{Tris[2-(imidazol-2-ylmethyl­imino)eth­yl]methyl­ammonium}iron(II) tris­(per­chlorate) dihydrate

Brewer, G.A.; Jasinski, J.P.; Butcher, R.J.

doi:10.1107/S1600536807061673

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m1

https://doi.org/10.1107/S1600536807061673

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{Tris[2-(imidazol-2-ylmethylimino)ethyl]methylammonium}iron(II) tris(perchlorate) dihydrate

Greg A. Brewer,^a Jerry P. Jasinski ^b ^* and Ray J. Butcher ^c

^aDepartment of Chemistry, Catholic University, 620 Michigan Ave. NE, Washington, DC 20064, USA, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington DC 20059 USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 6 November 2007; accepted 21 November 2007; online 6 December 2007)

The title complex, [Fe(C₁₉H₂₇N₁₀)](ClO₄)₃·2H₂O, is a new polymorph of an iron(II) Schiff base complex of tris(2-aminoethyl)methylammonium with imidazole-2-carboxaldehyde. The octahedral Fe^II atom is bound to three facial imidazole N atoms with average Fe—N_imidazole and Fe—N_imine bond distances of 1.963 (5) and 1.951 (5) Å, respectively. The central N atom of the tripodal ligand is outside the bonding distance at 3.92 Å. The crystal packing is stabilized by the hydrogen-bonding interactions between the two water molecules (acceptor) and two of the three imidazole NH groups (donor). The third imidazole NH group (donor) forms a hydrogen bond to one of the three perchlorate counter-ions (acceptor).

Related literature

For the synthesis, see: Brewer et al. (2005 ). For related structures, see: Brewer et al. (2006 , 2007 ).

Experimental

Crystal data

[Fe(C₁₉H₂₇N₁₀)](ClO₄)₃·2H₂O
M_r = 785.74
Orthorhombic, P b c a
a = 13.9630 (18) Å
b = 11.7810 (15) Å
c = 37.182 (5) Å
V = 6116.4 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 173 K
0.54 × 0.45 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.682, T_max = 0.904
65065 measured reflections
8324 independent reflections
6601 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 1.04
8324 reflections
436 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W2⋯O14ⁱ	0.807 (19)	2.29 (4)	2.938 (3)	138 (5)
O2W—H2W1⋯O14ⁱⁱ	0.820 (17)	2.26 (2)	2.987 (3)	148 (4)
O2W—H2W2⋯O22ⁱⁱⁱ	0.821 (18)	2.07 (2)	2.861 (3)	160 (4)
N3A—H3AB⋯O2W	0.88	1.91	2.730 (3)	155
N3B—H3BB⋯O1W	0.88	1.95	2.752 (3)	152
N3C—H3CB⋯O14	0.88	2.05	2.907 (3)	163
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) x, y+1, z; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2006 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807061673/tk2214sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061673/tk2214Isup2.hkl

checkCIF report

Comment top

Iron(II) and iron(III) Schiff base complexes of tris(2-aminoethyl)amine (tren) with imidazole carboxaldehyde have displayed spin crossover behavior (Brewer et al., 2006). Further, it has been demonstrated that the distance between the Fe atom and the central tren-N atom, N_ap, is an indicator of spin-state (Brewer et al., 2006). Shorter distances correlate with high spin and longer distances with low spin. Quarternization of N_ap, as observed in the title complex, (I), results in an elongated Fe—N_ap distance due to both the conformation of the N_ap atom (inverted away from the Fe atom) and the repulsive forces between the positively charged atoms (Brewer et al., 2005). Recently, it was shown that (I), without the methyl group on N_ap, could serve as a bidentate hydrogen bond donor to the perchlorate anion of potassium perchlorate using the adjacent imidazole-NH and imine-CH H atoms to give supramolecular complexes (Brewer et al., 2007). Since the present molecule possesses this same structural feature, the reaction of it with potassium perchlorate was investigated. The reaction did not yield the desired product but gave (I) as a polymorph (Brewer et al., 2007). The structure of the iron cation differs from the original report in that the three arms of the ligand are not identical. In addition, the hydrogen bonding interactions with coordinated water and perchlorate are significantly different. Investigation of these effects on the spin crossover process and reactivity of the complex will be aided by the structural characterization of this new polymorph. In view of the importance of the spin crossover phenomenom and supramolecular systems, the present paper reports the crystal structure of (I) (Fig. 1).

The octahedral iron(II) atom is bound to three facial imidazole-N atoms whose average Fe–N bond distances for the imidazole- and imine-N atoms are 1.963 (5)Å and 1.951 (5) Å, respectively. The central N atom of the tripodal ligand is outside the bonding distance at 3.92 Å. Crystal packing is stabilized by the hydrogen bonding interactions between the two water molecules (acceptor) and two of the three imidazole NH groups (donor). The third imidazole NH group (donor) hydrogen bonds to one of the three perchlorate counterions (acceptor) (Table 1 & Fig. 2).

