A nickel(II) complex with an unsymmetrical tetra­dentate chelating ligand derived from pyridine-2,6-dicarbaldehyde and 2-amino­thio­phenol

[(2-{[6-(1,3-Benzo­thia­zol-2-yl)pyridin-2-yl]carbonyl­aza­nid­yl}phen­yl)sulfanido]nickel(II) crystallizes in the centrosymmetric monoclinic space group P2₁/n. Both arms of the expected bis-Schiff base ligand based on pyridine-2,6-dicarbaldehyde and 2-amino­thio­phenol had oxidized; one by cyclization to a benzo­thia­zole, the other by oxidation of its imine linkage to the corresponding amide.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.039
• wR factor = 0.118
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (III)     .       2.72 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         54 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        3.0 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018); cell refinement: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND 4 (Brandenburg, 2017); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

[(2-{[6-(1,3-Benzothiazol-2-yl)pyridin-2-yl]carbonylazanidyl}phenyl)sulfanido]nickel(II)

Crystal data

[Ni(C19H11N3OS2)]	F(000) = 856
Mr = 420.14	Dx = 1.685 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 8.6790 (2) Å	Cell parameters from 3558 reflections
b = 17.3282 (7) Å	θ = 2.5–69.9°
c = 11.2211 (4) Å	µ = 4.16 mm^−1
β = 101.002 (3)°	T = 291 K
V = 1656.54 (10) Å^3	Needle, black
Z = 4	0.43 × 0.04 × 0.03 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3155 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	2567 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.022
Detector resolution: 8.0534 pixels mm^-1	θmax = 71.1°, θmin = 4.8°
ω scans	h = −7→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −20→21
Tmin = 0.675, Tmax = 1.000	l = −13→13
9403 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 0.6572P] where P = (Fo^2 + 2Fc^2)/3
3155 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.34262 (5)	0.45461 (3)	0.42355 (4)	0.04539 (17)
S1	0.38510 (9)	0.35936 (5)	0.54841 (7)	0.0545 (2)
S2	0.05248 (9)	0.65284 (5)	0.47762 (7)	0.0564 (2)
O1	0.5026 (3)	0.41006 (16)	0.1239 (2)	0.0731 (7)
N1	0.4482 (3)	0.40139 (14)	0.3182 (2)	0.0475 (5)
N2	0.3088 (3)	0.52692 (15)	0.3009 (2)	0.0479 (5)
N3	0.2213 (2)	0.52852 (15)	0.4992 (2)	0.0464 (5)
C1	0.5054 (3)	0.30515 (17)	0.4699 (3)	0.0510 (7)
C2	0.5821 (4)	0.23886 (19)	0.5187 (3)	0.0613 (8)
H2	0.569661	0.221941	0.594992	0.074*
C3	0.6770 (4)	0.1975 (2)	0.4553 (4)	0.0691 (9)
H3	0.729053	0.153451	0.489113	0.083*
C4	0.6935 (4)	0.2223 (2)	0.3413 (4)	0.0679 (9)
H4	0.756201	0.194189	0.298354	0.082*
C5	0.6186 (3)	0.28795 (19)	0.2902 (3)	0.0594 (8)
H5	0.630444	0.303622	0.213204	0.071*
C6	0.5241 (3)	0.33128 (17)	0.3547 (3)	0.0486 (6)
C7	0.4485 (3)	0.43536 (19)	0.2096 (3)	0.0531 (7)
C8	0.3688 (3)	0.5123 (2)	0.2014 (2)	0.0527 (7)
