[2-Acetyl­pyridine 1,1-(hexane-1,6-di­yl)thio­semicarbazone-κ³N,N′,S]chloro­platinum(II)

In the title compound, [Pt(C₁₄H₁₉N₄S)Cl], the azepane ring is partially disordered over two sites. The Pt atom coordination adopts a slightly distorted square-planar geometry. The 2-acetyl­pyridine thio­semicarbazone moiety is very close to planar. The azepane ring has a (−sc, +sc)₃, +sp conformation (sc is synclinal and sp is synperiplanar) and, for the minor disorder component, a (−sc, +sc)₃, −sp conformation. The computed bond valences for the Pt centre are ν_Pt—N = 0.467 and 0.587, ν_Pt—S = 0.60, and ν_Pt—Cl = 0.48 v.u. (valence units), and thus the computed valence of the Pt atom is 2.13 v.u. π–π stacking inter­actions give rise to π-bonded dimers.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.015 Å
• Disorder in main residue
• R factor = 0.047
• wR factor = 0.086
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C12

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.58 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C12'
PLAT301_ALERT_3_C Main Residue  Disorder .........................       9.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         15

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: CrysAlis CCD (UNIL IC and Kuma, 2000); cell refinement: CrysAlis RED (UNIL IC and Kuma, 2000); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Version 1.4; Bruno et al., 2002); software used to prepare material for publication: SHELXL97.

[2-Acetylpyridine 1,1-(hexane-1,6-diyl)thiosemicarbazone-κ³N,N',S]chloroplatinum(II)

