	0.00679 (15)	0.01158 (14)	−0.00204 (11)	0.00321 (11)	0.00141 (10)
Cl2	0.01370 (15)	0.00686 (15)	0.01705 (15)	−0.00509 (10)	−0.00075 (11)	−0.00279 (11)
O1	0.0089 (4)	0.0039 (4)	0.0146 (4)	−0.0005 (3)	−0.0017 (3)	0.0029 (3)
O2	0.0115 (4)	0.0047 (4)	0.0117 (4)	−0.0016 (3)	0.0018 (3)	0.0014 (3)
N1	0.0085 (5)	0.0051 (5)	0.0115 (5)	0.0001 (4)	−0.0005 (4)	0.0023 (4)
N2	0.0082 (5)	0.0031 (5)	0.0105 (5)	−0.0002 (4)	−0.0016 (4)	0.0019 (4)
C1	0.0100 (6)	0.0114 (6)	0.0132 (6)	−0.0008 (5)	−0.0009 (5)	0.0036 (5)
C2	0.0083 (5)	0.0179 (7)	0.0165 (6)	0.0022 (5)	−0.0004 (5)	0.0072 (5)
C3	0.0129 (6)	0.0134 (7)	0.0206 (7)	0.0072 (5)	0.0025 (5)	0.0074 (5)
C4	0.0144 (6)	0.0056 (6)	0.0191 (6)	0.0035 (5)	0.0025 (5)	0.0040 (5)
C5	0.0102 (5)	0.0045 (6)	0.0121 (6)	0.0012 (4)	0.0010 (4)	0.0023 (4)
C6	0.0120 (6)	0.0019 (5)	0.0172 (6)	−0.0010 (4)	−0.0033 (5)	0.0028 (4)
C7	0.0072 (5)	0.0068 (6)	0.0161 (6)	−0.0016 (4)	−0.0022 (4)	0.0025 (4)
C8	0.0079 (5)	0.0077 (6)	0.0207 (7)	−0.0005 (4)	−0.0041 (5)	0.0046 (5)
C9	0.0156 (6)	0.0083 (6)	0.0099 (6)	−0.0024 (5)	0.0001 (5)	−0.0024 (4)
C10	0.0147 (6)	0.0070 (6)	0.0140 (6)	0.0008 (5)	0.0041 (5)	−0.0012 (5)
O1W1	0.095 (4)	0.035 (2)	0.0249 (16)	−0.019 (2)	−0.0105 (19)	0.0025 (14)
O1W2	0.066 (3)	0.069 (3)	0.0270 (18)	−0.008 (2)	−0.0078 (18)	−0.0038 (18)
O2W	0.229 (6)	0.182 (5)	0.138 (4)	−0.037 (5)	0.023 (4)	0.009 (4)

Geometric parameters (Å, º) top

Fe1—O1	1.9165 (11)	C4—C5	1.3925 (18)
Fe1—O2	2.1036 (12)	C4—H4	0.9500
Fe1—N1	2.1704 (12)	C5—C6	1.5071 (19)
Fe1—N2	2.1939 (12)	C6—H6A	0.9900
Fe1—Cl2	2.2773 (5)	C6—H6B	0.9900
Fe1—Cl1	2.3581 (7)	C7—C8	1.5360 (19)
O1—C8	1.4229 (16)	C7—H7A	0.9900
O2—C10	1.4326 (17)	C7—H7B	0.9900
O2—H1O2	0.829 (15)	C8—H8A	0.9900
N1—C5	1.3433 (17)	C8—H8B	0.9900
N1—C1	1.3488 (17)	C9—C10	1.516 (2)
N2—C6	1.4759 (17)	C9—H9A	0.9900
N2—C7	1.4818 (17)	C9—H9B	0.9900
N2—C9	1.4878 (18)	C10—H10A	0.9900
C1—C2	1.387 (2)	C10—H10B	0.9900
C1—H1	0.9500	O1W1—H1W1	0.842 (10)
C2—C3	1.390 (2)	O1W1—H2W1	0.842 (10)
C2—H2	0.9500	O1W2—H1W2	0.842 (10)
C3—C4	1.386 (2)	O1W2—H2W2	0.839 (10)
C3—H3	0.9500

