Di-μ-chlorido-bis­[(2,2′-bi­pyridine-κ2N,N′)chlorido(N,N-di­methyl­formamide-κO)nickel(II)]

Glazier, B.M.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616002595

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160259

https://doi.org/10.1107/S2414314616002595

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Di-μ-chlorido-bis[(2,2′-bipyridine-κ²N,N′)chlorido(N,N-dimethylformamide-κO)nickel(II)]

Brian M. Glazier,^a James A. Golen ^a and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 5 February 2016; accepted 13 February 2016; online 20 February 2016)

The title compound, [Ni₂Cl₂(μ-Cl)₂(C₁₀H₈N₂)₂(C₃H₇NO)₂], exists as a centrosymmetric dimer of two octahedral nickel centers. In the crystal, two chloride ions bridge the two nickel centers with one terminal chloride ion bound to each nickel atom. Coupled with a chelating bipyridine ligand and an O-bound N,N-dimethylformamide solvent molecule, each nickel center exhibits an slightly distorted octahedral coordination environment. The meridional chloride ions all sit in equatorial positions, with the bipyridine ligand occupying one equatorial and one axial position, and the N,N-dimethylformamide ligand occupying the final axial position. The 2,2′-bipyridine ligand binds to nickel in a near planar fashion, with the non-H atoms possessing a mean devation from planarity of 0.046 Å. No π–π interactions are observed in the crystal.

Keywords: crystal structure; bipyridine; nickel(II) complex.

CCDC reference: 1453181

Structure description

The structure of the title compound possesses neutral (bipy)NiCl₂(DMF) units which dimerize and are related by a crystallographic inversion center (Fig. 1). Each octahedral Ni^II ion is surrounded by two nitrogen atoms from the bipyridine ligand, three chlorine atoms (one terminal and two bridging) and a coordinated N,N-dimethylformamide molecule. All three chlorine atoms sit on equatorial positions, while the axial positions are occupied by the DMF oxygen atom and a pyridyl nitrogen atom. This is in contrast to the closely related aquo complex, where the bipyridine occupies two equatorial positions and the terminal chlorine sits in an axial site (Ikotun et al., 2007 ). The arrangement with a terminal equatorial chloride is observed in tridentate bipyridine derivatives (Chen et al., 2009 ; Hirotsu et al., 2010 ). The Ni—Cl bond trans to the pyridine ring is significantly shorter [2.3971 (7) Å] than the Ni—Cl bond trans to the terminal Cl atom [2.5049 (7) Å], consistent with the trans influence. Packing of the crystal structure can be seen in Fig. 2. No π–π interactions wer noted in the structure.

Figure 1
The molecular structure of the title compound. The unlabeled atoms are generated by an inversion center. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres or arbitrary radius.

Figure 2
View of the molecular packing of the title compound along the b axis.

Synthesis and crystallization

A mixture of NiCl₂·6H₂O, 2,2′-bipyridine and N,N-dimethylformamide was heated in a sealed thick-walled glass tube at 373 K for 48 h. Pale-green needle-shaped crystals suitable for a single-crystal diffraction study were isolated from the tube. The synthesis of closely related complexes is described by Cocker & Bachman (2004 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Ni₂Cl₄(C₁₀H₈N₂)₂(C₃H₇NO)₂]
M_r	717.78
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	11.9130 (9), 11.445 (1), 20.7458 (17)
V (Å³)	2828.6 (4)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.44
Crystal size (mm)	0.15 × 0.05 × 0.02

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.240, 0.384
No. of measured, independent and observed [I > 2σ(I)] reflections	12752, 2670, 2139
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.073, 1.04
No. of reflections	2670
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.30
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1453181

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616002595/lh5805sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616002595/lh5805Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Di-µ-chlorido-bis[(2,2'-bipyridine-κ²N,N')chlorido(N,N-dimethylformamide-κO)nickel(II)] top

