Di-chlorido-[N-(N,N-di-methyl-carbamimido-yl)-N',N',4-tri-methyl-benzohydrazonamide]-platinum(II) nitro-methane hemisolvate.

In the title compound, [PtCl2(C13H21N5)]·0.5CH3NO2, the Pt(II) atom is coordinated in a slightly distorted square-planar geometry by two Cl atoms and two N atoms of the bidentate ligand. The (1,3,5-tri-aza-penta-diene)Pt(II) metalla ring is slightly bent and does not conjugate with the aromatic ring. In the crystal, N-H⋯Cl hydrogen bonds link the complex mol-ecules, forming chains along [001]. The nitromethane solvent molecule shows half-occupancy and is disordered over two sets of sites about an inversion centre.

Related literature

For the luminescent properties of 1,3,5-tri­aza­penta­diene metal complexes, see: Gushchin et al. (2008 ▶); Kopylovich & Pombeiro (2011 ▶); Sarova et al. (2006 ▶) and for the catalytic activity of related complexes, see: Kopylovich & Pombeiro (2011 ▶). For the synthesis of [PtCl2(C13H21N5)] and similar compounds, see: Bolotin et al. (2013 ▶). For standard bond lengths, see: Allen et al. (1987 ▶); Orpen et al. (1989 ▶).

Experimental

Crystal data

[PtCl2(C13H21N5)]·0.5CH3NO2

M = 543.86

Monoclinic,

a = 20.7561 (3) Å

b = 15.1847 (3) Å

c = 14.5191 (2) Å

β = 126.255 (1)°

V = 3690.1 (1) Å3

Z = 8

Mo Kα radiation

μ = 7.91 mm−1

T = 100 K

0.44 × 0.29 × 0.20 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer

Absorption correction: numerical (SADABS; Sheldrick, 2008a ▶) T min = 0.130, T max = 0.297

38976 measured reflections

9015 independent reflections

8276 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.015

wR(F 2) = 0.035

S = 1.06

9015 reflections

226 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −1.01 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: CrystalMaker (CrystalMaker Software, 2011 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814003894/zq2215sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003894/zq2215Isup2.hkl

CCDC reference: 987902

Additional supporting information: crystallographic information; 3D view; checkCIF report

[PtCl2(C13H21N5)]·0.5CH3NO2	F(000) = 2096
Mr = 543.86	Dx = 1.958 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9933 reflections
a = 20.7561 (3) Å	θ = 3.2–36.4°
b = 15.1847 (3) Å	µ = 7.91 mm−1
c = 14.5191 (2) Å	T = 100 K
β = 126.255 (1)°	Block, yellow
V = 3690.1 (1) Å3	0.44 × 0.29 × 0.20 mm
Z = 8

