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In the title complex, [Pt(C8H6NO2)Cl(C8H7NO2)], the PtII centre is coordinated by a monodentate and an N,O-chelating deprotonated benzoyl­formaldehyde oxime and a Cl atom. There is an intra­molecular N—O...H—O hydrogen-bonding system between the oxime OH group and the oximate O atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807015747/hg2220sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807015747/hg2220Isup2.hkl
Contains datablock I

CCDC reference: 646603

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.022
  • wR factor = 0.043
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

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Alert level C PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.64 Ratio PLAT432_ALERT_2_C Short Inter X...Y Contact O1 .. C9 .. 2.92 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1 .. C10 .. 2.97 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 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 2 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 0 ALERT type 5 Informative message, check

Comment top

In the title complex, (I), a chloride anion is coordinated to the PtII centre, two sites are occupied by the deprotonated chelate, coordinated via the oximato nitrogen and the carbonyl oxygen, with the remaining site occupied by the monodentate oxo(phenyl)acetaldehyde oxime, which is coordinated via the oxime nitrogen, located at the cis-position to the oximato N atom. The bond lengths obtained for the monodentate ligand (Table 1) are similar to those reported for 1-oxo(phenyl)acetaldehyde oxime (N–O,1.380 (2) Å, N=C, 1.284 (2) Å, C–C,1.491 (3) Å, C=O, 1.224 (2) Å) (Raston et al., 1978) These values are also in concord with the corresponding mean bond lengths values, obtained for N–O, N=C, C–C(unconjugated), C=O bonds: 1.394 (18), 1.281 (13), 1.478 (12), 1.210 (8) Å, respectively (Allen et al., 1987). In contrast, the bond lengths found for the deprotonated N,O-chelated oxime (Table 1) differ from those observed in the monodentate ligand, the free molecule and from the standard bond lengths. We assume that the noticeable decrease in the N=C and C=O and concomitant increase in the N–O and C–C bond lengths in the N,O-chelate are a consequence of the availability of a coplanar conjugated system in the chelated ring, which stabilizes the oximato anion by delocalization of the negative charge. The structure is stabilized also by an intramolecular N—O-···H–O hydrogen bond (Table 2).

The N=C–C=O torsion angles differ for the two ligands, being -0.1 (5)° for the chelated ligand and -100.1 (5)° for the monodentate species. The latter results in the phenyl plane being almost perpendicular to the coordination plane.

Related literature top

For related literature, see: Allen et al. (1987); Makarycheva-Mikhailova, Bokach, Haukka & Kukushkin (2003); Makarycheva-Mikhailova, Haukka, Bokach, Garnovskii, Galanski, Keppler, Pombeiro & Kukushkin (2002); Raston et al. (1978).

Experimental top

The title compound is formed in small quantities as a by-product of the reaction between trans-[PtCl4(EtCN)2] and the oxime leading mostly to trans-[PtCl4{NH=C(Et)ON=C(H)C(=O)Ph}2], followed by dehydration of the latter (Makarycheva-Mikhailova et al., 2002, 2003).

Refinement top

The OH hydrogen atom was located from the difference Fourier map and refined isotropically. Other H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95 Å, and Uiso(H) = 1.2 Ueq(parent atom). The highest peak is located 1.04Å from atom H16 and the deepest hole is located 0.86Å from atom Pt1.

Structure description top

In the title complex, (I), a chloride anion is coordinated to the PtII centre, two sites are occupied by the deprotonated chelate, coordinated via the oximato nitrogen and the carbonyl oxygen, with the remaining site occupied by the monodentate oxo(phenyl)acetaldehyde oxime, which is coordinated via the oxime nitrogen, located at the cis-position to the oximato N atom. The bond lengths obtained for the monodentate ligand (Table 1) are similar to those reported for 1-oxo(phenyl)acetaldehyde oxime (N–O,1.380 (2) Å, N=C, 1.284 (2) Å, C–C,1.491 (3) Å, C=O, 1.224 (2) Å) (Raston et al., 1978) These values are also in concord with the corresponding mean bond lengths values, obtained for N–O, N=C, C–C(unconjugated), C=O bonds: 1.394 (18), 1.281 (13), 1.478 (12), 1.210 (8) Å, respectively (Allen et al., 1987). In contrast, the bond lengths found for the deprotonated N,O-chelated oxime (Table 1) differ from those observed in the monodentate ligand, the free molecule and from the standard bond lengths. We assume that the noticeable decrease in the N=C and C=O and concomitant increase in the N–O and C–C bond lengths in the N,O-chelate are a consequence of the availability of a coplanar conjugated system in the chelated ring, which stabilizes the oximato anion by delocalization of the negative charge. The structure is stabilized also by an intramolecular N—O-···H–O hydrogen bond (Table 2).