Related literature top

For the synthesis, see: Brewer et al. (2005). For related structures, see: Brewer et al. (2006, 2007).

Experimental top

Complex (I) was synthesized as previously described (Brewer et al., 2005) and was recrystallized from methanol solution in the presence of equimolal potassium perchlorate. The resulting crystals were analyzed by X-ray diffraction.

Structure description top

For the synthesis, see: Brewer et al. (2005). For related structures, see: Brewer et al. (2006, 2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. Molecular structure of the cation in (I), showing atom labeling and 50% probability displacement ellipsoids.
	Fig. 2. Partial packing diagram for (I), viewed down the b axis. Dashed lines indicate C–H···O (water & perchlorate) hydrogen bonds.

{Tris[2-(imidazol-2-ylmethylimino)ethyl]methylammonium}iron(II) tris(perchlorate) dihydrate top

Crystal data top

[Fe(C₁₉H₂₇N₁₀)](ClO₄)₃·2H₂O	F(000) = 3232
M_r = 785.74	D_x = 1.707 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9963 reflections
a = 13.9630 (18) Å	θ = 2.2–28.9°
b = 11.7810 (15) Å	µ = 0.84 mm⁻¹
c = 37.182 (5) Å	T = 173 K
V = 6116.4 (14) Å³	Chunk, dark-red
Z = 8	0.54 × 0.45 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	8324 independent reflections
Radiation source: fine-focus sealed tube	6601 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
φ and ω scans	θ_max = 29.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
T_min = 0.682, T_max = 0.904	k = −16→13
65065 measured reflections	l = −51→51

