Crystal structure of di­aqua­bis­(2-chloro­pyridine-κN)bis­(thio­cyanato-κN)nickel(II)

Suckert, S.; Jess, I.; Näther, C.

doi:10.1107/S2056989016015218

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Volume 72| Part 10| October 2016| Pages 1492-1494

https://doi.org/10.1107/S2056989016015218

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Crystal structure of diaquabis(2-chloropyridine-κN)bis(thiocyanato-κN)nickel(II)

Stefan Suckert,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Str. 2, D-24118 Kiel, Germany
^*Correspondence e-mail: ssuckert@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 15 September 2016; accepted 27 September 2016; online 30 September 2016)

The asymmetric unit of the title compound, [Ni(NCS)₂(C₅H₄ClN)₂(H₂O)₂], consists of one nickel(II) cation that is located on a center of inversion and one thiocyanate anion, one water molecule and one 2-chloropyridine ligand all occupying general positions. The Ni^II cation is octahedrally coordinated by two terminal N-bound thiocyanato ligands, two aqua ligands and two N-bound 2-chloropyridine ligands into discrete complexes. Individual complexes are linked by intermolecular O—H⋯S and O—H⋯Cl hydrogen-bonding interactions into a layered network extending parallel to the bc plane. Weak interactions of types C—H⋯S and C—H⋯Cl consolidate the crystal packing.

Keywords: crystal structure; discrete metal complex; nickel(II) thiocyanate; 2-chloropyridine; hydrogen bonding.

CCDC reference: 1506903

1. Chemical context

The synthesis of materials with interesting cooperative magnetic properties is still a major field in coordination chemistry (Zhang et al., 2011 ). One feasible strategy for the preparation of such compounds is to link paramagnetic cations with small anionic ligands such as, for example, thiocyanate anions to enable a magnetic exchange between the cations (Palion-Gazda et al., 2015 ; Massoud et al., 2013 ). In this regard, our group has reported on a number of coordination polymers with bridging thiocyanato ligands. Dependent on the metal cation and the neutral co-ligand, they show different magnetic phenomena including a slow relaxation of the magnetization, which is indicative for single-chain magnetism (Werner et al., 2014 , 2015a ,b ,c ). In the context of this research, discrete complexes are likewise of interest because such compounds can be transformed into the desired polymeric systems by thermal decomposition (Näther et al., 2013 ). In view of our systematic studies, we became interested into compounds based on 2-chloropyridine as co-ligand, for which only two different polymorphs were found for representatives containing Zn or Co (Wöhlert et al., 2013 ). In a more recent study, investigations were also carried out for Ni that led to the title compound being characterized by single crystal X-ray diffraction. Unfortunately, no single-phase crystalline powder could be synthesized, which prevented further investigations of its physical properties.

2. Structural commentary

The asymmetric unit of the title compound, [Ni(NCS)₂(C₅H₄NCl)₂(H₂O)₂], consists of one Ni^II cation, one thiocyanate anion, one water molecule and one neutral 2-chloropyridine co-ligand. The cation is located on a center of inversion whereas all ligands are located on general positions. The Ni^II cation is coordinated by two terminal N-bound inorganic anionic ligands, two water molecules and two 2-chloropyridine ligands that are coordinated via the pyridine N atom in an all-trans configuration (Fig. 1). As expected, and in agreement with values reported in literature (Đaković et al., 2008 ; Werner et al., 2015b), the Ni—N bond lengths to the thiocyanato ligands are significantly shorter[2.018 (3) Å] than to the pyridine N atom of the neutral 2-chloropyridine ligand [2.208 (3) Å].

Figure 1
View of a discrete complex with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , -z.+1.]

3. Supramolecular features

In the crystal, discrete complexes are linked by pairs of intermolecular O—H⋯S hydrogen bonds between one of the two water H atoms and the thiocyanato S atoms of a neighboring complex into centrosymmetric dimers that are further connected into chains along the b axis (Fig. 2, Table 1). Neighbouring complexes are additionally linked in the same direction by pairs of C—H⋯Cl hydrogen bonds between the chloro substituent of one complex and one pyridine H atom of a neighbouring complex (Fig. 2, Table 1). These chains are further linked by O—H⋯S hydrogen bonding between the second water H atom of one complex and a thiocyanato S atom of a neighbouring complex into layers parallel to the bc plane (Fig. 3, Table 1). Within these layers, weak C—H⋯Cl hydrogen bonding is present (Table 1). Weak intramolecular O—H⋯Cl interactions are also observed (Figs. 2 and 3, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H21⋯S1ⁱ	0.95	2.99	3.904 (4)	162
C13—H23⋯S1ⁱⁱ	0.95	2.99	3.796 (4)	143
C14—H24⋯Cl1ⁱⁱⁱ	0.95	2.96	3.796 (4)	147
O1—H1O1⋯S1^iv	0.82	2.39	3.175 (2)	160
O1—H2O1⋯S1^v	0.82	2.53	3.239 (2)	145
O1—H2O1⋯Cl1^vi	0.82	2.75	3.180 (3)	115
Symmetry codes: (i) $[-x, y+1, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[x, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (vi) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 2
View of the hydrogen-bonded chain that elongates along the b axis. Hydrogen bonds are shown as dashed lines.

