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

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ISSN: 2056-9890
Volume 66| Part 6| June 2010| Pages m711-m712

[2,2′-(2,6,9,13-Tetra­aza­tetra­decane-1,14-di­yl)diphenolato]iron(III) iodide

aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com

(Received 11 May 2010; accepted 19 May 2010; online 26 May 2010)

The title FeIII complex, [Fe(C22H32N4O2)]I, contains a six-coordinate FeN4O2 cation in which the ligand is a reduced Schiff base resulting from the NaBH4 reduction of the condensation product between salicylaldehyde and 1,5,8,12-tetra­azadodecane. In spite of the increased flexibility of the saturated backbone of the ligand compared to the Schiff base from which it was synthesized, the complex adopts a cis-FeN4O2 conformation for the phenolic O-atom donors, which contrasts with the trans conformation adopted by the analogous ClO4 salt [Yisgedu et al. (2009[Yisgedu, T. B., Tesema, Y. T., Gultneh, Y. & Butcher, R. J. (2009). J. Chem. Crystallogr. 39, 315-319.]). J. Chem. Crystallogr. 39, 315–319]. In addition to extensive N—H⋯I hydrogen bonding between the amine H atoms and the anion there is a weak C—H⋯I inter­action.

Related literature

For early literature related to hexa­dentate ligands, see: Dwyer & Lions (1947[Dwyer, F. P. J. & Lions, F. (1947). J. Am. Chem. Soc. 69, 2917-2918.]); Das Sarma & Bailar (1955[Das Sarma, B. & Bailar, J. C. Jr (1955). J. Am. Chem. Soc. 77, 5476-5480.]). For geometric changes from cis to trans, see: Bera et al. (2005[Bera, M., Mukhopadhyay, U. & Ray, D. (2005). Inorg. Chim. Acta, 358, 437-443.]); Boinnard et al. (1994[Boinnard, D., Bousseksou, A., Dworkin, A., Savariault, J.-M., Varret, F. & Tuchagues, J.-P. (1994). Inorg. Chem. 33, 271-281.]); Dorbes et al. (2005[Dorbes, S., Valade, L., Real, J. A. & Faulmann, C. (2005). Chem. Commun. pp. 69-71.]); Floquet et al. (2004[Floquet, S., Munoz, M. C., Riviere, E., Clement, R., Audiere, J.-P. & Boillot, M.-L. (2004). New J. Chem. 28, 535-541.]); Hayami et al. (1997[Hayami, S., Matoba, T., Nomiyama, S., Kojima, T., Osaki, S. & Maeda, Y. (1997). Bull. Chem. Soc. Jpn, 70, 3001-3009.]); Ito et al. (1983[Ito, T., Sugimoto, M., Ito, H., Toriumi, K., Nakayama, H., Mori, W. & Sekizaki, M. (1983). Chem. Lett. 12, 121-124.]); Maeda et al. (1991[Maeda, Y., Oshio, H., Tanigawa, Y., Oniki, T. & Takashima, Y. (1991). Bull. Chem. Soc. Jpn, 64, 522-1527.]); McPartlin et al. (1978[McPartlin, M., Tasker, P. A., Bailey, N. A., McKenzie, E. D. & Worthington, J. M. (1978). Crystallogr. Struct. Commun. 7, pp. 115-120.]); Nishida et al. (1987[Nishida, Y., Kino, K. & Kida, S. (1987). J. Chem. Soc. Dalton Trans. pp. 1957-1961.]); Salmon et al. (1999[Salmon, L., Donnadieu, B., Bousseksou, A. & Tuchagues, J.-P. (1999). C. R. Acad. Sci. Ser. IIc Chim. 2, 305-309.]); Sinn et al. (1978[Sinn, E., Sim, G., Dose, E. V., Tweedle, M. F. & Wilson, L. J. (1978). J. Am. Chem. Soc. 100, 3375-3390.]). For complexes of reduced Schiff bases, see: Harpstrite et al. (2003[Harpstrite, S. E., Beatty, A. A., Collins, D., Oksman, A., Goldberg, D. E. & Sharma, V. (2003). Inorg. Chem. 42, 2294-2300.]). For the analogous ClO4 salt, see: Yisgedu et al. (2009[Yisgedu, T. B., Tesema, Y. T., Gultneh, Y. & Butcher, R. J. (2009). J. Chem. Crystallogr. 39, 315-319.]).

