Literature DB >> 21522247

Tris(4,4'-bi-1,3-thia-zole-κN,N')iron(II) tetra-bromidoferrate(III) bromide.

Anita Abedi, Vahid Amani, Nasser Safari.

Abstract

In the [Fe(4,4'-bit)(3)](2+) (4,4'-bit is 4,4'-bi-1,3-thia-zole) cation of the title compound, [Fe(C(6)H(4)N(2)S(2))(3)][FeBr(4)]Br, the Fe(II) atom (3 symmetry) is six-coordinated in a distorted octa-hedral geometry by six N atoms from three 4,4'-bit ligands. In the [FeBr(4)](-) anion, the Fe(III) atom (3 symmetry) is four-coordinated in a distorted tetra-hedral geometry. In the crystal, inter-molecular C-H⋯Br hydrogen bonds and Br⋯π inter-actions [Br⋯centroid distances = 3.562 (3) and 3.765 (2) Å] link the cations and anions, stabilizing the structure.

Entities: Chemical Disease Species

Year: 2011 PMID： 21522247 PMCID： PMC3052137 DOI： 10.1107/S1600536811004181

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For general background to metal complexes with 4,4′-bi-1,3-thiazole ligands, see: Baker & Goodwin (1985 ▶); Mahjoub & Morsali (2001 ▶, 2002a ▶,b ▶). For related structures, see: Al-Hashemi et al. (2009 ▶); Ali & Al-Far (2007 ▶); Amani et al. (2007a ▶,b ▶, 2009 ▶); Craig et al. (1988 ▶); Figgis et al. (1983 ▶); Jia et al. (2006 ▶); Khavasi et al. (2008 ▶); Kulkarni et al. (1998 ▶); Notash et al. (2008 ▶, 2009 ▶); Rahimi et al. (2009 ▶); Safari et al. (2009 ▶). For the synthesis of the ligand, see: Erlenmeyer & Ueberwasser (1939 ▶).

Experimental

Crystal data

[Fe(C6H4N2S2)3][FeBr4]Br M = 1015.95 Trigonal, a = 12.0638 (7) Å c = 17.6907 (13) Å V = 2229.7 (2) Å3 Z = 3 Mo Kα radiation μ = 8.14 mm−1 T = 100 K 0.45 × 0.35 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.031, T max = 0.086 8430 measured reflections 2508 independent reflections 2427 reflections with I > 2σ(I) R int = 0.099

Refinement

R[F 2 > 2σ(F 2)] = 0.036 wR(F 2) = 0.085 S = 1.01 2508 reflections 112 parameters 1 restraint H-atom parameters constrained Δρmax = 0.93 e Å−3 Δρmin = −0.78 e Å−3 Absolute structure: Flack (1983 ▶), 1195 Friedel pairs Flack parameter: 0.021 (9) Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004181/hy2404sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004181/hy2404Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe(C₆H₄N₂S₂)₃][FeBr₄]Br	D_x = 2.270 Mg m⁻³
M_r = 1015.95	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1635 reflections
Hall symbol: R 3	θ = 3.0–28.0°
a = 12.0638 (7) Å	µ = 8.14 mm⁻¹
c = 17.6907 (13) Å	T = 100 K
V = 2229.7 (2) Å³	Prism, dark-red
Z = 3	0.45 × 0.35 × 0.30 mm
F(000) = 1455

Bruker APEXII CCD diffractometer	2508 independent reflections
Radiation source: fine-focus sealed tube	2427 reflections with I > 2σ(I)
graphite	R_int = 0.099
φ and ω scans	θ_max = 28.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
T_min = 0.031, T_max = 0.086	k = −16→16
8430 measured reflections	l = −24→23

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0485P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2508 reflections	Δρ_max = 0.93 e Å⁻³
112 parameters	Δρ_min = −0.78 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1195 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.021 (9)

