Trans-Chloridobis[(Z)-1-imino-1-meth-oxy-ethane-N](triphenyl-phosphane-P) platinum(II) chloride monohydrate

Article abstract of DOI:10.1107/S0108270112040826

The title compound, [PtCl(C3H7NO)2(C18H15P)]Cl·H2O or trans-[PtCl{Z-HN=C(Me)OMe}2(PPh3)]Cl·H2O, crystallizes from an acetone solution of isomeric trans-[PtCl{E-HN=C(Me)OMe}2(PPh3)]Cl. The two HN=C(Me)OMe ligands show typical π-bond delocalization over the

Full text of DOI:10.1107/S0108270112040826

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
antitumour properties (Kalinowska-Lis et al., 2008; Coluccia &
Natile, 2007). Among these, the trans-[PtCl2(imino ether)2]
complexes were the first for which significant in vivo anti-
tumour activity was reported (Coluccia et al., 1995; Leng et al.,
2000). Imino ether ligands can have either an E or a Z
configuration, depending on the positions of the substituents
with respect to the C N double bond (Scheme 2). The
thermodynamic stability depends on the size of the alkyl
substituents. In the case of methyl substituents, the E config-
uration is the most stable.
In an investigation aimed at the synthesis of mixed imino-
ether/phosphane complexes, we synthesized the complex
trans-[PtCl{E-HN C(Me)OMe}2(PPh3)]ꢀClꢀH2O. However,
on crystallization from acetone, a complex in which the imino
ether ligands had switched to the less stable Z configuration
was obtained, the title compound, (I) (Scheme 1). The struc-
tural characterization of this compound has been undertaken
to clarify the reason for such isomerization.
ISSN 0108-2701
trans-Chloridobis[(Z)-1-imino-
1-methoxyethane-jN](triphenyl-
phosphane-jP)platinum(II) chloride
monohydrate
Daniela Giardina-Papa, Francesco Paolo Intini, Giovanni
Natile* and Concetta Pacifico
`
Dipartimento di Chimica, Universita degli Studi di Bari Aldo Moro, via E. Orabona 4,
70125 Bari, Italy
Correspondence e-mail: giovanni.natile@uniba.it
Received 11 September 2012
Accepted 27 September 2012
Online 18 October 2012
The title compound, [PtCl(C3H7NO)2(C18H15P)]ClꢀH2O or
trans-[PtCl{Z-HN C(Me)OMe}2(PPh3)]ClꢀH2O, crystallizes
from an acetone solution of isomeric trans-[PtCl{E-
HN C(Me)OMe}2(PPh3)]Cl. The two HN C(Me)OMe
ligands show typical ꢀ-bond delocalization over the
N—C—O group [Cini, Caputo, Intini & Natile (1995). Inorg.
Chem. 34, 1130–1137] and have the unprecedented Z–anti
configuration. The relative orientation of the imino ether
ligands is head-to-tail.
Comment
The development of new platinum drugs is ongoing, in order
to provide agents which are less toxic than cisplatin, cis-
[PtCl2(NH3)2] (cis-DDP), and active against different types of
tumours (Fuertes et al., 2003). Moreover, since the ultimate
target appears to be nuclear DNA, the interaction of platinum
complexes in the oxidation states II and IV (Hall & Hambley,
2002) with model nucleosides and nucleotides has been
investigated in great detail (Ali et al., 2005; Shen & Lippert,
2008; Suzuky et al., 1998; Yamanari et al., 2003; Messere et al.,
2007; Mikola et al., 2000).
Apart from amines, other neutral ligands such as phos-
phanes have been exploited and one phosphane compound,
the cisplatin analogue cis-Pt(PR3)2Cl2 (R = Me or Ph), has also
been widely investigated in relation to its reactivity with
nucleobases (Longato et al., 2006). In particular, the mixed
phosphane/nucleobase complex cis-bis(triphenylphosphane)-
[N-(1-methyl-2-oxo-1,2,3,4-tetrahydropyrimidin-4-ylidene)-
benzamidine]platinum(II) nitrate exhibits high antitumour
activity (Montagner et al., 2011).
