Bis(methanol-κO)bis­(quinoline-2-carboxyl­ato-κ² N,O)nickel(II)

Abstract

In the title complex, [Ni(C₁₀H₆NO₂)₂(CH₃OH)₂], the Ni^II ion lies on an inversion center and is coordinated by two quinoline-2-carboxyl­ate ligands in the equatorial sites and two axial methanol ligands, forming a distorted octa­hedral environment. In the crystal, mol­ecules are linked via O—H⋯O hydrogen bonds into a two-dimensional network parallel to (10).

Related literature

For inter­actions of metal ions with amino acids, see: Daniele et al. (2008 ▶); Parkin (2004 ▶); Tshuva & Lippard (2004 ▶); Stoumpos et al. (2009 ▶). For related structures, see: Lee et al. (2008 ▶); Park et al. (2008 ▶); Shin et al. (2009 ▶); Song et al. (2009 ▶); Yu et al. (2008 ▶, 2009 ▶, 2010 ▶); Kim et al. (2011 ▶).

Experimental

Crystal data

• [Ni(C₁₀H₆NO₂)₂(CH₄O)₂]

• M _r = 467.11

• Monoclinic,

• a = 10.411 (2) Å

• b = 7.3910 (15) Å

• c = 13.556 (3) Å

• β = 108.57 (3)°

• V = 988.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.03 mm⁻¹

• T = 293 K

• 0.40 × 0.10 × 0.10 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.884, T _max = 0.903

• 5292 measured reflections

• 1929 independent reflections

• 1666 reflections with I > 2σ(I)

• R _int = 0.018

Refinement

• R[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 0.076

• S = 1.07

• 1929 reflections

• 146 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O2i	0.86 (1)	1.81 (1)	2.655 (2)	167 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The interaction of transition metal ions with biologically active molecules such as amino acids, proteins, sugars, and various acids is of great importance in biological systems (Daniele, et al., 2008; Parkin, 2004; Tshuva & Lippard, 2004; Stoumpos, et al., 2009). As models to examine the interaction, we have intensively studied the interaction of transition metal ions with various acids such as benzoic acid, fulvic acids and humic acids and have reported a variety of structures of copper(II), cadmium(II), and zinc(II) benzoates with quinoxaline,6-methylquinoline, 3-methylquinoline, trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene, and di-2-pyridyl ketone (Lee, et al., 2008; Yu,et al., 2008; Park, et al., 2008; Shin, et al., 2009; Song, et al., 2009; Yu,et al., 2008,2009,2010; Kim, et al., 2011). In this work, we have employed nickel(II) chloride as a building block and quinaldic acid as a ligand. We report herin the structure of the title complex.

In the crystal structure of the title compound, [Ni(C₁₀H₆NO₂)₂(CH₃OH)₂], the Ni^II ion occupies a crystallographic inversion center. Two quinoline-2-carboxylate ligands coordinate the Ni^II ion in the equatorial sites and two methanol ligands coordinate the Ni^II ion in axial sites to form a distorted octahedral environment (Fig. 1). In the crystal, molecules are linked via O—H···O hydrogen bonds to form a two-dimensional network parallel to [1 0 -1].

Experimental

Quinaldic acid (17.7 mg, 0.1 mmol) and NH₄OH (13.9 ml, 0.1 mmol) were dissolved in 4 ml methanol and carefully layered with 4 ml methanol solution of nickel(II) chloride hexahydrate (11.9 mg, 0.05 mmol). Suitable crystals of the title compound for X-ray analysis were obtained in two weeks.

Refinement

H atoms bonded to C atoms were placed in calculated positions with C—H distances of 0.93-0.96Å. They were included in the refinement in a riding-motion approximation with U_iso(H)= 1.2U_eq(C) or U_iso(H) = 1.5U_eq(C_methyl). The positions of O—H atoms of the methanol ligands were refined with O—H restraints (0.86 Å) and U_iso(H)= 1.2U_eq(O).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids shown at the 30% probability level. Unlabeled atoms are related by the symmetry operator (-x+2, -y, -z+1).

