Poly[bis­[μ₂-1,4-bis­(1H-imidazol-1-yl)butane]­dichloridonickel(II)]

Abstract

The asymmetric unit of the title compound, [NiCl₂(C₁₀H₁₄N₄)₂]_n, consists of one Ni²⁺ ion which is located on an inversion center, one 1,4-bis­(imidazol-1-yl)butane (bimb) and one chloride ion. The Ni²⁺ ion exhibits a distorted octa­hedral coordination environment defined by four N atoms from four bimb ligands in the equatorial plane and two chloride ions in axial positions. The bridging coordination mode of the bimb ligands leads to the formation of inter­penetrating square Ni₄(bimb)₄ units that are arranged parallel to (001). The separation between the Ni atoms in these units is 13.740 (3) Å.

Related literature

For related structures based on bis­(imidazole)­alkane ligands, see: Ballester et al. (1998 ▶); Li et al. (2004 ▶); Zhu et al. (2006 ▶, 2009 ▶).

Experimental

Crystal data

• [NiCl₂(C₁₀H₁₄N₄)₂]

• M _r = 510.11

• Monoclinic,

• a = 7.4572 (15) Å

• b = 18.297 (4) Å

• c = 8.7321 (17) Å

• β = 113.60 (3)°

• V = 1091.8 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 1.16 mm⁻¹

• T = 293 K

• 0.20 × 0.15 × 0.10 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.801, T _max = 0.893

• 10382 measured reflections

• 2469 independent reflections

• 2158 reflections with I > 2σ(I)

• R _int = 0.037

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.089

• S = 1.11

• 2469 reflections

• 142 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Ni1—N4i	2.0980 (19)
Ni1—N1	2.111 (2)
Ni1—Cl1	2.5270 (8)

Symmetry code: (i) .

supplementary crystallographic information

Comment

A large number of novel topologies constructed from bis(pyridine)alkane, triazolealkane or bis(imidazole)alkane ligands have been reported in recent years, for example, [Co(bte)₂(NCS)₂]_n, {[Cd(bte)₂(H₂O)₂](NO₃)₂}_n, or [Cd(bimb)₂(NCO)₂]_n [bte=1,2-Bis (1,2,4-triazol-1-yl) ethane, bimb=1,4-bis (imidazol-1-yl) butane] (Ballester et al., 1998; Li et al., 2004; Zhu et al., 2006; Zhu et al., 2009). These ligands show flexible bridging modes and can adopt different conformations (Li et al., 2004). Herein, a new coordination polymer based on 1,4-bis(imidazol-1-yl)-butane, [Ni(bimb)₂Cl₂]_n, is reported.

The asymmetric unit of the title compound consists of one Ni²⁺ ion which is located on an inversion center, one bimb ligand and one chloride ion. The Ni²⁺ ion exhibits a distorted octahedral coordination environment defined by four N atoms from four bimp ligands in the equatorial plane [Ni1—N4 = 2.0980 (19) Å; Ni1—N1 = 2.111 (2) Å] and two chloride ions in axial positions [Ni1—Cl1 = 2.5270 (8) Å]. The dihedral angle between the imidazole rings in the bimp ligand is 60.99 (16)°.

Each bimb ligand connects two adjacent Ni²⁺ ions to form interpenetrating two-dimensional networks containing square Ni₄(bimb)₄ units parallel to (001) (Figure 2). The square Ni₄(bimb)₄ units are constructed from four Ni²⁺ ions which are situated in the four corners and four bimb ligands which are in the edge positions. The Ni ··· Ni distance in the net is 13.740 (3) Å.

Experimental

A solution of ethyl 2,2-difluoro-2-(pyridin-2-yl)acetate (10.0 mg, 0.05 mmol) in 2 ml ethanol was directly mixed with a solution of NiCl₂ in 1 ml water (0.10 mol dm^-3) at room temperature in a 15 ml beaker. A solution of bimb (9.5 mg, 0.05 mmol) in 3 ml e thanol in another 15 ml beaker was added the above-mentioned mixture. Then 2M HCl was added until the pH value of mixture arrives at 4.5. The resulted mixture was transferred and sealed in a 25 ml Teflon-lined stainless steel reactor, and heated at 85 °C for 72 h. Upon cooling to room temperature, the light green crystals were filtered and washed with water and ethanol.

Refinement

All H atoms were located in a difference Fourier map refined as riding, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The coordination environment of Ni(II) atom with displacement ellipsoids at the 50% probability level. H atome were omitted for clarity. [Symmetry codes: i) 1.5-x, 0.5+y, 0.5-z; ii) 1.5+x, 0.5+y, 0.5+z; iii) 3-x, 1-y, 1-z]

Fig. 2.

View of a two-dimensional layer containing square Ni4(bimb)4 units with dimension of 13.740 (3) × 13.740 (3) Å2 parallel to (001).