Although early structure–activity relationships suggested
that a cis geometry was required for antitumour activity of
platinum complexes, more recently some platinum compounds
with a trans geometry have been found to possess remarkable
Complex (I) has a square-planar coordination geometry
(Fig. 1). The trans Pt—P and Pt—Cl bond lengths (Table 1) fall
in the range previously observed in cis-dichloridobis-
(triphenylphosphane)platinum(II), cis-chlorido(1,2,3,6-tetra-
hydro-3,7-dimethylpurine-2,6-dionato-ꢁN1)bis(triphenyl-
phosphane-ꢁP)platinum(II) and cis-chlorido(3-hydroxypico-
linato-ꢁN)bis(triphenylphosphane)platinum(II), where the
˚
Pt—Cl and Pt—P bond lengths are ca 2.35 (1) and 2.25 (1) A,
respectively (Anderson et al., 1982; Dubler et al., 2002; Quintal
m300 # 2012 International Union of Crystallography
doi:10.1107/S0108270112040826
Acta Cryst. (2012). C68, m300–m302

metal-organic compounds
Figure 2
A view of the hydrogen bonding (dashed lines) present in (I).
Figure 1
A view of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
of decreasing the dielectric constant around the metal core, so
favouring electrostatic interactions. Among these is the
interaction between the lone pair of electrons on the O atom
and the positively charged metal core. This obviously requires
the imino ether to assume a Z–anti configuration. This
hypothesis appears to be supported by the observation that
the Clꢂ counter-ion is the acceptor of three hydrogen bonds
involving the iminic N atom of two adjacent complex mol-
ecules and the solvent water molecule, which bridges the Clꢂ
counter-ion and the chloride ligand. Such a hydrogen-bond
network would be favoured by a local decrease in the dieletric
constant.
The relative orientations of the imino ether ligands can be
head-to-head (HH) or head-to-tail (HT) (Scheme 2). In (I),
the relative orientation of the imino ether ligands is HT. The
two imino ether ligands are almost coplanar [dihedral angle
8.9 (2)ꢁ] and the dihedral angles between their planes and the
coordination plane are 74.9 (2) and 69.0 (2)ꢁ.
et al., 2000). The two imino ether ligands have similar
geometric parameters. The N—C, Csp2—O and Csp3—O bond
˚
lengths [average values = 1.27 (1), 1.33 (1) and 1.45 (1) A,
respectively] and the Pt—N—C and N—C—C angles [average
values = 128.5 (3) and 123.0 (4)ꢁ, respectively] are similar to
those previously observed in cis- and trans-bis[(E)-1-imino-1-
methoxyethane]dichloridoplatinum(II) (Cini et al., 1995), in
tetrakis[(E)-1-ethoxy-1-iminopropane]platinum bis(trifluoro-
methanesulfonate) (Prenzler et al., 1997) and in trans-
dichloridobis[(Z)-1-imino-1-methoxy-2,20-dimethylpropane]-
platinum(II) (Gonzalez et al., 2002), and are in accord with a
ꢀ-bond delocalized over the N—C—O group.
The imino ether ligands of (I) have the unprecedented
Z–anti configuration (Scheme 2). A Z configuration was
observed in our previous paper reporting the X-ray structure
of the complex trans-[PtCl2{Z-HN C(tBu)OMe}2] (Gonzalez
et al., 2002), but the conformation was syn and not anti as in
the present case. In the previously reported Z-imino ether
Fig. 2 shows the chloride anion interacting with the N—H
groups of two imino ether ligands from two adjacent complex
molecules and a water molecule as a trifurcated acceptor,
Clꢀ ꢀ ꢀH—X, with Clꢀ ꢀ ꢀX distances of 3.293 (3), 3.262 (4) and
complex there was a t-Bu substituent on the C atom of the
. . . . . .
N
C O group and the steric bulkiness of t-Bu was consid-
ered to be responsible for stabilization of the Z configuration
(t-Bu trans to the metal core with respect to the C N double
bond) over the E configuration (t-Bu cis to the metal core). In
that case, the bulkiness of t-Bu could also be responsible for
˚
3.337 (5) A for X = N, N and O, respectively, and Clꢀ ꢀ ꢀH—X
angles in the range 166 (4)–168 (4)ꢁ. Weaker C—Hꢀ ꢀ ꢀCl
hydrogen bonds (Table 2) are apparent between aryl or
methyl C—H groups and the chloride anion.
the stabilization of the syn conformation (the Me group on the
. . . . . .
