1,3-Dimethyl-1H-1,2,3-benzotriazol-3-ium tetra­chloridoferrate(III)

Abstract

The asymmetric unit of the title salt, (C₈H₁₀N₃)[FeCl₄], contains one 1,3-dimethyl-1H-1,2,3-benzotriazol-3-ium cation and one tetra­chloridoferrate anion. The Fe^III atom in the anion is tetra­hedrally coordinated by four Cl atoms. In the crystal, inter­actions are observed between the Cl atoms and the triazolium ring [Cl⋯centroid distances = 3.587 (3) and 3.866 (3) Å].

Related literature  

For related iron complexes, see: Hay et al. (2003 ▶); Liu et al. (2000 ▶); Lorenz et al. (2000 ▶); Shapley et al. (2003 ▶).

Experimental  

Crystal data  

• (C₈H₁₀N₃)[FeCl₄]

• M _r = 345.84

• Orthorhombic,

• a = 10.2920 (5) Å

• b = 12.5518 (6) Å

• c = 22.5857 (9) Å

• V = 2917.7 (2) ų

• Z = 8

• Mo Kα radiation

• μ = 1.74 mm⁻¹

• T = 293 K

• 0.32 × 0.28 × 0.25 mm

Data collection  

• Oxford Diffraction SuperNova (Dual, Cu at zero, Eos) diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012 ▶) T _min = 0.578, T _max = 0.647

• 8114 measured reflections

• 3016 independent reflections

• 1828 reflections with I > 2σ(I)

• R _int = 0.031

Refinement  

• R[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 0.183

• S = 1.05

• 3016 reflections

• 147 parameters

• H-atom parameters constrained

• Δρ_max = 0.53 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Supplementary Material

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

supplementary crystallographic information

Comment

Iron-containing compounds are ubiquitous throughout the field of coordination chemistry. Recently, a variety of iron compounds have been added to the list of iron coordination complexes (Hay et al., 2003; Liu et al., 2000; Lorenz et al., 2000; Shapley et al., 2003).

In the title compound (Fig. 1), the Fe^III atom in the [FeCl₄]^- anion is four-coordinated in a distorted tetrahedral geometry. The Cl—Fe—Cl bond angles are in the range of 108.35 (6)–111.33 (8) °, while the Fe—Cl bond lengths are in the range of 2.1634 (17)–2.1867 (14) Å. Three Cl—Fe—Cl angles are smaller than tetrahedral and the other three are greater than tetrahedral one. In the crystal, interactions between the Cl atoms and the triazolium rings are present [Cl···centroid distances = 3.587 (3) and 3.866 (3) Å].

Experimental

FeCl₃.6H₂O (0.1 mmol, 27.0 mg) was dissolved in 15 ml CH₃OH. To this yellow solution, one equivalent of 1,3-dimethyl-1H-benzo[1,2,3]triazolenium chlorate (0.1 mmol, 18.4 mg) was added with stirring. The mixture was filtered and held at room temperature to allow slow evaporation of solvent after stirring 30 min. Block crystals suitable for X-ray diffraction were obtained after one week (yield: 64%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.96 Å (CH₃), and with U_iso(H) = 1.5U_eq(C) for methyl groups or 1.2U_eq(C) otherwise.

Figures

Fig. 1.

Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Crystal packing of the title compound viewed along the a axis.

Crystal data

(C8H10N3)[FeCl4]	F(000) = 1384
Mr = 345.84	Dx = 1.575 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1751 reflections
a = 10.2920 (5) Å	θ = 3.1–28.5°
b = 12.5518 (6) Å	µ = 1.74 mm−1
c = 22.5857 (9) Å	T = 293 K
V = 2917.7 (2) Å3	Block, yellow
Z = 8	0.32 × 0.28 × 0.25 mm

Data collection

Oxford Diffraction SuperNova (Dual, Cu at zero, Eos) diffractometer	3016 independent reflections
Radiation source: fine-focus sealed tube	1828 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 16.0733 pixels mm-1	θmax = 26.5°, θmin = 3.1°
ω scans	h = −12→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012)	k = −15→12
Tmin = 0.578, Tmax = 0.647	l = −28→28
8114 measured reflections