Crystal data top

[Ni₂Cl₄(C₁₀H₈N₂)₂(C₃H₇NO)₂]	F(000) = 1472
M_r = 717.78	D_x = 1.686 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 5383 reflections
a = 11.9130 (9) Å	θ = 4.3–70.2°
b = 11.445 (1) Å	µ = 5.44 mm⁻¹
c = 20.7458 (17) Å	T = 120 K
V = 2828.6 (4) Å³	Plate, green
Z = 4	0.15 × 0.05 × 0.02 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	2670 independent reflections
Radiation source: Cu	2139 reflections with I > 2σ(I)
HELIOS MX monochromator	R_int = 0.053
φ and ω scans	θ_max = 70.2°, θ_min = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −14→13
T_min = 0.240, T_max = 0.384	k = −13→11
12752 measured reflections	l = −19→25

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0299P)² + 1.4865P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2670 reflections	Δρ_max = 0.26 e Å⁻³
183 parameters	Δρ_min = −0.30 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.49476 (3)	0.38808 (4)	0.43948 (2)	0.01585 (12)
Cl2	0.63495 (4)	0.46540 (5)	0.51055 (3)	0.01834 (14)
Cl1	0.61409 (5)	0.25008 (6)	0.38155 (3)	0.02148 (15)
O1	0.45006 (13)	0.26410 (15)	0.50647 (8)	0.0190 (4)
N2	0.36328 (15)	0.34487 (17)	0.37970 (9)	0.0156 (4)
N1	0.52288 (15)	0.50115 (17)	0.36496 (9)	0.0168 (4)
N3	0.49296 (15)	0.10292 (18)	0.56455 (10)	0.0196 (4)
C5	0.45302 (18)	0.4894 (2)	0.31397 (11)	0.0167 (5)
C6	0.35961 (18)	0.4053 (2)	0.32359 (11)	0.0171 (5)
C10	0.28304 (18)	0.2671 (2)	0.39238 (12)	0.0198 (5)
H10	0.2855	0.2259	0.4321	0.024*
C11	0.51802 (19)	0.1879 (2)	0.52417 (11)	0.0191 (5)
H11	0.5923	0.1911	0.5076	0.023*
C1	0.60826 (19)	0.5763 (2)	0.36081 (11)	0.0196 (5)
H1	0.6561	0.5859	0.3971	0.023*
C4	0.4687 (2)	0.5525 (2)	0.25765 (11)	0.0202 (5)
H4	0.4184	0.5435	0.2225	0.024*
C2	0.6298 (2)	0.6409 (2)	0.30573 (12)	0.0231 (6)
H2	0.6922	0.6924	0.3039	0.028*
C8	0.19164 (19)	0.3053 (2)	0.29244 (12)	0.0233 (6)
H8	0.1328	0.2913	0.2625	0.028*
C9	0.19615 (19)	0.2441 (2)	0.34992 (12)	0.0225 (6)
H9	0.1407	0.1873	0.3600	0.027*
C12	0.5762 (2)	0.0156 (2)	0.58366 (12)	0.0242 (6)
H12A	0.6429	0.0231	0.5564	0.036*
H12B	0.5442	−0.0628	0.5786	0.036*
H12C	0.5971	0.0279	0.6288	0.036*
C7	0.27354 (18)	0.3871 (2)	0.27914 (11)	0.0197 (5)
H7	0.2713	0.4305	0.2401	0.024*
C3	0.5587 (2)	0.6290 (2)	0.25328 (12)	0.0237 (6)
H3	0.5714	0.6726	0.2150	0.028*
C13	0.3814 (2)	0.0931 (3)	0.59311 (13)	0.0298 (6)
H13A	0.3298	0.1462	0.5709	0.045*
H13B	0.3852	0.1139	0.6389	0.045*
H13C	0.3545	0.0126	0.5887	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0160 (2)	0.0169 (2)	0.0146 (2)	−0.00102 (17)	−0.00107 (15)	0.00083 (17)
Cl2	0.0161 (3)	0.0210 (3)	0.0179 (3)	0.0006 (2)	−0.0021 (2)	−0.0016 (2)
Cl1	0.0209 (3)	0.0220 (3)	0.0215 (3)	0.0016 (2)	0.0026 (2)	−0.0017 (2)
O1	0.0196 (8)	0.0193 (10)	0.0180 (8)	−0.0006 (7)	0.0003 (6)	0.0032 (7)
N2	0.0158 (9)	0.0149 (11)	0.0160 (10)	0.0000 (8)	0.0001 (8)	−0.0025 (8)
N1	0.0173 (9)	0.0171 (12)	0.0160 (9)	0.0018 (8)	0.0012 (8)	0.0001 (8)
N3	0.0186 (9)	0.0192 (12)	0.0209 (10)	0.0006 (9)	−0.0008 (8)	0.0023 (9)
C5	0.0166 (11)	0.0180 (14)	0.0156 (11)	0.0036 (10)	0.0008 (9)	−0.0015 (10)
C6	0.0173 (11)	0.0171 (14)	0.0169 (11)	0.0036 (10)	0.0024 (9)	−0.0026 (10)
C10	0.0204 (11)	0.0181 (14)	0.0208 (12)	0.0003 (10)	0.0037 (9)	−0.0005 (10)
C11	0.0178 (11)	0.0222 (14)	0.0174 (11)	−0.0032 (11)	−0.0019 (9)	−0.0023 (11)
C1	0.0195 (11)	0.0200 (14)	0.0192 (12)	−0.0008 (10)	−0.0003 (10)	−0.0023 (10)
C4	0.0245 (12)	0.0212 (15)	0.0148 (11)	0.0023 (11)	−0.0003 (9)	−0.0003 (10)
C2	0.0215 (12)	0.0215 (15)	0.0263 (13)	−0.0029 (11)	0.0025 (10)	0.0025 (11)
C8	0.0177 (11)	0.0291 (17)	0.0230 (13)	0.0020 (11)	−0.0019 (10)	−0.0091 (12)
C9	0.0182 (11)	0.0200 (15)	0.0294 (13)	−0.0023 (10)	0.0029 (10)	−0.0067 (12)
C12	0.0264 (13)	0.0218 (15)	0.0242 (13)	0.0013 (11)	−0.0058 (10)	0.0020 (11)
C7	0.0206 (11)	0.0225 (15)	0.0161 (11)	0.0043 (11)	−0.0003 (9)	0.0005 (10)
C3	0.0284 (13)	0.0240 (16)	0.0187 (12)	0.0011 (11)	0.0054 (10)	0.0048 (11)
C13	0.0247 (13)	0.0319 (17)	0.0329 (15)	−0.0003 (12)	0.0052 (11)	0.0109 (13)