O atom cis to Pt with respect to the N C O group and trans
. . .
Experimental
to t-Bu with respect to the C O quasi-double bond).
However, in the present case of a small Me group on the C
. . . . . .
For the preparation of trans-[PtCl{E-HN C(Me)OMe}2(PPh3)]Cl,
an Et2O (5 ml) suspension of trans-[PtCl2{E-HN C(Me)OMe}2]
(100 mg, 0.24 mmol) was mixed with 1.2 equivalents of PPh3 (73.4 mg,
0.29 mmol). After stirring for 12 h at room temperature, the
suspension turned from yellow to white. The white solid, trans-
[PtCl{E-HN C(Me)OMe}2(PPh3)]Cl, was filtered off, washed with
Et2O (3 ꢃ 5 ml) and dried under vacuum (yield 159.9 mg, >98%).
Single crystals of trans-[PtCl{Z-HN C(Me)OMe}2(PPh3)]ClꢀH2O
suitable for X-ray diffraction analysis were obtained by evaporation
atom of the N
C O group, there is no steric interaction
which can account for the stabilization of the Z configuration,
as also witnessed by the anti conformation of the O—Me
. . .
group (O—Me cis to C—Me with respect to the C O quasi-
double bond and trans to Pt with respect to the planar
. . . . . .
N
C O group). Why, then, does the presence of a PPh3
group in the coordination environment of Pt stabilize the Z
configuration of the imino ether, accompanied by the anti
conformation of the O—Me group? Our hypothesis is that
replacement of a chloride anion by a phosphane ligand has the
effect of increasing the net positive charge on Pt and possibly
from
a
solution of trans-[PtCl{E-HN=C(Me)OMe}2(PPh3)]Cl
(10.0 mg, 0.024 mmol) in acetone (2 ml), where it isomerises to the
E,Z and Z,Z species. The latter form, (I), is the less soluble and
crystallizes preferentially.
ꢄ
Acta Cryst. (2012). C68, m300–m302
Papa et al.
[PtCl(C3H7NO)2(C18H15P)]ClꢀH2O m301

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
IRIX; program(s) used to solve structure: SIR2004 (Burla et al., 2005);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); soft-
ware used to prepare material for publication: PARST97 (Nardelli,
1983, 1995) and WinGX (Farrugia, 1999).
ꢁ
˚
Pt1—N1
Pt1—N2
2.010 (3)
2.014 (3)
Pt1—P1
Pt1—Cl1
2.2338 (11)
2.3559 (11)
N1—Pt1—P1
N2—Pt1—P1
90.99 (10)
93.01 (10)
N1—Pt1—Cl1
N2—Pt1—Cl1
87.84 (10)
88.16 (10)
The authors gratefully acknowledge Professors Ernesto
Mesto and Ferdinando Scordari (University of Bari Aldo
Moro) for the data collection.
Table 2
Hydrogen-bond geometry (A, ).
ꢁ
˚
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: EG3099). Services for accessing these data are
described at the back of the journal.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O1W—H1Wꢀ ꢀ ꢀCl1
O1W—H2Wꢀ ꢀ ꢀCl2
N1—H1ꢀ ꢀ ꢀCl2i
C2—H2Aꢀ ꢀ ꢀCl2i
C5—H5Cꢀ ꢀ ꢀCl2ii
C16—H16ꢀ ꢀ ꢀCl2iii
0.95 (2)
0.92 (2)
0.85 (4)
0.87 (4)
0.96
2.48 (2)
2.44 (2)
2.43 (4)
2.45 (4)
2.76
3.416 (5)
3.337 (5)
3.262 (4)
3.293 (3)
3.627 (5)
3.688 (5)
3.772 (5)
168 (6)
167 (6)
168 (4)
166 (4)
150
References
N2—H2ꢀ ꢀ ꢀCl2
Ali, M. S., Khan, S. R. A., Ojima, H., Guzman, I. Y., Whitmire, K. H., Siddik,
Z. H. & Khokhar, A. R. (2005). J. Inorg. Biochem. 99, 795–804.
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381–388.