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0471P)² + 5.7069P] where P = (F_o² + 2F_c²)/3
8324 reflections	(Δ/σ)_max = 0.001
436 parameters	Δρ_max = 0.76 e Å⁻³
6 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Fe(C₁₉H₂₇N₁₀)](ClO₄)₃·2H₂O	V = 6116.4 (14) Å³
M_r = 785.74	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.9630 (18) Å	µ = 0.84 mm⁻¹
b = 11.7810 (15) Å	T = 173 K
c = 37.182 (5) Å	0.54 × 0.45 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	8324 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6601 reflections with I > 2σ(I)
T_min = 0.682, T_max = 0.904	R_int = 0.054
65065 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	6 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.76 e Å⁻³
8324 reflections	Δρ_min = −0.62 e Å⁻³
436 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
Fe	0.542493 (19)	0.51159 (2)	0.110991 (7)	0.01627 (7)
Cl1	0.32256 (4)	0.00301 (5)	0.015096 (15)	0.02982 (12)
Cl2	0.24581 (4)	0.63667 (5)	0.208500 (15)	0.02861 (12)
Cl3	0.57715 (4)	0.00513 (5)	0.181644 (16)	0.03151 (13)
O11	0.3162 (2)	0.0909 (2)	−0.01088 (7)	0.0756 (8)
O12	0.23275 (13)	−0.05400 (18)	0.01888 (6)	0.0489 (5)
O13	0.39474 (14)	−0.07620 (18)	0.00529 (6)	0.0526 (5)
O14	0.34756 (14)	0.05377 (19)	0.04951 (5)	0.0494 (5)
O21	0.23376 (18)	0.51820 (17)	0.21519 (7)	0.0598 (6)
O22	0.19608 (18)	0.6630 (2)	0.17533 (6)	0.0610 (6)
O23	0.34507 (13)	0.66157 (19)	0.20374 (6)	0.0505 (5)
O24	0.20629 (13)	0.70357 (17)	0.23716 (5)	0.0437 (5)
O31	0.50024 (19)	−0.0216 (2)	0.15709 (7)	0.0687 (7)
O32	0.61507 (15)	−0.10022 (17)	0.19422 (8)	0.0617 (6)
O33	0.65127 (16)	0.06867 (16)	0.16416 (7)	0.0570 (6)
O34	0.53883 (17)	0.06912 (18)	0.21060 (6)	0.0576 (6)
O1W	0.96601 (19)	0.4969 (3)	0.08139 (9)	0.1023 (13)
H1W1	0.983 (4)	0.562 (3)	0.0904 (16)	0.153*
H1W2	1.003 (4)	0.489 (5)	0.0650 (12)	0.153*
O2W	0.28606 (16)	0.98531 (17)	0.12333 (6)	0.0461 (5)
H2W1	0.287 (3)	1.024 (3)	0.1051 (6)	0.069*
H2W2	0.304 (3)	1.029 (3)	0.1392 (7)	0.069*
N	0.56728 (13)	0.38916 (15)	0.20854 (4)	0.0215 (3)
N1A	0.54566 (12)	0.61049 (14)	0.15322 (4)	0.0190 (3)
N2A	0.44316 (12)	0.61938 (14)	0.09684 (5)	0.0199 (3)
N3A	0.36892 (13)	0.78081 (16)	0.10830 (5)	0.0269 (4)
H3AB	0.3517	0.8440	0.1192	0.032*
N1B	0.65376 (12)	0.42147 (14)	0.12542 (4)	0.0193 (3)
N2B	0.64328 (12)	0.60169 (14)	0.08733 (4)	0.0198 (3)
N3B	0.79608 (13)	0.61176 (17)	0.07239 (5)	0.0288 (4)
H3BB	0.8573	0.5947	0.0707	0.035*
N1C	0.45107 (12)	0.40472 (14)	0.13101 (4)	0.0192 (3)
N2C	0.52259 (12)	0.41612 (14)	0.06825 (4)	0.0198 (3)
N3C	0.44957 (15)	0.26827 (17)	0.04444 (5)	0.0304 (4)
H3CB	0.4121	0.2086	0.0422	0.036*
C	0.57789 (18)	0.3404 (2)	0.24639 (6)	0.0301 (5)
H0A	0.5769	0.2573	0.2452	0.045*
H0B	0.5248	0.3669	0.2615	0.045*
H0C	0.6388	0.3656	0.2568	0.045*
C1A	0.56992 (16)	0.51802 (17)	0.21406 (5)	0.0236 (4)
H1AA	0.5037	0.5427	0.2195	0.028*
H1AB	0.6084	0.5327	0.2359	0.028*
C2A	0.60808 (15)	0.59560 (17)	0.18461 (5)	0.0220 (4)
H2AA	0.6205	0.6712	0.1952	0.026*
H2AB	0.6702	0.5650	0.1762	0.026*
C3A	0.49249 (15)	0.69994 (17)	0.15189 (5)	0.0214 (4)
H3AA	0.4921	0.7567	0.1701	0.026*
C4A	0.43400 (14)	0.70505 (17)	0.12017 (5)	0.0209 (4)
C5A	0.33456 (16)	0.7412 (2)	0.07621 (6)	0.0301 (5)
H5AA	0.2875	0.7764	0.0615	0.036*
C6A	0.38088 (15)	0.64128 (19)	0.06928 (6)	0.0258 (4)
H6AA	0.3714	0.5947	0.0487	0.031*
C1B	0.65416 (15)	0.34079 (18)	0.18863 (6)	0.0238 (4)
H1BA	0.7086	0.3924	0.1934	0.029*
H1BB	0.6700	0.2674	0.2001	0.029*
C2B	0.65151 (15)	0.32028 (17)	0.14818 (5)	0.0221 (4)
H2BA	0.7068	0.2718	0.1417	0.026*
H2BB	0.5926	0.2771	0.1425	0.026*
C3B	0.73460 (15)	0.45056 (18)	0.11120 (5)	0.0221 (4)
H3BA	0.7922	0.4088	0.1144	0.027*
C4B	0.72866 (14)	0.55230 (18)	0.09009 (5)	0.0219 (4)
C5B	0.65706 (16)	0.69750 (18)	0.06694 (6)	0.0243 (4)
H5BA	0.6089	0.7507	0.0605	0.029*
C6B	0.75165 (17)	0.7035 (2)	0.05749 (6)	0.0300 (5)
H6BA	0.7809	0.7609	0.0433	0.036*
C1C	0.47042 (15)	0.34435 (18)	0.19572 (6)	0.0233 (4)
H1CA	0.4811	0.2670	0.1861	0.028*
H1CB	0.4291	0.3363	0.2172	0.028*
