catena-Poly[[dichloridoiron(II)]-μ-4,4′′-bis­(benzimidazol-1-yl)-1,1′:4′,1′′-terphen­yl]

Li, H.; Wei, Z.; Gong, Q.; Han, Q.

doi:10.1107/S1600536810002837

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m267

doi:10.1107/S1600536810002837

Open

access

catena-Poly[[dichloridoiron(II)]-μ-4,4′′-bis(benzimidazol-1-yl)-1,1′:4′,1′′-terphenyl]

Hui Li,^a ^* Zhuangwei Wei,^a Qiaojuan Gong ^a and Qiuping Han ^a

^aDepartment of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, People's Republic of China
^*Correspondence e-mail: lihuiwf@yahoo.com

(Received 18 January 2010; accepted 22 January 2010; online 6 February 2010)

In the title coordination polymer, [FeCl₂(C₃₂H₂₂N₄)]_n, the Fe^II atom lies on a crystallographic twofold axis and a distorted FeCl₂N₂ tetrahedral coordination geometry arises. The complete ligand is generated by crystallographic twofold symmetry, resulting in an infinite one-dimensional architecture along [101].

Related literature

For background to benzimidazoles as ligands, see: Vijayan et al. (2006 ).

Experimental

Crystal data

[FeCl₂(C₃₂H₂₂N₄)]
M_r = 589.29
Monoclinic, C 2/c
a = 14.519 (3) Å
b = 14.303 (3) Å
c = 12.461 (3) Å
β = 101.94 (3)°
V = 2531.6 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.846, T_max = 0.882
9515 measured reflections
2218 independent reflections
1960 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.117
S = 1.12
2218 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N1	2.076 (2)
Fe1—Cl1	2.2489 (10)

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536810002837/hb5310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810002837/hb5310Isup2.hkl

checkCIF report

Comment top

Benzimidazole has been well used in crystal engineering, and a large number of benzimidazole-containing flexible ligands have been extensively studied. However, to our knowledge, the research on benzoimidazole ligands bearing rigid spacers is still less developed.

Single-crystal X-ray diffraction analysis reveals that the title compound crystallizes in the monoclinic space group C2/c. The geometry of the Fe^II ion is surrounded by two benzimidazole rings of distinct L ligands and two chlorine anions, which illustrates a slightly distorted tetrahedral coordination environment (Fig. 1). Notably, as shown in Fig. 2, the four-coordinated Fe^II center is bridged by the linear ligand L to form an infinite one-dimensional architecture along crystallographic [101] axis.

Related literature top

For background to benzimidazoles as ligands, see: Vijayan et al. (2006).

Experimental top

A mixture of (CH₃)₂CHOH and CHCl₃ (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of 4,4'-Bis(benzimidazol-1-yl)terphenyl (L, 0.06 mmol) in CHCl₃ (6 ml). Then a solution of FeCl₂ (0.02 mmol) in (CH₃)₂CHOH (6 ml) was layered over the buffer layer, and the resultant reaction was left to stand at room temperature. After ca three weeks, yellow blocks of (I) appeared at the boundary. Yield: ~10% (based on L).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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. A fragment of a polymeric chain in (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius.

catena-Poly[[dichloridoiron(II)]-µ- 4,4''-bis(benzimidazol-1-yl)-1,1':4',1''-terphenyl] top