Refinement

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0779P)2 + 1.072P] where P = (Fo2 + 2Fc2)/3
3016 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2130 (5)	0.5085 (4)	0.3377 (2)	0.0934 (14)
N2	0.1550 (5)	0.5572 (4)	0.3863 (2)	0.0907 (14)
N3	0.2259 (5)	0.5203 (4)	0.4309 (2)	0.0912 (13)
C1	0.3237 (4)	0.4541 (4)	0.4130 (2)	0.0650 (11)
C2	0.4177 (6)	0.3997 (5)	0.4452 (2)	0.0927 (17)
H2	0.4238	0.4034	0.4863	0.111*
C3	0.5016 (6)	0.3393 (5)	0.4106 (3)	0.0986 (17)
H3	0.5669	0.3006	0.4293	0.118*
C4	0.4922 (6)	0.3345 (6)	0.3510 (3)	0.1023 (18)
H4	0.5522	0.2937	0.3302	0.123*
C5	0.3950 (6)	0.3889 (5)	0.3193 (2)	0.0877 (16)
H5	0.3874	0.3845	0.2783	0.105*
C6	0.3140 (6)	0.4478 (5)	0.3524 (2)	0.0823 (15)
C7	0.1582 (6)	0.5291 (6)	0.2780 (3)	0.124 (3)
H7A	0.1317	0.4630	0.2604	0.186*
H7B	0.2230	0.5622	0.2535	0.186*
H7C	0.0844	0.5755	0.2814	0.186*
C8	0.1916 (6)	0.5507 (5)	0.4913 (2)	0.111 (2)
H8A	0.1229	0.6023	0.4903	0.166*
H8B	0.2662	0.5808	0.5106	0.166*
H8C	0.1632	0.4888	0.5127	0.166*
Fe1	0.53140 (7)	0.75129 (5)	0.36820 (3)	0.0621 (3)
Cl1	0.40700 (15)	0.76662 (12)	0.44622 (6)	0.0934 (5)
Cl2	0.6707 (2)	0.62448 (18)	0.38165 (8)	0.1478 (9)
Cl3	0.63300 (15)	0.90130 (13)	0.35368 (7)	0.0997 (5)
Cl4	0.40818 (16)	0.71994 (13)	0.29142 (6)	0.1007 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.089 (3)	0.084 (3)	0.108 (4)	−0.025 (3)	−0.029 (3)	0.027 (3)
N2	0.086 (3)	0.079 (3)	0.107 (4)	−0.005 (3)	−0.020 (3)	0.016 (3)
N3	0.094 (3)	0.083 (3)	0.097 (3)	−0.019 (3)	0.010 (3)	−0.012 (3)
C1	0.064 (3)	0.070 (3)	0.060 (3)	−0.009 (2)	0.001 (2)	0.004 (2)
C2	0.105 (4)	0.108 (4)	0.064 (3)	−0.027 (4)	−0.012 (3)	0.008 (3)
C3	0.100 (4)	0.116 (5)	0.080 (4)	0.019 (4)	−0.001 (3)	0.007 (4)
C4	0.097 (4)	0.127 (5)	0.083 (4)	0.001 (4)	0.002 (3)	−0.012 (4)
C5	0.105 (4)	0.108 (4)	0.050 (3)	−0.030 (3)	0.009 (3)	−0.009 (3)
C6	0.089 (4)	0.087 (4)	0.071 (3)	−0.036 (3)	−0.003 (3)	0.003 (3)
C7	0.127 (5)	0.136 (6)	0.110 (5)	−0.039 (4)	−0.062 (4)	0.046 (4)
C8	0.130 (5)	0.109 (5)	0.093 (4)	−0.037 (4)	0.042 (4)	−0.043 (4)
Fe1	0.0725 (5)	0.0589 (5)	0.0548 (4)	0.0043 (3)	0.0006 (3)	0.0041 (3)
Cl1	0.1005 (10)	0.1047 (11)	0.0749 (9)	0.0156 (8)	0.0246 (8)	0.0135 (7)
Cl2	0.1852 (19)	0.1443 (18)	0.1138 (14)	0.1036 (16)	0.0155 (12)	0.0183 (11)
Cl3	0.1123 (11)	0.1022 (11)	0.0847 (10)	−0.0438 (9)	−0.0079 (8)	0.0060 (8)
Cl4	0.1173 (11)	0.1100 (11)	0.0748 (9)	−0.0393 (9)	−0.0193 (8)	0.0016 (8)