0.96
0.93
2.79
2.89
156
160
1
2
1
2
Symmetry codes: (i) ꢂx þ 1; y þ ; ꢂz þ ; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz þ 1; (iii) ꢂx þ 1,
ꢂy þ 1; ꢂz.
Crystal data
Cini, R., Caputo, P. A., Intini, F. P. & Natile, G. (1995). Inorg. Chem. 34, 1130–
1137.
3
˚
V = 2731.03 (7) A
Z = 4
Mo Kꢃ radiation
ꢄ = 5.42 mmꢂ1
T = 294 K
[PtCl(C3H7NO)2(C18H15P)]ClꢀH2O
Coluccia, M., Boccarelli, A., Mariggio, M. A., Cardellicchio, N., Caputo, P.,
Intini, F. P. & Natile, G. (1995). Chem. Biol. Interact. 98, 251–266.
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Dubler, E., Schmalle, H. W., Arod, F. & Schneider, A. (2002). Acta Cryst. C58,
m111–m115.
Mr = 692.47
Monoclinic, P21=c
˚
˚
˚
a = 10.7361 (2) A
b = 17.1215 (2) A
c = 15.6226 (2) A
ꢂ = 108.0087 (8)ꢁ
0.12 ꢃ 0.10 ꢃ 0.09 mm
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
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Chem. 41, 470–478.
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Chem. Rev. 252, 1328–1345.
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Pisano, C., Boccarelli, A., Giordano, D. & Coluccia, M. (2000). Mol.
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¨ ¨
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3404–3413.
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Biochem. 105, 919–926.
Data collection
Bruker X8 APEX CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.889, Tmax = 1.000
30501 measured reflections
8334 independent reflections
5675 reflections with I > 2ꢅ(I)
Rint = 0.057
Refinement
R[F2 > 2ꢅ(F2)] = 0.036
wR(F2) = 0.065
S = 0.99
8334 reflections
314 parameters
4 restraints
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢆmax = 0.83 e A
ꢂ3
˚
Áꢆmin = ꢂ0.58 e A
Nardelli, M. (1983). Comput. Chem. 7, 95–97.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Prenzler, P. D., Hockless, D. C. R. & Heath, G. A. (1997). Inorg. Chem. 36,
5845–5849.
Quintal, S. M. O., Nogueira, H. I. S., Felix, V. & Drew, M. G. B. (2000). New J.
Chem. 24, 511–517.
The H atoms of the imino groups and of the water molecule were
found in a difference Fourier map and were refined with Uiso(H) =
1.2Ueq(parent). Soft distance restraints were applied to ensure
suitable hydrogen-bond geometries for atoms H1W and H2W
(Sheldrick, 2008). The other H atoms were included in idealized
positions and constrained to ride on their parent atoms, with C—H =
¨
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Shen, W. Z. & Lippert, B. (2008). J. Inorg. Biochem. 102, 1134–1140.
Suzuky, Y., Tanokura, M. & Shimizu, T. (1998). Eur. J. Biochem. 257, 466–
471.
Yamanari, K., Yto, R., Yamamoto, S., Konno, T., Fuyuhiro, A., Kobayashi, M.
& Arakawa, R. (2003). Dalton Trans. pp. 380–386.
