Platinum(II) com­plex with 4-nitro-N-(pyridin-2-yl­methyl­idene)aniline: synthesis, characterization, crystal structure and anti­oxidant activity

A novel com­plex has been prepared using the (E)-4-nitro-N-(pyridin-2-yl­methyl­idene)aniline bidentate Schiff base ligand and PtCl₂, namely, di­chlorido­[(E)-4-nitro-N-(pyridin-2-yl­methyl­idene)aniline-κ²N,N′]platinum(II) acetonitrile hemisolvate, [PtCl₂(C₁₂H₉N₃O₂)]·0.5CH₃CN, 1. According to the X-ray measurements of the crystal structure, the Pt^II ion adopts a PtCl₂N₂ square-planar coordination. The coordination of the Schiff base ligand to the Pt^II ion occurs in a cyclic bidentate fashion, as a result of which a five-membered metallacycle is formed. Furthermore, in the structure of 1, the neutral mol­ecules form a one-dimensional chain structure through C—H...Cl and C—H...O hydrogen bonds. The characterization of the com­plex was performed via single-crystal X-ray diffraction, IR spectroscopy and elemental analysis, and the anti­oxidant activity of the com­plex was evaluated using spec­trophotometry by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method.

Computing details

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL.

Dichlorido[(E)-4-nitro-N-(pyridin-2-ylmethylidene)aniline]platinum(II) acetonitrile hemisolvate

Crystal data

[PtCl2(C12H9N3O2)]·0.5C2H3N	Dx = 2.293 Mg m^−3
Mr = 513.74	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C2221	Cell parameters from 15181 reflections
a = 7.4469 (2) Å	θ = 2.8–27.5°
b = 27.9271 (11) Å	µ = 9.80 mm^−1
c = 14.3092 (5) Å	T = 147 K
V = 2975.89 (18) Å^3	Needle, red
Z = 8	0.10 × 0.06 × 0.06 mm
F(000) = 1928

Data collection

Nonius KappaCCD diffractometer	3418 independent reflections
Radiation source: fine-focus sealed tube	2830 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	Rint = 0.072
φ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −9→9
Tmin = 0.385, Tmax = 0.570	k = −36→36
15181 measured reflections	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0106P)^2 + 24.5578P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.069	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 1.78 e Å^−3
3418 reflections	Δρmin = −0.81 e Å^−3
227 parameters	Absolute structure: Flack x determined using 1041 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
30 restraints	Absolute structure parameter: −0.030 (8)
Primary atom site location: structure-invariant direct methods

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.