O1—Fe1—O2	94.79 (4)	C3—C4—H4	120.6
O1—Fe1—N1	156.10 (4)	C5—C4—H4	120.6
O2—Fe1—N1	81.45 (4)	N1—C5—C4	122.05 (13)
O1—Fe1—N2	79.52 (5)	N1—C5—C6	116.46 (11)
O2—Fe1—N2	79.66 (4)	C4—C5—C6	121.45 (12)
N1—Fe1—N2	76.59 (5)	N2—C6—C5	110.93 (10)
O1—Fe1—Cl2	103.25 (4)	N2—C6—H6A	109.5
O2—Fe1—Cl2	88.96 (3)	C5—C6—H6A	109.5
N1—Fe1—Cl2	100.28 (4)	N2—C6—H6B	109.5
N2—Fe1—Cl2	168.51 (3)	C5—C6—H6B	109.5
O1—Fe1—Cl1	94.54 (4)	H6A—C6—H6B	108.0
O2—Fe1—Cl1	166.87 (3)	N2—C7—C8	109.06 (11)
N1—Fe1—Cl1	86.28 (3)	N2—C7—H7A	109.9
N2—Fe1—Cl1	92.98 (3)	C8—C7—H7A	109.9
Cl2—Fe1—Cl1	97.869 (19)	N2—C7—H7B	109.9
C8—O1—Fe1	119.26 (8)	C8—C7—H7B	109.9
C10—O2—Fe1	114.30 (8)	H7A—C7—H7B	108.3
C10—O2—H1O2	110.1 (14)	O1—C8—C7	110.95 (11)
Fe1—O2—H1O2	121.2 (14)	O1—C8—H8A	109.4
C5—N1—C1	118.97 (12)	C7—C8—H8A	109.4
C5—N1—Fe1	116.11 (9)	O1—C8—H8B	109.4
C1—N1—Fe1	124.88 (9)	C7—C8—H8B	109.4
C6—N2—C7	112.22 (11)	H8A—C8—H8B	108.0
C6—N2—C9	112.75 (11)	N2—C9—C10	111.01 (11)
C7—N2—C9	110.38 (11)	N2—C9—H9A	109.4
C6—N2—Fe1	109.90 (8)	C10—C9—H9A	109.4
C7—N2—Fe1	103.42 (8)	N2—C9—H9B	109.4
C9—N2—Fe1	107.66 (8)	C10—C9—H9B	109.4
N1—C1—C2	122.02 (13)	H9A—C9—H9B	108.0
N1—C1—H1	119.0	O2—C10—C9	108.90 (11)
C2—C1—H1	119.0	O2—C10—H10A	109.9
C1—C2—C3	118.93 (13)	C9—C10—H10A	109.9
C1—C2—H2	120.5	O2—C10—H10B	109.9
C3—C2—H2	120.5	C9—C10—H10B	109.9
C4—C3—C2	119.12 (13)	H10A—C10—H10B	108.3
C4—C3—H3	120.4	H1W1—O1W1—H2W1	108 (3)
C2—C3—H3	120.4	H1W2—O1W2—H2W2	109 (3)
C3—C4—C5	118.90 (14)