˚
0.96 A and Uiso(H) = 1.5Ueq(C) for methyl H atoms, and with C—H =
˚
0.93 A and Uiso(H) = 1.2Ueq(C) for the phenyl H atoms.
Data collection: COSMO, APEX2 and BIS (Bruker, 2004); cell
refinement: SAINT-IRIX (Bruker, 2004); data reduction: SAINT-
ꢄ
m302 Papa et al. [PtCl(C3H7NO)2(C18H15P)]ClꢀH2O
Acta Cryst. (2012). C68, m300–m302

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, m300–m302 [doi:10.1107/S0108270112040826]
trans-Chloridobis[(Z)-1-imino-1-methoxyethane-κN](triphenylphosphane-
κP)platinum(II) chloride monohydrate
Daniela Giardina-Papa, Francesco Paolo Intini, Giovanni Natile and Concetta Pacifico
trans-Chloridobis[(Z)-1-imino-1-methoxyethane- κN](triphenylphosphane-κP)platinum(II) chloride monohydrate
Crystal data
[PtCl(C3H7NO)2(C18H15P)]Cl·H2O
Mr = 692.47
F(000) = 1360
Dx = 1.684 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 30501 reflections
θ = 1.8–30.5°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 10.7361 (2) Å
b = 17.1215 (2) Å
c = 15.6226 (2) Å
β = 108.0087 (8)°
V = 2731.03 (7) Å3
Z = 4
µ = 5.42 mm−1
T = 294 K
Prismatic, white
0.12 × 0.10 × 0.09 mm
Data collection
Nonius KappaCCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
30501 measured reflections
8334 independent reflections
5675 reflections with I > 2σ(I)
Rint = 0.057
θ
max = 30.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = −15→15
k = −24→24
l = −22→22
T
min = 0.889, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.036
wR(F2) = 0.065
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 0.99
8334 reflections
314 parameters
4 restraints
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0214P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.83 e Å−3
Δρmin = −0.58 e Å−3
Acta Cryst. (2012). C68, m300–m302
sup-1

supplementary materials
Special details
Experimental. All H atoms (except those of the methyl group) were found in the difference Fourier map and and refined
with a global isotropic displacement parameter with isotropic parameters equivalent to 1.2 times those of the atom to
which they are attached (except for H1W and H2W). The positions of H1w and H2w atoms were restrained using the
DANG instructions of the SHELXL97 program (Sheldrick, 2008). Final X—H distances varied from 0.82 (4) to 1.08 (4)
Å. The H atoms of the methyl group have been included in idealized positions and constrained to ride on their parent
atoms, with a C—H distance of 0.96 Å and with Uiso(H) = 1.5Ueq(C).
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)
x
y
z
Uiso*/Ueq
Pt1
0.474780 (15)