Geometric parameters (Å, º)

N1—C6	1.332 (7)	C4—H4	0.9300
N1—N2	1.390 (7)	C5—C6	1.342 (7)
N1—C7	1.485 (7)	C5—H5	0.9300
N2—N3	1.327 (6)	C7—H7A	0.9600
N3—C1	1.367 (6)	C7—H7B	0.9600
N3—C8	1.460 (6)	C7—H7C	0.9600
C1—C6	1.373 (7)	C8—H8A	0.9600
C1—C2	1.390 (7)	C8—H8B	0.9600
C2—C3	1.390 (8)	C8—H8C	0.9600
C2—H2	0.9300	Fe1—Cl2	2.1636 (17)
C3—C4	1.351 (8)	Fe1—Cl3	2.1786 (15)
C3—H3	0.9300	Fe1—Cl4	2.1840 (14)
C4—C5	1.408 (8)	Fe1—Cl1	2.1867 (15)
C6—N1—N2	112.9 (5)	N1—C6—C5	131.3 (6)
C6—N1—C7	128.6 (6)	N1—C6—C1	105.8 (5)
N2—N1—C7	118.5 (5)	C5—C6—C1	122.9 (6)
N3—N2—N1	102.2 (4)	N1—C7—H7A	109.5
N2—N3—C1	113.1 (5)	N1—C7—H7B	109.5
N2—N3—C8	119.1 (5)	H7A—C7—H7B	109.5
C1—N3—C8	127.9 (5)	N1—C7—H7C	109.5
N3—C1—C6	106.1 (5)	H7A—C7—H7C	109.5
N3—C1—C2	131.0 (5)	H7B—C7—H7C	109.5
C6—C1—C2	122.9 (5)	N3—C8—H8A	109.5
C3—C2—C1	113.9 (5)	N3—C8—H8B	109.5
C3—C2—H2	123.0	H8A—C8—H8B	109.5
C1—C2—H2	123.0	N3—C8—H8C	109.5
C4—C3—C2	122.7 (5)	H8A—C8—H8C	109.5
C4—C3—H3	118.6	H8B—C8—H8C	109.5
C2—C3—H3	118.6	Cl2—Fe1—Cl3	109.81 (10)
C3—C4—C5	122.4 (6)	Cl2—Fe1—Cl4	111.32 (8)
C3—C4—H4	118.8	Cl3—Fe1—Cl4	108.36 (6)
C5—C4—H4	118.8	Cl2—Fe1—Cl1	109.85 (7)
C6—C5—C4	115.1 (5)	Cl3—Fe1—Cl1	109.04 (7)
C6—C5—H5	122.4	Cl4—Fe1—Cl1	108.41 (7)
C4—C5—H5	122.4
C6—N1—N2—N3	−1.1 (5)	C3—C4—C5—C6	1.3 (8)
C7—N1—N2—N3	179.0 (4)	N2—N1—C6—C5	−179.6 (5)
N1—N2—N3—C1	0.9 (5)	C7—N1—C6—C5	0.4 (9)
N1—N2—N3—C8	−177.7 (4)	N2—N1—C6—C1	0.9 (5)
N2—N3—C1—C6	−0.4 (5)	C7—N1—C6—C1	−179.2 (5)
C8—N3—C1—C6	178.0 (5)	C4—C5—C6—N1	180.0 (5)
N2—N3—C1—C2	−179.8 (5)	C4—C5—C6—C1	−0.6 (7)
C8—N3—C1—C2	−1.4 (8)	N3—C1—C6—N1	−0.3 (5)
N3—C1—C2—C3	180.0 (5)	C2—C1—C6—N1	179.2 (5)
C6—C1—C2—C3	0.7 (7)	N3—C1—C6—C5	−179.9 (5)
C1—C2—C3—C4	0.1 (8)	C2—C1—C6—C5	−0.4 (7)
C2—C3—C4—C5	−1.1 (9)