[Scheme 1]

Experimental

Crystal data
  • [Fe(C22H32N4O2)]I

  • Mr = 567.27

  • Orthorhombic, P 21 21 21

  • a = 9.3958 (1) Å

  • b = 13.0509 (1) Å

  • c = 19.4047 (3) Å

  • V = 2379.48 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.96 mm−1

  • T = 200 K

  • 0.51 × 0.47 × 0.39 mm

Data collection
  • Oxford Diffraction Gemini R diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]) Tmin = 0.428, Tmax = 0.466

  • 43714 measured reflections

  • 9836 independent reflections

  • 7672 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.066

  • S = 0.94

  • 9836 reflections

  • 271 parameters

  • H-atom parameters constrained

  • Δρmax = 1.32 e Å−3

  • Δρmin = −0.45 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 4113 Friedel pairs

  • Flack parameter: −0.018 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1A—H1AA⋯I 0.93 2.77 3.6800 (16) 168
N2A—H2AA⋯Ii 0.93 2.96 3.8227 (17) 155
N1B—H1BA⋯Ii 0.93 2.80 3.7285 (16) 178
N2B—H2BA⋯I 0.93 2.81 3.6911 (17) 158
C11B—H11C⋯Ii 0.99 3.10 3.942 (2) 144
Symmetry code: (i) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrysAlis CCD (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Metal complexes of linear hexadentate ligands have fascinated inorganic chemists since their first report in 1947 (Dwyer & Lions, 1947). The first such report of an Fe complex of a linear FeN4O2 ligand derived from the Schiff base condensation of salicylaldehyde and triethylenetetraamine was in 1955 (Das Sarma & Bailar, 1955). However, this interest lapsed for several years until the discovery that such complexes exhibited spin-crossover magnetic behavior (Sinn et al., 1978). Hexadentate linear FeN4O2 ligands derived from the Schiff base condensation of salicylaldehyde and linear tetramines can be characterized by the number of linking carbon atoms in the tetramine backbone (from 222 to 333). The structures of Fe complexes of Sal222 (Sinn et al., 1978; Hayami et al., 1997; Floquet et al., 2004; Dorbes et al., 2005; Bera et al., 2005; Nishida et al., 1987; Salmon et al., 1999; McPartlin et al., 1978; Maeda et al., 1991; Boinnard et al., 1994), Sal232 (Hayami et al., 1997), Sal323 (Hayami et al., 1997; Ito, et al., 1983), and Sal333 (Ito, et al., 1983) derivatives have been reported. When chelating to Fe, as the number of carbon atoms in the tetramine backbone increases from 6 to 9, the conformation adopted by the ligand changes from a cis-FeN4O2 to a trans-FeN4O2 arrangement for the phenolic O donors. All structurally characterized Fe complexes with Sal222 have adopted the cis-FeN4O2 conformation while all those with either Sal323 or Sal333 have adopted the trans-FeN4O2 conformation. For Sal232, both conformations have been observed (Hayami et al., 1997). Further, it has been observed that, in addition to the usual reduction in metal ligand bond distances when going from high spin to low spin, the angles subtended at the Fe center reflect the magnetic properties of the compound (Hayami et al., 1997; Nishida et al., 1987) with low-spin compounds having such angles closer to 90° and 180°.

Despite the interest shown in salicylaldimine complexes with FeIII due to their interesting structural and magnetic properties, there have been very few structures reported on related complexes where the C=N imine groups have been reduced to C–N–H amine groups (Harpstrite et al., 2003; Yisgedu et al., 2009). One of these is the perchlorate analog of the title compound (Harpstrite et al., 2003). As expected, due to increased flexibility of the saturated amine, compared to the more rigid Schiff base, and also the length of the carbon backbone, this compound has adopted a trans-FeN4O2 conformation. To further characterize such compounds and determine the conformation adopted the structure of an FeIII complex of the iodide salt of reduced Sal323 is reported.

The title compound, [1,12-bis(2-hydroxybenzyl)-1,5,8,12-tetraazadodecane]iron(III) iodide, C22H32FeIN4O6, contains a six-coordinate FeN4O2 cation where the ligand (H2L) is the NaBH4 reduction product of the Schiff base resulting from the condensation of salicylaldehyde and 1,4,8,12-tetraazadodecane. In marked contrast to the perchlorate salt with the same 323 backbone, the title compound has adopted a cis FeN4O2 conformation. It is of interest to compare the metrical parameters of both the cis and trans structures with the same central Schiff base core. In the title compound, the Fe—O distances are shorter [1.8898 (13)/1.8999 (14) Å versus 1.9575 (10)/1.9142 (10) Å] while the Fe—N distances are longer [Fe—N average of 2.202 (1) Å versus 2.162 (1) Å]. Thus, even though they adopt different conformations, the bond distances and angles of both the perchlorate and iodide salts are more indicative of a high spin FeIII complex compared to the similar reduced 232 complex (Yisgedu et al., 2009).