Crystal data

[NiCl2(C10H14N4)2]	F(000) = 532
Mr = 510.11	Dx = 1.552 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2469 reflections
a = 7.4572 (15) Å	θ = 3.1–27.5°
b = 18.297 (4) Å	µ = 1.16 mm−1
c = 8.7321 (17) Å	T = 293 K
β = 113.60 (3)°	Block, green
V = 1091.8 (4) Å3	0.20 × 0.15 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer	2469 independent reflections
Radiation source: fine-focus sealed tube	2158 reflections with I > 2σ(I)
graphite	Rint = 0.037
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.801, Tmax = 0.893	k = −23→23
10382 measured reflections	l = −10→11

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0274P)2 + 1.1307P] where P = (Fo2 + 2Fc2)/3
2469 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N4	0.1415 (3)	0.10177 (10)	0.0471 (3)	0.0289 (4)
C9	0.0664 (4)	0.16648 (14)	0.0733 (4)	0.0440 (7)
H9	−0.0615	0.1733	0.0630	0.053*
C10	0.2054 (4)	0.21922 (14)	0.1165 (4)	0.0456 (7)
H10	0.1917	0.2678	0.1415	0.055*
C8	0.3245 (3)	0.11623 (13)	0.0740 (3)	0.0298 (5)
H8	0.4118	0.0819	0.0650	0.036*
N3	0.3700 (3)	0.18646 (11)	0.1160 (3)	0.0335 (5)
C7	0.5640 (4)	0.21996 (15)	0.1668 (4)	0.0457 (7)
H7A	0.6545	0.1835	0.1592	0.055*
H7B	0.6092	0.2347	0.2829	0.055*
C6	0.5694 (4)	0.28506 (14)	0.0646 (3)	0.0383 (6)
H6A	0.4725	0.3204	0.0647	0.046*
H6B	0.5361	0.2699	−0.0500	0.046*
Ni1	1.5000	0.5000	0.5000	0.02315 (12)
Cl1	1.30895 (8)	0.46277 (3)	0.66987 (8)	0.03495 (16)
N1	1.2760 (3)	0.45639 (10)	0.2843 (2)	0.0269 (4)
N2	0.9912 (3)	0.41380 (11)	0.1097 (3)	0.0323 (4)
C3	1.0969 (3)	0.43850 (14)	0.2651 (3)	0.0329 (5)
H3	1.0496	0.4425	0.3485	0.039*
C1	1.2840 (4)	0.44240 (13)	0.1329 (3)	0.0320 (5)
H1	1.3929	0.4500	0.1083	0.038*
C2	1.1099 (4)	0.41598 (13)	0.0245 (3)	0.0355 (5)
H2	1.0776	0.4021	−0.0859	0.043*
C5	0.7692 (4)	0.32062 (14)	0.1322 (4)	0.0414 (6)
H5A	0.8052	0.3315	0.2495	0.050*
H5B	0.8631	0.2855	0.1253	0.050*
C4	0.7874 (4)	0.38856 (16)	0.0476 (4)	0.0481 (7)
H4A	0.7393	0.3799	−0.0717	0.058*
H4B	0.7072	0.4264	0.0661	0.058*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N4	0.0205 (10)	0.0275 (10)	0.0382 (11)	0.0007 (7)	0.0113 (9)	0.0027 (8)
C9	0.0290 (13)	0.0301 (13)	0.079 (2)	0.0015 (10)	0.0275 (14)	0.0015 (13)
C10	0.0374 (15)	0.0263 (12)	0.080 (2)	−0.0011 (10)	0.0303 (15)	−0.0013 (13)
C8	0.0236 (12)	0.0295 (11)	0.0370 (13)	0.0006 (9)	0.0128 (10)	0.0031 (9)
N3	0.0224 (10)	0.0295 (10)	0.0472 (12)	−0.0034 (8)	0.0126 (9)	0.0058 (9)
C7	0.0240 (13)	0.0422 (15)	0.0624 (18)	−0.0085 (11)	0.0085 (13)	0.0115 (13)
C6	0.0279 (13)	0.0359 (13)	0.0446 (14)	−0.0107 (10)	0.0078 (11)	0.0010 (11)
Ni1	0.01420 (19)	0.0230 (2)	0.0300 (2)	−0.00183 (14)	0.00640 (16)	−0.00287 (15)
Cl1	0.0247 (3)	0.0419 (3)	0.0393 (3)	−0.0057 (2)	0.0139 (3)	−0.0037 (2)
N1	0.0174 (9)	0.0279 (9)	0.0321 (10)	−0.0033 (7)	0.0066 (8)	−0.0038 (8)
N2	0.0238 (10)	0.0306 (10)	0.0337 (10)	−0.0097 (8)	0.0023 (9)	0.0023 (8)
C3	0.0225 (12)	0.0410 (13)	0.0327 (12)	−0.0079 (10)	0.0086 (10)	−0.0021 (10)
C1	0.0283 (13)	0.0310 (12)	0.0390 (13)	−0.0020 (9)	0.0157 (11)	−0.0035 (10)
C2	0.0390 (14)	0.0321 (12)	0.0305 (12)	−0.0053 (10)	0.0089 (11)	−0.0053 (10)
C5	0.0253 (13)	0.0344 (13)	0.0570 (17)	−0.0059 (10)	0.0086 (12)	0.0077 (12)
C4	0.0254 (13)	0.0481 (16)	0.0522 (16)	−0.0159 (11)	−0.0041 (12)	0.0121 (13)

