Crystal structure of di­bromido­tetra­kis(propan-2-ol-κO)nickel(II)

Lv, Y.; Liu, M.; Ji, L.; Zhang, C.; Ouyang, M.

doi:10.1107/S2056989015023555

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m263-m264

https://doi.org/10.1107/S2056989015023555

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Crystal structure of dibromidotetrakis(propan-2-ol-κO)nickel(II)

Yaokang Lv,^a,^b Mingxian Liu,^a ^* Lvlv Ji,^a,^b Cheng Zhang ^b and Mi Ouyang ^b

^aDepartment of Chemistry, Tongji University, Shanghai 200092, People's Republic of China, and ^bCollege of Chemical Engineering, Zhejiang University of Technology, 310014 Hangzhou, People's Republic of China
^*Correspondence e-mail: liumx@tongji.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 November 2015; accepted 8 December 2015; online 19 December 2015)

The asymmetric unit of the mononuclear title complex, [NiBr₂(C₃H₈O)₄], comprises a Ni^II cation located on a centre of inversion, one Br⁻ anion and two propan-2-ol ligands. The Ni^II cation exhibits a distorted trans-Br₂O₄ environment. There are O—H⋯Br hydrogen bonds connecting neighbouring molecules into rows along [100]. These rows are arranged in a distorted hexagonal packing and are held together by van der Waals forces only.

Keywords: crystal structure; nickel(II) complex; isopropanol ligand.

CCDC reference: 1441097

1. Related literature

Nickel complexes have attracted attention due to their coordination chemistry and electrochemical properties. For background to such nickel complexes, see: Kapoor et al. (2012 ); Kant et al. (2015 ). For similar crystal structures with propan-2-ol ligands coordinating Ni²⁺ cations, see: Veith et al. (2008 ).

2. Experimental

2.1. Crystal data

[NiBr₂(C₃H₈O)₄]
M_r = 458.91
Monoclinic, P 2₁ /c
a = 5.8341 (7) Å
b = 10.4902 (15) Å
c = 16.613 (2) Å
β = 97.074 (4)°
V = 1009.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 199 K
0.42 × 0.21 × 0.07 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.305, T_max = 0.710
9106 measured reflections
1770 independent reflections
1451 reflections with I > 2σ(I)
R_int = 0.056

2.3. Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.071
S = 1.01
1770 reflections
94 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br1ⁱ	0.81 (2)	2.58 (2)	3.372 (2)	166 (4)
O2—H2⋯Br1ⁱⁱ	0.83 (2)	2.51 (2)	3.315 (2)	165 (3)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); 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, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1441097

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023555/wm5238sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023555/wm5238Isup2.hkl

checkCIF report

Synthesis and crystallization top

Anhydrous NiBr₂ and isopropanol were purchased from Sigma-Aldrich. The title complex was synthesized by stirring 0.537 g (2 mmol) NiBr₂ in 50 ml isopropanol at 330 K for ten hours. Green needle/lath-shaped crystals were obtained after slow evaporation of the solvent at room temperature.

Refinement top

The carbon-bound H atoms were positioned with idealized geometries and were refined with C—H = 0.98 Å (methyl) and C—H = 1.00 Å (methine) and with U_eq(H) = 1.2 U_eq(C) using a riding model approximation. The H atom of the hydroxy groups were initially found from a difference map and were refined with O—H distance restraints of 0.82 (2) Å and with U_eq(H) = 1.2U_eq(O).

Related literature top

Nickel complexes have attracted attention due to their coordination chemistry and electrochemical properties. For background to such nickel complexes, see: Kapoor et al. (2012); Kant et al. (2015). For similar crystal structures with propan-2-ol ligands in coordination to Ni²⁺ cations, see: Veith et al. (2008).

Structure description top

Nickel complexes have attracted attention due to their coordination chemistry and electrochemical properties. For background to such nickel complexes, see: Kapoor et al. (2012); Kant et al. (2015). For similar crystal structures with propan-2-ol ligands in coordination to Ni²⁺ cations, see: Veith et al. (2008).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius. [Symmetry code: (i) 2 - x, -y, -z.]
	Fig. 2. The chain structure of the title complex generated by O—H···Br hydrogen bonds (dotted lines).