	x	y	z	U_iso*/U_eq
Br1	0.53314 (4)	0.70585 (5)	0.46767 (3)	0.02946 (13)
Br2	0.3333	0.6667	0.64196 (3)	0.01401 (14)
Br3	1.6667	1.3333	0.53208 (4)	0.01483 (14)
Fe1	1.0000	1.0000	0.48640 (5)	0.00941 (17)
Fe2	0.3333	0.6667	0.50986 (6)	0.01351 (18)
S1	1.25908 (10)	1.31480 (10)	0.64504 (6)	0.0182 (2)
S2	1.33303 (9)	1.07879 (10)	0.33584 (6)	0.01552 (19)
N1	1.1247 (3)	1.1426 (3)	0.54875 (19)	0.0120 (6)
N2	1.1543 (3)	1.0443 (3)	0.42603 (19)	0.0121 (6)
C1	1.1756 (4)	1.0038 (4)	0.3613 (2)	0.0141 (7)
H1A	1.1107	0.9401	0.3323	0.017*
C2	1.3758 (4)	1.1697 (4)	0.4169 (2)	0.0161 (7)
H2A	1.4589	1.2296	0.4310	0.019*
C3	1.2677 (4)	1.1394 (4)	0.4572 (2)	0.0132 (7)
C4	1.2524 (4)	1.1950 (4)	0.5268 (2)	0.0127 (7)
C5	1.3381 (4)	1.2906 (4)	0.5716 (3)	0.0185 (8)
H5A	1.4262	1.3361	0.5639	0.022*
C6	1.1159 (4)	1.1969 (4)	0.6109 (2)	0.0154 (7)
H6A	1.0383	1.1732	0.6345	0.019*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0213 (2)	0.0518 (3)	0.0176 (2)	0.0201 (2)	0.00229 (16)	−0.0064 (2)
Br2	0.01593 (18)	0.01593 (18)	0.0102 (3)	0.00796 (9)	0.000	0.000
Br3	0.01604 (19)	0.01604 (19)	0.0124 (3)	0.00802 (9)	0.000	0.000
Fe1	0.0096 (2)	0.0096 (2)	0.0090 (4)	0.00479 (11)	0.000	0.000
Fe2	0.0153 (3)	0.0153 (3)	0.0099 (4)	0.00764 (13)	0.000	0.000
S1	0.0184 (4)	0.0170 (4)	0.0170 (5)	0.0072 (4)	−0.0042 (4)	−0.0073 (4)
S2	0.0162 (4)	0.0198 (4)	0.0128 (4)	0.0107 (3)	0.0037 (3)	0.0013 (3)
N1	0.0113 (13)	0.0118 (14)	0.0122 (14)	0.0052 (12)	0.0016 (11)	0.0003 (11)
N2	0.0143 (14)	0.0143 (14)	0.0102 (13)	0.0090 (12)	0.0021 (12)	0.0016 (12)
C1	0.0135 (16)	0.0138 (16)	0.0157 (17)	0.0074 (14)	0.0000 (13)	−0.0008 (13)
C2	0.0161 (16)	0.0175 (17)	0.0139 (18)	0.0078 (14)	0.0027 (14)	0.0035 (14)
C3	0.0173 (17)	0.0131 (15)	0.0134 (16)	0.0106 (14)	0.0009 (13)	0.0036 (13)
C4	0.0156 (16)	0.0101 (15)	0.0126 (16)	0.0065 (13)	0.0010 (13)	0.0001 (12)
C5	0.0168 (17)	0.0198 (19)	0.0192 (19)	0.0092 (15)	−0.0020 (14)	−0.0002 (15)
C6	0.0135 (16)	0.0148 (17)	0.0151 (17)	0.0048 (13)	−0.0024 (14)	−0.0020 (13)

Fe1—N1	1.962 (3)	N2—C1	1.320 (5)
Fe1—N2	1.974 (3)	N2—C3	1.385 (5)
Fe2—Br1	2.3348 (5)	C1—H1A	0.9300
Fe2—Br2	2.3370 (12)	C2—C3	1.366 (6)
S1—C6	1.706 (4)	C2—H2A	0.9300
S1—C5	1.721 (4)	C3—C4	1.458 (5)
S2—C1	1.706 (4)	C4—C5	1.355 (6)
S2—C2	1.720 (4)	C5—H5A	0.9300
N1—C6	1.312 (5)	C6—H6A	0.9300
N1—C4	1.396 (5)