Crystal data

[Pt(C14H19N4S)Cl]	F(000) = 968
Mr = 505.93	Dx = 2.064 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2976 (11) Å	Cell parameters from 4615 reflections
b = 24.999 (2) Å	θ = 2–20°
c = 9.2074 (14) Å	µ = 8.91 mm^−1
β = 104.272 (13)°	T = 291 K
V = 1627.9 (4) Å^3	Prism, red
Z = 4	0.24 × 0.12 × 0.06 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	2900 independent reflections
Radiation source: fine-focus sealed tube	2556 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 25.1°, θmin = 3.0°
Absorption correction: numerical (X-RED; Stoe & Cie, 1999)	h = −8→8
Tmin = 0.109, Tmax = 0.596	k = −29→29
16639 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0001P)^2 + 11.6759P] where P = (Fo^2 + 2Fc^2)/3
2900 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 1.11 e Å^−3
0 restraints	Δρmin = −0.99 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.23139 (5)	0.071258 (14)	0.39283 (4)	0.03867 (12)
Cl1	0.0748 (4)	0.09464 (12)	0.1499 (3)	0.0650 (8)
C1	0.2284 (12)	−0.0352 (4)	0.5085 (10)	0.038 (2)
N1	0.1678 (10)	−0.0088 (3)	0.3744 (8)	0.0404 (18)
C2	0.0802 (13)	−0.0368 (4)	0.2519 (11)	0.048 (2)
H2	0.0421	−0.0192	0.1605	0.058*
C3	0.0453 (14)	−0.0911 (4)	0.2583 (12)	0.054 (3)
H3	−0.0190	−0.1093	0.1728	0.065*
C4	0.1063 (13)	−0.1177 (4)	0.3915 (12)	0.050 (3)
H4	0.0855	−0.1542	0.3974	0.060*
C5	0.2003 (13)	−0.0890 (4)	0.5186 (12)	0.047 (2)
H5	0.2437	−0.1066	0.6097	0.056*
C6	0.3266 (12)	−0.0012 (4)	0.6334 (10)	0.037 (2)
C7	0.3981 (14)	−0.0219 (4)	0.7930 (11)	0.051 (3)
H7A	0.5083	−0.0436	0.7993	0.077*
H7B	0.3012	−0.0430	0.8195	0.077*
H7C	0.4298	0.0078	0.8607	0.077*
N2	0.3491 (10)	0.0491 (3)	0.5998 (8)	0.0334 (16)
N3	0.4405 (10)	0.0844 (3)	0.7088 (9)	0.0427 (19)
C8	0.4469 (12)	0.1340 (4)	0.6590 (11)	0.043 (2)
S1	0.3401 (4)	0.15415 (10)	0.4707 (3)	0.0505 (6)
N4	0.5398 (12)	0.1703 (3)	0.7572 (9)	0.050 (2)
C9	0.6168 (15)	0.1557 (4)	0.9162 (11)	0.056 (3)
H9A	0.7181	0.1802	0.9606	0.068*
H9B	0.6702	0.1200	0.9212	0.068*
C10	0.4705 (16)	0.1570 (4)	1.0061 (11)	0.061 (3)
H10A	0.3711	0.1319	0.9618	0.073*	0.63 (4)
H10B	0.5289	0.1445	1.1066	0.073*	0.63 (4)
H10C	0.5291	0.1683	1.1064	0.073*	0.37 (4)
H10D	0.4234	0.1214	1.0111	0.073*	0.37 (4)
C11	0.3818 (16)	0.2099 (4)	1.0179 (11)	0.096 (13)	0.63 (4)
H11A	0.4801	0.2350	1.0644	0.115*	0.63 (4)
H11B	0.2969	0.2063	1.0835	0.115*	0.63 (4)