In addition to extensive hydrogen bonding between the amine H atoms and the anion there is a weak C—H···I interaction (see table 1).

Related literature top

For early literature related to hexadentate ligands, see: Dwyer & Lions (1947); Das Sarma & Bailar (1955). For geometric changes from cis to trans, see: Bera et al. (2005); Boinnard et al. (1994); Dorbes et al. (2005); Floquet et al. (2004); Hayami et al. (1997); Ito et al. (1983); Maeda et al. (1991); McPartlin et al. (1978); Nishida et al. (1987); Salmon et al. (1999); Sinn et al. (1978). For complexes of reduced Schiff bases, see: Harpstrite et al. (2003). For the analogous ClO4- salt, see: Yisgedu et al. (2009).

Experimental top

Synthesis of ligand: The procedure for the synthesis of the ligand 1,12-bis(2-hydroxybenzyl)-1,4,8,12-tetraazaundecane (H2L) (Yisgedu et al., 2009) is as follows: A solution of 6.1 g (50 mmol) of salicylaldehyde in 10 ml ethanol was added drop-wise to a solution of 4.0 g (25 mmol) of 1,5,8,12-tetraazadodecane in 15 ml of ethanol. A deep yellow solution was obtained and was stirred for half an hour. To this yellow solution was added a NaBH4 solution (3.0 g NaBH4, 0.4 g NaOH, and 40 ml H2O). The volume of the solution was reduced to 20 ml and extracted with chloroform (3 x 40 ml). The extracts were combined and dried with Na2SO4. The Na2SO4 was filtered and the filtrate concentrated to a colorless thick oil (8.1 g, 87%).

Synthesis of [FeIIIL](ClO4): The synthesis of the above complex (Yisgedu et al., 2009) is as follows: To 0.85 g (2 mmol) of H2L dissolved in 10.0 ml of methanol was added 0.58 g (1 mmol) of Fe(ClO4)2.xH2O. The solution became violet and red-purple solids precipitated. This was stirred overnight, the solids filtered, washed with methanol and dried to give 1.65 g of red powder. Crystallization was effected by evaporation of a DMF solution of the complex (yield, 0.96 g, 67%).