Refinement. X-ray diffraction data were measured at 147K with a Mo K? radiation (? = 0.7107 ) using a Rigaku SuperNova E (dual source) four-circle diffractometer equipped with an Eos CCD detector. For all operations (data collection, cell refinement, data reduction, and multi-scan absorption correction), the CrysAlis PRO software was used (Agilent, 2014). The structure was solved by direct methods and refined by a full-matrix least-squares technique on F2 data using SHELXTL programs (Sheldrick, 2015). All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.31897 (6)	0.81317 (2)	0.15900 (3)	0.02861 (13)
Cl1	0.3837 (5)	0.87583 (12)	0.0619 (2)	0.0435 (9)
Cl2	0.4380 (4)	0.76332 (12)	0.04850 (19)	0.0339 (7)
O1	0.313 (5)	0.5360 (8)	0.2850 (18)	0.065 (7)	0.60 (4)
O2	0.154 (4)	0.5415 (8)	0.155 (2)	0.070 (7)	0.60 (4)
O1A	0.206 (7)	0.5368 (14)	0.274 (3)	0.066 (8)	0.40 (4)
O2A	0.247 (6)	0.5498 (11)	0.131 (2)	0.066 (9)	0.40 (4)
N1	0.2324 (12)	0.8557 (4)	0.2639 (6)	0.028 (2)
N2	0.2458 (11)	0.7621 (3)	0.2534 (6)	0.022 (2)
N3	0.2263 (18)	0.5612 (5)	0.2186 (10)	0.059 (4)
C1	0.2284 (17)	0.9030 (5)	0.2676 (9)	0.041 (3)
H1A	0.264033	0.920798	0.214200	0.049*
C2	0.1730 (18)	0.9275 (4)	0.3478 (9)	0.043 (3)
H2A	0.173181	0.961510	0.348509	0.051*
C3	0.1189 (17)	0.9029 (5)	0.4249 (9)	0.042 (3)
H3A	0.077882	0.919350	0.478955	0.051*
C4	0.1249 (16)	0.8529 (4)	0.4229 (8)	0.032 (3)
H4A	0.090668	0.834780	0.476228	0.039*
C5	0.1813 (15)	0.8303 (3)	0.3423 (8)	0.029 (2)
C6	0.1893 (14)	0.7798 (4)	0.3320 (7)	0.027 (2)
H6A	0.153921	0.759318	0.381733	0.032*
C8	0.3035 (14)	0.6822 (4)	0.3167 (7)	0.031 (2)
H8A	0.346746	0.696473	0.372599	0.037*
C9	0.2971 (17)	0.6333 (4)	0.3091 (8)	0.036 (3)
H9A	0.333057	0.613405	0.359668	0.043*
C10	0.2366 (16)	0.6133 (4)	0.2253 (9)	0.034 (3)
C11	0.1787 (16)	0.6409 (4)	0.1522 (8)	0.034 (2)
H11A	0.134526	0.626370	0.096726	0.041*
C12	0.1855 (13)	0.6899 (4)	0.1604 (7)	0.028 (2)
H12A	0.148294	0.709494	0.109675	0.034*
C13	0.2472 (14)	0.7110 (4)	0.2433 (8)	0.027 (3)
C1S	−0.398 (3)	1.003 (5)	0.503 (13)	0.060 (10)	0.5
H1S1	−0.463091	0.972649	0.492814	0.090*	0.5
H1S2	−0.413320	1.023625	0.448778	0.090*	0.5
H1S3	−0.446101	1.018662	0.558883	0.090*	0.5
C2S	−0.214 (4)	0.9929 (19)	0.516 (4)	0.065 (10)	0.5
N1S	−0.059 (4)	0.9897 (12)	0.537 (2)	0.081 (10)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0293 (2)	0.0323 (2)	0.02423 (19)	0.0004 (2)	−0.0009 (2)	0.0042 (2)
Cl1	0.054 (2)	0.038 (2)	0.0379 (18)	0.0005 (15)	0.0075 (15)	0.0145 (16)
Cl2	0.0364 (17)	0.0437 (19)	0.0216 (15)	0.0011 (14)	0.0008 (12)	0.0010 (13)
O1	0.11 (2)	0.027 (9)	0.061 (12)	0.004 (15)	−0.009 (16)	0.006 (8)
O2	0.110 (18)	0.036 (10)	0.066 (14)	−0.025 (11)	−0.021 (14)	−0.003 (11)
O1A	0.11 (2)	0.039 (13)	0.046 (13)	−0.010 (19)	−0.014 (19)	0.011 (11)
O2A	0.11 (2)	0.023 (14)	0.069 (18)	0.009 (14)	0.051 (16)	0.022 (12)
N1	0.032 (6)	0.027 (6)	0.025 (5)	0.008 (4)	−0.006 (4)	0.003 (4)
N2	0.019 (5)	0.033 (6)	0.014 (5)	−0.004 (4)	−0.003 (4)	0.001 (4)
N3	0.065 (9)	0.050 (8)	0.062 (9)	−0.002 (7)	0.025 (8)	0.005 (8)
C1	0.046 (9)	0.044 (9)	0.033 (7)	0.004 (6)	−0.002 (6)	0.006 (6)
C2	0.053 (7)	0.036 (7)	0.039 (7)	−0.001 (7)	0.002 (9)	−0.001 (6)
C3	0.045 (8)	0.046 (9)	0.036 (7)	0.009 (6)	−0.008 (6)	−0.011 (7)
C4	0.036 (7)	0.035 (8)	0.026 (6)	−0.006 (6)	−0.007 (5)	0.004 (6)
C5	0.028 (5)	0.031 (6)	0.027 (5)	0.001 (5)	0.012 (7)	0.000 (5)
C6	0.019 (5)	0.041 (6)	0.019 (5)	−0.005 (5)	−0.010 (6)	0.007 (5)
C8	0.026 (5)	0.037 (6)	0.029 (6)	0.001 (6)	−0.004 (5)	0.004 (5)
C9	0.041 (7)	0.035 (7)	0.033 (7)	0.001 (6)	0.008 (6)	0.005 (5)
C10	0.041 (8)	0.028 (7)	0.035 (7)	−0.007 (5)	0.009 (5)	0.001 (6)
C11	0.031 (5)	0.034 (6)	0.038 (6)	−0.005 (6)	0.003 (8)	−0.004 (6)
C12	0.024 (4)	0.038 (6)	0.023 (4)	0.003 (6)	0.002 (5)	0.004 (6)
C13	0.029 (6)	0.031 (7)	0.020 (6)	−0.006 (5)	0.002 (4)	0.008 (5)
C1S	0.077 (14)	0.02 (3)	0.08 (2)	−0.01 (3)	0.00 (3)	−0.004 (15)
C2S	0.073 (15)	0.03 (2)	0.09 (2)	−0.015 (18)	0.00 (2)	−0.035 (16)
N1S	0.069 (16)	0.07 (2)	0.10 (3)	−0.010 (16)	0.003 (16)	−0.055 (19)

