(2-{[2-(Di­methyl­amino)­eth­yl]imino­meth­yl}benzene­thiol­ato-κ3N,N′,S)(4-meth­oxy­benzene­thiol­ato-κS)nickel(II)

Freige, M.J.; Senaratne, N.K.; Eichhorn, D.M.

doi:10.1107/S2414314618011677

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 8| August 2018| x181167

https://doi.org/10.1107/S2414314618011677

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(2-{[2-(Dimethylamino)ethyl]iminomethyl}benzenethiolato-κ³N,N′,S)(4-methoxybenzenethiolato-κS)nickel(II)

Mackenzie J. Freige,^a Nilmini K. Senaratne ^a and David M. Eichhorn ^a ^*

^aDepartment of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260, USA
^*Correspondence e-mail: david.eichhorn@wichita.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 August 2018; accepted 17 August 2018; online 24 August 2018)

In the title compound, [Ni(C₁₁H₁₅N₂S)(C₇H₇OS)] or [Ni(NN^ImS)(4-OCH₃PhS)] (NN^ImS = 2-{[2-(dimethylamino)ethyl]iminomethyl}benzenethiolato), the Ni^II cation is coordinated by a tridentate NN^ImS ligand and a monodentate thiolate ligand giving an N₂S₂ coordination set defining an almost square-planar environment. The Ni—N_amine bond in the coordination plane is approximately 0.1 Å longer than the Ni—N_imine bond.

Keywords: crystal structure; nickel complex; tridentate ligand; thiolate ligand; imine ligand; amine ligand.

CCDC reference: 1862616

Structure description

In recent years, complexes comprising an NiN₂S₂ moiety have attracted considerable interest as synthetic mimics of the NiSOD active site (Shearer & Zhao, 2006 ; Fiedler & Brunold, 2007 ; Jenkins et al., 2009 ; Gale et al., 2009 , 2010 ; Mathrubootham et al., 2010 ; Senaratne et al., 2018 ). We have prepared a series of Ni^II complexes containing the tridentate NN^ImS ligand (NN^ImS = {2-{[2-(dimethylamino)ethyl]iminomethyl}benzenethiolato}) with amine, imine, and thiolate donors, and various monodentate thiolate ligands (Senaratne et al., 2018). The title compound represents another in this series.

In the crystal, the molecule (Fig. 1) sits on general positions in the orthorhombic space group Pna2₁. The NN^ImS ligand is essentially coplanar with the coordination sphere, with an 11.84 (17)° dihedral angle between the least-squares plane of the phenyl ring and the average plane of the N₃S donors. The thiolate substituent protrudes from the coordination plane, with an Ni—S—C angle of 109.04 (15)°. The Ni—N and Ni—S bond lengths (Table 1) are very similar to those in the previously reported members of this series. No significant intermolecular interactions are evident in the crystal structure (Fig. 2). There is a potential C—H⋯π interaction between the para C atom of the NN^imS phenyl ring and the phenyl ring (C12–C17) of the monodentate ligand (C8⋯centroid 3.64 Å, C8—H8⋯centroid 156°).

Table 1
Selected geometric parameters (Å, °)

Ni1—S1	2.1383 (11)	Ni1—N2	1.888 (3)
Ni1—S2	2.2272 (12)	Ni1—N1	2.016 (3)

S1—Ni1—S2	85.25 (5)	N1—Ni1—S1	177.11 (12)
N2—Ni1—S1	95.97 (11)	N1—Ni1—S2	92.58 (11)
N2—Ni1—S2	173.07 (12)	C11—S1—Ni1	111.67 (14)
N2—Ni1—N1	86.41 (16)	C12—S2—Ni1	109.04 (15)

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.

Figure 2
Packing diagram showing the C—H⋯π interaction as a red line.

Synthesis and crystallization

Ni(NN^ImS)Cl was synthesized as previously reported (Zimmerman et al., 2011 ). Under nitrogen, NaOH (0.265 g, 7.00 mmol) was added to a solution of 4-methoxythiophenol (0.820 mL 7.00 mmol) in 10 mL methanol. After stirring for 5 min, the resulting yellow Na(4-OCH₃PhS) solution was added to a solution of [Ni(NN^ImS)Cl] (1.06 g, 3.50 mmol) in 30 ml of CH₂Cl₂. After stirring for 24 h the solution was filtered and the solvent was removed by rotary evaporation yielding 1.07 g (68.6%) of the desired title compound as a dark-brown solid. X-ray quality crystals were grown by vapor diffusion of hexanes into a CH₂Cl₂ solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. In the final refinement, ten reflections were omitted because they were obstructed by the beam stop.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(C₁₁H₁₅N₂S)(C₇H₇OS)]
M_r	405.20
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	17.625 (3), 8.8348 (16), 11.677 (2)
V (Å³)	1818.3 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.30
Crystal size (mm)	0.63 × 0.32 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Numerical (SADABS; Bruker, 2013 )
T_min, T_max	0.669, 0.831
No. of measured, independent and observed [I > 2σ(I)] reflections	58307, 3969, 3439
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.07
No. of reflections	3969
No. of parameters	220
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.21
Absolute structure	Flack x determined using 1487 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.008 (5)
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2013 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1862616