Figure 3
Crystal structure of the title compound showing the hydrogen-bonded layers with hydrogen bonds shown as dashed lines.

4. Database survey

To the best of our knowledge, there are only four coordination compounds containing thiocyanato and 2-chloropyridine ligands deposited in the Cambridge Structure Database (Version 5.37, last update 2015; Groom et al., 2016 ). The structures consist of tetrahedrally coordinated metal cations (Co and Zn) where each metal cation is surrounded by two 2-chloropyridine ligands as well as two thiocyanate anions (Wöhlert et al., 2013). A general search for coordination compounds with 2-chloropyridine ligands resulted in 16 structures including the aforementioned ones. Two examples relate to a Pd compound, similar to the Co and Zn ones, however with the Pd^II cation in a square-planar conformation coordinated by two 2-chloropyridine ligands as well as two azide anions (Beck et al., 2001 ) as well as a Cu compound with a square-pyramidal coordinated metal cation surrounded by two 2-chloropyridine ligands, one water ligand and two chloride anions (Jin et al., 2005 ).

5. Synthesis and crystallization

Ba(NCS)₂·3H₂O, Ni(SO₄)·6H₂O and 2-chloropyridine were purchased from Alfa Aesar. Ni(NCS)₂ was synthesized by stirring 17.5 g Ba(NCS)₂·3H₂O (57 mmol) with 15.0 g Ni(SO₄)·6H₂O (57 mmol) in 500 ml water. The green residue was filtered off and the filtrate was dried using a rotary evaporator. The homogeneity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 26.2 mg Ni(NCS)₂ (0.15 mmol) with 56.0 µl 2-chloropyridine (0.6 mmol) in ethanol (1.0 ml) after a few days.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2. The CH H atoms were positioned with idealized geometry and were refined in a riding model with U_iso(H) = 1.2U_eq(C). The OH H atoms were located in a difference map, and their bond lengths constrained to 0.82 Å, with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₅H₄ClN)₂(H₂O)₂]
M_r	437.99
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	19.5045 (15), 7.5486 (5), 14.9387 (11)
β (°)	125.560 (7)
V (Å³)	1789.3 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.63
Crystal size (mm)	0.14 × 0.09 × 0.06

Data collection
Diffractometer	STOE IPDS1
Absorption correction	Numerical (X-RED32 and X-SHAPE; Stoe, 2008 )
T_min, T_max	0.796, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	7195, 1568, 1321
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.123, 1.03
No. of reflections	1568
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.87
Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1506903

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016015218/wm5326sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016015218/wm5326Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Diaquabis(2-chloropyridine-κN)bis(thiocyanato-κN)nickel(II) top

Crystal data top

[Ni(NCS)₂(C₅H₄ClN)₂(H₂O)₂]	F(000) = 888
M_r = 437.99	D_x = 1.626 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.5045 (15) Å	Cell parameters from 7195 reflections
b = 7.5486 (5) Å	θ = 2.8–25.1°
c = 14.9387 (11) Å	µ = 1.63 mm⁻¹
β = 125.560 (7)°	T = 200 K
V = 1789.3 (3) Å³	Block, blue
Z = 4	0.14 × 0.09 × 0.06 mm

Data collection top

STOE IPDS-1 diffractometer	1321 reflections with I > 2σ(I)
Phi scans	R_int = 0.086
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	θ_max = 25.1°, θ_min = 2.8°
T_min = 0.796, T_max = 0.881	h = −23→23
7195 measured reflections	k = −8→8
1568 independent reflections	l = −17→17

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.0887P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.87 e Å⁻³
1568 reflections	Δρ_min = −0.87 e Å⁻³
107 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0046 (11)