The N=C–C=O torsion angles differ for the two ligands, being -0.1 (5)° for the chelated ligand and -100.1 (5)° for the monodentate species. The latter results in the phenyl plane being almost perpendicular to the coordination plane.

For related literature, see: Allen et al. (1987); Makarycheva-Mikhailova, Bokach, Haukka & Kukushkin (2003); Makarycheva-Mikhailova, Haukka, Bokach, Garnovskii, Galanski, Keppler, Pombeiro & Kukushkin (2002); Raston et al. (1978).

Computing details top

Data collection: COLLECT (Nonius, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen is indicated by dashed line.
(Benzoylformaldehyde oximato-κ2N,O)(benzoylformaldehyde oxime-κN)chloridoplatinum(II) top
Crystal data top
[Pt(C8H6NO2)Cl(C8H7NO2)]F(000) = 1000
Mr = 527.82Dx = 2.193 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 16177 reflections
a = 7.1236 (2) Åθ = 2.3–25.2°
b = 18.0103 (6) ŵ = 8.97 mm1
c = 12.5569 (4) ÅT = 100 K
β = 97.163 (2)°Needle, orange red
V = 1598.45 (9) Å30.14 × 0.05 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
2855 independent reflections
Radiation source: fine-focus sealed tube2439 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.051
Detector resolution: 9 pixels mm-1θmax = 25.2°, θmin = 2.3°
φ scans and ω scans with κ offseth = 88
Absorption correction: multi-scan
(XPREP in SHELXTL; Sheldrick, 2005)
k = 2121
Tmin = 0.352, Tmax = 0.636l = 1515
16177 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: mixed
wR(F2) = 0.043H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0141P)2 + 1.3333P]
where P = (Fo2 + 2Fc2)/3
2855 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 1.21 e Å3
0 restraintsΔρmin = 1.17 e Å3
Crystal data top
[Pt(C8H6NO2)Cl(C8H7NO2)]V = 1598.45 (9) Å3
Mr = 527.82Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.1236 (2) ŵ = 8.97 mm1
b = 18.0103 (6) ÅT = 100 K
c = 12.5569 (4) Å0.14 × 0.05 × 0.05 mm
β = 97.163 (2)°
Data collection top
Nonius KappaCCD
diffractometer
2855 independent reflections
Absorption correction: multi-scan
(XPREP in SHELXTL; Sheldrick, 2005)
2439 reflections with I > 2σ(I)
Tmin = 0.352, Tmax = 0.636Rint = 0.051
16177 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.043H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 1.21 e Å3
2855 reflectionsΔρmin = 1.17 e Å3
221 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.1876 (5)0.4606 (2)0.0671 (3)0.0183 (9)
H10.17270.48030.13790.022*
C20.2619 (5)0.5028 (2)0.0253 (3)0.0181 (9)
C30.3210 (5)0.5805 (2)0.0197 (3)0.0175 (9)
C40.3804 (6)0.6181 (2)0.1148 (4)0.0239 (10)
H40.38260.59320.18160.029*
C50.4363 (6)0.6916 (2)0.1125 (4)0.0281 (11)
H50.47650.71710.17750.034*
C60.4335 (6)0.7279 (2)0.0145 (4)0.0278 (11)
H60.47110.77840.01290.033*
C70.3765 (6)0.6910 (2)0.0801 (4)0.0265 (10)
H70.37590.71610.14670.032*
C80.3200 (5)0.6175 (2)0.0786 (4)0.0220 (10)
H80.28070.59220.14390.026*
C90.0374 (5)0.2189 (2)0.1658 (3)0.0210 (9)
H90.05880.23610.23780.025*
C100.0491 (6)0.1426 (2)0.1463 (3)0.0201 (9)
C110.0789 (5)0.0790 (2)0.1372 (3)0.0197 (9)
C120.0063 (6)0.0068 (2)0.1389 (3)0.0212 (10)
H120.12360.00080.14580.025*
C130.1232 (6)0.0531 (2)0.1304 (3)0.0247 (10)
H130.07430.10210.13220.030*
C140.3121 (6)0.0421 (3)0.1192 (4)0.0296 (11)
H140.39190.08370.11240.036*
C150.3855 (6)0.0293 (3)0.1179 (4)0.0325 (11)
H150.51550.03640.11080.039*
C160.2703 (6)0.0897 (3)0.1270 (3)0.0264 (10)
H160.32070.13850.12630.032*
N10.1419 (4)0.39174 (18)0.0447 (3)0.0193 (8)
N20.0835 (4)0.26159 (18)0.0929 (3)0.0177 (7)
O10.0805 (4)0.34699 (16)0.1200 (2)0.0263 (7)
O20.2757 (4)0.47114 (15)0.1162 (2)0.0186 (6)