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011677/wm4084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011677/wm4084Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(2-{[2-(Dimethylamino)ethyl]iminomethyl}benzenethiolato-\ κ³N,N',S}(4-methoxybenzenethiolato-\ κS)nickel(II) top

Crystal data top

[Ni(C₁₁H₁₅N₂S)(C₇H₇OS)]	D_x = 1.480 Mg m⁻³
M_r = 405.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 9817 reflections
a = 17.625 (3) Å	θ = 3.3–24.9°
b = 8.8348 (16) Å	µ = 1.30 mm⁻¹
c = 11.677 (2) Å	T = 150 K
V = 1818.3 (6) Å³	Block, dark brown
Z = 4	0.63 × 0.32 × 0.19 mm
F(000) = 848

Data collection top

Bruker APEXII CCD diffractometer	3969 independent reflections
Radiation source: sealed X-ray tube	3439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 5.6 pixels mm^-1	θ_max = 27.2°, θ_min = 3.7°
φ and ω scans	h = −22→22
Absorption correction: numerical (SADABS; Bruker, 2013)	k = −11→11
T_min = 0.669, T_max = 0.831	l = −14→15
58307 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0391P)² + 0.4445P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.53 e Å⁻³
3969 reflections	Δρ_min = −0.21 e Å⁻³
220 parameters	Absolute structure: Flack x determined using 1487 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.008 (5)
Primary atom site location: dual