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	0.2500	0.7500	0.5000	0.0294 (3)
N1	0.2189 (2)	0.5551 (4)	0.3900 (2)	0.0374 (7)
C1	0.2063 (2)	0.4433 (4)	0.3291 (3)	0.0307 (7)
S1	0.18836 (7)	0.28294 (11)	0.24339 (8)	0.0404 (3)
N10	0.1155 (2)	0.7772 (4)	0.4334 (3)	0.0360 (7)
C10	0.0670 (2)	0.9202 (4)	0.4075 (3)	0.0367 (8)
C11	−0.0154 (3)	0.9163 (6)	0.3732 (3)	0.0500 (10)
H21	−0.0466	1.0227	0.3568	0.060*
C12	−0.0520 (3)	0.7528 (6)	0.3630 (4)	0.0586 (12)
H22	−0.1088	0.7447	0.3395	0.070*
C13	−0.0039 (3)	0.6027 (6)	0.3879 (4)	0.0520 (10)
H23	−0.0271	0.4888	0.3814	0.062*
C14	0.0780 (3)	0.6201 (5)	0.4222 (3)	0.0425 (8)
H24	0.1104	0.5153	0.4391	0.051*
Cl1	0.11007 (7)	1.12552 (11)	0.41519 (9)	0.0523 (4)
O1	0.26098 (19)	0.5775 (3)	0.6135 (2)	0.0506 (8)
H1O1	0.2506	0.5933	0.6588	0.076*
H2O1	0.2750	0.4730	0.6262	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0383 (4)	0.0205 (4)	0.0375 (4)	0.0053 (2)	0.0267 (3)	0.0031 (2)
N1	0.0443 (18)	0.0298 (14)	0.0434 (17)	0.0060 (11)	0.0285 (15)	−0.0008 (12)
C1	0.0350 (18)	0.0247 (15)	0.0417 (19)	0.0052 (12)	0.0276 (17)	0.0077 (13)
S1	0.0613 (7)	0.0251 (4)	0.0505 (6)	−0.0030 (3)	0.0415 (5)	−0.0032 (3)
N10	0.0388 (17)	0.0317 (14)	0.0423 (17)	0.0040 (11)	0.0264 (15)	0.0018 (11)
C10	0.036 (2)	0.0375 (17)	0.0383 (19)	0.0087 (14)	0.0225 (17)	0.0037 (14)
C11	0.036 (2)	0.064 (2)	0.043 (2)	0.0151 (18)	0.019 (2)	0.0064 (18)
C12	0.034 (2)	0.087 (4)	0.050 (3)	−0.0007 (19)	0.022 (2)	−0.004 (2)
C13	0.042 (2)	0.057 (2)	0.054 (3)	−0.0120 (19)	0.026 (2)	−0.0078 (19)
C14	0.042 (2)	0.0371 (18)	0.051 (2)	−0.0066 (14)	0.029 (2)	−0.0054 (15)
Cl1	0.0574 (7)	0.0308 (5)	0.0770 (8)	0.0163 (4)	0.0438 (6)	0.0128 (4)
O1	0.079 (2)	0.0367 (13)	0.0661 (18)	0.0270 (13)	0.0597 (18)	0.0243 (12)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.018 (3)	C10—Cl1	1.734 (4)
Ni1—N1	2.018 (3)	C11—C12	1.389 (6)
Ni1—O1	2.048 (2)	C11—H21	0.9500
Ni1—O1ⁱ	2.048 (2)	C12—C13	1.377 (6)
Ni1—N10	2.208 (3)	C12—H22	0.9500
Ni1—N10ⁱ	2.208 (3)	C13—C14	1.372 (6)
N1—C1	1.158 (4)	C13—H23	0.9500
C1—S1	1.645 (3)	C14—H24	0.9500
N10—C10	1.336 (4)	O1—H1O1	0.8198
N10—C14	1.352 (4)	O1—H2O1	0.8201
C10—C11	1.375 (6)

N1ⁱ—Ni1—N1	180.0	C14—N10—Ni1	112.9 (2)
N1ⁱ—Ni1—O1	87.27 (12)	N10—C10—C11	124.6 (4)
N1—Ni1—O1	92.73 (12)	N10—C10—Cl1	117.9 (3)
N1ⁱ—Ni1—O1ⁱ	92.73 (12)	C11—C10—Cl1	117.4 (3)
N1—Ni1—O1ⁱ	87.27 (12)	C10—C11—C12	118.3 (4)
O1—Ni1—O1ⁱ	180.0	C10—C11—H21	120.8
N1ⁱ—Ni1—N10	90.88 (11)	C12—C11—H21	120.8
N1—Ni1—N10	89.12 (11)	C13—C12—C11	118.4 (4)
O1—Ni1—N10	87.55 (11)	C13—C12—H22	120.8
O1ⁱ—Ni1—N10	92.45 (11)	C11—C12—H22	120.8
N1ⁱ—Ni1—N10ⁱ	89.11 (11)	C14—C13—C12	119.0 (4)
N1—Ni1—N10ⁱ	90.88 (11)	C14—C13—H23	120.5
O1—Ni1—N10ⁱ	92.45 (11)	C12—C13—H23	120.5
O1ⁱ—Ni1—N10ⁱ	87.55 (11)	N10—C14—C13	124.0 (4)
N10—Ni1—N10ⁱ	180.0	N10—C14—H24	118.0
C1—N1—Ni1	175.7 (3)	C13—C14—H24	118.0
N1—C1—S1	179.4 (3)	Ni1—O1—H1O1	129.3
C10—N10—C14	115.6 (3)	Ni1—O1—H2O1	131.5
C10—N10—Ni1	131.4 (2)	H1O1—O1—H2O1	99.1

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H21···S1ⁱⁱ	0.95	2.99	3.904 (4)	162
C13—H23···S1ⁱⁱⁱ	0.95	2.99	3.796 (4)	143
C14—H24···Cl1^iv	0.95	2.96	3.796 (4)	147
O1—H1O1···S1^v	0.82	2.39	3.175 (2)	160
O1—H2O1···S1^vi	0.82	2.53	3.239 (2)	145
O1—H2O1···Cl1ⁱ	0.82	2.75	3.180 (3)	115

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

Acknowledgements

This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

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