O30.0550 (5)0.23008 (18)0.0082 (3)0.0316 (8)
H030.061 (8)0.270 (4)0.056 (5)0.08 (2)*
O40.2187 (4)0.13761 (15)0.1456 (2)0.0251 (7)
Cl10.26457 (14)0.34896 (6)0.28994 (8)0.0236 (2)
Pt10.18476 (2)0.365032 (8)0.108499 (12)0.01658 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.020 (2)0.016 (2)0.019 (2)0.0014 (17)0.0037 (17)0.0049 (18)
C20.009 (2)0.018 (2)0.028 (3)0.0041 (16)0.0037 (17)0.0009 (19)
C30.015 (2)0.016 (2)0.021 (2)0.0045 (16)0.0032 (16)0.0001 (18)
C40.022 (2)0.023 (3)0.027 (3)0.0002 (18)0.0050 (18)0.0026 (19)
C50.029 (3)0.023 (2)0.032 (3)0.0059 (19)0.005 (2)0.006 (2)
C60.023 (2)0.018 (2)0.043 (3)0.0000 (18)0.010 (2)0.000 (2)
C70.021 (2)0.025 (3)0.034 (3)0.0015 (19)0.0084 (19)0.010 (2)
C80.018 (2)0.023 (2)0.025 (3)0.0024 (17)0.0027 (18)0.0009 (18)
C90.024 (2)0.019 (2)0.020 (2)0.0011 (18)0.0023 (18)0.0009 (19)
C100.029 (2)0.016 (2)0.015 (2)0.0036 (19)0.0007 (17)0.0043 (18)
C110.024 (2)0.018 (2)0.017 (2)0.0021 (18)0.0010 (17)0.0004 (18)
C120.022 (2)0.023 (2)0.018 (2)0.0027 (18)0.0011 (17)0.0003 (19)
C130.033 (3)0.019 (2)0.021 (3)0.0042 (19)0.0024 (19)0.0018 (19)
C140.031 (3)0.024 (3)0.032 (3)0.007 (2)0.003 (2)0.005 (2)
C150.020 (2)0.038 (3)0.039 (3)0.001 (2)0.002 (2)0.006 (2)
C160.026 (2)0.024 (3)0.028 (3)0.009 (2)0.0015 (18)0.003 (2)
N10.0146 (17)0.0199 (19)0.024 (2)0.0008 (14)0.0054 (14)0.0022 (16)
N20.0205 (18)0.0172 (18)0.0158 (19)0.0001 (15)0.0036 (14)0.0017 (15)
O10.0374 (18)0.0210 (17)0.0201 (17)0.0086 (13)0.0016 (13)0.0041 (13)
O20.0179 (14)0.0163 (15)0.0213 (17)0.0022 (12)0.0011 (11)0.0006 (13)
O30.053 (2)0.0237 (18)0.0195 (18)0.0125 (15)0.0093 (15)0.0039 (15)
O40.0198 (16)0.0215 (16)0.0342 (19)0.0010 (13)0.0031 (13)0.0031 (14)
Cl10.0298 (6)0.0211 (6)0.0192 (6)0.0015 (4)0.0001 (4)0.0008 (4)
Pt10.01681 (9)0.01454 (9)0.01845 (10)0.00001 (7)0.00242 (6)0.00053 (8)
Geometric parameters (Å, º) top
C1—N11.322 (5)C10—C111.477 (6)
C1—C21.432 (6)C11—C161.398 (6)
C1—H10.9500C11—C121.401 (6)
C2—O21.270 (5)C12—C131.375 (6)
C2—C31.465 (5)C12—H120.9500
C3—C41.392 (6)C13—C141.384 (6)
C3—C81.402 (6)C13—H130.9500
C4—C51.383 (6)C14—C151.389 (6)
C4—H40.9500C14—H140.9500
C5—C61.391 (6)C15—C161.377 (6)
C5—H50.9500C15—H150.9500
C6—C71.378 (6)C16—H160.9500
C6—H60.9500N1—O11.278 (4)
C7—C81.384 (6)N1—Pt11.970 (3)
C7—H70.9500N2—O31.383 (4)
C8—H80.9500N2—Pt11.999 (3)
C9—N21.269 (5)O2—Pt12.016 (3)
C9—C101.514 (6)O3—H030.94 (7)
C9—H90.9500Cl1—Pt12.2967 (10)
C10—O41.211 (5)
N1—C1—C2113.7 (4)C16—C11—C10121.3 (4)
N1—C1—H1123.2C12—C11—C10119.1 (4)
C2—C1—H1123.2C13—C12—C11119.9 (4)
O2—C2—C1118.0 (3)C13—C12—H12120.0
O2—C2—C3118.8 (4)C11—C12—H12120.0
C1—C2—C3123.2 (4)C12—C13—C14120.1 (4)
C4—C3—C8119.4 (4)C12—C13—H13119.9
C4—C3—C2118.9 (4)C14—C13—H13119.9
C8—C3—C2121.7 (4)C13—C14—C15120.3 (4)
C5—C4—C3120.4 (4)C13—C14—H14119.8
C5—C4—H4119.8C15—C14—H14119.8
C3—C4—H4119.8C16—C15—C14120.1 (4)
C4—C5—C6119.7 (4)C16—C15—H15119.9
C4—C5—H5120.2C14—C15—H15119.9
C6—C5—H5120.2C15—C16—C11119.8 (4)
C7—C6—C5120.5 (4)C15—C16—H16120.1
C7—C6—H6119.8C11—C16—H16120.1
C5—C6—H6119.8O1—N1—C1120.3 (4)
C6—C7—C8120.2 (4)O1—N1—Pt1124.5 (3)
C6—C7—H7119.9C1—N1—Pt1115.1 (3)
C8—C7—H7119.9C9—N2—O3113.1 (3)
C7—C8—C3119.8 (4)C9—N2—Pt1128.1 (3)
C7—C8—H8120.1O3—N2—Pt1118.8 (2)
C3—C8—H8120.1C2—O2—Pt1113.2 (2)
N2—C9—C10124.7 (4)N2—O3—H03105 (4)
N2—C9—H9117.6N1—Pt1—N297.01 (14)
C10—C9—H9117.6N1—Pt1—O279.94 (12)
O4—C10—C11124.5 (4)N2—Pt1—O2176.47 (12)
O4—C10—C9117.0 (4)N1—Pt1—Cl1171.42 (10)
C11—C10—C9118.3 (3)N2—Pt1—Cl191.22 (10)
C16—C11—C12119.7 (4)O2—Pt1—Cl191.91 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H03···O10.94 (7)1.62 (7)2.550 (4)170 (6)