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	0.31015 (3)	0.79896 (5)	0.67113 (5)	0.04074 (14)
S1	0.34725 (6)	0.60772 (12)	0.57387 (8)	0.0477 (3)
S2	0.25283 (6)	0.87128 (13)	0.51019 (9)	0.0507 (3)
O1	0.47643 (19)	1.1565 (4)	0.1956 (3)	0.0694 (9)
N2	0.3471 (2)	0.7292 (4)	0.8134 (3)	0.0487 (8)
C9	0.4990 (3)	0.2846 (5)	0.6419 (4)	0.0605 (13)
H9	0.5227	0.2064	0.5991	0.073*
C15	0.4217 (3)	1.0920 (5)	0.2640 (4)	0.0516 (10)
N1	0.2763 (2)	0.9859 (4)	0.7559 (3)	0.0551 (9)
C10	0.4461 (3)	0.3780 (5)	0.5902 (4)	0.0557 (11)
H10	0.4337	0.3624	0.5119	0.067*
C16	0.3500 (3)	1.0535 (5)	0.2292 (4)	0.0529 (10)
H16	0.3342	1.0743	0.1530	0.063*
C8	0.5175 (3)	0.3052 (5)	0.7571 (5)	0.0671 (14)
H8	0.5544	0.2427	0.7927	0.080*
C11	0.4104 (2)	0.4958 (4)	0.6511 (4)	0.0452 (9)
C17	0.3007 (2)	0.9844 (5)	0.3052 (4)	0.0473 (10)
H17	0.2516	0.9566	0.2791	0.057*
C18	0.4536 (3)	1.2082 (6)	0.0876 (4)	0.0690 (14)
H18A	0.4341	1.1231	0.0426	0.104*
H18B	0.4971	1.2533	0.0480	0.104*
H18C	0.4137	1.2845	0.0967	0.104*
C14	0.4432 (3)	1.0639 (5)	0.3757 (4)	0.0542 (10)
H14	0.4925	1.0920	0.4006	0.065*
C7	0.4821 (3)	0.4157 (5)	0.8175 (4)	0.0634 (13)
H7	0.4943	0.4283	0.8962	0.076*
C5	0.3928 (3)	0.6212 (5)	0.8410 (4)	0.0529 (10)
H5	0.4046	0.6130	0.9202	0.064*
C6	0.4278 (2)	0.5124 (5)	0.7679 (4)	0.0491 (9)
C12	0.3202 (2)	0.9538 (5)	0.4186 (4)	0.0441 (9)
C4	0.3142 (3)	0.8191 (6)	0.9091 (4)	0.0694 (15)
H4A	0.3458	0.8089	0.9788	0.083*
H4B	0.2622	0.7840	0.9268	0.083*
C1	0.3012 (4)	1.1295 (6)	0.7016 (6)	0.098 (2)
H1A	0.3558	1.1248	0.6861	0.147*
H1B	0.2906	1.2143	0.7533	0.147*
H1C	0.2737	1.1442	0.6295	0.147*
C13	0.3937 (3)	0.9950 (5)	0.4524 (4)	0.0532 (11)
H13	0.4099	0.9756	0.5286	0.064*
C3	0.3131 (3)	0.9795 (7)	0.8693 (5)	0.0723 (16)
H3A	0.2847	1.0429	0.9245	0.087*
H3B	0.3656	1.0188	0.8639	0.087*
C2	0.1937 (3)	0.9892 (9)	0.7675 (5)	0.0809 (17)
H2A	0.1704	0.9943	0.6913	0.121*
H2B	0.1787	1.0783	0.8121	0.121*
H2C	0.1765	0.8973	0.8067	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0428 (3)	0.0447 (3)	0.0347 (2)	−0.00039 (19)	0.0018 (2)	−0.0028 (2)
S1	0.0554 (7)	0.0521 (6)	0.0356 (5)	0.0060 (5)	−0.0032 (4)	−0.0056 (4)
S2	0.0458 (6)	0.0612 (6)	0.0450 (5)	0.0018 (5)	−0.0011 (4)	0.0041 (5)
O1	0.0545 (19)	0.089 (2)	0.064 (2)	−0.0138 (18)	0.0003 (15)	0.0129 (18)
N2	0.057 (2)	0.054 (2)	0.0354 (17)	−0.0019 (18)	0.0011 (15)	−0.0055 (15)
C9	0.059 (3)	0.047 (2)	0.076 (4)	0.007 (2)	0.005 (2)	−0.001 (2)
C15	0.054 (3)	0.049 (2)	0.052 (2)	−0.003 (2)	0.004 (2)	0.0017 (18)
N1	0.054 (2)	0.060 (2)	0.050 (2)	0.0098 (19)	0.0007 (17)	−0.0142 (17)
C10	0.060 (3)	0.050 (2)	0.056 (3)	−0.001 (2)	0.004 (2)	0.000 (2)
C16	0.056 (3)	0.057 (3)	0.045 (2)	0.000 (2)	−0.0070 (19)	0.0035 (19)
C8	0.067 (3)	0.052 (3)	0.083 (4)	0.001 (2)	−0.016 (3)	0.010 (2)
C11	0.044 (2)	0.0406 (19)	0.051 (2)	−0.0051 (16)	−0.0015 (17)	−0.0006 (18)
C17	0.045 (2)	0.049 (2)	0.047 (2)	0.0055 (18)	−0.0063 (17)	−0.0013 (19)
C18	0.063 (3)	0.090 (4)	0.054 (3)	−0.001 (3)	0.004 (2)	0.015 (3)
C14	0.043 (2)	0.064 (3)	0.055 (2)	−0.006 (2)	−0.0051 (19)	−0.003 (2)
C7	0.079 (4)	0.054 (3)	0.058 (3)	−0.004 (2)	−0.017 (2)	0.009 (2)
C5	0.064 (3)	0.056 (3)	0.039 (2)	−0.003 (2)	−0.0086 (19)	0.0036 (18)
C6	0.054 (3)	0.046 (2)	0.048 (2)	−0.006 (2)	−0.0068 (19)	0.0034 (18)
C12	0.047 (3)	0.038 (2)	0.047 (2)	0.0042 (17)	−0.0009 (18)	−0.0012 (17)
C4	0.091 (4)	0.083 (4)	0.034 (2)	0.006 (3)	0.002 (2)	−0.013 (2)
C1	0.153 (7)	0.048 (3)	0.094 (5)	−0.004 (3)	0.023 (4)	−0.011 (3)
C13	0.055 (3)	0.063 (3)	0.042 (2)	0.003 (2)	−0.0054 (18)	−0.0016 (19)
C3	0.071 (4)	0.085 (4)	0.061 (3)	0.011 (3)	−0.003 (2)	−0.031 (3)
C2	0.056 (3)	0.121 (5)	0.065 (3)	0.021 (3)	0.003 (2)	−0.028 (3)