Crystal data top

[FeCl₂(C₃₂H₂₂N₄)]	F(000) = 1208
M_r = 589.29	D_x = 1.546 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2574 reflections
a = 14.519 (3) Å	θ = 2.0–27.9°
b = 14.303 (3) Å	µ = 0.84 mm⁻¹
c = 12.461 (3) Å	T = 293 K
β = 101.94 (3)°	Block, yellow
V = 2531.6 (9) Å³	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2218 independent reflections
Radiation source: fine-focus sealed tube	1960 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 9 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ω scans	h = −17→16
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −16→15
T_min = 0.846, T_max = 0.882	l = −14→14
9515 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0565P)² + 2.1075P] where P = (F_o² + 2F_c²)/3
2218 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[FeCl₂(C₃₂H₂₂N₄)]	V = 2531.6 (9) Å³
M_r = 589.29	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.519 (3) Å	µ = 0.84 mm⁻¹
b = 14.303 (3) Å	T = 293 K
c = 12.461 (3) Å	0.20 × 0.18 × 0.15 mm
β = 101.94 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2218 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1960 reflections with I > 2σ(I)
T_min = 0.846, T_max = 0.882	R_int = 0.052
9515 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.12	Δρ_max = 0.35 e Å⁻³
2218 reflections	Δρ_min = −0.41 e Å⁻³
177 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Fe1	0.0000	1.12084 (4)	0.7500	0.0240 (2)
Cl1	0.02255 (6)	1.20219 (6)	0.90773 (8)	0.0423 (3)
N2	0.20786 (16)	0.96985 (16)	0.63670 (19)	0.0186 (6)
N1	0.10013 (17)	1.02547 (17)	0.72169 (19)	0.0207 (6)
C15	0.4708 (2)	0.8783 (2)	0.2868 (2)	0.0176 (6)
H15	0.4516	0.8216	0.3115	0.021*
C11	0.3788 (2)	0.9625 (2)	0.4047 (2)	0.0181 (6)
C14	0.4398 (2)	0.9609 (2)	0.3250 (2)	0.0185 (6)
C8	0.2661 (2)	0.9662 (2)	0.5587 (2)	0.0187 (6)
C13	0.3223 (2)	1.0412 (2)	0.5485 (2)	0.0183 (6)
H13	0.3231	1.0931	0.5937	0.022*
C3	0.1067 (2)	0.8921 (2)	0.8545 (2)	0.0213 (7)
H3	0.0598	0.9141	0.8887	0.026*
C10	0.3213 (2)	0.8878 (2)	0.4174 (3)	0.0228 (7)
H10	0.3212	0.8351	0.3736	0.027*
C1	0.1466 (2)	1.0385 (2)	0.6442 (2)	0.0203 (7)
H1	0.1381	1.0905	0.5984	0.024*
C9	0.2649 (2)	0.8892 (2)	0.4924 (3)	0.0233 (7)
H9	0.2261	0.8387	0.4986	0.028*
C16	0.4710 (2)	1.0437 (2)	0.2859 (2)	0.0199 (6)
H16	0.4514	1.1005	0.3098	0.024*
C7	0.2006 (2)	0.9061 (2)	0.7177 (2)	0.0171 (6)
C12	0.3767 (2)	1.0395 (2)	0.4721 (2)	0.0184 (6)
H12	0.4137	1.0913	0.4647	0.022*
C2	0.1330 (2)	0.9411 (2)	0.7698 (2)	0.0177 (6)
C5	0.2242 (2)	0.7782 (2)	0.8350 (2)	0.0245 (7)
H5	0.2559	0.7235	0.8605	0.029*
C6	0.2490 (2)	0.8247 (2)	0.7494 (2)	0.0212 (7)
H6	0.2957	0.8027	0.7149	0.025*
C4	0.1526 (2)	0.8102 (2)	0.8854 (2)	0.0235 (7)
H4	0.1360	0.7750	0.9412	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0229 (4)	0.0202 (4)	0.0323 (4)	0.000	0.0134 (3)	0.000
Cl1	0.0413 (6)	0.0368 (5)	0.0522 (6)	−0.0083 (4)	0.0174 (5)	−0.0199 (4)
N2	0.0184 (13)	0.0194 (13)	0.0205 (13)	0.0010 (10)	0.0099 (10)	0.0014 (10)
N1	0.0213 (14)	0.0203 (14)	0.0226 (13)	0.0014 (11)	0.0097 (11)	0.0035 (11)
C15	0.0176 (16)	0.0168 (15)	0.0187 (14)	−0.0018 (12)	0.0041 (12)	0.0017 (12)
C11	0.0186 (16)	0.0178 (15)	0.0182 (14)	0.0007 (12)	0.0043 (12)	0.0020 (12)
C14	0.0170 (15)	0.0204 (16)	0.0185 (14)	−0.0008 (12)	0.0047 (12)	0.0003 (12)
C8	0.0172 (15)	0.0216 (16)	0.0192 (14)	0.0036 (12)	0.0082 (12)	0.0026 (12)
C13	0.0190 (16)	0.0155 (15)	0.0203 (15)	0.0014 (12)	0.0041 (12)	−0.0030 (12)
C3	0.0202 (16)	0.0266 (17)	0.0182 (15)	−0.0030 (13)	0.0066 (12)	−0.0023 (13)
C10	0.0272 (18)	0.0191 (17)	0.0253 (16)	−0.0050 (13)	0.0125 (14)	−0.0069 (13)
C1	0.0193 (16)	0.0190 (16)	0.0242 (15)	0.0009 (13)	0.0081 (13)	0.0044 (13)
C9	0.0243 (17)	0.0193 (16)	0.0281 (17)	−0.0046 (13)	0.0097 (14)	−0.0021 (13)
C16	0.0224 (16)	0.0167 (15)	0.0218 (15)	−0.0004 (12)	0.0074 (12)	−0.0023 (12)
C7	0.0199 (16)	0.0134 (14)	0.0189 (14)	−0.0024 (12)	0.0057 (12)	0.0013 (12)
C12	0.0183 (16)	0.0171 (15)	0.0200 (14)	−0.0018 (12)	0.0044 (12)	0.0004 (12)
C2	0.0159 (15)	0.0170 (15)	0.0211 (15)	0.0003 (12)	0.0058 (12)	−0.0011 (12)
C5	0.0288 (18)	0.0147 (16)	0.0284 (17)	0.0007 (13)	0.0018 (14)	0.0025 (13)
C6	0.0203 (16)	0.0185 (16)	0.0257 (16)	0.0001 (13)	0.0066 (13)	−0.0037 (13)
C4	0.0315 (18)	0.0207 (16)	0.0181 (15)	−0.0060 (13)	0.0048 (13)	0.0024 (13)