Geometric parameters (Å, º)

Pt1—N1	2.021 (10)	C4—C5	1.381 (15)
Pt1—N2	2.039 (9)	C4—H4A	0.9500
Pt1—Cl1	2.286 (3)	C5—C6	1.418 (14)
Pt1—Cl2	2.286 (3)	C6—H6A	0.9500
O1—N3	1.35 (3)	C8—C9	1.372 (16)
O2—N3	1.19 (2)	C8—C13	1.389 (15)
O1A—N3	1.06 (4)	C8—H8A	0.9500
O2A—N3	1.30 (4)	C9—C10	1.397 (16)
N1—C1	1.320 (15)	C9—H9A	0.9500
N1—C5	1.382 (14)	C10—C11	1.369 (16)
N2—C6	1.298 (13)	C11—C12	1.375 (15)
N2—C13	1.434 (15)	C11—H11A	0.9500
N3—C10	1.459 (18)	C12—C13	1.403 (15)
C1—C2	1.399 (17)	C12—H12A	0.9500
C1—H1A	0.9500	C1S—C2S	1.41 (5)
C2—C3	1.361 (17)	C1S—H1S1	0.9800
C2—H2A	0.9500	C1S—H1S2	0.9800
C3—C4	1.397 (17)	C1S—H1S3	0.9800
C3—H3A	0.9500	C2S—N1S	1.19 (4)
N1—Pt1—N2	80.4 (4)	C4—C5—C6	123.7 (11)
N1—Pt1—Cl1	93.9 (3)	N1—C5—C6	114.6 (10)
N2—Pt1—Cl1	174.1 (3)	N2—C6—C5	118.8 (10)
N1—Pt1—Cl2	174.9 (3)	N2—C6—H6A	120.6
N2—Pt1—Cl2	97.8 (3)	C5—C6—H6A	120.6
Cl1—Pt1—Cl2	87.94 (12)	C9—C8—C13	120.5 (11)
C1—N1—C5	118.4 (10)	C9—C8—H8A	119.8
C1—N1—Pt1	128.7 (9)	C13—C8—H8A	119.8
C5—N1—Pt1	112.8 (7)	C8—C9—C10	118.5 (11)
C6—N2—C13	118.0 (9)	C8—C9—H9A	120.8
C6—N2—Pt1	113.3 (8)	C10—C9—H9A	120.8
C13—N2—Pt1	128.8 (7)	C11—C10—C9	122.2 (12)
O1A—N3—O2A	126 (3)	C11—C10—N3	119.6 (12)
O2—N3—O1	120.8 (19)	C9—C10—N3	118.1 (12)
O1A—N3—C10	127 (3)	C10—C11—C12	118.9 (11)
O2—N3—C10	122.3 (17)	C10—C11—H11A	120.5
O2A—N3—C10	107.6 (19)	C12—C11—H11A	120.5
O1—N3—C10	116.8 (16)	C11—C12—C13	120.2 (11)
N1—C1—C2	121.9 (12)	C11—C12—H12A	119.9
N1—C1—H1A	119.0	C13—C12—H12A	119.9
C2—C1—H1A	119.0	C8—C13—C12	119.7 (11)
C3—C2—C1	120.3 (12)	C8—C13—N2	120.1 (10)
C3—C2—H2A	119.8	C12—C13—N2	120.2 (10)
C1—C2—H2A	119.8	C2S—C1S—H1S1	109.5
C2—C3—C4	118.6 (12)	C2S—C1S—H1S2	109.5
C2—C3—H3A	120.7	H1S1—C1S—H1S2	109.5
C4—C3—H3A	120.7	C2S—C1S—H1S3	109.5
C5—C4—C3	119.0 (11)	H1S1—C1S—H1S3	109.5
C5—C4—H4A	120.5	H1S2—C1S—H1S3	109.5
C3—C4—H4A	120.5	N1S—C2S—C1S	171 (9)
C4—C5—N1	121.7 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1	0.95	2.67	3.252 (14)	120
C2—H2A···O2^i	0.95	2.58	3.44 (3)	150
C2—H2A···O2A^i	0.95	2.55	3.48 (3)	165
C4—H4A···Cl2^ii	0.95	2.94	3.739 (13)	143
C6—H6A···Cl2^ii	0.95	2.56	3.456 (11)	157
C8—H8A···Cl2^iii	0.95	2.71	3.544 (12)	147
C11—H11A···Cl1^iv	0.95	2.94	3.799 (13)	151
C12—H12A···Cl2^iv	0.95	2.86	3.746 (11)	157
C1S—H1S1···Cl1^v	0.98	2.88	3.67 (14)	138
C1S—H1S3···Cl1^vi	0.98	2.98	3.50 (14)	114
C1S—H1S2···O2^vii	0.97	2.38	3.15 (15)	135

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