Synthesis of [C22H32FeN4O2]I complex: A solution of 0.05 g (0.088 mmol) of the complex [FeIIIL]ClO4 was mixed with a solution of 10 % w/v aqueous solution of iodine and potassium iodide. 0.095 g of the aqueous solution of iodine/KI mixture in 5 ml methanol was mixed with the complex. The mixture was then stirred at room temperature for 24 hours. The solution was then evaporated, dissolved in DMF and filtered. The filtrate was layered with diethyl ether. After the diffusion process, brownish red crystals suitable for x-ray diffraction were obtained.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Diagram of C22H32FeIN4O6 showing atom labeling. Thermal ellipsoids are at the 50% probability level.
[Figure 2] Fig. 2. The molecular packing for C22H32FeIN4O6 viewed down the a axis. Hydrogen bonds are shown by dashed lines.
[2,2'-(2,6,9,13-Tetraazatetradecane-1,14-diyl)diphenolato]iron(III) iodide top
Crystal data top
[Fe(C22H32N4O2)]IF(000) = 1148
Mr = 567.27Dx = 1.583 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 18399 reflections
a = 9.3958 (1) Åθ = 4.6–34.7°
b = 13.0509 (1) ŵ = 1.96 mm1
c = 19.4047 (3) ÅT = 200 K
V = 2379.48 (5) Å3Chunk, dark brown-red
Z = 40.51 × 0.47 × 0.39 mm
Data collection top
Oxford Diffraction Gemini R
diffractometer
9836 independent reflections
Radiation source: fine-focus sealed tube7672 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 10.5081 pixels mm-1θmax = 34.8°, θmin = 4.7°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
k = 2020
Tmin = 0.428, Tmax = 0.466l = 3031
43714 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.066 w = 1/[σ2(Fo2) + (0.0354P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.001
9836 reflectionsΔρmax = 1.32 e Å3
271 parametersΔρmin = 0.45 e Å3
0 restraintsAbsolute structure: Flack (1983), 4113 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.018 (11)
Crystal data top
[Fe(C22H32N4O2)]IV = 2379.48 (5) Å3
Mr = 567.27Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.3958 (1) ŵ = 1.96 mm1
b = 13.0509 (1) ÅT = 200 K
c = 19.4047 (3) Å0.51 × 0.47 × 0.39 mm
Data collection top
Oxford Diffraction Gemini R
diffractometer
9836 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
7672 reflections with I > 2σ(I)
Tmin = 0.428, Tmax = 0.466Rint = 0.036
43714 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.066Δρmax = 1.32 e Å3
S = 0.94Δρmin = 0.45 e Å3
9836 reflectionsAbsolute structure: Flack (1983), 4113 Friedel pairs
271 parametersAbsolute structure parameter: 0.018 (11)
0 restraints
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
xyzUiso*/Ueq
I0.773383 (17)0.160323 (12)0.264361 (9)0.04200 (5)
Fe0.82534 (3)0.15269 (2)0.131418 (12)0.01814 (5)
O1A0.79828 (16)0.08061 (11)0.04737 (7)0.0277 (3)
O1B0.71110 (15)0.26909 (10)0.11418 (7)0.0254 (3)
N1A0.64230 (16)0.07176 (12)0.17734 (8)0.0203 (3)
H1AA0.67630.01950.20540.024*
N2A0.86624 (18)0.20378 (12)0.23797 (9)0.0247 (3)
H2AA0.93440.25510.23420.030*