Geometric parameters (Å, º) top

Fe1—N1ⁱ	2.076 (2)	C13—H13	0.9300
Fe1—N1	2.076 (2)	C3—C4	1.362 (4)
Fe1—Cl1ⁱ	2.2489 (10)	C3—C2	1.384 (4)
Fe1—Cl1	2.2489 (10)	C3—H3	0.9300
N2—C1	1.342 (4)	C10—C9	1.364 (4)
N2—C7	1.381 (4)	C10—H10	0.9300
N2—C8	1.415 (4)	C1—H1	0.9300
N1—C1	1.300 (4)	C9—H9	0.9300
N1—C2	1.388 (4)	C16—C16ⁱⁱ	1.349 (6)
C15—C15ⁱⁱ	1.373 (6)	C16—H16	0.9300
C15—C14	1.383 (4)	C7—C6	1.375 (4)
C15—H15	0.9300	C7—C2	1.379 (4)
C11—C10	1.386 (4)	C12—H12	0.9300
C11—C12	1.389 (4)	C5—C6	1.367 (4)
C11—C14	1.461 (4)	C5—C4	1.398 (4)
C14—C16	1.392 (4)	C5—H5	0.9300
C8—C13	1.368 (4)	C6—H6	0.9300
C8—C9	1.375 (4)	C4—H4	0.9300
C13—C12	1.358 (4)

N1ⁱ—Fe1—N1	97.86 (13)	C9—C10—C11	121.9 (3)
N1ⁱ—Fe1—Cl1ⁱ	120.53 (7)	C9—C10—H10	119.1
N1—Fe1—Cl1ⁱ	99.90 (7)	C11—C10—H10	119.1
N1ⁱ—Fe1—Cl1	99.90 (7)	N1—C1—N2	113.6 (3)
N1—Fe1—Cl1	120.53 (7)	N1—C1—H1	123.2
Cl1ⁱ—Fe1—Cl1	117.69 (6)	N2—C1—H1	123.2
C1—N2—C7	106.3 (2)	C10—C9—C8	119.3 (3)
C1—N2—C8	125.0 (2)	C10—C9—H9	120.4
C7—N2—C8	128.6 (2)	C8—C9—H9	120.4
C1—N1—C2	105.1 (2)	C16ⁱⁱ—C16—C14	121.72 (17)
C1—N1—Fe1	121.4 (2)	C16ⁱⁱ—C16—H16	119.1
C2—N1—Fe1	133.50 (19)	C14—C16—H16	119.1
C15ⁱⁱ—C15—C14	121.33 (17)	C6—C7—C2	122.9 (3)
C15ⁱⁱ—C15—H15	119.3	C6—C7—N2	131.2 (3)
C14—C15—H15	119.3	C2—C7—N2	105.9 (2)
C10—C11—C12	117.0 (3)	C13—C12—C11	121.8 (3)
C10—C11—C14	122.0 (3)	C13—C12—H12	119.1
C12—C11—C14	121.0 (3)	C11—C12—H12	119.1
C15—C14—C16	117.0 (3)	C7—C2—C3	120.7 (3)
C15—C14—C11	122.2 (3)	C7—C2—N1	109.1 (2)
C16—C14—C11	120.8 (3)	C3—C2—N1	130.2 (3)
C13—C8—C9	120.3 (3)	C6—C5—C4	122.1 (3)
C13—C8—N2	119.2 (3)	C6—C5—H5	118.9
C9—C8—N2	120.5 (3)	C4—C5—H5	118.9
C12—C13—C8	119.7 (3)	C5—C6—C7	115.8 (3)
C12—C13—H13	120.1	C5—C6—H6	122.1
C8—C13—H13	120.1	C7—C6—H6	122.1
C4—C3—C2	117.1 (3)	C3—C4—C5	121.3 (3)
C4—C3—H3	121.5	C3—C4—H4	119.3
C2—C3—H3	121.5	C5—C4—H4	119.3

