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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m204.
Published online 2010 January 27. doi:  10.1107/S1600536810002783
PMCID: PMC2979845

Bis[2-(8-quinolylimino­meth­yl)phenolato-κ3 N,N′,O]iron(III) azide

Abstract

The title compound, [Fe(C16H11N2O)2]N3, consists of a [Fe(qsal)2]+ cation [Hqsal = N-(8-quinol­yl)salicylaldimine] and an azide anion. The FeIII ion, lying on a twofold rotation axis, is coordinated by four N atoms and two O atoms from two tridentate qsal ligands in an octa­hedral geometry. The mol­ecules are connected into a three-dimensional network by inter­molecular C—H(...)N and C—H(...)O inter­actions. π–π inter­actions [inter­planar distance = 3.58 (1) Å] between the quinoline rings of adjacent mol­ecules further stabilize the crystal structure.

Related literature

For Fe(III) complexes with qsal ligands, see: Hayami et al. (2001 [triangle]); Takahashi et al. (2006 [triangle]). For bond lengths in Fe(III) complexes, see: Nihei et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m204-scheme1.jpg

Experimental

Crystal data

  • [Fe(C16H11N2O)2]N3
  • M r = 592.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m204-efi1.jpg
  • a = 11.3717 (8) Å
  • b = 10.1190 (8) Å
  • c = 11.7734 (6) Å
  • β = 109.3542 (15)°
  • V = 1278.21 (15) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.64 mm−1
  • T = 200 K
  • 0.50 × 0.20 × 0.20 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.741, T max = 0.883
  • 11530 measured reflections
  • 2929 independent reflections
  • 2556 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.104
  • S = 0.86
  • 2929 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.39 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002783/hy2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002783/hy2271Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

Fe(III) complexes with the qsal ligands [Hqsal = N-(8-quinolyl)salicylaldimine] were reported previously (Hayami et al., 2001; Takahashi et al., 2006). It was showed that the spin states of the complexes can be tuned by the different counter anions. Some of the complexes were observed spin crossover or spin transition. The title compound (Fig. 1) does not show both spin-crossover behaviors but is in the low-spin state at room temperature. In the complex, Fe1—O1, Fe1—N1 and Fe1—N2 bond lengths (Table 1) are close to those for other low-spin Fe(III) complexes (Nihei et al., 2007).

In addition, many intermolecular interactions are observed in the crystal structure. The intermolecular C—H···N hydrogen bond (involving quinoline ring H15 and the azide N4), C—H···O hydrogen bond (involving quinoline ring H9 and phenolate O1) (Table 2), and π–π interaction [interplanar distance = 3.58 (1) Å] between the quinoline rings of adjacent molecules link the molecules and provide stability into the crystal structure.

Experimental

Hqsal and [Fe(qsal)2]Cl were prepared from 8-aminoquinoline and salicylaldehyde according to the method described previously (Hayami et al., 2001). The title compound was prepared by slow addition of a MeOH solution (30 ml) containing [Fe(qsal)2]Cl (0.5 mmol) to a MeOH solution (30 ml) containing an excess of NaN3 (2 mmol).

Refinement

All H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding atoms, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound drawn with the 50% probability displacement ellipsoids. [Symmetry codes: (i) 1/2-x, y, 3/2-z; (ii) 1/2-x, y, 5/2-z.]

Crystal data

[Fe(C16H11N2O)2]N3F(000) = 610
Mr = 592.42Dx = 1.539 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yacCell parameters from 11530 reflections
a = 11.3717 (8) Åθ = 1.8–27.5°
b = 10.1190 (8) ŵ = 0.64 mm1
c = 11.7734 (6) ÅT = 200 K
β = 109.3542 (15)°Block, black
V = 1278.21 (15) Å30.50 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer2929 independent reflections
Radiation source: rotation anode2556 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = 0→14
Tmin = 0.741, Tmax = 0.883k = 0→13
11530 measured reflectionsl = −15→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 0.86w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2929 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.39 e Å3