N1B1.01197 (16)0.23195 (12)0.09118 (8)0.0199 (3)
H1BA1.06390.25790.12810.024*
N2B0.97740 (18)0.03588 (13)0.16943 (9)0.0250 (3)
H2BA0.92180.02070.18050.030*
C1A0.7469 (2)0.01336 (15)0.03747 (10)0.0243 (4)
C2A0.8057 (3)0.07758 (19)0.01269 (12)0.0385 (5)
H2AB0.88460.05510.03930.046*
C3A0.7485 (3)0.17422 (19)0.02343 (14)0.0450 (6)
H3AA0.78900.21780.05740.054*
C4A0.6331 (3)0.20817 (18)0.01467 (13)0.0447 (6)
H4AA0.59440.27440.00680.054*
C5A0.5753 (3)0.14535 (17)0.06366 (11)0.0352 (5)
H5AA0.49690.16910.09020.042*
C6A0.6286 (2)0.04757 (15)0.07560 (10)0.0253 (4)
C7A0.5530 (2)0.02586 (16)0.12218 (10)0.0250 (4)
H7AA0.51300.08190.09380.030*
H7AB0.47220.01040.14400.030*
C8A0.5495 (2)0.14035 (17)0.21940 (11)0.0293 (4)
H8AA0.46210.10250.23220.035*
H8AB0.52060.19960.19080.035*
C9A0.6201 (3)0.17974 (17)0.28458 (11)0.0327 (5)
H9AA0.54730.21580.31240.039*
H9AB0.65300.12010.31170.039*
C10A0.7452 (2)0.25153 (15)0.27417 (10)0.0305 (4)
H10A0.71290.31180.24750.037*
H10B0.77800.27620.31970.037*
C11A0.9351 (3)0.12131 (18)0.27913 (12)0.0338 (5)
H11A0.86240.07160.29480.041*
H11B0.98140.15120.32030.041*
C1B0.74548 (19)0.36819 (14)0.10896 (9)0.0226 (4)
C2B0.6501 (2)0.44332 (17)0.13160 (11)0.0310 (4)
H2BB0.56320.42390.15290.037*
C3B0.6827 (3)0.54589 (17)0.12298 (12)0.0352 (5)
H3BA0.61610.59650.13710.042*
C4B0.8109 (2)0.57591 (16)0.09400 (12)0.0329 (5)
H4BA0.83260.64660.08870.040*
C5B0.9073 (2)0.50167 (15)0.07286 (11)0.0273 (4)
H5BA0.99630.52190.05400.033*
C6B0.8749 (2)0.39720 (14)0.07890 (10)0.0216 (4)
C7B0.9688 (2)0.31914 (15)0.04574 (10)0.0247 (4)
H7BA1.05600.35390.02910.030*
H7BB0.91890.29100.00500.030*
C8B1.1072 (2)0.16359 (18)0.04945 (10)0.0285 (4)
H8BA1.18040.20630.02660.034*
H8BB1.04980.13060.01290.034*
C9B1.1806 (2)0.08143 (18)0.09064 (12)0.0332 (5)
H9BA1.23070.11420.12970.040*
H9BB1.25340.04870.06110.040*
C10B1.0824 (2)0.00223 (16)0.11913 (12)0.0315 (5)
H10C1.03110.03470.08030.038*
H10D1.14130.05570.14140.038*
C11B1.0443 (2)0.06764 (17)0.23547 (12)0.0322 (4)
H11C1.12520.11430.22620.039*
H11D1.08100.00670.26010.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I0.03535 (8)0.03358 (7)0.05708 (10)0.00127 (7)0.00778 (7)0.01797 (7)
Fe0.01560 (10)0.02019 (11)0.01862 (11)0.00004 (10)0.00055 (9)0.00102 (10)
O1A0.0264 (8)0.0351 (7)0.0216 (7)0.0061 (6)0.0031 (5)0.0040 (5)
O1B0.0174 (6)0.0267 (6)0.0321 (7)0.0016 (5)0.0029 (5)0.0081 (5)
N1A0.0186 (7)0.0219 (7)0.0203 (7)0.0002 (6)0.0024 (6)0.0010 (6)
N2A0.0264 (8)0.0245 (7)0.0233 (8)0.0040 (6)0.0009 (7)0.0012 (6)
N1B0.0131 (7)0.0245 (7)0.0219 (7)0.0000 (6)0.0008 (6)0.0021 (6)
N2B0.0220 (8)0.0217 (7)0.0314 (9)0.0003 (6)0.0027 (7)0.0021 (6)
C1A0.0229 (10)0.0284 (9)0.0215 (8)0.0018 (7)0.0041 (7)0.0035 (7)
C2A0.0375 (13)0.0475 (13)0.0305 (11)0.0073 (10)0.0024 (9)0.0118 (9)
C3A0.0488 (16)0.0396 (12)0.0466 (13)0.0141 (11)0.0102 (11)0.0189 (10)
C4A0.0655 (18)0.0248 (10)0.0439 (14)0.0010 (11)0.0180 (13)0.0027 (9)
C5A0.0441 (13)0.0296 (11)0.0318 (11)0.0085 (10)0.0093 (9)0.0050 (9)