N1ⁱ—Fe1—N1—C1	139.0 (3)	N2—C8—C9—C10	179.6 (3)
Cl1ⁱ—Fe1—N1—C1	16.0 (2)	C15—C14—C16—C16ⁱⁱ	−0.1 (5)
Cl1—Fe1—N1—C1	−114.6 (2)	C11—C14—C16—C16ⁱⁱ	178.6 (3)
N1ⁱ—Fe1—N1—C2	−40.2 (2)	C1—N2—C7—C6	−177.4 (3)
Cl1ⁱ—Fe1—N1—C2	−163.2 (3)	C8—N2—C7—C6	3.3 (5)
Cl1—Fe1—N1—C2	66.2 (3)	C1—N2—C7—C2	0.4 (3)
C15ⁱⁱ—C15—C14—C16	−0.3 (5)	C8—N2—C7—C2	−178.9 (3)
C15ⁱⁱ—C15—C14—C11	−179.0 (3)	C8—C13—C12—C11	−1.3 (4)
C10—C11—C14—C15	−23.9 (4)	C10—C11—C12—C13	1.1 (4)
C12—C11—C14—C15	155.5 (3)	C14—C11—C12—C13	−178.3 (3)
C10—C11—C14—C16	157.5 (3)	C6—C7—C2—C3	−3.6 (5)
C12—C11—C14—C16	−23.2 (4)	N2—C7—C2—C3	178.3 (3)
C1—N2—C8—C13	53.0 (4)	C6—C7—C2—N1	177.6 (3)
C7—N2—C8—C13	−127.8 (3)	N2—C7—C2—N1	−0.5 (3)
C1—N2—C8—C9	−125.7 (3)	C4—C3—C2—C7	2.0 (4)
C7—N2—C8—C9	53.5 (4)	C4—C3—C2—N1	−179.4 (3)
C9—C8—C13—C12	0.3 (4)	C1—N1—C2—C7	0.4 (3)
N2—C8—C13—C12	−178.4 (3)	Fe1—N1—C2—C7	179.6 (2)
C12—C11—C10—C9	0.1 (5)	C1—N1—C2—C3	−178.3 (3)
C14—C11—C10—C9	179.5 (3)	Fe1—N1—C2—C3	1.0 (5)
C2—N1—C1—N2	−0.1 (3)	C4—C5—C6—C7	1.4 (4)
Fe1—N1—C1—N2	−179.48 (19)	C2—C7—C6—C5	1.8 (4)
C7—N2—C1—N1	−0.2 (3)	N2—C7—C6—C5	179.3 (3)
C8—N2—C1—N1	179.1 (3)	C2—C3—C4—C5	1.1 (4)
C11—C10—C9—C8	−1.2 (5)	C6—C5—C4—C3	−2.9 (5)
C13—C8—C9—C10	0.9 (5)

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

Experimental details

Crystal data
Chemical formula	[FeCl₂(C₃₂H₂₂N₄)]
M_r	589.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.519 (3), 14.303 (3), 12.461 (3)
β (°)	101.94 (3)
V (Å³)	2531.6 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.846, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	9515, 2218, 1960
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.117, 1.12
No. of reflections	2218
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.41

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Fe1—N1

2.076 (2)

Fe1—Cl1

2.2489 (10)

Acknowledgements

We thank the College Research Program of Yuncheng University [2008114] for funding.

References

Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vijayan, N., Bhagavannarayana, G., Balamurugan, N., Babu, R. R., Maurya, K. K., Gopalakrishnan, R. & Ramasamy, P. (2006). J. Cryst. Growth, 293, 318–323. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.