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

xyzUiso*/Ueq
Fe10.25000.12760 (3)0.75000.01593 (12)
O10.13778 (10)0.00441 (11)0.77255 (10)0.0230 (2)
N10.35553 (12)0.13158 (12)0.91699 (11)0.0181 (3)
N20.36114 (11)0.27008 (12)0.73375 (11)0.0184 (3)
N30.25000.28128 (19)1.25000.0279 (4)
N40.26580 (17)0.28132 (18)1.15630 (15)0.0433 (4)
C10.14342 (14)−0.05156 (14)0.87550 (13)0.0211 (3)
C20.04475 (17)−0.13609 (16)0.87415 (16)0.0286 (4)
H2−0.0224−0.14910.80120.034*
C30.04411 (18)−0.20050 (19)0.97754 (16)0.0352 (4)
H3−0.0236−0.25690.97450.042*
C40.1411 (2)−0.1841 (2)1.08613 (16)0.0395 (5)
H40.1409−0.23071.15610.047*
C50.23689 (18)−0.09964 (19)1.09040 (15)0.0321 (4)
H50.3022−0.08651.16460.038*
C60.24043 (15)−0.03176 (15)0.98671 (14)0.0230 (3)
C70.34174 (14)0.05762 (15)1.00231 (13)0.0218 (3)
H70.40310.06361.07990.026*
C80.45447 (14)0.22483 (14)0.94235 (13)0.0207 (3)
C90.54613 (16)0.24933 (17)1.05052 (15)0.0293 (4)
H90.54930.19921.11970.035*
C100.63516 (17)0.3487 (2)1.05877 (17)0.0355 (4)
H100.69880.36391.13370.043*
C110.63210 (16)0.42458 (18)0.96008 (16)0.0323 (4)
H110.69240.49200.96790.039*
C120.53937 (15)0.40166 (16)0.84810 (15)0.0252 (3)
C130.52736 (15)0.47520 (17)0.74226 (16)0.0291 (4)
H130.58290.54600.74430.035*
C140.43587 (15)0.44350 (16)0.63807 (15)0.0272 (3)
H140.42700.49250.56690.033*
C150.35431 (14)0.33827 (16)0.63543 (14)0.0221 (3)
H150.29260.31530.56130.027*
C160.45197 (13)0.30040 (15)0.83972 (13)0.0194 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Fe10.01757 (17)0.01657 (17)0.01266 (17)0.0000.00365 (11)0.000
O10.0252 (5)0.0240 (5)0.0169 (5)−0.0063 (4)0.0032 (4)0.0021 (4)
N10.0187 (6)0.0199 (6)0.0149 (6)0.0007 (4)0.0045 (5)−0.0004 (4)
N20.0174 (5)0.0205 (6)0.0174 (6)0.0000 (5)0.0059 (5)0.0001 (4)
N30.0242 (9)0.0256 (10)0.0281 (10)0.0000.0009 (8)0.000
N40.0472 (10)0.0516 (10)0.0297 (9)−0.0174 (8)0.0110 (7)−0.0039 (7)
C10.0265 (7)0.0198 (7)0.0175 (7)−0.0006 (6)0.0079 (6)0.0011 (5)
C20.0292 (8)0.0309 (9)0.0244 (8)−0.0087 (7)0.0071 (7)0.0009 (6)
C30.0408 (10)0.0377 (9)0.0293 (9)−0.0159 (8)0.0147 (8)0.0011 (7)
C40.0536 (11)0.0434 (11)0.0224 (8)−0.0161 (9)0.0138 (8)0.0049 (7)
C50.0408 (10)0.0356 (9)0.0166 (8)−0.0079 (8)0.0052 (7)0.0038 (6)
C60.0286 (8)0.0216 (7)0.0188 (7)−0.0012 (6)0.0080 (6)0.0010 (6)
C70.0247 (7)0.0223 (7)0.0155 (7)0.0008 (6)0.0027 (6)0.0006 (5)
C80.0195 (6)0.0215 (7)0.0199 (7)−0.0003 (5)0.0049 (5)−0.0024 (5)
C90.0290 (8)0.0341 (9)0.0215 (8)−0.0055 (7)0.0039 (6)−0.0012 (6)
C100.0284 (9)0.0451 (10)0.0254 (9)−0.0118 (8)−0.0012 (7)−0.0045 (7)
C110.0282 (8)0.0346 (9)0.0315 (9)−0.0123 (7)0.0064 (7)−0.0049 (7)
C120.0217 (7)0.0249 (8)0.0288 (9)−0.0027 (6)0.0080 (6)−0.0026 (6)
C130.0280 (8)0.0266 (8)0.0346 (9)−0.0066 (7)0.0129 (7)0.0012 (7)
C140.0283 (8)0.0263 (8)0.0295 (8)−0.0013 (6)0.0128 (7)0.0066 (6)
C150.0204 (7)0.0248 (7)0.0213 (7)0.0005 (6)0.0071 (6)0.0035 (6)
C160.0172 (6)0.0203 (7)0.0202 (7)−0.0001 (5)0.0054 (5)−0.0020 (5)