C2C	0.41328 (14)	0.40958 (18)	0.16763 (5)	0.0217 (4)
H2CA	0.3470	0.3797	0.1674	0.026*
H2CB	0.4100	0.4901	0.1751	0.026*
C3C	0.41876 (15)	0.32709 (18)	0.10959 (6)	0.0243 (4)
H3CA	0.3723	0.2723	0.1165	0.029*
C4C	0.46053 (15)	0.33235 (18)	0.07423 (6)	0.0244 (4)
C5C	0.55206 (15)	0.40500 (19)	0.03331 (6)	0.0245 (4)
H5CA	0.5964	0.4533	0.0214	0.029*
C6C	0.50736 (18)	0.3132 (2)	0.01838 (6)	0.0310 (5)
H6CA	0.5150	0.2858	−0.0055	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.01808 (13)	0.01279 (13)	0.01794 (13)	−0.00035 (10)	0.00077 (10)	−0.00083 (10)
Cl1	0.0326 (3)	0.0217 (3)	0.0352 (3)	0.0011 (2)	−0.0064 (2)	−0.0012 (2)
Cl2	0.0264 (2)	0.0239 (3)	0.0356 (3)	0.00118 (19)	0.0062 (2)	−0.0030 (2)
Cl3	0.0313 (3)	0.0234 (3)	0.0399 (3)	0.0000 (2)	0.0070 (2)	−0.0013 (2)
O11	0.118 (2)	0.0463 (14)	0.0629 (15)	0.0105 (14)	−0.0153 (15)	0.0256 (12)
O12	0.0305 (9)	0.0428 (11)	0.0734 (14)	−0.0057 (8)	−0.0084 (9)	−0.0190 (10)
O13	0.0387 (11)	0.0425 (12)	0.0765 (15)	0.0111 (9)	0.0060 (10)	−0.0037 (10)
O14	0.0471 (11)	0.0592 (13)	0.0418 (11)	−0.0193 (10)	−0.0031 (9)	−0.0152 (10)
O21	0.0761 (16)	0.0259 (10)	0.0775 (16)	−0.0005 (10)	0.0343 (13)	0.0033 (10)
O22	0.0761 (16)	0.0557 (14)	0.0512 (12)	0.0259 (12)	−0.0215 (11)	−0.0124 (10)
O23	0.0311 (9)	0.0589 (13)	0.0615 (13)	−0.0122 (9)	0.0157 (9)	−0.0303 (10)
O24	0.0441 (10)	0.0425 (11)	0.0447 (10)	0.0049 (9)	0.0181 (8)	−0.0097 (8)
O31	0.0615 (15)	0.0787 (18)	0.0660 (16)	−0.0064 (13)	−0.0182 (12)	0.0026 (13)
O32	0.0452 (12)	0.0272 (10)	0.113 (2)	0.0029 (9)	−0.0029 (12)	0.0131 (11)
O33	0.0592 (13)	0.0294 (10)	0.0824 (16)	−0.0085 (9)	0.0369 (12)	−0.0004 (10)
O34	0.0787 (16)	0.0403 (12)	0.0538 (13)	−0.0004 (11)	0.0307 (11)	−0.0083 (10)
O1W	0.0430 (14)	0.185 (4)	0.079 (2)	0.0426 (19)	0.0211 (13)	0.056 (2)
O2W	0.0545 (12)	0.0397 (11)	0.0442 (11)	0.0104 (10)	−0.0002 (10)	−0.0089 (9)
N	0.0263 (8)	0.0185 (8)	0.0196 (8)	−0.0007 (7)	0.0005 (7)	0.0020 (6)
N1A	0.0221 (8)	0.0159 (8)	0.0190 (8)	−0.0029 (6)	0.0008 (6)	0.0002 (6)
N2A	0.0207 (8)	0.0163 (8)	0.0227 (8)	0.0005 (6)	0.0009 (6)	0.0007 (6)
N3A	0.0275 (9)	0.0192 (9)	0.0340 (10)	0.0054 (7)	0.0034 (8)	0.0025 (7)
N1B	0.0221 (8)	0.0155 (8)	0.0203 (8)	0.0013 (6)	0.0020 (6)	−0.0021 (6)
N2B	0.0230 (8)	0.0168 (8)	0.0195 (8)	−0.0023 (6)	0.0008 (6)	−0.0013 (6)
N3B	0.0237 (9)	0.0324 (10)	0.0304 (9)	−0.0048 (8)	0.0048 (7)	0.0049 (8)
N1C	0.0198 (8)	0.0161 (8)	0.0218 (8)	−0.0002 (6)	0.0013 (6)	0.0000 (6)
N2C	0.0227 (8)	0.0158 (8)	0.0209 (8)	0.0024 (6)	0.0001 (6)	−0.0013 (6)
N3C	0.0373 (10)	0.0250 (10)	0.0288 (9)	−0.0055 (8)	−0.0040 (8)	−0.0109 (8)
C	0.0424 (13)	0.0268 (11)	0.0212 (10)	−0.0012 (10)	−0.0011 (9)	0.0066 (8)
C1A	0.0323 (10)	0.0193 (10)	0.0193 (9)	−0.0004 (8)	−0.0019 (8)	−0.0014 (7)
C2A	0.0267 (10)	0.0177 (9)	0.0217 (9)	−0.0037 (8)	−0.0044 (8)	−0.0026 (7)
C3A	0.0268 (10)	0.0150 (9)	0.0224 (9)	−0.0010 (7)	0.0047 (8)	−0.0023 (7)
C4A	0.0212 (9)	0.0170 (9)	0.0243 (10)	0.0005 (7)	0.0040 (7)	0.0015 (7)
C5A	0.0277 (11)	0.0297 (12)	0.0329 (12)	0.0038 (9)	−0.0022 (9)	0.0069 (9)
C6A	0.0246 (10)	0.0276 (11)	0.0251 (10)	−0.0010 (8)	−0.0022 (8)	0.0025 (8)
C1B	0.0246 (10)	0.0214 (10)	0.0254 (10)	0.0031 (8)	−0.0014 (8)	0.0038 (8)
C2B	0.0254 (10)	0.0163 (9)	0.0245 (10)	0.0025 (8)	0.0021 (8)	0.0021 (7)
C3B	0.0213 (9)	0.0220 (10)	0.0231 (9)	0.0014 (8)	0.0009 (8)	−0.0022 (8)
C4B	0.0218 (9)	0.0231 (10)	0.0209 (9)	−0.0026 (8)	0.0033 (7)	−0.0012 (8)
C5B	0.0301 (10)	0.0191 (10)	0.0236 (10)	−0.0033 (8)	−0.0012 (8)	0.0022 (8)
C6B	0.0344 (12)	0.0275 (12)	0.0279 (10)	−0.0087 (9)	0.0032 (9)	0.0049 (9)
C1C	0.0250 (10)	0.0211 (10)	0.0238 (10)	−0.0045 (8)	0.0026 (8)	0.0025 (8)
C2C	0.0199 (9)	0.0213 (10)	0.0241 (10)	−0.0008 (8)	0.0039 (8)	−0.0003 (8)
C3C	0.0240 (10)	0.0195 (10)	0.0293 (10)	−0.0046 (8)	0.0004 (8)	−0.0019 (8)
C4C	0.0273 (10)	0.0197 (10)	0.0261 (10)	−0.0011 (8)	−0.0039 (8)	−0.0056 (8)
C5C	0.0292 (10)	0.0229 (10)	0.0213 (9)	0.0046 (8)	−0.0007 (8)	−0.0019 (8)
C6C	0.0384 (12)	0.0309 (12)	0.0236 (10)	0.0044 (10)	−0.0027 (9)	−0.0080 (9)