Crystal data

[Ni(C10H6NO2)2(CH4O)2]	F(000) = 484
Mr = 467.11	Dx = 1.569 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3640 reflections
a = 10.411 (2) Å	θ = 2.6–28.1°
b = 7.3910 (15) Å	µ = 1.03 mm−1
c = 13.556 (3) Å	T = 293 K
β = 108.57 (3)°	Rod, colorless
V = 988.8 (3) Å3	0.40 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1929 independent reflections
Radiation source: fine-focus sealed tube	1666 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
Tmin = 0.884, Tmax = 0.903	k = −9→9
5292 measured reflections	l = −9→16

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0451P)2 + 0.2296P] where P = (Fo2 + 2Fc2)/3
1929 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.22 e Å−3
1 restraint	Δρmin = −0.31 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
Ni1	1.0000	0.0000	0.5000	0.02463 (12)
N1	0.79816 (13)	0.10618 (19)	0.48009 (11)	0.0270 (3)
O1	0.94209 (12)	0.07175 (19)	0.35013 (9)	0.0314 (3)
O2	0.78467 (15)	0.2090 (2)	0.22280 (11)	0.0530 (4)
O3	0.91781 (13)	−0.25715 (18)	0.45429 (10)	0.0362 (3)
H3O	0.8599 (16)	−0.259 (3)	0.3928 (7)	0.043*
C1	0.72490 (17)	0.1223 (2)	0.54860 (13)	0.0296 (4)
C2	0.77500 (19)	0.0457 (3)	0.64897 (15)	0.0360 (4)
H2	0.8589	−0.0116	0.6698	0.043*
C3	0.7003 (2)	0.0554 (3)	0.71576 (16)	0.0427 (5)
H3	0.7331	0.0020	0.7811	0.051*
C4	0.5748 (2)	0.1451 (3)	0.68685 (17)	0.0453 (5)
H4	0.5257	0.1514	0.7333	0.054*
C5	0.5250 (2)	0.2221 (3)	0.59184 (17)	0.0429 (5)
H5	0.4425	0.2826	0.5740	0.051*
C6	0.59717 (18)	0.2118 (2)	0.51872 (15)	0.0347 (4)
C7	0.54761 (19)	0.2841 (3)	0.41796 (17)	0.0414 (5)
H7	0.4653	0.3455	0.3971	0.050*
C8	0.61990 (19)	0.2645 (3)	0.35068 (15)	0.0385 (4)
H8	0.5871	0.3101	0.2833	0.046*
C9	0.74535 (17)	0.1737 (2)	0.38513 (14)	0.0300 (4)
C10	0.82890 (17)	0.1504 (3)	0.31228 (14)	0.0315 (4)
C11	0.8677 (2)	−0.3714 (3)	0.51879 (17)	0.0481 (5)
H11A	0.9424	−0.4196	0.5740	0.072*
H11B	0.8167	−0.4690	0.4779	0.072*
H11C	0.8102	−0.3025	0.5478	0.072*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Ni1	0.02223 (18)	0.03058 (19)	0.01837 (18)	0.00163 (12)	0.00265 (12)	−0.00029 (12)
N1	0.0236 (7)	0.0301 (8)	0.0250 (7)	0.0008 (6)	0.0045 (6)	−0.0006 (6)
O1	0.0268 (6)	0.0448 (7)	0.0206 (6)	0.0047 (6)	0.0045 (5)	0.0017 (6)
O2	0.0390 (7)	0.0871 (12)	0.0295 (7)	0.0141 (8)	0.0060 (6)	0.0189 (8)
O3	0.0352 (7)	0.0369 (7)	0.0291 (7)	−0.0050 (6)	0.0000 (5)	−0.0025 (6)
C1	0.0267 (8)	0.0299 (9)	0.0320 (10)	−0.0015 (7)	0.0089 (7)	−0.0048 (7)
C2	0.0307 (9)	0.0458 (11)	0.0317 (10)	0.0052 (8)	0.0105 (8)	−0.0009 (8)
C3	0.0430 (11)	0.0562 (12)	0.0317 (10)	0.0024 (10)	0.0158 (9)	−0.0019 (9)
C4	0.0414 (11)	0.0561 (13)	0.0459 (12)	−0.0013 (10)	0.0246 (10)	−0.0108 (10)
C5	0.0323 (10)	0.0456 (12)	0.0539 (13)	0.0064 (9)	0.0182 (9)	−0.0057 (10)
C6	0.0292 (9)	0.0328 (10)	0.0419 (11)	0.0019 (8)	0.0110 (8)	−0.0035 (8)
C7	0.0288 (9)	0.0418 (11)	0.0511 (12)	0.0112 (8)	0.0094 (9)	0.0063 (9)
C8	0.0304 (9)	0.0429 (11)	0.0366 (10)	0.0061 (8)	0.0027 (8)	0.0114 (9)
C9	0.0249 (8)	0.0317 (9)	0.0302 (9)	−0.0013 (7)	0.0043 (7)	0.0015 (8)
C10	0.0275 (8)	0.0384 (10)	0.0241 (9)	−0.0002 (8)	0.0017 (7)	0.0025 (8)
C11	0.0544 (13)	0.0428 (12)	0.0447 (12)	−0.0066 (10)	0.0124 (10)	0.0000 (10)