C6A0.0268 (10)0.0275 (9)0.0217 (9)0.0018 (8)0.0071 (7)0.0017 (7)
C7A0.0169 (8)0.0316 (9)0.0264 (10)0.0027 (7)0.0000 (7)0.0002 (7)
C8A0.0231 (9)0.0333 (11)0.0314 (10)0.0005 (8)0.0099 (7)0.0013 (8)
C9A0.0370 (12)0.0345 (11)0.0267 (10)0.0021 (9)0.0115 (8)0.0040 (8)
C10A0.0400 (13)0.0268 (9)0.0246 (9)0.0037 (8)0.0064 (8)0.0060 (7)
C11A0.0376 (12)0.0371 (11)0.0267 (11)0.0007 (9)0.0071 (9)0.0059 (8)
C1B0.0217 (10)0.0257 (8)0.0204 (8)0.0031 (6)0.0008 (6)0.0043 (6)
C2B0.0251 (10)0.0347 (10)0.0331 (10)0.0072 (8)0.0044 (9)0.0054 (9)
C3B0.0404 (12)0.0304 (10)0.0350 (12)0.0141 (9)0.0024 (10)0.0017 (9)
C4B0.0372 (13)0.0243 (9)0.0373 (12)0.0035 (9)0.0072 (9)0.0026 (8)
C5B0.0262 (10)0.0298 (10)0.0260 (10)0.0022 (8)0.0030 (8)0.0049 (8)
C6B0.0206 (9)0.0242 (8)0.0201 (9)0.0007 (7)0.0009 (7)0.0041 (7)
C7B0.0211 (9)0.0297 (10)0.0233 (9)0.0015 (7)0.0028 (7)0.0083 (7)
C8B0.0195 (8)0.0346 (10)0.0315 (10)0.0057 (9)0.0086 (7)0.0007 (9)
C9B0.0188 (9)0.0382 (11)0.0427 (13)0.0100 (9)0.0023 (9)0.0006 (9)
C10B0.0285 (11)0.0273 (10)0.0388 (12)0.0089 (8)0.0002 (9)0.0005 (8)
C11B0.0325 (11)0.0343 (10)0.0296 (11)0.0014 (8)0.0115 (9)0.0047 (9)
Geometric parameters (Å, º) top
Fe—O1B1.8898 (13)C8A—H8AA0.9900
Fe—O1A1.8999 (14)C8A—H8AB0.9900
Fe—N1B2.1805 (15)C9A—C10A1.517 (3)
Fe—N1A2.2062 (15)C9A—H9AA0.9900
Fe—N2A2.2062 (17)C9A—H9AB0.9900
Fe—N2B2.2158 (17)C10A—H10A0.9900
O1A—C1A1.332 (2)C10A—H10B0.9900
O1B—C1B1.337 (2)C11A—C11B1.504 (3)
N1A—C7A1.486 (2)C11A—H11A0.9900
N1A—C8A1.493 (2)C11A—H11B0.9900
N1A—H1AA0.9300C1B—C2B1.399 (3)
N2A—C10A1.475 (3)C1B—C6B1.401 (3)
N2A—C11A1.488 (3)C2B—C3B1.383 (3)
N2A—H2AA0.9300C2B—H2BB0.9500
N1B—C7B1.496 (2)C3B—C4B1.386 (3)
N1B—C8B1.501 (2)C3B—H3BA0.9500
N1B—H1BA0.9300C4B—C5B1.388 (3)
N2B—C10B1.474 (3)C4B—H4BA0.9500
N2B—C11B1.486 (3)C5B—C6B1.402 (3)
N2B—H2BA0.9300C5B—H5BA0.9500
C1A—C2A1.398 (3)C6B—C7B1.493 (3)
C1A—C6A1.408 (3)C7B—H7BA0.9900
C2A—C3A1.387 (3)C7B—H7BB0.9900
C2A—H2AB0.9500C8B—C9B1.505 (3)
C3A—C4A1.385 (4)C8B—H8BA0.9900
C3A—H3AA0.9500C8B—H8BB0.9900
C4A—C5A1.368 (4)C9B—C10B1.533 (3)
C4A—H4AA0.9500C9B—H9BA0.9900
C5A—C6A1.390 (3)C9B—H9BB0.9900
C5A—H5AA0.9500C10B—H10C0.9900
C6A—C7A1.497 (3)C10B—H10D0.9900
C7A—H7AA0.9900C11B—H11C0.9900
C7A—H7AB0.9900C11B—H11D0.9900
C8A—C9A1.518 (3)
O1B—Fe—O1A99.79 (6)C9A—C8A—H8AB108.8
O1B—Fe—N1B90.69 (6)H8AA—C8A—H8AB107.7
O1A—Fe—N1B92.02 (6)C10A—C9A—C8A115.90 (17)
O1B—Fe—N1A90.78 (6)C10A—C9A—H9AA108.3
O1A—Fe—N1A90.31 (6)C8A—C9A—H9AA108.3
N1B—Fe—N1A177.01 (6)C10A—C9A—H9AB108.3
O1B—Fe—N2A91.25 (6)C8A—C9A—H9AB108.3
O1A—Fe—N2A167.81 (6)H9AA—C9A—H9AB107.4
N1B—Fe—N2A92.99 (6)N2A—C10A—C9A113.59 (16)
N1A—Fe—N2A84.37 (6)N2A—C10A—H10A108.8
O1B—Fe—N2B168.01 (6)C9A—C10A—H10A108.8
O1A—Fe—N2B91.80 (6)N2A—C10A—H10B108.8
N1B—Fe—N2B85.82 (6)C9A—C10A—H10B108.8
N1A—Fe—N2B92.22 (6)H10A—C10A—H10B107.7
N2A—Fe—N2B77.50 (6)N2A—C11A—C11B109.34 (17)
C1A—O1A—Fe128.92 (12)N2A—C11A—H11A109.8
C1B—O1B—Fe130.83 (12)C11B—C11A—H11A109.8
C7A—N1A—C8A107.79 (15)N2A—C11A—H11B109.8
C7A—N1A—Fe110.01 (11)C11B—C11A—H11B109.8