Geometric parameters (Å, º) top

Fe—N1C	1.9414 (17)	N1C—C3C	1.294 (3)
Fe—N2A	1.9528 (17)	N1C—C2C	1.461 (3)
Fe—N1A	1.9559 (17)	N2C—C4C	1.332 (3)
Fe—N1B	1.9567 (17)	N2C—C5C	1.369 (3)
Fe—N2C	1.9665 (17)	N3C—C4C	1.349 (3)
Fe—N2B	1.9701 (17)	N3C—C6C	1.368 (3)
Cl1—O11	1.418 (2)	N3C—H3CB	0.8800
Cl1—O13	1.421 (2)	C—H0A	0.9800
Cl1—O12	1.4295 (19)	C—H0B	0.9800
Cl1—O14	1.4548 (19)	C—H0C	0.9800
Cl2—O23	1.4277 (18)	C1A—C2A	1.523 (3)
Cl2—O21	1.428 (2)	C1A—H1AA	0.9900
Cl2—O24	1.4357 (18)	C1A—H1AB	0.9900
Cl2—O22	1.449 (2)	C2A—H2AA	0.9900
Cl3—O34	1.419 (2)	C2A—H2AB	0.9900
Cl3—O32	1.428 (2)	C3A—C4A	1.436 (3)
Cl3—O33	1.4330 (19)	C3A—H3AA	0.9500
Cl3—O31	1.444 (2)	C5A—C6A	1.368 (3)
O1W—H1W1	0.866 (19)	C5A—H5AA	0.9500
O1W—H1W2	0.807 (19)	C6A—H6AA	0.9500
O2W—H2W1	0.820 (17)	C1B—C2B	1.524 (3)
O2W—H2W2	0.821 (18)	C1B—H1BA	0.9900
N—C	1.527 (3)	C1B—H1BB	0.9900
N—C1C	1.528 (3)	C2B—H2BA	0.9900
N—C1B	1.531 (3)	C2B—H2BB	0.9900
N—C1A	1.532 (3)	C3B—C4B	1.435 (3)
N1A—C3A	1.290 (3)	C3B—H3BA	0.9500
N1A—C2A	1.467 (2)	C5B—C6B	1.369 (3)
N2A—C4A	1.337 (3)	C5B—H5BA	0.9500
N2A—C6A	1.368 (3)	C6B—H6BA	0.9500
N3A—C4A	1.348 (3)	C1C—C2C	1.523 (3)
N3A—C5A	1.368 (3)	C1C—H1CA	0.9900
N3A—H3AB	0.8800	C1C—H1CB	0.9900
N1B—C3B	1.293 (3)	C2C—H2CA	0.9900
N1B—C2B	1.462 (3)	C2C—H2CB	0.9900
N2B—C4B	1.330 (3)	C3C—C4C	1.440 (3)
N2B—C5B	1.373 (3)	C3C—H3CA	0.9500
N3B—C4B	1.345 (3)	C5C—C6C	1.367 (3)
N3B—C6B	1.364 (3)	C5C—H5CA	0.9500
N3B—H3BB	0.8800	C6C—H6CA	0.9500