N1—Fe1—N1ⁱ	91.50 (14)	C6—N1—Fe1	133.8 (3)
N1—Fe1—N1ⁱⁱ	91.50 (14)	C4—N1—Fe1	115.4 (3)
N1ⁱ—Fe1—N1ⁱⁱ	91.50 (14)	C1—N2—C3	111.0 (3)
N1—Fe1—N2ⁱ	171.87 (13)	C1—N2—Fe1	134.5 (3)
N1ⁱ—Fe1—N2ⁱ	82.00 (14)	C3—N2—Fe1	114.6 (3)
N1ⁱⁱ—Fe1—N2ⁱ	93.53 (13)	N2—C1—S2	113.8 (3)
N1—Fe1—N2	82.00 (14)	N2—C1—H1A	123.1
N1ⁱ—Fe1—N2	93.53 (13)	S2—C1—H1A	123.1
N1ⁱⁱ—Fe1—N2	171.87 (13)	C3—C2—S2	108.8 (3)
N2ⁱ—Fe1—N2	93.49 (14)	C3—C2—H2A	125.6
N1—Fe1—N2ⁱⁱ	93.53 (13)	S2—C2—H2A	125.6
N1ⁱ—Fe1—N2ⁱⁱ	171.87 (14)	C2—C3—N2	115.4 (3)
N1ⁱⁱ—Fe1—N2ⁱⁱ	82.00 (14)	C2—C3—C4	129.9 (4)
N2ⁱ—Fe1—N2ⁱⁱ	93.49 (14)	N2—C3—C4	114.7 (3)
N2—Fe1—N2ⁱⁱ	93.49 (14)	C5—C4—N1	115.0 (4)
Br1ⁱⁱⁱ—Fe2—Br1^iv	110.29 (3)	C5—C4—C3	131.9 (4)
Br1ⁱⁱⁱ—Fe2—Br1	110.29 (3)	N1—C4—C3	113.0 (3)
Br1^iv—Fe2—Br1	110.29 (3)	C4—C5—S1	109.5 (3)
Br1ⁱⁱⁱ—Fe2—Br2	108.64 (3)	C4—C5—H5A	125.2
Br1^iv—Fe2—Br2	108.64 (3)	S1—C5—H5A	125.2
Br1—Fe2—Br2	108.64 (3)	N1—C6—S1	114.3 (3)
C6—S1—C5	90.4 (2)	N1—C6—H6A	122.8
C1—S2—C2	91.01 (19)	S1—C6—H6A	122.8
C6—N1—C4	110.7 (3)

N1ⁱ—Fe1—N1—C6	−86.9 (3)	S2—C2—C3—N2	1.7 (4)
N1ⁱⁱ—Fe1—N1—C6	4.6 (4)	S2—C2—C3—C4	−175.8 (3)
N2—Fe1—N1—C6	179.8 (4)	C1—N2—C3—C2	−1.2 (5)
N2ⁱⁱ—Fe1—N1—C6	86.7 (4)	Fe1—N2—C3—C2	178.8 (3)
N1ⁱ—Fe1—N1—C4	88.3 (3)	C1—N2—C3—C4	176.7 (3)
N1ⁱⁱ—Fe1—N1—C4	179.8 (3)	Fe1—N2—C3—C4	−3.3 (4)
N2—Fe1—N1—C4	−5.1 (3)	C6—N1—C4—C5	−1.7 (5)
N2ⁱⁱ—Fe1—N1—C4	−98.1 (3)	Fe1—N1—C4—C5	−178.0 (3)
N1—Fe1—N2—C1	−175.5 (4)	C6—N1—C4—C3	−179.1 (3)
N1ⁱ—Fe1—N2—C1	93.5 (4)	Fe1—N1—C4—C3	4.7 (4)
N2ⁱ—Fe1—N2—C1	11.3 (4)	C2—C3—C4—C5	−0.2 (7)
N2ⁱⁱ—Fe1—N2—C1	−82.4 (3)	N2—C3—C4—C5	−177.7 (4)
N1—Fe1—N2—C3	4.6 (3)	C2—C3—C4—N1	176.7 (4)
N1ⁱ—Fe1—N2—C3	−86.5 (3)	N2—C3—C4—N1	−0.8 (5)
N2ⁱ—Fe1—N2—C3	−168.6 (3)	N1—C4—C5—S1	1.4 (5)
N2ⁱⁱ—Fe1—N2—C3	97.6 (3)	C3—C4—C5—S1	178.2 (3)
C3—N2—C1—S2	0.0 (4)	C6—S1—C5—C4	−0.6 (3)
Fe1—N2—C1—S2	−180.0 (2)	C4—N1—C6—S1	1.2 (4)
C2—S2—C1—N2	0.8 (3)	Fe1—N1—C6—S1	176.5 (2)
C1—S2—C2—C3	−1.4 (3)	C5—S1—C6—N1	−0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Br3	0.93	2.81	3.665 (5)	153
C5—H5A···Br3	0.93	2.97	3.798 (5)	149

Table 1

Selected bond lengths (Å)

Fe1—N1	1.962 (3)
Fe1—N2	1.974 (3)
Fe2—Br1	2.3348 (5)
Fe2—Br2	2.3370 (12)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Br3	0.93	2.81	3.665 (5)	153
C5—H5A⋯Br3	0.93	2.97	3.798 (5)	149

4 in total

1. A novel framework of N-H...Br hydrogen bonds forming Br(4,4'-bipyridinium)(4) supramolecular synthons: bis(4,4'-bipyridinium) tris[tetrabromidoferrate(III)] bromide.

Authors: Basem Fares Ali; Rawhi Al-Far
Journal: Acta Crystallogr C Date: 2007-09-22 Impact factor: 1.172