C8A—N1A—Fe112.91 (12)H11A—C11A—H11B108.3
C7A—N1A—H1AA108.7O1B—C1B—C2B119.97 (17)
C8A—N1A—H1AA108.7O1B—C1B—C6B120.18 (16)
Fe—N1A—H1AA108.7C2B—C1B—C6B119.82 (17)
C10A—N2A—C11A112.66 (17)C3B—C2B—C1B119.9 (2)
C10A—N2A—Fe116.09 (13)C3B—C2B—H2BB120.0
C11A—N2A—Fe111.11 (13)C1B—C2B—H2BB120.0
C10A—N2A—H2AA105.3C2B—C3B—C4B121.0 (2)
C11A—N2A—H2AA105.3C2B—C3B—H3BA119.5
Fe—N2A—H2AA105.3C4B—C3B—H3BA119.5
C7B—N1B—C8B107.20 (15)C3B—C4B—C5B119.31 (19)
C7B—N1B—Fe110.74 (11)C3B—C4B—H4BA120.3
C8B—N1B—Fe112.99 (12)C5B—C4B—H4BA120.3
C7B—N1B—H1BA108.6C4B—C5B—C6B120.9 (2)
C8B—N1B—H1BA108.6C4B—C5B—H5BA119.6
Fe—N1B—H1BA108.6C6B—C5B—H5BA119.6
C10B—N2B—C11B112.46 (17)C1B—C6B—C5B119.06 (18)
C10B—N2B—Fe116.31 (13)C1B—C6B—C7B120.53 (17)
C11B—N2B—Fe111.58 (12)C5B—C6B—C7B119.96 (18)
C10B—N2B—H2BA105.1C6B—C7B—N1B115.16 (15)
C11B—N2B—H2BA105.1C6B—C7B—H7BA108.5
Fe—N2B—H2BA105.1N1B—C7B—H7BA108.5
O1A—C1A—C2A120.62 (19)C6B—C7B—H7BB108.5
O1A—C1A—C6A120.15 (17)N1B—C7B—H7BB108.5
C2A—C1A—C6A119.18 (19)H7BA—C7B—H7BB107.5
C3A—C2A—C1A119.8 (2)N1B—C8B—C9B114.22 (16)
C3A—C2A—H2AB120.1N1B—C8B—H8BA108.7
C1A—C2A—H2AB120.1C9B—C8B—H8BA108.7
C4A—C3A—C2A120.9 (2)N1B—C8B—H8BB108.7
C4A—C3A—H3AA119.5C9B—C8B—H8BB108.7
C2A—C3A—H3AA119.5H8BA—C8B—H8BB107.6
C5A—C4A—C3A119.3 (2)C8B—C9B—C10B115.07 (18)
C5A—C4A—H4AA120.3C8B—C9B—H9BA108.5
C3A—C4A—H4AA120.3C10B—C9B—H9BA108.5
C4A—C5A—C6A121.5 (2)C8B—C9B—H9BB108.5
C4A—C5A—H5AA119.2C10B—C9B—H9BB108.5
C6A—C5A—H5AA119.2H9BA—C9B—H9BB107.5
C5A—C6A—C1A119.21 (19)N2B—C10B—C9B113.66 (17)
C5A—C6A—C7A121.14 (19)N2B—C10B—H10C108.8
C1A—C6A—C7A119.29 (17)C9B—C10B—H10C108.8
N1A—C7A—C6A115.14 (16)N2B—C10B—H10D108.8
N1A—C7A—H7AA108.5C9B—C10B—H10D108.8
C6A—C7A—H7AA108.5H10C—C10B—H10D107.7
N1A—C7A—H7AB108.5N2B—C11B—C11A109.10 (17)
C6A—C7A—H7AB108.5N2B—C11B—H11C109.9
H7AA—C7A—H7AB107.5C11A—C11B—H11C109.9
N1A—C8A—C9A113.79 (17)N2B—C11B—H11D109.9
N1A—C8A—H8AA108.8C11A—C11B—H11D109.9
C9A—C8A—H8AA108.8H11C—C11B—H11D108.3
N1A—C8A—H8AB108.8
O1B—Fe—O1A—C1A121.63 (16)C6A—C1A—C2A—C3A1.0 (3)
N1B—Fe—O1A—C1A147.32 (16)C1A—C2A—C3A—C4A0.3 (4)
N1A—Fe—O1A—C1A30.79 (16)C2A—C3A—C4A—C5A0.2 (4)
N2A—Fe—O1A—C1A33.1 (4)C3A—C4A—C5A—C6A0.8 (4)
N2B—Fe—O1A—C1A61.45 (16)C4A—C5A—C6A—C1A1.5 (3)
O1A—Fe—O1B—C1B116.70 (15)C4A—C5A—C6A—C7A171.5 (2)
N1B—Fe—O1B—C1B24.54 (15)O1A—C1A—C6A—C5A178.97 (18)
N1A—Fe—O1B—C1B152.85 (15)C2A—C1A—C6A—C5A1.6 (3)
N2A—Fe—O1B—C1B68.47 (16)O1A—C1A—C6A—C7A5.8 (3)
N2B—Fe—O1B—C1B48.3 (4)C2A—C1A—C6A—C7A171.55 (19)
O1B—Fe—N1A—C7A82.12 (12)C8A—N1A—C7A—C6A178.68 (16)
O1A—Fe—N1A—C7A17.68 (12)Fe—N1A—C7A—C6A57.82 (18)
N2A—Fe—N1A—C7A173.30 (13)C5A—C6A—C7A—N1A127.69 (19)
N2B—Fe—N1A—C7A109.49 (12)C1A—C6A—C7A—N1A59.3 (2)
O1B—Fe—N1A—C8A38.34 (13)C7A—N1A—C8A—C9A170.82 (17)
O1A—Fe—N1A—C8A138.14 (13)Fe—N1A—C8A—C9A67.46 (19)
N2A—Fe—N1A—C8A52.85 (13)N1A—C8A—C9A—C10A66.2 (2)
N2B—Fe—N1A—C8A130.06 (13)C11A—N2A—C10A—C9A66.6 (2)
O1B—Fe—N2A—C10A38.47 (13)Fe—N2A—C10A—C9A63.1 (2)
O1A—Fe—N2A—C10A116.6 (3)C8A—C9A—C10A—N2A62.7 (3)
N1B—Fe—N2A—C10A129.23 (13)C10A—N2A—C11A—C11B172.73 (16)