N1C—Fe—N2A	93.33 (7)	H0B—C—H0C	109.5
N1C—Fe—N1A	95.36 (7)	C2A—C1A—N	120.44 (17)
N2A—Fe—N1A	81.09 (7)	C2A—C1A—H1AA	107.2
N1C—Fe—N1B	93.73 (7)	N—C1A—H1AA	107.2
N2A—Fe—N1B	172.17 (7)	C2A—C1A—H1AB	107.2
N1A—Fe—N1B	94.88 (7)	N—C1A—H1AB	107.2
N1C—Fe—N2C	81.14 (7)	H1AA—C1A—H1AB	106.8
N2A—Fe—N2C	93.08 (7)	N1A—C2A—C1A	115.85 (17)
N1A—Fe—N2C	173.05 (7)	N1A—C2A—H2AA	108.3
N1B—Fe—N2C	91.34 (7)	C1A—C2A—H2AA	108.3
N1C—Fe—N2B	172.05 (7)	N1A—C2A—H2AB	108.3
N2A—Fe—N2B	92.10 (7)	C1A—C2A—H2AB	108.3
N1A—Fe—N2B	91.22 (7)	H2AA—C2A—H2AB	107.4
N1B—Fe—N2B	81.23 (7)	N1A—C3A—C4A	113.15 (18)
N2C—Fe—N2B	92.77 (7)	N1A—C3A—H3AA	123.4
O11—Cl1—O13	110.43 (16)	C4A—C3A—H3AA	123.4
O11—Cl1—O12	110.79 (16)	N2A—C4A—N3A	110.61 (18)
O13—Cl1—O12	109.80 (12)	N2A—C4A—C3A	116.54 (18)
O11—Cl1—O14	108.29 (15)	N3A—C4A—C3A	132.85 (19)
O13—Cl1—O14	108.99 (13)	C6A—C5A—N3A	106.98 (19)
O12—Cl1—O14	108.48 (12)	C6A—C5A—H5AA	126.5
O23—Cl2—O21	109.69 (14)	N3A—C5A—H5AA	126.5
O23—Cl2—O24	110.63 (11)	C5A—C6A—N2A	108.8 (2)
O21—Cl2—O24	111.22 (13)	C5A—C6A—H6AA	125.6
O23—Cl2—O22	108.41 (15)	N2A—C6A—H6AA	125.6
O21—Cl2—O22	107.53 (15)	C2B—C1B—N	121.13 (17)
O24—Cl2—O22	109.27 (13)	C2B—C1B—H1BA	107.0
O34—Cl3—O32	110.68 (15)	N—C1B—H1BA	107.0
O34—Cl3—O33	109.81 (13)	C2B—C1B—H1BB	107.0
O32—Cl3—O33	109.56 (13)	N—C1B—H1BB	107.0
O34—Cl3—O31	108.37 (16)	H1BA—C1B—H1BB	106.8
O32—Cl3—O31	107.02 (15)	N1B—C2B—C1B	116.20 (17)
O33—Cl3—O31	111.37 (16)	N1B—C2B—H2BA	108.2
H1W1—O1W—H1W2	103 (3)	C1B—C2B—H2BA	108.2
H2W1—O2W—H2W2	104 (2)	N1B—C2B—H2BB	108.2
C—N—C1C	104.07 (16)	C1B—C2B—H2BB	108.2
C—N—C1B	103.21 (16)	H2BA—C2B—H2BB	107.4
C1C—N—C1B	114.95 (16)	N1B—C3B—C4B	113.24 (18)
C—N—C1A	104.30 (16)	N1B—C3B—H3BA	123.4
C1C—N—C1A	113.92 (16)	C4B—C3B—H3BA	123.4
C1B—N—C1A	114.49 (16)	N2B—C4B—N3B	111.19 (19)
C3A—N1A—C2A	118.04 (17)	N2B—C4B—C3B	117.34 (18)
C3A—N1A—Fe	116.28 (14)	N3B—C4B—C3B	131.4 (2)
C2A—N1A—Fe	125.51 (13)	C6B—C5B—N2B	108.64 (19)
C4A—N2A—C6A	106.42 (17)	C6B—C5B—H5BA	125.7
C4A—N2A—Fe	112.58 (14)	N2B—C5B—H5BA	125.7
C6A—N2A—Fe	140.88 (15)	N3B—C6B—C5B	107.06 (19)
C4A—N3A—C5A	107.23 (18)	N3B—C6B—H6BA	126.5
C4A—N3A—H3AB	126.4	C5B—C6B—H6BA	126.5
C5A—N3A—H3AB	126.4	C2C—C1C—N	120.22 (17)
C3B—N1B—C2B	118.14 (17)	C2C—C1C—H1CA	107.3
C3B—N1B—Fe	115.93 (14)	N—C1C—H1CA	107.3
C2B—N1B—Fe	125.72 (13)	C2C—C1C—H1CB	107.3
C4B—N2B—C5B	106.05 (17)	N—C1C—H1CB	107.3
C4B—N2B—Fe	111.71 (13)	H1CA—C1C—H1CB	106.9
C5B—N2B—Fe	142.13 (15)	N1C—C2C—C1C	115.48 (17)
C4B—N3B—C6B	107.04 (19)	N1C—C2C—H2CA	108.4
C4B—N3B—H3BB	126.5	C1C—C2C—H2CA	108.4
C6B—N3B—H3BB	126.5	N1C—C2C—H2CB	108.4
C3C—N1C—C2C	118.37 (17)	C1C—C2C—H2CB	108.4
C3C—N1C—Fe	116.85 (14)	H2CA—C2C—H2CB	107.5
C2C—N1C—Fe	124.70 (13)	N1C—C3C—C4C	112.98 (18)
C4C—N2C—C5C	106.43 (17)	N1C—C3C—H3CA	123.5
C4C—N2C—Fe	112.39 (14)	C4C—C3C—H3CA	123.5
C5C—N2C—Fe	141.17 (15)	N2C—C4C—N3C	110.58 (19)
C4C—N3C—C6C	107.37 (19)	N2C—C4C—C3C	116.60 (18)
C4C—N3C—H3CB	126.3	N3C—C4C—C3C	132.8 (2)
C6C—N3C—H3CB	126.3	C6C—C5C—N2C	108.9 (2)
N—C—H0A	109.5	C6C—C5C—H5CA	125.5
N—C—H0B	109.5	N2C—C5C—H5CA	125.5
H0A—C—H0B	109.5	C5C—C6C—N3C	106.71 (19)
N—C—H0C	109.5	C5C—C6C—H6CA	126.6
H0A—C—H0C	109.5	N3C—C6C—H6CA	126.6