Experimental details

Crystal data
Chemical formula[Pt(C8H6NO2)Cl(C8H7NO2)]
Mr527.82
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)7.1236 (2), 18.0103 (6), 12.5569 (4)
β (°) 97.163 (2)
V3)1598.45 (9)
Z4
Radiation typeMo Kα
µ (mm1)8.97
Crystal size (mm)0.14 × 0.05 × 0.05
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(XPREP in SHELXTL; Sheldrick, 2005)
Tmin, Tmax0.352, 0.636
No. of measured, independent and
observed [I > 2σ(I)] reflections
16177, 2855, 2439
Rint0.051
(sin θ/λ)max1)0.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.043, 1.06
No. of reflections2855
No. of parameters221
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.21, 1.17

Computer programs: COLLECT (Nonius, 2004), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2006), SHELXL97.

Selected geometric parameters (Å, º) top
C1—N11.322 (5)N1—Pt11.970 (3)
C2—O21.270 (5)N2—O31.383 (4)
C9—N21.269 (5)N2—Pt11.999 (3)
C10—O41.211 (5)O2—Pt12.016 (3)
N1—O11.278 (4)Cl1—Pt12.2967 (10)
O2—C2—C1118.0 (3)N1—Pt1—O279.94 (12)
O1—N1—C1120.3 (4)N2—Pt1—Cl191.22 (10)
C9—N2—O3113.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H03···O10.94 (7)1.62 (7)2.550 (4)170 (6)
 

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