C5—N1—C1—C2	0.7 (2)	Fe1—N2—C6—C5	34.62 (13)
Fe1—N1—C1—C2	178.26 (10)	N1—C5—C6—N2	−26.63 (17)
N1—C1—C2—C3	−0.6 (2)	C4—C5—C6—N2	155.71 (13)
C1—C2—C3—C4	−0.2 (2)	C6—N2—C7—C8	−161.67 (11)
C2—C3—C4—C5	0.8 (2)	C9—N2—C7—C8	71.64 (14)
C1—N1—C5—C4	−0.1 (2)	Fe1—N2—C7—C8	−43.28 (12)
Fe1—N1—C5—C4	−177.80 (10)	Fe1—O1—C8—C7	−0.47 (15)
C1—N1—C5—C6	−177.70 (12)	N2—C7—C8—O1	31.76 (16)
Fe1—N1—C5—C6	4.56 (16)	C6—N2—C9—C10	83.81 (14)
C3—C4—C5—N1	−0.7 (2)	C7—N2—C9—C10	−149.79 (11)
C3—C4—C5—C6	176.80 (13)	Fe1—N2—C9—C10	−37.58 (12)
C7—N2—C6—C5	149.11 (12)	Fe1—O2—C10—C9	−35.00 (13)
C9—N2—C6—C5	−85.49 (14)	N2—C9—C10—O2	48.37 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W1—H1W1···Cl1	0.84 (1)	2.51 (3)	3.279 (4)	152 (5)
O1W2—H2W2···Cl1	0.84 (1)	2.91 (5)	3.470 (4)	125 (5)
O2—H1O2···O1ⁱ	0.83 (2)	1.69 (2)	2.5196 (14)	177 (2)
O1W1—H2W1···O2Wⁱⁱ	0.84 (1)	2.15 (4)	2.876 (7)	144 (7)
O1W2—H1W2···O2Wⁱⁱ	0.84 (1)	2.06 (5)	2.647 (8)	126 (5)
O1W2—H1W2···O2Wⁱⁱⁱ	0.84 (1)	2.06 (3)	2.836 (8)	153 (6)
C4—H4···Cl1^iv	0.95	2.76	3.5962 (16)	147
C9—H9A···Cl1^v	0.99	2.78	3.6371 (15)	145
C3—H3···Cl2^vi	0.95	2.80	3.5721 (16)	139

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W1—H1W1···Cl1	0.842 (10)	2.51 (3)	3.279 (4)	152 (5)
O1W2—H2W2···Cl1	0.839 (10)	2.91 (5)	3.470 (4)	125 (5)
O2—H1O2···O1ⁱ	0.829 (15)	1.691 (15)	2.5196 (14)	177 (2)
O1W1—H2W1···O2Wⁱⁱ	0.842 (10)	2.15 (4)	2.876 (7)	144 (7)
O1W2—H1W2···O2Wⁱⁱ	0.842 (10)	2.06 (5)	2.647 (8)	126 (5)
O1W2—H1W2···O2Wⁱⁱⁱ	0.842 (10)	2.06 (3)	2.836 (8)	153 (6)
C4—H4···Cl1^iv	0.95	2.76	3.5962 (16)	147
C9—H9A···Cl1^v	0.99	2.78	3.6371 (15)	145
C3—H3···Cl2^vi	0.95	2.80	3.5721 (16)	139

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₀H₁₅N₂O₂)Cl₂]·2H₂O
M_r	358.02
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.2690 (15), 14.497 (3), 14.094 (3)
β (°)	95.86 (3)
V (Å³)	1477.4 (5)
Z	4
Radiation type	Synchrotron, λ = 0.62998 Å
µ (mm⁻¹)	0.99
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	ADSC Q210 CCD area-detector diffractometer
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.907, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	14975, 4056, 3866
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.04
No. of reflections	4056
No. of parameters	197
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.51, −0.84

Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983), HKL3000sm (Otwinowski & Minor, 1997), SHELXS2013/1 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Acknowledgements

This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2012R1A1A2002507) and supported by the Institute for Basic Science (IBS, IBS-R007-D1-2014-a01). X-ray crystallography at the PLS-II 2D-SMC beamline was supported in part by MSIP and POSTECH.

References

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Volume 70| Part 11| November 2014| Pages 334-336

doi:10.1107/S1600536814022089

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