N1C—Fe—N1A—C3A	−98.03 (15)	Fe—N1A—C3A—C4A	4.9 (2)
N2A—Fe—N1A—C3A	−5.49 (15)	C6A—N2A—C4A—N3A	−0.5 (2)
N1B—Fe—N1A—C3A	167.75 (15)	Fe—N2A—C4A—N3A	176.30 (13)
N2B—Fe—N1A—C3A	86.44 (15)	C6A—N2A—C4A—C3A	179.43 (18)
N2A—Fe—N1A—C2A	179.28 (16)	Fe—N2A—C4A—C3A	−3.7 (2)
N1B—Fe—N1A—C2A	−7.49 (16)	C5A—N3A—C4A—N2A	0.6 (2)
N2B—Fe—N1A—C2A	−88.79 (16)	C5A—N3A—C4A—C3A	−179.4 (2)
N1C—Fe—N2A—C4A	99.71 (14)	N1A—C3A—C4A—N2A	−0.7 (3)
N1A—Fe—N2A—C4A	4.80 (14)	N1A—C3A—C4A—N3A	179.3 (2)
N2C—Fe—N2A—C4A	−178.99 (14)	C4A—N3A—C5A—C6A	−0.4 (2)
N2B—Fe—N2A—C4A	−86.10 (14)	N3A—C5A—C6A—N2A	0.0 (2)
N1C—Fe—N2A—C6A	−85.1 (2)	C4A—N2A—C6A—C5A	0.3 (2)
N1A—Fe—N2A—C6A	180.0 (2)	Fe—N2A—C6A—C5A	−175.06 (17)
N2C—Fe—N2A—C6A	−3.8 (2)	C—N—C1B—C2B	151.74 (19)
N2B—Fe—N2A—C6A	89.1 (2)	C1C—N—C1B—C2B	39.1 (3)
N1C—Fe—N1B—C3B	167.02 (15)	C1A—N—C1B—C2B	−95.6 (2)
N1A—Fe—N1B—C3B	−97.27 (15)	C3B—N1B—C2B—C1B	99.6 (2)
N2C—Fe—N1B—C3B	85.81 (15)	Fe—N1B—C2B—C1B	−85.8 (2)
N2B—Fe—N1B—C3B	−6.79 (15)	N—C1B—C2B—N1B	72.2 (2)
N1C—Fe—N1B—C2B	−7.71 (16)	C2B—N1B—C3B—C4B	−178.72 (17)
N1A—Fe—N1B—C2B	88.00 (16)	Fe—N1B—C3B—C4B	6.1 (2)
N2C—Fe—N1B—C2B	−88.92 (16)	C5B—N2B—C4B—N3B	−0.2 (2)
N2B—Fe—N1B—C2B	178.48 (16)	Fe—N2B—C4B—N3B	177.05 (14)
N2A—Fe—N2B—C4B	−178.30 (14)	C5B—N2B—C4B—C3B	178.36 (18)
N1A—Fe—N2B—C4B	100.57 (14)	Fe—N2B—C4B—C3B	−4.4 (2)
N1B—Fe—N2B—C4B	5.82 (14)	C6B—N3B—C4B—N2B	−0.1 (2)
N2C—Fe—N2B—C4B	−85.11 (14)	C6B—N3B—C4B—C3B	−178.4 (2)
N2A—Fe—N2B—C5B	−2.7 (2)	N1B—C3B—C4B—N2B	−1.0 (3)
N1A—Fe—N2B—C5B	−83.8 (2)	N1B—C3B—C4B—N3B	177.2 (2)
N1B—Fe—N2B—C5B	−178.5 (2)	C4B—N2B—C5B—C6B	0.4 (2)
N2C—Fe—N2B—C5B	90.5 (2)	Fe—N2B—C5B—C6B	−175.37 (17)
N2A—Fe—N1C—C3C	91.28 (16)	C4B—N3B—C6B—C5B	0.4 (3)
N1A—Fe—N1C—C3C	172.62 (16)	N2B—C5B—C6B—N3B	−0.5 (3)
N1B—Fe—N1C—C3C	−92.11 (16)	C—N—C1C—C2C	153.57 (18)
N2C—Fe—N1C—C3C	−1.33 (15)	C1B—N—C1C—C2C	−94.3 (2)
N2A—Fe—N1C—C2C	−85.53 (16)	C1A—N—C1C—C2C	40.6 (2)
N1A—Fe—N1C—C2C	−4.18 (16)	C3C—N1C—C2C—C1C	93.2 (2)
N1B—Fe—N1C—C2C	91.09 (16)	Fe—N1C—C2C—C1C	−90.1 (2)
N2C—Fe—N1C—C2C	−178.13 (16)	N—C1C—C2C—N1C	72.7 (2)
N1C—Fe—N2C—C4C	0.15 (14)	C2C—N1C—C3C—C4C	179.14 (18)
N2A—Fe—N2C—C4C	−92.75 (15)	Fe—N1C—C3C—C4C	2.1 (2)
N1B—Fe—N2C—C4C	93.72 (15)	C5C—N2C—C4C—N3C	0.1 (2)
N2B—Fe—N2C—C4C	175.00 (15)	Fe—N2C—C4C—N3C	−179.40 (14)
N2A—Fe—N2C—C5C	88.0 (2)	C5C—N2C—C4C—C3C	−179.55 (18)
N1B—Fe—N2C—C5C	−85.6 (2)	Fe—N2C—C4C—C3C	0.9 (2)
N2B—Fe—N2C—C5C	−4.3 (2)	C6C—N3C—C4C—N2C	0.1 (3)
C—N—C1A—C2A	150.83 (19)	C6C—N3C—C4C—C3C	179.7 (2)
C1C—N—C1A—C2A	−96.4 (2)	N1C—C3C—C4C—N2C	−2.0 (3)
C1B—N—C1A—C2A	38.8 (3)	N1C—C3C—C4C—N3C	178.4 (2)
C3A—N1A—C2A—C1A	98.1 (2)	C4C—N2C—C5C—C6C	−0.3 (2)
Fe—N1A—C2A—C1A	−86.8 (2)	Fe—N2C—C5C—C6C	178.98 (18)
N—C1A—C2A—N1A	73.3 (2)	N2C—C5C—C6C—N3C	0.4 (3)
C2A—N1A—C3A—C4A	−179.54 (17)	C4C—N3C—C6C—C5C	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W2···O14ⁱ	0.81 (2)	2.29 (4)	2.938 (3)	138 (5)
O2W—H2W1···O14ⁱⁱ	0.82 (2)	2.26 (2)	2.987 (3)	148 (4)
O2W—H2W2···O22ⁱⁱⁱ	0.82 (2)	2.07 (2)	2.861 (3)	160 (4)
N3A—H3AB···O2W	0.88	1.91	2.730 (3)	155
N3B—H3BB···O1W	0.88	1.95	2.752 (3)	152
N3C—H3CB···O14	0.88	2.05	2.907 (3)	163