Dibromidotetrakis(propan-2-ol-κO)nickel(II) top

Crystal data top

[NiBr₂(C₃H₈O)₄]	F(000) = 468
M_r = 458.91	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2876 reflections
a = 5.8341 (7) Å	θ = 2.3–24.6°
b = 10.4902 (15) Å	µ = 4.93 mm⁻¹
c = 16.613 (2) Å	T = 199 K
β = 97.074 (4)°	Lath, green
V = 1009.0 (2) Å³	0.42 × 0.21 × 0.07 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1770 independent reflections
Radiation source: fine-focus sealed tube	1451 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 25.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −6→6
T_min = 0.305, T_max = 0.710	k = −12→12
9106 measured reflections	l = −19→19

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0304P)² + 0.450P] where P = (F_o² + 2F_c²)/3
1770 reflections	(Δ/σ)_max < 0.001
94 parameters	Δρ_max = 0.60 e Å⁻³
2 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[NiBr₂(C₃H₈O)₄]	V = 1009.0 (2) Å³
M_r = 458.91	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8341 (7) Å	µ = 4.93 mm⁻¹
b = 10.4902 (15) Å	T = 199 K
c = 16.613 (2) Å	0.42 × 0.21 × 0.07 mm
β = 97.074 (4)°

Data collection top

Bruker APEXII CCD diffractometer	1770 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1451 reflections with I > 2σ(I)
T_min = 0.305, T_max = 0.710	R_int = 0.056
9106 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	2 restraints
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.60 e Å⁻³
1770 reflections	Δρ_min = −0.34 e Å⁻³
94 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
Br1	0.71762 (5)	−0.08471 (4)	0.09301 (2)	0.04316 (14)
Ni1	1.0000	0.0000	0.0000	0.02592 (16)
O1	1.2185 (4)	0.0765 (3)	0.09534 (13)	0.0434 (6)
H1	1.350 (4)	0.051 (3)	0.096 (2)	0.052*
O2	0.8057 (4)	0.1654 (2)	−0.00752 (15)	0.0427 (6)
H2	0.667 (3)	0.149 (4)	−0.020 (2)	0.051*
C1	1.2416 (8)	0.0311 (5)	0.2387 (2)	0.0759 (14)
H1A	1.1464	−0.0454	0.2276	0.091*
H1B	1.2137	0.0674	0.2910	0.091*
H1C	1.4051	0.0084	0.2406	0.091*
C5	0.8588 (6)	0.2959 (3)	−0.0232 (2)	0.0486 (9)
H5A	1.0299	0.3070	−0.0118	0.058*
C2	1.1799 (6)	0.1270 (4)	0.17316 (19)	0.0447 (9)
H2A	1.0116	0.1466	0.1713	0.054*
C4	0.7475 (9)	0.3790 (4)	0.0349 (3)	0.0859 (16)
H4A	0.8065	0.3557	0.0907	0.103*
H4B	0.5797	0.3669	0.0263	0.103*
H4C	0.7839	0.4686	0.0254	0.103*
C6	0.7873 (8)	0.3295 (5)	−0.1100 (3)	0.0852 (16)
H6A	0.8630	0.2718	−0.1449	0.102*
H6B	0.8325	0.4176	−0.1197	0.102*
H6C	0.6193	0.3210	−0.1223	0.102*
C3	1.3116 (9)	0.2494 (4)	0.1882 (3)	0.0796 (14)
H3A	1.2848	0.2843	0.2410	0.096*
H3B	1.2591	0.3108	0.1454	0.096*
H3C	1.4769	0.2330	0.1881	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0251 (2)	0.0584 (3)	0.0462 (2)	−0.00264 (16)	0.00532 (15)	0.01303 (16)
Ni1	0.0212 (3)	0.0256 (3)	0.0302 (3)	−0.0008 (2)	0.0002 (2)	0.0006 (2)
O1	0.0280 (13)	0.0622 (17)	0.0388 (13)	0.0019 (12)	−0.0008 (11)	−0.0168 (11)
O2	0.0243 (12)	0.0292 (12)	0.0733 (16)	−0.0001 (11)	0.0006 (11)	0.0071 (12)
C1	0.080 (3)	0.093 (4)	0.053 (2)	−0.006 (3)	0.000 (2)	0.009 (2)
C5	0.034 (2)	0.030 (2)	0.080 (3)	−0.0017 (15)	0.0010 (19)	0.0072 (17)
C2	0.039 (2)	0.057 (2)	0.0371 (18)	−0.0003 (17)	0.0038 (15)	−0.0118 (16)
C4	0.077 (3)	0.048 (3)	0.135 (5)	0.008 (2)	0.023 (3)	−0.016 (3)
C6	0.078 (3)	0.075 (3)	0.098 (3)	−0.014 (3)	−0.006 (3)	0.043 (3)
C3	0.103 (4)	0.065 (3)	0.070 (3)	−0.020 (3)	0.009 (3)	−0.024 (2)