Geometric parameters (Å, °)

Fe1—O11.8648 (11)C5—H50.9500
Fe1—N11.9347 (13)C6—C71.428 (2)
Fe1—N21.9680 (12)C7—H70.9500
O1—C11.3201 (17)C8—C91.375 (2)
N1—C71.3031 (19)C8—C161.422 (2)
N1—C81.4222 (19)C9—C101.407 (2)
N2—C151.3276 (19)C9—H90.9500
N2—C161.3650 (18)C10—C111.384 (3)
N3—N41.1750 (17)C10—H100.9500
N3—N4i1.1750 (17)C11—C121.408 (2)
C1—C21.407 (2)C11—H110.9500
C1—C61.419 (2)C12—C131.418 (2)
C2—C31.383 (2)C12—C161.408 (2)
C2—H20.9500C13—H130.9500
C3—H30.9500C14—C131.358 (2)
C4—C31.394 (3)C15—C141.406 (2)
C4—C51.372 (3)C14—H140.9500
C4—H40.9500C15—H150.9500
C5—C61.413 (2)
O1—Fe1—O1ii96.10 (7)C4—C5—H5119.3
O1—Fe1—N195.31 (5)C6—C5—H5119.3
O1—Fe1—N1ii86.29 (5)C1—C6—C5119.50 (14)
O1ii—Fe1—N186.29 (5)C1—C6—C7123.74 (14)
O1ii—Fe1—N1ii95.31 (5)C5—C6—C7116.72 (14)
O1—Fe1—N2174.51 (5)N1—C7—C6124.24 (14)
O1—Fe1—N2ii89.09 (5)N1—C7—H7117.9
O1ii—Fe1—N289.09 (5)C6—C7—H7117.9
O1ii—Fe1—N2ii174.51 (5)N1—C8—C9128.20 (14)
N1ii—Fe1—N1177.62 (7)N1—C8—C16112.74 (13)
N1—Fe1—N283.19 (5)C9—C8—C16119.05 (14)
N1—Fe1—N2ii95.05 (5)C8—C9—C10120.01 (16)
N1ii—Fe1—N295.05 (5)C8—C9—H9120.0
N1ii—Fe1—N2ii83.19 (5)C10—C9—H9120.0
N2ii—Fe1—N285.79 (7)C9—C10—C11121.43 (16)
Fe1—O1—C1126.18 (10)C9—C10—H10119.3
Fe1—N1—C7125.36 (11)C11—C10—H10119.3
Fe1—N1—C8114.10 (10)C10—C11—C12119.83 (16)
C7—N1—C8120.54 (13)C10—C11—H11120.1
Fe1—N2—C15127.71 (10)C12—C11—H11120.1
Fe1—N2—C16113.05 (9)C11—C12—C13124.08 (16)
C15—N2—C16119.21 (13)C11—C12—C16118.54 (15)
N4—N3—N4i180.0 (3)C13—C12—C16117.39 (15)
O1—C1—C2117.04 (14)C12—C13—C14119.44 (15)
O1—C1—C6124.95 (14)C14—C13—H13120.3
C2—C1—C6118.00 (14)C12—C13—H13120.3
C1—C2—C3120.89 (16)C13—C14—C15120.09 (15)
C1—C2—H2119.6C13—C14—H14120.0
C3—C2—H2119.6C15—C14—H14120.0
C2—C3—C4121.17 (16)N2—C15—C14121.80 (14)
C2—C3—H3119.4N2—C15—H15119.1
C4—C3—H3119.4C14—C15—H15119.1
C3—C4—C5119.02 (16)N2—C16—C12122.03 (14)
C5—C4—H4120.5N2—C16—C8116.85 (13)
C3—C4—H4120.5C8—C16—C12121.12 (14)
C4—C5—C6121.37 (16)
O1ii—Fe1—O1—C186.71 (12)C15—N2—C16—C12−0.3 (2)
N1—Fe1—O1—C1−0.11 (13)O1—C1—C2—C3178.95 (16)
N1ii—Fe1—O1—C1−178.34 (13)C6—C1—C2—C3−1.6 (3)
O1—Fe1—N1—C73.95 (13)O1—C1—C6—C5−178.78 (16)
O1ii—Fe1—N1—C7−91.84 (13)O1—C1—C6—C73.5 (2)