0.66397 (11)
0.5383 (4)
0.495 (4)
0.4236 (4)
0.475 (4)
0.29706 (10)
0.6304 (5)
0.6756 (5)
0.6203
0.639305 (8)
0.66329 (6)
0.72129 (19)
0.763 (2)
0.55760 (17)
0.517 (2)
0.61815 (5)
0.7141 (2)
0.7779 (3)
0.8227
0.262503 (10)
0.38493 (8)
0.1938 (2)
0.182 (3)
0.3381 (2)
0.354 (3)
0.14464 (7)
0.1593 (3)
0.1119 (3)
0.1076
0.02790 (5)
0.0494 (3)
0.0358 (8)
0.043*
Cl1
N1
H1
N2
0.0335 (8)
0.040*
H2
P1
0.0286 (2)
0.0443 (11)
0.0638 (15)
0.096*
C1
C2
H2A
H2B
H2C
C3
0.6716
0.7608
0.0526
0.096*
0.7642
0.7915
0.1449
0.096*
0.8019 (7)
0.7825
0.6321 (3)
0.6425
0.1438 (6)
0.0806
0.121 (3)
0.182*
H3A
H3B
H3C
C4
0.8308
0.5790
0.1560
0.182*
0.8697
0.6668
0.1773
0.182*
0.3323 (5)
0.3099 (5)
0.3752
0.5578 (2)
0.4923 (2)
0.4528
0.3742 (3)
0.4299 (3)
0.4349
0.0378 (10)
0.0539 (13)
0.081*
C5
H5A
H5B
H5C
C6
0.2246
0.4704
0.4020
0.081*
0.3154
0.5112
0.4888
0.081*
0.1477 (6)
0.0870
0.6250 (3)
0.5830
0.3957 (5)
0.3740
0.084 (2)
0.126*
H6A
H6B
H6C
O1
0.1033
0.6740
0.3792
0.126*
0.1831
0.6219
0.4601
0.126*
0.6863 (3)
0.2535 (3)
0.2200 (4)
0.2947 (4)
0.3832
0.64405 (18)
0.61922 (16)
0.5243 (2)
0.4569 (2)
0.4601
0.1698 (3)
0.3561 (2)
0.1507 (3)
0.1648 (3)
0.1699
0.0639 (10)
0.0535 (9)
0.0332 (9)
0.0425 (11)
0.051*
O2
C7
C8
H8
C9
0.2405 (6)
0.3853 (2)
0.1713 (3)
0.0544 (14)
Acta Cryst. (2012). C68, m300–m302
sup-2

supplementary materials
H9
0.2905
0.3401
0.1770
0.065*
C10
H10
C11
H11
C12
H12
C13
C14
H14
C15
H15
C16
H16
C17
H17
C18
H18
C19
C20
H20
C21
H21
C22
H22
C23
H23
C24
H24
Cl2
0.1126 (6)
0.0767
0.3812 (3)
0.3330
0.1692 (4)
0.1756
0.0646 (16)
0.078*
0.0367 (5)
−0.0502
0.4464 (3)
0.4429
0.1580 (4)
0.1570
0.0699 (17)
0.084*
0.0913 (5)
0.0399
0.5187 (3)
0.5635
0.1480 (3)
0.1395
0.0534 (13)
0.064*
0.3298 (4)
0.3523 (5)
0.3439
0.6192 (2)
0.6919 (2)
0.7375
0.0372 (3)
0.0027 (3)
0.0328
0.0323 (9)
0.0441 (11)
0.053*
0.3868 (5)
0.4043
0.6964 (3)
0.7448
−0.0754 (3)
−0.0962
0.0540 (13)
0.065*
0.3953 (5)
0.4172
0.6297 (3)
0.6329
−0.1223 (3)
−0.1753
0.0597 (14)
0.072*
0.3711 (5)
0.3749
0.5583 (3)
0.5133
−0.0906 (3)
−0.1230
0.0538 (13)
0.065*
0.3410 (5)
0.3283
0.5528 (2)
0.5039
−0.0102 (3)
0.0117
0.0439 (11)
0.053*
0.1728 (4)
0.1858 (4)
0.2524
0.6935 (2)
0.7513 (2)
0.7488
0.1282 (3)
0.1925 (3)
0.2471
0.0325 (9)
0.0433 (11)
0.052*
0.0974 (5)
0.1056
0.8131 (3)
0.8521
0.1738 (4)
0.2166
0.0651 (16)
0.078*
−0.0006 (5)
−0.0574
0.8179 (3)
0.8603
0.0945 (4)
0.0828
0.0653 (17)
0.078*
−0.0154 (5)
−0.0838
0.7600 (3)
0.7625
0.0318 (4)
−0.0219
0.0628 (15)
0.075*
0.0713 (4)
0.0611
0.6976 (3)
0.6584
0.0481 (3)
0.0052
0.0495 (12)