Geometric parameters (Å, º) top

Ni1—Cl2	2.3971 (7)	C11—H11	0.9500
Ni1—Cl2ⁱ	2.5049 (7)	C1—H1	0.9500
Ni1—Cl1	2.4413 (7)	C1—C2	1.385 (3)
Ni1—O1	2.0563 (17)	C4—H4	0.9500
Ni1—N2	2.0582 (19)	C4—C3	1.387 (4)
Ni1—N1	2.044 (2)	C2—H2	0.9500
Cl2—Ni1ⁱ	2.5049 (7)	C2—C3	1.385 (3)
O1—C11	1.246 (3)	C8—H8	0.9500
N2—C6	1.355 (3)	C8—C9	1.384 (4)
N2—C10	1.332 (3)	C8—C7	1.380 (3)
N1—C5	1.353 (3)	C9—H9	0.9500
N1—C1	1.335 (3)	C12—H12A	0.9800
N3—C11	1.318 (3)	C12—H12B	0.9800
N3—C12	1.463 (3)	C12—H12C	0.9800
N3—C13	1.459 (3)	C7—H7	0.9500
C5—C6	1.484 (3)	C3—H3	0.9500
C5—C4	1.387 (3)	C13—H13A	0.9800
C6—C7	1.395 (3)	C13—H13B	0.9800
C10—H10	0.9500	C13—H13C	0.9800
C10—C9	1.385 (3)