Geometric parameters (Å, º) top

Br1—Ni1	2.5532 (4)	C5—C6	1.493 (6)
Ni1—O2	2.068 (2)	C5—C4	1.506 (6)
Ni1—O2ⁱ	2.068 (2)	C5—H5A	1.0000
Ni1—O1	2.069 (2)	C2—C3	1.502 (5)
Ni1—O1ⁱ	2.069 (2)	C2—H2A	1.0000
Ni1—Br1ⁱ	2.5532 (4)	C4—H4A	0.9800
O1—C2	1.440 (4)	C4—H4B	0.9800
O1—H1	0.814 (18)	C4—H4C	0.9800
O2—C5	1.434 (4)	C6—H6A	0.9800
O2—H2	0.825 (18)	C6—H6B	0.9800
C1—C2	1.494 (5)	C6—H6C	0.9800
C1—H1A	0.9800	C3—H3A	0.9800
C1—H1B	0.9800	C3—H3B	0.9800
C1—H1C	0.9800	C3—H3C	0.9800

O2—Ni1—O2ⁱ	180.00 (12)	C6—C5—C4	113.0 (4)
O2—Ni1—O1	90.12 (9)	O2—C5—H5A	108.0
O2ⁱ—Ni1—O1	89.88 (9)	C6—C5—H5A	108.0
O2—Ni1—O1ⁱ	89.88 (9)	C4—C5—H5A	108.0
O2ⁱ—Ni1—O1ⁱ	90.12 (9)	O1—C2—C1	110.9 (3)
O1—Ni1—O1ⁱ	180.00 (15)	O1—C2—C3	109.3 (3)
O2—Ni1—Br1	86.49 (7)	C1—C2—C3	112.5 (3)
O2ⁱ—Ni1—Br1	93.51 (7)	O1—C2—H2A	108.0
O1—Ni1—Br1	93.12 (7)	C1—C2—H2A	108.0
O1ⁱ—Ni1—Br1	86.88 (7)	C3—C2—H2A	108.0
O2—Ni1—Br1ⁱ	93.51 (7)	C5—C4—H4A	109.5
O2ⁱ—Ni1—Br1ⁱ	86.49 (7)	C5—C4—H4B	109.5
O1—Ni1—Br1ⁱ	86.88 (7)	H4A—C4—H4B	109.5
O1ⁱ—Ni1—Br1ⁱ	93.12 (7)	C5—C4—H4C	109.5
Br1—Ni1—Br1ⁱ	180.000 (18)	H4A—C4—H4C	109.5
C2—O1—Ni1	132.8 (2)	H4B—C4—H4C	109.5
C2—O1—H1	111 (3)	C5—C6—H6A	109.5
Ni1—O1—H1	112 (3)	C5—C6—H6B	109.5
C5—O2—Ni1	133.0 (2)	H6A—C6—H6B	109.5
C5—O2—H2	112 (3)	C5—C6—H6C	109.5
Ni1—O2—H2	111 (3)	H6A—C6—H6C	109.5
C2—C1—H1A	109.5	H6B—C6—H6C	109.5
C2—C1—H1B	109.5	C2—C3—H3A	109.5
H1A—C1—H1B	109.5	C2—C3—H3B	109.5
C2—C1—H1C	109.5	H3A—C3—H3B	109.5
H1A—C1—H1C	109.5	C2—C3—H3C	109.5
H1B—C1—H1C	109.5	H3A—C3—H3C	109.5
O2—C5—C6	111.1 (3)	H3B—C3—H3C	109.5
O2—C5—C4	108.4 (3)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1ⁱⁱ	0.81 (2)	2.58 (2)	3.372 (2)	166 (4)
O2—H2···Br1ⁱⁱⁱ	0.83 (2)	2.51 (2)	3.315 (2)	165 (3)

Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1ⁱ	0.814 (18)	2.58 (2)	3.372 (2)	166 (4)
O2—H2···Br1ⁱⁱ	0.825 (18)	2.51 (2)	3.315 (2)	165 (3)

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

Acknowledgements

We gratefully acknowledge financial support by the National Natural Science Foundation of China (NSFC, Nos. 51403060, 51003095 and 51103132). We thank Professor Dr Dominic S. Wright (University of Cambridge) for access to his experimental facilities.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m263-m264

https://doi.org/10.1107/S2056989015023555

Open

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