C12	0.272 (3)	0.2331 (11)	0.869 (3)	0.063 (7)	0.63 (4)
H12A	0.1846	0.2597	0.8897	0.076*	0.63 (4)
H12B	0.1966	0.2047	0.8119	0.076*	0.63 (4)
C11'	0.297 (6)	0.1985 (14)	0.946 (6)	0.072 (16)	0.37 (4)
H11C	0.2112	0.1836	0.8576	0.086*	0.37 (4)
H11D	0.2278	0.2031	1.0223	0.086*	0.37 (4)
C12'	0.366 (8)	0.2517 (14)	0.908 (4)	0.064 (13)	0.37 (4)
H12C	0.2767	0.2785	0.9244	0.077*	0.37 (4)
H12D	0.4852	0.2588	0.9790	0.077*	0.37 (4)
C13	0.391 (2)	0.2596 (5)	0.7690 (19)	0.090 (4)
H13A	0.3038	0.2723	0.6784	0.108*	0.63 (4)
H13B	0.4526	0.2909	0.8218	0.108*	0.63 (4)
H13C	0.4154	0.2968	0.7547	0.108*	0.37 (4)
H13D	0.2722	0.2510	0.7014	0.108*	0.37 (4)
C14	0.5391 (19)	0.2273 (5)	0.7230 (13)	0.070 (4)
H14A	0.5227	0.2313	0.6158	0.084*
H14B	0.6620	0.2419	0.7718	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0377 (2)	0.0457 (2)	0.0331 (2)	0.00385 (18)	0.00948 (14)	0.00341 (18)
Cl1	0.0728 (19)	0.0749 (18)	0.0410 (15)	−0.0010 (15)	0.0022 (13)	0.0153 (13)
C1	0.036 (5)	0.042 (5)	0.038 (5)	0.003 (4)	0.016 (4)	−0.002 (4)
N1	0.035 (4)	0.049 (5)	0.040 (5)	0.002 (3)	0.014 (4)	−0.003 (4)
C2	0.039 (5)	0.067 (7)	0.040 (6)	−0.005 (5)	0.013 (4)	−0.005 (5)
C3	0.052 (6)	0.064 (7)	0.049 (6)	−0.020 (5)	0.018 (5)	−0.021 (5)
C4	0.047 (6)	0.050 (6)	0.056 (7)	−0.014 (5)	0.020 (5)	−0.013 (5)
C5	0.043 (6)	0.052 (6)	0.047 (6)	0.006 (4)	0.013 (5)	0.008 (5)
C6	0.041 (5)	0.042 (5)	0.031 (5)	0.006 (4)	0.012 (4)	0.000 (4)
C7	0.056 (6)	0.053 (6)	0.041 (6)	0.005 (5)	0.005 (5)	0.013 (5)
N2	0.033 (4)	0.039 (4)	0.027 (4)	0.003 (3)	0.005 (3)	−0.002 (3)
N3	0.045 (5)	0.041 (5)	0.041 (5)	0.001 (3)	0.009 (4)	−0.008 (3)
C8	0.031 (5)	0.045 (5)	0.056 (6)	0.000 (4)	0.017 (4)	0.002 (5)
S1	0.0587 (16)	0.0436 (14)	0.0481 (15)	−0.0006 (12)	0.0108 (12)	0.0072 (12)
N4	0.054 (5)	0.046 (5)	0.052 (5)	−0.011 (4)	0.016 (4)	−0.005 (4)
C9	0.062 (7)	0.050 (6)	0.052 (7)	−0.007 (5)	0.004 (5)	−0.011 (5)
C10	0.087 (9)	0.049 (6)	0.051 (7)	0.008 (6)	0.025 (6)	0.005 (5)
C11	0.11 (2)	0.15 (3)	0.037 (13)	0.06 (2)	0.026 (13)	0.019 (14)
C12	0.053 (14)	0.062 (16)	0.072 (17)	0.001 (11)	0.012 (11)	−0.022 (13)
C11'	0.08 (3)	0.04 (2)	0.11 (4)	0.022 (18)	0.05 (3)	0.04 (2)
C12'	0.09 (3)	0.030 (18)	0.06 (3)	0.010 (18)	0.00 (2)	−0.022 (16)
C13	0.110 (12)	0.049 (8)	0.111 (13)	0.005 (7)	0.025 (10)	0.015 (8)
C14	0.098 (10)	0.063 (7)	0.055 (7)	−0.030 (7)	0.029 (7)	−0.011 (6)