0.059*
0.59138 (13)
0.8280 (6)
0.795 (6)
0.774 (5)
0.39386 (6)
0.5086 (3)
0.556 (3)
0.473 (4)
0.35942 (9)
0.3327 (5)
0.350 (6)
0.347 (5)
0.0528 (3)
0.151 (3)
0.182*
O1W
H1W
H2W
0.182*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Pt1
Cl1
N1
N2
P1
0.02826 (8)
0.0435 (7)
0.036 (2)
0.041 (2)
0.0282 (5)
0.045 (3)
0.065 (4)
0.109 (6)
0.051 (3)
0.072 (4)
0.078 (5)
0.060 (2)
0.056 (2)
0.02965 (7)
0.0570 (6)
0.0359 (18)
0.0306 (17)
0.0299 (5)
0.044 (2)
0.02617 (8)
−0.00112 (7)
−0.0102 (5)
−0.0043 (15)
0.0016 (15)
0.0009 (4)
−0.009 (2)
−0.016 (3)
0.017 (4)
0.00895 (6)
−0.0006 (5)
0.0126 (17)
0.0089 (16)
0.0082 (4)
0.017 (2)
−0.00012 (7)
−0.0030 (5)
0.0020 (16)
0.0047 (14)
0.0010 (4)
−0.004 (2)
0.013 (3)
0.0385 (7)
0.036 (2)
0.0274 (19)
0.0275 (6)
0.045 (3)
0.061 (4)
0.219 (10)
0.029 (2)
0.049 (3)
0.103 (5)
0.095 (3)
0.063 (2)
C1
C2
C3
C4
C5
C6
O1
O2
0.076 (3)
0.035 (3)
0.085 (4)
0.124 (7)
−0.006 (5)
−0.0014 (17)
0.003 (2)
0.033 (2)
−0.007 (2)
−0.011 (2)
0.024 (3)
0.012 (2)
0.047 (3)
0.027 (3)
0.093 (4)
0.059 (4)
0.012 (4)
0.0545 (19)
0.0528 (18)
0.0013 (18)
0.0092 (16)
0.051 (2)
0.0012 (19)
0.0105 (16)
0.0343 (19)
Acta Cryst. (2012). C68, m300–m302
sup-3

supplementary materials
C7
0.031 (2)
0.043 (3)
0.072 (4)
0.074 (4)
0.039 (3)
0.039 (3)
0.031 (2)
0.055 (3)
0.058 (3)
0.064 (4)
0.058 (3)
0.052 (3)
0.033 (2)
0.040 (3)
0.057 (4)
0.049 (3)
0.034 (3)
0.040 (3)
0.0595 (8)
0.146 (5)
0.036 (2)
0.042 (2)
0.035 (2)
0.041 (3)
0.069 (3)
0.046 (3)
0.039 (2)
0.042 (2)
0.065 (3)
0.085 (4)
0.063 (3)
0.046 (2)
0.0302 (19)
0.038 (2)
0.041 (3)
0.049 (3)
0.086 (4)
0.055 (3)
0.0423 (6)
0.074 (3)
0.030 (2)
0.041 (3)
0.052 (3)
0.066 (4)
0.098 (5)
0.074 (4)
0.027 (2)
0.034 (3)
0.041 (3)
0.037 (3)
0.043 (3)
0.038 (3)
0.036 (2)
0.055 (3)
0.109 (5)
0.113 (5)
0.067 (4)
0.051 (3)
0.0607 (8)
0.280 (8)
−0.0038 (17)
0.005 (2)
0.003 (2)
−0.019 (3)
−0.021 (3)
−0.002 (2)
0.0062 (17)
0.006 (2)
0.007 (3)
0.019 (3)
0.014 (3)
0.007 (2)
0.0003 (17)
0.002 (2)
0.005 (3)
0.021 (3)
0.021 (3)
0.014 (2)
0.0027 (5)
0.008 (3)
0.0069 (18)
0.011 (2)
0.012 (3)
0.002 (3)
0.015 (3)
0.016 (3)
0.0103 (18)
0.013 (2)
0.018 (3)
0.025 (3)
0.019 (3)
0.020 (2)
0.0123 (19)
0.021 (2)
0.042 (4)
0.048 (4)
0.014 (3)
0.010 (2)
0.0245 (7)
0.133 (5)
−0.0025 (17)
0.003 (2)
0.004 (2)
0.006 (2)
0.016 (3)
0.012 (2)
0.0003 (16)
0.006 (2)
0.014 (2)
0.014 (3)
−0.008 (2)
0.001 (2)
0.0028 (17)
−0.005 (2)
−0.013 (3)
0.021 (3)
0.023 (3)
0.004 (2)
−0.0072 (5)
0.006 (4)
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
Cl2
O1W
Geometric parameters (Å, º)
Pt1—N1