O1—Fe1—N1—C8−176.17 (10)C2—C1—C6—C51.9 (2)
O1ii—Fe1—N1—C888.04 (10)C2—C1—C6—C7−175.91 (15)
N2—Fe1—N1—C7178.64 (13)C1—C2—C3—C4−0.2 (3)
N2ii—Fe1—N1—C793.51 (13)C2—C3—C4—C51.7 (3)
N2—Fe1—N1—C8−1.49 (10)C3—C4—C5—C6−1.5 (3)
N2ii—Fe1—N1—C8−86.62 (10)C4—C5—C6—C1−0.3 (3)
O1ii—Fe1—N2—C1595.66 (13)C4—C5—C6—C7177.60 (17)
N1—Fe1—N2—C15−177.97 (13)C1—C6—C7—N10.8 (2)
N1ii—Fe1—N2—C150.41 (13)C5—C6—C7—N1−177.02 (15)
N2ii—Fe1—N2—C15−82.36 (13)N1—C8—C9—C10−178.44 (16)
O1ii—Fe1—N2—C16−86.28 (10)C16—C8—C9—C100.5 (2)
N1—Fe1—N2—C160.09 (10)N1—C8—C16—N2−2.56 (19)
N1ii—Fe1—N2—C16178.47 (10)N1—C8—C16—C12177.32 (13)
N2ii—Fe1—N2—C1695.70 (11)C9—C8—C16—N2178.36 (14)
Fe1—O1—C1—C2176.17 (11)C9—C8—C16—C12−1.8 (2)
Fe1—O1—C1—C6−3.2 (2)C8—C9—C10—C110.8 (3)
Fe1—N1—C7—C6−4.7 (2)C9—C10—C11—C12−0.9 (3)
C8—N1—C7—C6175.48 (14)C10—C11—C12—C13179.10 (17)
Fe1—N1—C8—C9−178.46 (14)C10—C11—C12—C16−0.4 (3)
Fe1—N1—C8—C162.56 (16)C11—C12—C13—C14178.80 (17)
C7—N1—C8—C91.4 (2)C16—C12—C13—C14−1.7 (2)
C7—N1—C8—C16−177.56 (13)C11—C12—C16—N2−178.43 (15)
Fe1—N2—C15—C14176.08 (11)C11—C12—C16—C81.7 (2)
C16—N2—C15—C14−1.9 (2)C13—C12—C16—N22.1 (2)
Fe1—N2—C16—C81.35 (16)C13—C12—C16—C8−177.80 (14)
Fe1—N2—C16—C12−178.52 (11)C12—C13—C14—C15−0.3 (3)
C15—N2—C16—C8179.59 (13)C13—C14—C15—N22.2 (2)

Symmetry codes: (i) −x+1/2, y, −z+5/2; (ii) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···O1iii0.952.703.565 (2)151
C15—H15···N4ii0.952.453.299 (2)149

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2271).

References

  • Hayami, S., Gu, Z.-Z., Yoshiki, H., Fujishima, A. & Sato, O. (2001). J. Am. Chem. Soc.123, 11644–11650. [PubMed]
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Nihei, M., Shiga, T., Maeda, Y. & Oshio, H. (2007). Coord. Chem. Rev.251, 2606–2621.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku (2002). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Takahashi, K., Cui, H.-B., Okano, Y., Kobayashi, H., Einaga, Y. & Sato, O. (2006). Inorg. Chem.45, 5739–5741. [PubMed]
  • Wakita, K. (2000). Yadokari-XG Department of Chemistry, Graduate School of Science, The University of Tokyo, Japan.

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