Cl2—Ni1—Cl2ⁱ	85.88 (2)	O1—C11—H11	118.1
Cl2—Ni1—Cl1	97.81 (2)	N3—C11—H11	118.1
Cl1—Ni1—Cl2ⁱ	174.92 (2)	N1—C1—H1	118.7
O1—Ni1—Cl2ⁱ	91.29 (5)	N1—C1—C2	122.6 (2)
O1—Ni1—Cl2	91.12 (5)	C2—C1—H1	118.7
O1—Ni1—Cl1	92.13 (5)	C5—C4—H4	120.4
O1—Ni1—N2	92.55 (7)	C5—C4—C3	119.2 (2)
N2—Ni1—Cl2ⁱ	86.61 (6)	C3—C4—H4	120.4
N2—Ni1—Cl2	171.71 (6)	C1—C2—H2	120.6
N2—Ni1—Cl1	89.49 (6)	C1—C2—C3	118.8 (2)
N1—Ni1—Cl2	96.73 (6)	C3—C2—H2	120.6
N1—Ni1—Cl2ⁱ	89.44 (6)	C9—C8—H8	120.4
N1—Ni1—Cl1	86.66 (6)	C7—C8—H8	120.4
N1—Ni1—O1	172.15 (7)	C7—C8—C9	119.2 (2)
N1—Ni1—N2	79.69 (8)	C10—C9—H9	120.6
Ni1—Cl2—Ni1ⁱ	94.12 (2)	C8—C9—C10	118.7 (2)
C11—O1—Ni1	120.95 (15)	C8—C9—H9	120.6
C6—N2—Ni1	114.81 (15)	N3—C12—H12A	109.5
C10—N2—Ni1	125.98 (16)	N3—C12—H12B	109.5
C10—N2—C6	119.2 (2)	N3—C12—H12C	109.5
C5—N1—Ni1	115.31 (16)	H12A—C12—H12B	109.5
C1—N1—Ni1	125.58 (16)	H12A—C12—H12C	109.5
C1—N1—C5	118.8 (2)	H12B—C12—H12C	109.5
C11—N3—C12	121.5 (2)	C6—C7—H7	120.4
C11—N3—C13	121.4 (2)	C8—C7—C6	119.3 (2)
C13—N3—C12	117.0 (2)	C8—C7—H7	120.4
N1—C5—C6	114.9 (2)	C4—C3—H3	120.6
N1—C5—C4	121.6 (2)	C2—C3—C4	118.9 (2)
C4—C5—C6	123.5 (2)	C2—C3—H3	120.6
N2—C6—C5	115.0 (2)	N3—C13—H13A	109.5
N2—C6—C7	121.0 (2)	N3—C13—H13B	109.5
C7—C6—C5	124.0 (2)	N3—C13—H13C	109.5
N2—C10—H10	118.7	H13A—C13—H13B	109.5
N2—C10—C9	122.5 (2)	H13A—C13—H13C	109.5
C9—C10—H10	118.7	H13B—C13—H13C	109.5
O1—C11—N3	123.8 (2)

Ni1—O1—C11—N3	−176.70 (18)	C5—C4—C3—C2	−0.6 (4)
Ni1—N2—C6—C5	1.9 (3)	C6—N2—C10—C9	0.9 (4)
Ni1—N2—C6—C7	−178.44 (18)	C6—C5—C4—C3	−180.0 (2)
Ni1—N2—C10—C9	179.02 (18)	C10—N2—C6—C5	−179.8 (2)
Ni1—N1—C5—C6	6.5 (3)	C10—N2—C6—C7	−0.1 (3)
Ni1—N1—C5—C4	−173.88 (18)	C1—N1—C5—C6	−179.0 (2)
Ni1—N1—C1—C2	172.30 (19)	C1—N1—C5—C4	0.6 (3)
N2—C6—C7—C8	−0.6 (4)	C1—C2—C3—C4	−0.3 (4)
N2—C10—C9—C8	−0.9 (4)	C4—C5—C6—N2	174.8 (2)
N1—C5—C6—N2	−5.6 (3)	C4—C5—C6—C7	−4.8 (4)
N1—C5—C6—C7	174.8 (2)	C9—C8—C7—C6	0.6 (4)
N1—C5—C4—C3	0.5 (4)	C12—N3—C11—O1	180.0 (2)
N1—C1—C2—C3	1.4 (4)	C7—C8—C9—C10	0.1 (4)
C5—N1—C1—C2	−1.5 (4)	C13—N3—C11—O1	−1.2 (4)
C5—C6—C7—C8	179.0 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We greatly acknowledge support from the National Science Foundation (CHE-1429086).

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