Geometric parameters (Å, º) top

Ni1—S1	2.1383 (11)	C17—H17	0.9500
Ni1—S2	2.2272 (12)	C17—C12	1.394 (6)
Ni1—N2	1.888 (3)	C18—H18A	0.9800
Ni1—N1	2.016 (3)	C18—H18B	0.9800
S1—C11	1.740 (4)	C18—H18C	0.9800
S2—C12	1.756 (5)	C14—H14	0.9500
O1—C15	1.376 (5)	C14—C13	1.389 (6)
O1—C18	1.400 (6)	C7—H7	0.9500
N2—C5	1.289 (6)	C7—C6	1.407 (6)
N2—C4	1.488 (6)	C5—H5	0.9500
C9—H9	0.9500	C5—C6	1.427 (6)
C9—C10	1.383 (7)	C12—C13	1.403 (6)
C9—C8	1.396 (8)	C4—H4A	0.9900
C15—C16	1.370 (6)	C4—H4B	0.9900
C15—C14	1.381 (6)	C4—C3	1.492 (8)
N1—C1	1.484 (7)	C1—H1A	0.9800
N1—C3	1.475 (7)	C1—H1B	0.9800
N1—C2	1.463 (6)	C1—H1C	0.9800
C10—H10	0.9500	C13—H13	0.9500
C10—C11	1.409 (6)	C3—H3A	0.9900
C16—H16	0.9500	C3—H3B	0.9900
C16—C17	1.385 (6)	C2—H2A	0.9800
C8—H8	0.9500	C2—H2B	0.9800
C8—C7	1.357 (7)	C2—H2C	0.9800
C11—C6	1.405 (6)

S1—Ni1—S2	85.25 (5)	H18B—C18—H18C	109.5
N2—Ni1—S1	95.97 (11)	C15—C14—H14	119.5
N2—Ni1—S2	173.07 (12)	C15—C14—C13	121.0 (4)
N2—Ni1—N1	86.41 (16)	C13—C14—H14	119.5
N1—Ni1—S1	177.11 (12)	C8—C7—H7	118.8
N1—Ni1—S2	92.58 (11)	C8—C7—C6	122.4 (5)
C11—S1—Ni1	111.67 (14)	C6—C7—H7	118.8
C12—S2—Ni1	109.04 (15)	N2—C5—H5	115.9
C15—O1—C18	117.2 (4)	N2—C5—C6	128.3 (4)
C5—N2—Ni1	132.6 (3)	C6—C5—H5	115.9
C5—N2—C4	116.8 (4)	C11—C6—C7	119.0 (4)
C4—N2—Ni1	110.6 (3)	C11—C6—C5	123.8 (4)
C10—C9—H9	120.0	C7—C6—C5	117.1 (4)
C10—C9—C8	120.0 (5)	C17—C12—S2	119.5 (3)
C8—C9—H9	120.0	C17—C12—C13	116.4 (4)
O1—C15—C14	115.5 (4)	C13—C12—S2	124.1 (3)
C16—C15—O1	125.2 (4)	N2—C4—H4A	110.5
C16—C15—C14	119.2 (4)	N2—C4—H4B	110.5
C1—N1—Ni1	113.7 (3)	N2—C4—C3	106.1 (4)
C3—N1—Ni1	106.2 (3)	H4A—C4—H4B	108.7
C3—N1—C1	106.6 (5)	C3—C4—H4A	110.5
C2—N1—Ni1	110.9 (3)	C3—C4—H4B	110.5
C2—N1—C1	108.5 (5)	N1—C1—H1A	109.5
C2—N1—C3	110.9 (4)	N1—C1—H1B	109.5
C9—C10—H10	119.3	N1—C1—H1C	109.5
C9—C10—C11	121.4 (4)	H1A—C1—H1B	109.5
C11—C10—H10	119.3	H1A—C1—H1C	109.5
C15—C16—H16	120.1	H1B—C1—H1C	109.5
C15—C16—C17	119.9 (4)	C14—C13—C12	120.8 (4)
C17—C16—H16	120.1	C14—C13—H13	119.6
C9—C8—H8	120.4	C12—C13—H13	119.6
C7—C8—C9	119.2 (5)	N1—C3—C4	108.8 (4)
C7—C8—H8	120.4	N1—C3—H3A	109.9
C10—C11—S1	116.3 (3)	N1—C3—H3B	109.9
C6—C11—S1	125.7 (3)	C4—C3—H3A	109.9
C6—C11—C10	118.0 (4)	C4—C3—H3B	109.9
C16—C17—H17	118.7	H3A—C3—H3B	108.3
C16—C17—C12	122.7 (4)	N1—C2—H2A	109.5
C12—C17—H17	118.7	N1—C2—H2B	109.5
O1—C18—H18A	109.5	N1—C2—H2C	109.5
O1—C18—H18B	109.5	H2A—C2—H2B	109.5
O1—C18—H18C	109.5	H2A—C2—H2C	109.5
H18A—C18—H18B	109.5	H2B—C2—H2C	109.5
H18A—C18—H18C	109.5

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