C9	0.3518 (4)	0.5655 (2)	0.1084 (3)	0.0656 (9)
H9	0.393805	0.556056	0.039524	0.079*
C10	0.2713 (4)	0.6330 (2)	0.1194 (3)	0.0709 (10)
H10	0.260753	0.669613	0.057878	0.085*
C11	0.2056 (4)	0.6471 (2)	0.2215 (3)	0.0624 (8)
H11	0.149448	0.691964	0.228923	0.075*
C12	0.2277 (3)	0.59104 (19)	0.3115 (3)	0.0505 (7)
C13	0.1742 (3)	0.58832 (18)	0.4275 (3)	0.0479 (6)
C14	0.1634 (3)	0.53493 (17)	0.6065 (3)	0.0477 (6)
C15	0.1941 (4)	0.48480 (19)	0.7055 (3)	0.0555 (7)
H15	0.257444	0.441587	0.704734	0.067*
C16	0.1273 (4)	0.5015 (2)	0.8048 (3)	0.0648 (8)
H16	0.146543	0.469043	0.871969	0.078*
C17	0.0323 (4)	0.5655 (2)	0.8065 (3)	0.0671 (9)
H17	−0.010553	0.574915	0.874946	0.081*
C18	−0.0003 (4)	0.6153 (2)	0.7104 (3)	0.0620 (8)
H18	−0.064878	0.658034	0.711846	0.074*
C19	0.0681 (3)	0.59909 (19)	0.6096 (3)	0.0525 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0467 (3)	0.0507 (3)	0.0415 (3)	−0.0033 (2)	0.01543 (19)	0.0003 (2)
S1	0.0616 (4)	0.0555 (5)	0.0508 (4)	0.0004 (3)	0.0219 (3)	0.0050 (3)
S2	0.0559 (4)	0.0555 (5)	0.0600 (4)	0.0036 (3)	0.0168 (3)	−0.0024 (4)
O1	0.0971 (17)	0.0780 (17)	0.0525 (12)	0.0047 (14)	0.0353 (12)	−0.0035 (12)
N1	0.0491 (11)	0.0501 (14)	0.0458 (12)	−0.0054 (11)	0.0154 (9)	0.0003 (11)
N2	0.0453 (11)	0.0565 (15)	0.0430 (12)	−0.0044 (11)	0.0115 (9)	0.0005 (11)
N3	0.0428 (11)	0.0536 (14)	0.0452 (12)	−0.0062 (10)	0.0143 (9)	−0.0040 (11)
C1	0.0557 (15)	0.0431 (16)	0.0562 (16)	−0.0079 (13)	0.0158 (13)	−0.0041 (13)
C2	0.0726 (19)	0.0483 (18)	0.0645 (19)	−0.0051 (16)	0.0167 (16)	0.0015 (15)
C3	0.076 (2)	0.0449 (18)	0.086 (3)	0.0026 (16)	0.0166 (19)	−0.0030 (17)
C4	0.072 (2)	0.0515 (19)	0.084 (2)	0.0001 (16)	0.0237 (18)	−0.0175 (18)
C5	0.0619 (17)	0.0582 (19)	0.0615 (19)	−0.0075 (15)	0.0203 (14)	−0.0115 (15)
C6	0.0491 (14)	0.0458 (16)	0.0524 (15)	−0.0099 (12)	0.0137 (12)	−0.0088 (13)
C7	0.0550 (15)	0.0629 (19)	0.0441 (15)	−0.0077 (14)	0.0164 (12)	−0.0066 (14)
C8	0.0519 (14)	0.066 (2)	0.0414 (14)	−0.0036 (14)	0.0128 (11)	0.0009 (14)
C9	0.0668 (19)	0.086 (3)	0.0488 (17)	0.0057 (18)	0.0224 (14)	0.0096 (17)
C10	0.077 (2)	0.085 (3)	0.0524 (18)	0.011 (2)	0.0162 (15)	0.0239 (18)
C11	0.0569 (17)	0.068 (2)	0.0627 (19)	0.0094 (16)	0.0131 (14)	0.0150 (16)
C12	0.0437 (13)	0.0591 (18)	0.0496 (15)	0.0003 (13)	0.0117 (11)	0.0045 (14)
C13	0.0446 (13)	0.0515 (17)	0.0487 (15)	−0.0045 (13)	0.0114 (11)	−0.0023 (13)
C14	0.0468 (14)	0.0496 (16)	0.0486 (14)	−0.0112 (12)	0.0140 (11)	−0.0068 (12)
C15	0.0621 (16)	0.0563 (18)	0.0519 (16)	−0.0039 (15)	0.0205 (13)	−0.0047 (14)
C16	0.086 (2)	0.063 (2)	0.0501 (17)	−0.0095 (18)	0.0248 (16)	−0.0021 (15)
C17	0.079 (2)	0.072 (2)	0.0581 (19)	−0.0118 (18)	0.0330 (17)	−0.0155 (17)
C18	0.0654 (18)	0.063 (2)	0.0631 (19)	−0.0049 (16)	0.0261 (15)	−0.0161 (16)
C19	0.0494 (14)	0.0577 (18)	0.0529 (16)	−0.0101 (14)	0.0163 (12)	−0.0099 (14)