Bruker Kappa APEXII DUO CCD diffractometer	9015 independent reflections
Radiation source: fine-focus sealed tube	8276 reflections with I > 2σ(I)
Curved graphite crystal monochromator	Rint = 0.017
Detector resolution: 16 pixels mm-1	θmax = 36.5°, θmin = 2.0°
φ scans and ω scans with κ offset	h = −34→33
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	k = −25→24
Tmin = 0.130, Tmax = 0.297	l = −20→24
38976 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.035	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0133P)2 + 5.9064P] where P = (Fo2 + 2Fc2)/3
9015 reflections	(Δ/σ)max = 0.002
226 parameters	Δρmax = 0.78 e Å−3
2 restraints	Δρmin = −1.01 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.086711 (3)	0.544103 (3)	0.926821 (4)	0.01177 (1)
Cl1	0.101415 (19)	0.39718 (2)	0.89820 (3)	0.01527 (5)
Cl2	0.22139 (2)	0.56194 (2)	1.00525 (4)	0.02319 (7)
N1	0.06341 (7)	0.66831 (7)	0.95151 (10)	0.01384 (18)
N2	0.10725 (7)	0.74645 (8)	0.96392 (11)	0.0178 (2)
N3	−0.05540 (7)	0.62871 (8)	0.92740 (10)	0.01448 (18)
H3N	−0.0805	0.6409	0.9571	0.022*
N4	−0.15323 (7)	0.52601 (8)	0.81191 (10)	0.01497 (19)
N5	−0.02759 (7)	0.51555 (8)	0.84918 (10)	0.01401 (18)
H5N	−0.0494	0.4762	0.7988	0.021*
C1	0.11579 (9)	0.75208 (11)	0.87141 (14)	0.0222 (3)
H1A	0.1448	0.7003	0.8734	0.033*
H1B	0.1455	0.8055	0.8806	0.033*
H1C	0.0628	0.7542	0.7980	0.033*
C2	0.18337 (9)	0.75253 (11)	1.07686 (14)	0.0223 (3)
H2A	0.1735	0.7596	1.1346	0.033*
H2B	0.2134	0.8034	1.0793	0.033*
H2C	0.2143	0.6987	1.0925	0.033*
C3	0.00349 (8)	0.68722 (8)	0.95483 (11)	0.01326 (19)
C4	−0.00996 (8)	0.77467 (9)	0.98743 (11)	0.0143 (2)
C5	0.03328 (10)	0.80236 (10)	1.10020 (13)	0.0214 (3)
H5A	0.0757	0.7671	1.1591	0.026*
C6	0.01455 (10)	0.88207 (11)	1.12719 (14)	0.0241 (3)
H6	0.0446	0.9005	1.2047	0.029*
C7	−0.04716 (9)	0.93496 (10)	1.04312 (14)	0.0204 (3)
C8	−0.06930 (11)	1.01952 (11)	1.07194 (18)	0.0287 (3)
H8A	−0.1182	1.0107	1.0665	0.043*
H8B	−0.0783	1.0656	1.0182	0.043*
H8C	−0.0258	1.0374	1.1499	0.043*
C9	−0.09025 (9)	0.90607 (10)	0.93054 (14)	0.0220 (3)
H9	−0.1323	0.9416	0.8715	0.026*
C10	−0.07310 (9)	0.82650 (10)	0.90270 (13)	0.0196 (2)
H10	−0.1045	0.8072	0.8255	0.023*
C11	−0.07838 (8)	0.55407 (8)	0.86030 (11)	0.01253 (19)
C12	−0.17809 (9)	0.43894 (9)	0.76070 (13)	0.0182 (2)
H12A	−0.2021	0.4431	0.6790	0.027*
H12B	−0.2174	0.4151	0.7709	0.027*
H12C	−0.1315	0.3999	0.7977	0.027*
C13	−0.21699 (8)	0.58213 (10)	0.79291 (13)	0.0197 (2)
H13A	−0.2321	0.5628	0.8421	0.030*
H13B	−0.2634	0.5781	0.7127	0.030*
H13C	−0.1984	0.6433	0.8111	0.030*
O1	0.23109 (19)	0.25839 (19)	0.8531 (2)	0.0342 (6)	0.50
N6	0.24020 (19)	0.2509 (2)	0.9450 (3)	0.0313 (6)	0.50
C14	0.1897 (11)	0.1872 (12)	0.958 (2)	0.0371 (7)	0.50
H14A	0.1352	0.1861	0.8870	0.056*	0.50
H14B	0.1883	0.2062	1.0211	0.056*	0.50
H14C	0.2129	0.1280	0.9737	0.056*	0.50
O2	0.1983 (8)	0.1969 (8)	0.9556 (13)	0.0371 (7)	0.50