Geometric parameters (Å, º)

Pt1—N2	1.967 (7)	C9—H9A	0.9700
Pt1—N1	2.052 (8)	C9—H9B	0.9700
Pt1—S1	2.271 (3)	C10—C11	1.4879
Pt1—Cl1	2.322 (3)	C10—C11'	1.62 (4)
C1—C5	1.368 (13)	C10—H10A	0.9700
C1—N1	1.373 (11)	C10—H10B	0.9700
C1—C6	1.468 (12)	C10—H10C	0.9600
N1—C2	1.348 (12)	C10—H10D	0.9600
C2—C3	1.384 (14)	C11—C12	1.52 (3)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.369 (14)	C11—H11B	0.9700
C3—H3	0.9300	C12—C13	1.56 (3)
C4—C5	1.399 (13)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—H5	0.9300	C11'—C12'	1.49 (6)
C6—N2	1.314 (11)	C11'—H11C	0.9700
C6—C7	1.524 (12)	C11'—H11D	0.9700
C7—H7A	0.9600	C12'—C13	1.35 (4)
C7—H7B	0.9600	C12'—H12C	0.9700
C7—H7C	0.9600	C12'—H12D	0.9700
N2—N3	1.378 (10)	C13—C14	1.492 (17)
N3—C8	1.328 (11)	C13—H13A	0.9700
C8—N4	1.342 (12)	C13—H13B	0.9700
C8—S1	1.789 (10)	C13—H13C	0.9601
N4—C14	1.457 (13)	C13—H13D	0.9600
N4—C9	1.479 (12)	C14—H14A	0.9700
C9—C10	1.504 (14)	C14—H14B	0.9700
N2—Pt1—N1	80.9 (3)	C11—C10—H10A	108.3
N2—Pt1—S1	85.2 (2)	C9—C10—H10A	108.3
N1—Pt1—S1	166.0 (2)	C11—C10—H10B	108.3
N2—Pt1—Cl1	176.3 (2)	C9—C10—H10B	108.3
N1—Pt1—Cl1	96.8 (2)	H10A—C10—H10B	107.4
S1—Pt1—Cl1	97.18 (10)	C9—C10—H10C	109.1
C5—C1—N1	120.9 (9)	C11'—C10—H10C	105.4
C5—C1—C6	124.7 (9)	C9—C10—H10D	108.5
N1—C1—C6	114.4 (8)	C11'—C10—H10D	110.6
C2—N1—C1	118.9 (8)	H10C—C10—H10D	107.9
C2—N1—Pt1	128.8 (7)	C10—C11—C12	114.6 (10)
C1—N1—Pt1	112.3 (6)	C10—C11—H11A	108.6
N1—C2—C3	121.9 (10)	C12—C11—H11A	108.6
N1—C2—H2	119.1	C10—C11—H11B	108.6
C3—C2—H2	119.1	C12—C11—H11B	108.6
C4—C3—C2	119.4 (10)	H11A—C11—H11B	107.6
C4—C3—H3	120.3	C11—C12—C13	116.4 (18)
C2—C3—H3	120.3	C11—C12—H12A	108.2
C3—C4—C5	119.0 (10)	C13—C12—H12A	108.2
C3—C4—H4	120.5	C11—C12—H12B	108.2
C5—C4—H4	120.5	C13—C12—H12B	108.2
C1—C5—C4	119.8 (9)	H12A—C12—H12B	107.3
C1—C5—H5	120.1	C12'—C11'—C10	112 (4)
C4—C5—H5	120.1	C12'—C11'—H11C	109.2
N2—C6—C1	115.8 (8)	C10—C11'—H11C	109.2
N2—C6—C7	121.3 (8)	C12'—C11'—H11D	109.2
C1—C6—C7	122.9 (8)	C10—C11'—H11D	109.2
C6—C7—H7A	109.5	H11C—C11'—H11D	107.9
C6—C7—H7B	109.5	C13—C12'—C11'	119 (4)
H7A—C7—H7B	109.5	C13—C12'—H12C	107.6
C6—C7—H7C	109.5	C11'—C12'—H12C	107.6
H7A—C7—H7C	109.5	C13—C12'—H12D	107.6
H7B—C7—H7C	109.5	C11'—C12'—H12D	107.6
C6—N2—N3	120.4 (7)	H12C—C12'—H12D	107.0
C6—N2—Pt1	116.6 (6)	C12'—C13—C14	118 (2)
N3—N2—Pt1	122.8 (5)	C14—C13—C12	119.0 (12)
C8—N3—N2	113.5 (8)	C14—C13—H13A	107.6
N3—C8—N4	117.1 (9)	C12—C13—H13A	107.6
N3—C8—S1	123.6 (7)	C14—C13—H13B	107.6
N4—C8—S1	119.3 (7)	C12—C13—H13B	107.6
C8—S1—Pt1	94.8 (3)	H13A—C13—H13B	107.0
C8—N4—C14	122.8 (9)	C12'—C13—H13C	110.2
C8—N4—C9	120.3 (8)	C14—C13—H13C	108.4
C14—N4—C9	115.8 (8)	C12'—C13—H13D	105.5
N4—C9—C10	113.0 (9)	C14—C13—H13D	107.2
N4—C9—H9A	109.0	H13C—C13—H13D	107.3
C10—C9—H9A	109.0	N4—C14—C13	115.6 (10)
N4—C9—H9B	109.0	N4—C14—H14A	108.4
C10—C9—H9B	109.0	C13—C14—H14A	108.4
H9A—C9—H9B	107.8	N4—C14—H14B	108.4
C11—C10—C9	116.1 (6)	C13—C14—H14B	108.4
C9—C10—C11'	115.1 (16)	H14A—C14—H14B	107.4
N4—C9—C10—C11	−62.2 (9)	C14—N4—C9—C10	87.4 (11)
C9—C10—C11—C12	62.2 (12)	N4—C9—C10—C11'	−28 (2)
C10—C11—C12—C13	−78 (2)	C9—C10—C11'—C12'	−45 (4)
C11—C12—C13—C14	57 (3)	C10—C11'—C12'—C13	87 (6)
C12—C13—C14—N4	9 (2)	C11'—C12'—C13—C14	−64 (5)
C13—C14—N4—C9	−75.0 (14)	C12'—C13—C14—N4	46 (3)