Geometric parameters (Å, °)

N4—C8	1.316 (3)	Ni1—N1iv	2.111 (2)
N4—C9	1.368 (3)	Ni1—N1	2.111 (2)
N4—Ni1i	2.0980 (19)	Ni1—Cl1	2.5270 (8)
C9—C10	1.355 (4)	Ni1—Cl1iv	2.5270 (8)
C9—H9	0.9300	N1—C3	1.319 (3)
C10—N3	1.368 (3)	N1—C1	1.371 (3)
C10—H10	0.9300	N2—C3	1.346 (3)
C8—N3	1.342 (3)	N2—C2	1.366 (3)
C8—H8	0.9300	N2—C4	1.469 (3)
N3—C7	1.467 (3)	C3—H3	0.9300
C7—C6	1.499 (4)	C1—C2	1.353 (3)
C7—H7A	0.9700	C1—H1	0.9300
C7—H7B	0.9700	C2—H2	0.9300
C6—C5	1.512 (3)	C5—C4	1.480 (4)
C6—H6A	0.9700	C5—H5A	0.9700
C6—H6B	0.9700	C5—H5B	0.9700
Ni1—N4ii	2.0980 (19)	C4—H4A	0.9700
Ni1—N4iii	2.0980 (19)	C4—H4B	0.9700
C8—N4—C9	105.1 (2)	N1iv—Ni1—Cl1	90.51 (6)
C8—N4—Ni1i	128.15 (16)	N1—Ni1—Cl1	89.49 (6)
C9—N4—Ni1i	126.43 (16)	N4ii—Ni1—Cl1iv	89.81 (6)
C10—C9—N4	110.2 (2)	N4iii—Ni1—Cl1iv	90.19 (6)
C10—C9—H9	124.9	N1iv—Ni1—Cl1iv	89.49 (6)
N4—C9—H9	124.9	N1—Ni1—Cl1iv	90.51 (6)
C9—C10—N3	105.9 (2)	Cl1—Ni1—Cl1iv	180.0
C9—C10—H10	127.0	C3—N1—C1	105.3 (2)
N3—C10—H10	127.0	C3—N1—Ni1	127.33 (17)
N4—C8—N3	111.9 (2)	C1—N1—Ni1	127.36 (15)
N4—C8—H8	124.1	C3—N2—C2	107.1 (2)
N3—C8—H8	124.1	C3—N2—C4	125.4 (2)
C8—N3—C10	106.9 (2)	C2—N2—C4	127.5 (2)
C8—N3—C7	126.4 (2)	N1—C3—N2	111.4 (2)
C10—N3—C7	126.4 (2)	N1—C3—H3	124.3
N3—C7—C6	114.2 (2)	N2—C3—H3	124.3
N3—C7—H7A	108.7	C2—C1—N1	110.0 (2)
C6—C7—H7A	108.7	C2—C1—H1	125.0
N3—C7—H7B	108.7	N1—C1—H1	125.0
C6—C7—H7B	108.7	C1—C2—N2	106.2 (2)
H7A—C7—H7B	107.6	C1—C2—H2	126.9
C7—C6—C5	111.5 (2)	N2—C2—H2	126.9
C7—C6—H6A	109.3	C4—C5—C6	116.1 (2)
C5—C6—H6A	109.3	C4—C5—H5A	108.3
C7—C6—H6B	109.3	C6—C5—H5A	108.3
C5—C6—H6B	109.3	C4—C5—H5B	108.3
H6A—C6—H6B	108.0	C6—C5—H5B	108.3
N4ii—Ni1—N4iii	180.0	H5A—C5—H5B	107.4
N4ii—Ni1—N1iv	90.26 (8)	N2—C4—C5	111.6 (2)
N4iii—Ni1—N1iv	89.74 (8)	N2—C4—H4A	109.3
N4ii—Ni1—N1	89.74 (8)	C5—C4—H4A	109.3
N4iii—Ni1—N1	90.26 (8)	N2—C4—H4B	109.3
N1iv—Ni1—N1	180.000 (1)	C5—C4—H4B	109.3
N4ii—Ni1—Cl1	90.19 (6)	H4A—C4—H4B	108.0
N4iii—Ni1—Cl1	89.81 (6)

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