Geometric parameters (Å, º)

Ni1—S1	2.1508 (9)	C5—H5	0.9300
Ni1—N1	1.871 (2)	C5—C6	1.409 (4)
Ni1—N2	1.843 (2)	C7—C8	1.496 (5)
Ni1—N3	1.952 (2)	C8—C9	1.380 (4)
S1—C1	1.761 (3)	C9—H9	0.9300
S2—C13	1.706 (3)	C9—C10	1.379 (5)
S2—C19	1.733 (3)	C10—H10	0.9300
O1—C7	1.229 (4)	C10—C11	1.396 (5)
N1—C6	1.405 (4)	C11—H11	0.9300
N1—C7	1.354 (4)	C11—C12	1.387 (4)
N2—C8	1.343 (3)	C12—C13	1.464 (4)
N2—C12	1.332 (4)	C14—C15	1.395 (4)
N3—C13	1.328 (4)	C14—C19	1.390 (4)
N3—C14	1.395 (3)	C15—H15	0.9300
C1—C2	1.387 (4)	C15—C16	1.381 (4)
C1—C6	1.408 (4)	C16—H16	0.9300
C2—H2	0.9300	C16—C17	1.384 (5)
C2—C3	1.387 (5)	C17—H17	0.9300
C3—H3	0.9300	C17—C18	1.368 (5)
C3—C4	1.382 (5)	C18—H18	0.9300
C4—H4	0.9300	C18—C19	1.403 (4)
C4—C5	1.380 (5)	Ni1—Ni1^i	3.3305 (9)
N1—Ni1—S1	89.40 (8)	N1—C7—C8	111.2 (2)
N1—Ni1—N3	165.47 (10)	N2—C8—C7	111.5 (3)
N2—Ni1—S1	172.45 (8)	N2—C8—C9	120.0 (3)
N2—Ni1—N1	83.74 (11)	C9—C8—C7	128.6 (3)
N2—Ni1—N3	81.75 (10)	C8—C9—H9	120.6
N3—Ni1—S1	105.05 (8)	C10—C9—C8	118.8 (3)
C1—S1—Ni1	97.34 (10)	C10—C9—H9	120.6
C13—S2—C19	88.68 (14)	C9—C10—H10	119.5
C6—N1—Ni1	120.08 (18)	C9—C10—C11	121.0 (3)
C7—N1—Ni1	116.1 (2)	C11—C10—H10	119.5
C7—N1—C6	123.8 (2)	C10—C11—H11	121.5
C8—N2—Ni1	117.4 (2)	C12—C11—C10	116.9 (3)
C12—N2—Ni1	120.79 (19)	C12—C11—H11	121.5
C12—N2—C8	121.8 (3)	N2—C12—C11	121.4 (3)
C13—N3—Ni1	112.18 (18)	N2—C12—C13	108.4 (3)
C13—N3—C14	109.9 (2)	C11—C12—C13	130.2 (3)
C14—N3—Ni1	137.8 (2)	N3—C13—S2	116.7 (2)
C2—C1—S1	122.0 (2)	N3—C13—C12	116.8 (3)
C2—C1—C6	119.9 (3)	C12—C13—S2	126.4 (2)
C6—C1—S1	118.1 (2)	N3—C14—C15	126.3 (3)
C1—C2—H2	119.6	C19—C14—N3	113.5 (3)
C1—C2—C3	120.8 (3)	C19—C14—C15	120.1 (3)
C3—C2—H2	119.6	C14—C15—H15	121.1
C2—C3—H3	120.3	C16—C15—C14	117.8 (3)
C4—C3—C2	119.4 (3)	C16—C15—H15	121.1
C4—C3—H3	120.3	C15—C16—H16	119.3
C3—C4—H4	119.4	C15—C16—C17	121.5 (3)
C5—C4—C3	121.1 (3)	C17—C16—H16	119.3
C5—C4—H4	119.4	C16—C17—H17	119.0
C4—C5—H5	120.0	C18—C17—C16	122.0 (3)
C4—C5—C6	120.0 (3)	C18—C17—H17	119.0
C6—C5—H5	120.0	C17—C18—H18	121.5
N1—C6—C1	114.6 (2)	C17—C18—C19	116.9 (3)
N1—C6—C5	126.7 (3)	C19—C18—H18	121.5
