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

Sun, Z.; Hu, D.-C.; Liu, J.-C.

doi:10.1107/S1600536813003711

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page m148

doi:10.1107/S1600536813003711

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

Zan Sun,^a Dong-Cheng Hu ^a and Jia-Cheng Liu ^a ^*

^aKey Laboratory of Eco-Environment-Related Polymer Materials of the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: jcliu8@nwnu.edu.cn

(Received 26 January 2013; accepted 6 February 2013; online 13 February 2013)

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, P b c a
a = 10.2920 (5) Å
b = 12.5518 (6) Å
c = 22.5857 (9) Å
V = 2917.7 (2) Å³
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 $[Oxford Diffraction (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]$ ) 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[F² > 2σ(F²)] = 0.057
wR(F²) = 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 $[Oxford Diffraction (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813003711/hy2615sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003711/hy2615Isup2.hkl

checkCIF report

Comment top

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].

Related literature top

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

Experimental top

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%).

Computing details top

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

	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.

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

Crystal data top

(C₈H₁₀N₃)[FeCl₄]	F(000) = 1384
M_r = 345.84	D_x = 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 top

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	R_int = 0.031
Detector resolution: 16.0733 pixels mm^-1	θ_max = 26.5°, θ_min = 3.1°
ω scans	h = −12→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012)	k = −15→12
T_min = 0.578, T_max = 0.647	l = −28→28
8114 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0779P)² + 1.072P] where P = (F_o² + 2F_c²)/3
3016 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

(C₈H₁₀N₃)[FeCl₄]	V = 2917.7 (2) Å³
M_r = 345.84	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.2920 (5) Å	µ = 1.74 mm⁻¹
b = 12.5518 (6) Å	T = 293 K
c = 22.5857 (9) Å	0.32 × 0.28 × 0.25 mm

Data collection top

Oxford Diffraction SuperNova (Dual, Cu at zero, Eos) diffractometer	3016 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012)	1828 reflections with I > 2σ(I)
T_min = 0.578, T_max = 0.647	R_int = 0.031
8114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.183	H-atom parameters constrained
S = 1.05	Δρ_max = 0.53 e Å⁻³
3016 reflections	Δρ_min = −0.39 e Å⁻³
147 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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)

Experimental details

Crystal data
Chemical formula	(C₈H₁₀N₃)[FeCl₄]
M_r	345.84
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.2920 (5), 12.5518 (6), 22.5857 (9)
V (Å³)	2917.7 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.74
Crystal size (mm)	0.32 × 0.28 × 0.25

Data collection
Diffractometer	Oxford Diffraction SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2012)
T_min, T_max	0.578, 0.647
No. of measured, independent and observed [I > 2σ(I)] reflections	8114, 3016, 1828
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.183, 1.05
No. of reflections	3016
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.39

Computer programs: CrysAlis PRO (Oxford Diffraction, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We are thankful for support of this study by the National Natural Science Foundation of China (grant No. J0730425) and the Gansu Provincial Natural Science Foundation of China (grant No. 0710RJZA113).

References

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