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

Experimental details

Crystal data
Chemical formula	[Fe(C₁₉H₂₇N₁₀)](ClO₄)₃·2H₂O
M_r	785.74
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	13.9630 (18), 11.7810 (15), 37.182 (5)
V (Å³)	6116.4 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.54 × 0.45 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.682, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	65065, 8324, 6601
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.04
No. of reflections	8324
No. of parameters	436
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.62

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W2···O14ⁱ	0.807 (19)	2.29 (4)	2.938 (3)	138 (5)
O2W—H2W1···O14ⁱⁱ	0.820 (17)	2.26 (2)	2.987 (3)	148 (4)
O2W—H2W2···O22ⁱⁱⁱ	0.821 (18)	2.07 (2)	2.861 (3)	160 (4)
N3A—H3AB···O2W	0.88	1.91	2.730 (3)	155
N3B—H3BB···O1W	0.88	1.95	2.752 (3)	152
N3C—H3CB···O14	0.88	2.05	2.907 (3)	163

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

Acknowledgements

RJB acknowleges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

References

Brewer, C., Brewer, G., Patil, G., Sun, Y., Viragh, C. & Butcher, R. J. (2005). Inorg. Chim. Acta. 358, 3441–3448. Web of Science CSD CrossRef CAS Google Scholar
Brewer, G., Butcher, R. J., Viragh, C. & White, G. (2007). Dalton Trans. pp. 4132–4142. Web of Science CSD CrossRef Google Scholar
Brewer, G., Olida, M. J., Schmiedekamp, A. M., Viragh, C. & Zavalij, P. (2006). Dalton Trans. pp. 5617–5629. Web of Science CSD CrossRef Google Scholar
Bruker (2000). SMART and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar

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

{Tris[2-(imidazol-2-ylmethyl­imino)eth­yl]methyl­ammonium}iron(II) tris­­(per­chlorate) dihydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

{Tris[2-(imidazol-2-ylmethylimino)ethyl]methylammonium}iron(II) tris(perchlorate) dihydrate