Geometric parameters (Å, °)

Ni1—O1i	1.9979 (12)	C3—C4	1.405 (3)
Ni1—O1	1.9980 (12)	C3—H3	0.9300
Ni1—O3i	2.0954 (13)	C4—C5	1.351 (3)
Ni1—O3	2.0954 (13)	C4—H4	0.9300
Ni1—N1	2.1779 (14)	C5—C6	1.423 (3)
Ni1—N1i	2.1779 (14)	C5—H5	0.9300
N1—C9	1.326 (2)	C6—C7	1.403 (3)
N1—C1	1.382 (2)	C7—C8	1.363 (3)
O1—C10	1.267 (2)	C7—H7	0.9300
O2—C10	1.231 (2)	C8—C9	1.409 (3)
O3—C11	1.429 (3)	C8—H8	0.9300
O3—H3O	0.859 (2)	C9—C10	1.519 (3)
C1—C2	1.411 (3)	C11—H11A	0.9600
C1—C6	1.424 (2)	C11—H11B	0.9600
C2—C3	1.371 (3)	C11—H11C	0.9600
C2—H2	0.9300
O1i—Ni1—O1	180.0	C2—C3—H3	119.5
O1i—Ni1—O3i	88.71 (6)	C4—C3—H3	119.5
O1—Ni1—O3i	91.29 (6)	C5—C4—C3	120.31 (19)
O1i—Ni1—O3	91.29 (6)	C5—C4—H4	119.8
O1—Ni1—O3	88.71 (6)	C3—C4—H4	119.8
O3i—Ni1—O3	180.00 (7)	C4—C5—C6	120.93 (18)
O1i—Ni1—N1	100.86 (6)	C4—C5—H5	119.5
O1—Ni1—N1	79.14 (6)	C6—C5—H5	119.5
O3i—Ni1—N1	89.82 (5)	C7—C6—C5	123.07 (17)
O3—Ni1—N1	90.18 (5)	C7—C6—C1	118.33 (17)
O1i—Ni1—N1i	79.14 (6)	C5—C6—C1	118.60 (17)
O1—Ni1—N1i	100.86 (6)	C8—C7—C6	120.06 (17)
O3i—Ni1—N1i	90.18 (5)	C8—C7—H7	120.0
O3—Ni1—N1i	89.82 (5)	C6—C7—H7	120.0
N1—Ni1—N1i	180.0	C7—C8—C9	118.69 (18)
C9—N1—C1	118.24 (14)	C7—C8—H8	120.7
C9—N1—Ni1	109.96 (11)	C9—C8—H8	120.7
C1—N1—Ni1	131.69 (11)	N1—C9—C8	123.71 (17)
C10—O1—Ni1	118.31 (11)	N1—C9—C10	116.25 (15)
C11—O3—Ni1	123.34 (12)	C8—C9—C10	120.04 (16)
C11—O3—H3O	107.6 (15)	O2—C10—O1	124.64 (18)
Ni1—O3—H3O	113.5 (15)	O2—C10—C9	119.26 (16)
N1—C1—C2	119.98 (15)	O1—C10—C9	116.09 (15)