N1A—Fe—N2A—C10A52.18 (13)Fe—N2A—C11A—C11B40.5 (2)
N2B—Fe—N2A—C10A145.72 (14)Fe—O1B—C1B—C2B146.23 (16)
O1B—Fe—N2A—C11A168.93 (14)Fe—O1B—C1B—C6B35.7 (2)
O1A—Fe—N2A—C11A13.8 (4)O1B—C1B—C2B—C3B176.72 (19)
N1B—Fe—N2A—C11A100.31 (14)C6B—C1B—C2B—C3B1.3 (3)
N1A—Fe—N2A—C11A78.27 (14)C1B—C2B—C3B—C4B2.0 (3)
N2B—Fe—N2A—C11A15.27 (14)C2B—C3B—C4B—C5B0.6 (3)
O1B—Fe—N1B—C7B20.81 (13)C3B—C4B—C5B—C6B1.6 (3)
O1A—Fe—N1B—C7B79.02 (13)O1B—C1B—C6B—C5B178.81 (17)
N2A—Fe—N1B—C7B112.10 (12)C2B—C1B—C6B—C5B0.8 (3)
N2B—Fe—N1B—C7B170.67 (13)O1B—C1B—C6B—C7B6.5 (3)
O1B—Fe—N1B—C8B141.09 (13)C2B—C1B—C6B—C7B171.54 (18)
O1A—Fe—N1B—C8B41.26 (13)C4B—C5B—C6B—C1B2.2 (3)
N2A—Fe—N1B—C8B127.62 (12)C4B—C5B—C6B—C7B170.12 (19)
N2B—Fe—N1B—C8B50.39 (13)C1B—C6B—C7B—N1B56.4 (2)
O1B—Fe—N2B—C10B122.7 (3)C5B—C6B—C7B—N1B131.38 (19)
O1A—Fe—N2B—C10B42.58 (14)C8B—N1B—C7B—C6B178.95 (16)
N1B—Fe—N2B—C10B49.31 (14)Fe—N1B—C7B—C6B57.38 (19)
N1A—Fe—N2B—C10B132.95 (14)C7B—N1B—C8B—C9B170.13 (18)
N2A—Fe—N2B—C10B143.31 (15)Fe—N1B—C8B—C9B67.59 (19)
O1B—Fe—N2B—C11B8.1 (4)N1B—C8B—C9B—C10B68.4 (2)
O1A—Fe—N2B—C11B173.41 (14)C11B—N2B—C10B—C9B69.6 (2)
N1B—Fe—N2B—C11B81.52 (14)Fe—N2B—C10B—C9B60.8 (2)
N1A—Fe—N2B—C11B96.21 (13)C8B—C9B—C10B—N2B63.9 (3)
N2A—Fe—N2B—C11B12.48 (13)C10B—N2B—C11B—C11A170.70 (16)
Fe—O1A—C1A—C2A141.17 (18)Fe—N2B—C11B—C11A37.91 (19)
Fe—O1A—C1A—C6A41.5 (2)N2A—C11A—C11B—N2B51.6 (2)
O1A—C1A—C2A—C3A178.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1AA···I0.932.773.6800 (16)168
N2A—H2AA···Ii0.932.963.8227 (17)155
N1B—H1BA···Ii0.932.803.7285 (16)178
N2B—H2BA···I0.932.813.6911 (17)158
C11B—H11C···Ii0.993.103.942 (2)144
Symmetry code: (i) x+2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe(C22H32N4O2)]I
Mr567.27
Crystal system, space groupOrthorhombic, P212121
Temperature (K)200
a, b, c (Å)9.3958 (1), 13.0509 (1), 19.4047 (3)
V3)2379.48 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.96
Crystal size (mm)0.51 × 0.47 × 0.39
Data collection
DiffractometerOxford Diffraction Gemini R
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2007)
Tmin, Tmax0.428, 0.466
No. of measured, independent and
observed [I > 2σ(I)] reflections
43714, 9836, 7672
Rint0.036
(sin θ/λ)max1)0.804
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.066, 0.94
No. of reflections9836
No. of parameters271
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.32, 0.45
Absolute structureFlack (1983), 4113 Friedel pairs
Absolute structure parameter0.018 (11)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1AA···I0.932.773.6800 (16)168.1
N2A—H2AA···Ii0.932.963.8227 (17)155.1
N1B—H1BA···Ii0.932.803.7285 (16)177.9
N2B—H2BA···I0.932.813.6911 (17)157.9
C11B—H11C···Ii0.993.103.942 (2)144.0
Symmetry code: (i) x+2, y+1/2, z+1/2.
 

Acknowledgements

RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

References

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Volume 66| Part 6| June 2010| Pages m711-m712
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