metal-organic compounds
(2-{[2-(Dimethylamino)ethyl]iminomethyl}benzenethiolato-κ3N,N′,S)(4-methoxybenzenethiolato-κS)nickel(II)
aDepartment of Chemistry, Wichita State University, 1845 Fairmount, Wichita, KS 67260, USA
*Correspondence e-mail: david.eichhorn@wichita.edu
In the title compound, [Ni(C11H15N2S)(C7H7OS)] or [Ni(NNImS)(4-OCH3PhS)] (NNImS = 2-{[2-(dimethylamino)ethyl]iminomethyl}benzenethiolato), the NiII cation is coordinated by a tridentate NNImS ligand and a monodentate thiolate ligand giving an N2S2 coordination set defining an almost square-planar environment. The Ni—Namine bond in the coordination plane is approximately 0.1 Å longer than the Ni—Nimine 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 NiII complexes containing the tridentate NNImS ligand (NNImS = {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 Pna21. The NNImS 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 (Fig. 2). There is a potential C—H⋯π interaction between the para C atom of the NNimS phenyl ring and the phenyl ring (C12–C17) of the monodentate ligand (C8⋯centroid 3.64 Å, C8—H8⋯centroid 156°).
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Synthesis and crystallization
Ni(NNImS)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(NNImS)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 . In the final ten reflections were omitted because they were obstructed by the beam stop.
details are summarized in Table 2Structural data
CCDC reference: 1862616
https://doi.org/10.1107/S2414314618011677/wm4084sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011677/wm4084Isup2.hkl
Data collection: APEX2 (Bruker, 2013); cell
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).[Ni(C11H15N2S)(C7H7OS)] | Dx = 1.480 Mg m−3 |
Mr = 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 |
Bruker APEXII CCD diffractometer | 3969 independent reflections |
Radiation source: sealed X-ray tube | 3439 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 5.6 pixels mm-1 | θmax = 27.2°, θmin = 3.7° |
φ and ω scans | h = −22→22 |
Absorption correction: numerical (SADABS; Bruker, 2013) | k = −11→11 |
Tmin = 0.669, Tmax = 0.831 | l = −14→15 |
58307 measured reflections |
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(Fo2) + (0.0391P)2 + 0.4445P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.53 e Å−3 |
3969 reflections | Δρmin = −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 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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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