N1—C1—C6	120.95 (16)	O3—C11—H11A	109.5
C2—C1—C6	119.06 (17)	O3—C11—H11B	109.5
C3—C2—C1	120.16 (18)	H11A—C11—H11B	109.5
C3—C2—H2	119.9	O3—C11—H11C	109.5
C1—C2—H2	119.9	H11A—C11—H11C	109.5
C2—C3—C4	120.9 (2)	H11B—C11—H11C	109.5
O1i—Ni1—N1—C9	175.65 (12)	C2—C3—C4—C5	0.6 (3)
O1—Ni1—N1—C9	−4.35 (12)	C3—C4—C5—C6	1.0 (3)
O3i—Ni1—N1—C9	87.00 (12)	C4—C5—C6—C7	177.7 (2)
O3—Ni1—N1—C9	−93.00 (12)	C4—C5—C6—C1	−1.5 (3)
O1i—Ni1—N1—C1	−0.27 (16)	N1—C1—C6—C7	−0.3 (3)
O1—Ni1—N1—C1	179.73 (16)	C2—C1—C6—C7	−178.75 (18)
O3i—Ni1—N1—C1	−88.92 (15)	N1—C1—C6—C5	179.02 (16)
O3—Ni1—N1—C1	91.08 (15)	C2—C1—C6—C5	0.5 (3)
O3i—Ni1—O1—C10	−85.58 (14)	C5—C6—C7—C8	−177.88 (19)
O3—Ni1—O1—C10	94.42 (14)	C1—C6—C7—C8	1.4 (3)
N1—Ni1—O1—C10	3.98 (13)	C6—C7—C8—C9	−1.1 (3)
N1i—Ni1—O1—C10	−176.02 (13)	C1—N1—C9—C8	1.4 (3)
O1i—Ni1—O3—C11	27.49 (15)	Ni1—N1—C9—C8	−175.15 (15)
O1—Ni1—O3—C11	−152.51 (15)	C1—N1—C9—C10	−179.23 (14)
N1—Ni1—O3—C11	−73.38 (15)	Ni1—N1—C9—C10	4.23 (18)
N1i—Ni1—O3—C11	106.62 (15)	C7—C8—C9—N1	−0.3 (3)
C9—N1—C1—C2	177.39 (17)	C7—C8—C9—C10	−179.64 (18)
Ni1—N1—C1—C2	−7.0 (2)	Ni1—O1—C10—O2	176.36 (16)
C9—N1—C1—C6	−1.1 (2)	Ni1—O1—C10—C9	−2.9 (2)
Ni1—N1—C1—C6	174.56 (12)	N1—C9—C10—O2	179.42 (18)
N1—C1—C2—C3	−177.54 (18)	C8—C9—C10—O2	−1.2 (3)
C6—C1—C2—C3	1.0 (3)	N1—C9—C10—O1	−1.3 (2)
C1—C2—C3—C4	−1.5 (3)	C8—C9—C10—O1	178.12 (17)

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2ii	0.86 (1)	1.81 (1)	2.655 (2)	167.(2)

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