	U11	U22	U33	U12	U13	U23
Pt1	0.01165 (2)	0.01170 (2)	0.01451 (2)	0.00007 (1)	0.00913 (2)	−0.00061 (1)
Cl1	0.01681 (12)	0.01324 (12)	0.01993 (12)	0.00183 (10)	0.01316 (11)	0.00001 (10)
Cl2	0.01519 (13)	0.02011 (15)	0.03501 (18)	−0.00179 (11)	0.01526 (14)	−0.00348 (13)
N1	0.0138 (4)	0.0127 (4)	0.0187 (5)	−0.0007 (3)	0.0116 (4)	−0.0007 (4)
N2	0.0186 (5)	0.0140 (5)	0.0267 (6)	−0.0036 (4)	0.0167 (5)	−0.0011 (4)
N3	0.0164 (4)	0.0130 (4)	0.0197 (5)	−0.0019 (4)	0.0138 (4)	−0.0030 (4)
N4	0.0124 (4)	0.0142 (5)	0.0196 (5)	−0.0008 (3)	0.0102 (4)	−0.0019 (4)
N5	0.0132 (4)	0.0136 (5)	0.0165 (4)	−0.0017 (4)	0.0095 (4)	−0.0027 (4)
C1	0.0186 (6)	0.0260 (7)	0.0252 (6)	−0.0016 (5)	0.0146 (5)	0.0058 (5)
C2	0.0220 (6)	0.0211 (6)	0.0266 (7)	−0.0084 (5)	0.0159 (6)	−0.0085 (5)
C3	0.0149 (5)	0.0120 (5)	0.0158 (5)	−0.0003 (4)	0.0106 (4)	−0.0001 (4)
C4	0.0155 (5)	0.0120 (5)	0.0192 (5)	−0.0003 (4)	0.0124 (5)	−0.0009 (4)
C5	0.0278 (7)	0.0177 (6)	0.0187 (6)	0.0067 (5)	0.0137 (5)	0.0000 (5)
C6	0.0300 (7)	0.0202 (7)	0.0243 (6)	0.0044 (5)	0.0172 (6)	−0.0040 (5)
C7	0.0229 (6)	0.0132 (5)	0.0346 (7)	0.0003 (5)	0.0222 (6)	−0.0019 (5)
C8	0.0349 (8)	0.0158 (6)	0.0492 (10)	0.0023 (6)	0.0326 (8)	−0.0035 (6)
C9	0.0180 (6)	0.0179 (6)	0.0303 (7)	0.0045 (5)	0.0144 (6)	0.0018 (5)
C10	0.0165 (5)	0.0180 (6)	0.0226 (6)	0.0025 (5)	0.0107 (5)	−0.0013 (5)
C11	0.0133 (5)	0.0117 (5)	0.0146 (5)	0.0000 (4)	0.0094 (4)	0.0005 (4)
C12	0.0175 (5)	0.0166 (6)	0.0221 (6)	−0.0038 (4)	0.0126 (5)	−0.0042 (5)
C13	0.0138 (5)	0.0198 (6)	0.0246 (6)	0.0040 (4)	0.0107 (5)	0.0023 (5)
O1	0.0462 (16)	0.0301 (13)	0.0322 (13)	0.0129 (12)	0.0263 (13)	0.0062 (10)
N6	0.0300 (14)	0.0254 (14)	0.0396 (16)	0.0101 (11)	0.0211 (13)	0.0053 (12)
C14	0.032 (3)	0.028 (3)	0.0494 (12)	−0.0033 (15)	0.0232 (15)	0.0019 (18)
O2	0.032 (3)	0.028 (3)	0.0494 (12)	−0.0033 (15)	0.0232 (15)	0.0019 (18)