C1—C6—C5	118.7 (3)	C14—C19—S2	111.0 (2)
O1—C7—N1	128.0 (3)	C14—C19—C18	121.7 (3)
O1—C7—C8	120.7 (3)	C18—C19—S2	127.2 (3)
Ni1—S1—C1—C2	173.1 (2)	C2—C1—C6—N1	−176.4 (3)
Ni1—S1—C1—C6	−6.3 (2)	C2—C1—C6—C5	1.4 (4)
Ni1—N1—C6—C1	3.2 (3)	C2—C3—C4—C5	0.7 (5)
Ni1—N1—C6—C5	−174.4 (2)	C3—C4—C5—C6	0.4 (5)
Ni1—N1—C7—O1	−176.1 (3)	C4—C5—C6—N1	176.0 (3)
Ni1—N1—C7—C8	3.1 (3)	C4—C5—C6—C1	−1.5 (4)
Ni1—N2—C8—C7	2.4 (3)	C6—N1—C7—O1	5.4 (5)
Ni1—N2—C8—C9	−177.8 (2)	C6—N1—C7—C8	−175.4 (2)
Ni1—N2—C12—C11	177.9 (2)	C6—C1—C2—C3	−0.3 (5)
Ni1—N2—C12—C13	−2.0 (3)	C7—N1—C6—C1	−178.3 (3)
Ni1—N3—C13—S2	174.38 (13)	C7—N1—C6—C5	4.1 (4)
Ni1—N3—C13—C12	−3.7 (3)	C7—C8—C9—C10	179.1 (3)
Ni1—N3—C14—C15	6.6 (5)	C8—N2—C12—C11	−2.0 (4)
Ni1—N3—C14—C19	−174.1 (2)	C8—N2—C12—C13	178.0 (2)
S1—Ni1—N1—C6	−6.08 (19)	C8—C9—C10—C11	−1.1 (5)
S1—Ni1—N1—C7	175.3 (2)	C9—C10—C11—C12	1.2 (5)
S1—C1—C2—C3	−179.6 (3)	C10—C11—C12—N2	0.3 (5)
S1—C1—C6—N1	2.9 (3)	C10—C11—C12—C13	−179.8 (3)
S1—C1—C6—C5	−179.2 (2)	C11—C12—C13—S2	5.9 (5)
O1—C7—C8—N2	175.8 (3)	C11—C12—C13—N3	−176.3 (3)
O1—C7—C8—C9	−4.0 (5)	C12—N2—C8—C7	−177.6 (2)
N1—Ni1—N2—C8	−0.6 (2)	C12—N2—C8—C9	2.2 (4)
N1—Ni1—N2—C12	179.4 (2)	C13—S2—C19—C14	−0.7 (2)
N1—C7—C8—N2	−3.5 (4)	C13—S2—C19—C18	178.1 (3)
N1—C7—C8—C9	176.7 (3)	C13—N3—C14—C15	−177.0 (3)
N2—Ni1—N1—C6	177.1 (2)	C13—N3—C14—C19	2.4 (3)
N2—Ni1—N1—C7	−1.6 (2)	C14—N3—C13—S2	−3.0 (3)
N2—C8—C9—C10	−0.6 (5)	C14—N3—C13—C12	178.9 (2)
N2—C12—C13—S2	−174.2 (2)	C14—C15—C16—C17	0.3 (5)
N2—C12—C13—N3	3.7 (4)	C15—C14—C19—S2	178.6 (2)
N3—Ni1—N1—C6	−179.9 (3)	C15—C14—C19—C18	−0.3 (4)
N3—Ni1—N1—C7	1.4 (5)	C15—C16—C17—C18	0.0 (5)
N3—Ni1—N2—C8	−179.9 (2)	C16—C17—C18—C19	−0.5 (5)
N3—Ni1—N2—C12	0.2 (2)	C17—C18—C19—S2	−178.1 (2)
N3—C14—C15—C16	179.1 (3)	C17—C18—C19—C14	0.7 (5)
N3—C14—C19—S2	−0.8 (3)	C19—S2—C13—N3	2.2 (2)
N3—C14—C19—C18	−179.7 (3)	C19—S2—C13—C12	−179.9 (3)
C1—C2—C3—C4	−0.8 (5)	C19—C14—C15—C16	−0.2 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1^ii	0.93	2.27	3.135 (4)	155
C15—H15···S1	0.93	2.66	3.420 (3)	139

Symmetry code: (ii) −x+1, −y+1, −z.