Pt1—N5	1.9809 (11)	C4—C10	1.3941 (19)
Pt1—N1	2.0309 (11)	C5—C6	1.396 (2)
Pt1—Cl1	2.3223 (3)	C5—H5A	0.9500
Pt1—Cl2	2.3279 (3)	C6—C7	1.388 (2)
N1—C3	1.3049 (16)	C6—H6	0.9500
N1—N2	1.4402 (16)	C7—C9	1.391 (2)
N2—C1	1.4576 (19)	C7—C8	1.504 (2)
N2—C2	1.459 (2)	C8—H8A	0.9800
N3—C3	1.3660 (17)	C8—H8B	0.9800
N3—C11	1.3826 (17)	C8—H8C	0.9800
N3—H3N	0.8702	C9—C10	1.386 (2)
N4—C11	1.3408 (17)	C9—H9	0.9500
N4—C12	1.4537 (18)	C10—H10	0.9500
N4—C13	1.4567 (18)	C12—H12A	0.9800
N5—C11	1.2966 (16)	C12—H12B	0.9800
N5—H5N	0.8399	C12—H12C	0.9800
C1—H1A	0.9800	C13—H13A	0.9800
C1—H1B	0.9800	C13—H13B	0.9800
C1—H1C	0.9800	C13—H13C	0.9800
C2—H2A	0.9800	O1—N6	1.237 (3)
C2—H2B	0.9800	N6—C14	1.518 (8)
C2—H2C	0.9800	C14—H14A	0.9800
C3—C4	1.4904 (18)	C14—H14B	0.9800
C4—C5	1.3875 (19)	C14—H14C	0.9800
N5—Pt1—N1	88.49 (5)	C10—C4—C3	118.53 (12)
N5—Pt1—Cl1	85.86 (3)	C4—C5—C6	120.05 (14)
N1—Pt1—Cl1	173.69 (3)	C4—C5—H5A	120.0
N5—Pt1—Cl2	172.48 (3)	C6—C5—H5A	120.0
N1—Pt1—Cl2	98.51 (3)	C7—C6—C5	121.33 (14)
Cl1—Pt1—Cl2	87.274 (12)	C7—C6—H6	119.3
C3—N1—N2	111.07 (11)	C5—C6—H6	119.3
C3—N1—Pt1	122.86 (9)	C6—C7—C9	117.95 (13)
N2—N1—Pt1	126.04 (8)	C6—C7—C8	121.61 (15)
N1—N2—C1	110.19 (11)	C9—C7—C8	120.41 (15)
N1—N2—C2	112.14 (11)	C7—C8—H8A	109.5
C1—N2—C2	113.01 (11)	C7—C8—H8B	109.5
C3—N3—C11	127.96 (11)	H8A—C8—H8B	109.5
C3—N3—H3N	114.3	C7—C8—H8C	109.5
C11—N3—H3N	117.7	H8A—C8—H8C	109.5
C11—N4—C12	120.52 (11)	H8B—C8—H8C	109.5
C11—N4—C13	123.69 (12)	C10—C9—C7	121.34 (14)
C12—N4—C13	115.29 (11)	C10—C9—H9	119.3
C11—N5—Pt1	128.23 (9)	C7—C9—H9	119.3
C11—N5—H5N	111.7	C9—C10—C4	120.30 (14)
Pt1—N5—H5N	119.9	C9—C10—H10	119.9
N2—C1—H1A	109.5	C4—C10—H10	119.9
N2—C1—H1B	109.5	N5—C11—N4	124.54 (12)
H1A—C1—H1B	109.5	N5—C11—N3	119.36 (12)
N2—C1—H1C	109.5	N4—C11—N3	116.09 (11)
H1A—C1—H1C	109.5	N4—C12—H12A	109.5
H1B—C1—H1C	109.5	N4—C12—H12B	109.5
N2—C2—H2A	109.5	H12A—C12—H12B	109.5
N2—C2—H2B	109.5	N4—C12—H12C	109.5
H2A—C2—H2B	109.5	H12A—C12—H12C	109.5
N2—C2—H2C	109.5	H12B—C12—H12C	109.5
H2A—C2—H2C	109.5	N4—C13—H13A	109.5
H2B—C2—H2C	109.5	N4—C13—H13B	109.5
N1—C3—N3	123.64 (12)	H13A—C13—H13B	109.5
N1—C3—C4	124.71 (12)	N4—C13—H13C	109.5
N3—C3—C4	111.65 (11)	H13A—C13—H13C	109.5
C5—C4—C10	118.99 (13)	H13B—C13—H13C	109.5
C5—C4—C3	122.20 (12)	O1—N6—C14	121.0 (10)
N5—Pt1—N1—C3	24.61 (11)	N3—C3—C4—C10	−70.06 (15)
Cl2—Pt1—N1—C3	−158.15 (10)	C10—C4—C5—C6	−1.5 (2)
N5—Pt1—N1—N2	−153.35 (11)	C3—C4—C5—C6	−175.32 (14)
Cl2—Pt1—N1—N2	23.89 (11)	C4—C5—C6—C7	0.2 (3)
C3—N1—N2—C1	−127.66 (12)	C5—C6—C7—C9	0.2 (2)
Pt1—N1—N2—C1	50.50 (15)	C5—C6—C7—C8	178.10 (16)
C3—N1—N2—C2	105.52 (13)	C6—C7—C9—C10	0.8 (2)
Pt1—N1—N2—C2	−76.31 (14)	C8—C7—C9—C10	−177.14 (15)
N1—Pt1—N5—C11	−23.40 (12)	C7—C9—C10—C4	−2.2 (2)
Cl1—Pt1—N5—C11	153.79 (12)	C5—C4—C10—C9	2.5 (2)
N2—N1—C3—N3	169.27 (12)	C3—C4—C10—C9	176.52 (13)
Pt1—N1—C3—N3	−8.97 (18)	Pt1—N5—C11—N4	−173.99 (10)
N2—N1—C3—C4	−10.04 (18)	Pt1—N5—C11—N3	5.04 (18)
Pt1—N1—C3—C4	171.73 (9)	C12—N4—C11—N5	12.4 (2)
C11—N3—C3—N1	−22.1 (2)	C13—N4—C11—N5	−159.13 (13)
C11—N3—C3—C4	157.24 (12)	C12—N4—C11—N3	−166.66 (12)
N1—C3—C4—C5	−76.83 (18)	C13—N4—C11—N3	21.81 (19)
N3—C3—C4—C5	103.79 (15)	C3—N3—C11—N5	24.5 (2)
N1—C3—C4—C10	109.32 (16)	C3—N3—C11—N4	−156.34 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···Cl1i	0.87	2.45	3.2154 (11)	147
N5—H5N···Cl1ii	0.84	2.67	3.4598 (12)	157

Table 1

Selected bond lengths (Å)

Pt1—N5	1.9809 (11)
Pt1—N1	2.0309 (11)
Pt1—Cl1	2.3223 (3)
Pt1—Cl2	2.3279 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯Cl1i	0.87	2.45	3.2154 (11)	147
N5—H5N⋯Cl1ii	0.84	2.67	3.4598 (12)	157

Symmetry codes: (i) ; (ii) .