Pt1—N2
Pt1—P1
Pt1—Cl1
N1—C1
N1—H1
N2—C4
N2—H2
P1—C19
P1—C13
P1—C7
2.010 (3)
2.014 (3)
C8—H8
0.93
C9—C10
1.366 (7)
0.93
2.2338 (11)
2.3559 (11)
1.270 (5)
0.85 (4)
1.273 (5)
0.87 (4)
1.816 (4)
1.819 (4)
1.823 (4)
1.328 (5)
1.484 (6)
0.96
C9—H9
C10—C11
C10—H10
C11—C12
C11—H11
C12—H12
C13—C18
C13—C14
C14—C15
C14—H14
C15—C16
C15—H15
C16—C17
C16—H16
C17—C18
C17—H17
C18—H18
C19—C24
C19—C20
C20—C21
C20—H20
C21—C22
C21—H21
C22—C23
C22—H22
1.361 (7)
0.93
1.399 (6)
0.93
0.93
1.382 (5)
1.407 (5)
1.381 (6)
0.93
C1—O1
C1—C2
1.376 (6)
0.93
C2—H2A
C2—H2B
C2—H2C
C3—O1
C3—H3A
C3—H3B
C3—H3C
C4—O2
C4—C5
0.96
1.374 (6)
0.93
0.96
1.435 (6)
0.96
1.393 (6)
0.93
0.96
0.93
0.96
1.384 (6)
1.386 (5)
1.391 (6)
0.93
1.324 (5)
1.485 (5)
0.96
C5—H5A
C5—H5B
C5—H5C
C6—O2
C6—H6A
0.96
1.357 (7)
0.93
0.96
1.455 (6)
0.96
1.367 (7)
0.93
Acta Cryst. (2012). C68, m300–m302
sup-4

supplementary materials
C6—H6B
C6—H6C
C7—C12
C7—C8
0.96
C23—C24
C23—H23
C24—H24
O1W—H1W
O1W—H2W
1.389 (6)
0.93
0.96
1.372 (6)
1.384 (5)
1.373 (6)
0.93
0.953 (16)
0.921 (16)
C8—C9
N1—Pt1—N2
N1—Pt1—P1
N2—Pt1—P1
N1—Pt1—Cl1
N2—Pt1—Cl1
P1—Pt1—Cl1
C1—N1—Pt1
C1—N1—H1
Pt1—N1—H1
C4—N2—Pt1
C4—N2—H2
Pt1—N2—H2
C19—P1—C13
C19—P1—C7
C13—P1—C7
C19—P1—Pt1
C13—P1—Pt1
C7—P1—Pt1
175.94 (14)
90.99 (10)
93.01 (10)
87.84 (10)
88.16 (10)
178.81 (4)
126.6 (3)
116 (3)
C9—C8—C7
121.2 (4)
119.4
C9—C8—H8
C7—C8—H8
119.4
C10—C9—C8
119.3 (4)
120.3
C10—C9—H9
C8—C9—H9
120.3
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C7—C12—C11
C7—C12—H12
C11—C12—H12
C18—C13—C14
C18—C13—P1
C14—C13—P1
C15—C14—C13
C15—C14—H14
C13—C14—H14
C16—C15—C14
C16—C15—H15
C14—C15—H15
C17—C16—C15
C17—C16—H16
C15—C16—H16
C16—C17—C18
C16—C17—H17
C18—C17—H17
C13—C18—C17
C13—C18—H18
C17—C18—H18
C24—C19—C20
C24—C19—P1
C20—C19—P1
C19—C20—C21
C19—C20—H20
C21—C20—H20
C22—C21—C20
C22—C21—H21
C20—C21—H21
C21—C22—C23
121.2 (4)
119.4
117 (3)
119.4
130.2 (3)
113 (3)
119.0 (5)
120.5
117 (3)
120.5
101.86 (18)
107.93 (18)
106.09 (18)
113.85 (13)
113.57 (14)
112.69 (13)
114.6 (4)
123.9 (4)
121.4 (4)
109.5
120.7 (4)
119.6
119.6
118.0 (4)
124.0 (3)
117.9 (3)
120.8 (4)
119.6
N1—C1—O1
N1—C1—C2
O1—C1—C2
119.6
C1—C2—H2A
C1—C2—H2B
H2A—C2—H2B
C1—C2—H2C
H2A—C2—H2C
H2B—C2—H2C
O1—C3—H3A
O1—C3—H3B
H3A—C3—H3B
O1—C3—H3C
H3A—C3—H3C
H3B—C3—H3C
N2—C4—O2
N2—C4—C5
120.3 (4)
119.9
109.5
109.5
119.9
109.5
119.7 (5)
120.2
109.5
109.5
120.2
109.5
120.6 (4)
119.7
109.5
109.5
119.7
109.5
120.6 (4)
119.7
109.5
109.5
119.7
115.9 (4)
122.9 (4)
121.1 (4)
109.5
119.6 (4)
120.2 (3)
120.0 (3)
118.8 (5)
120.6
O2—C4—C5
C4—C5—H5A
C4—C5—H5B
H5A—C5—H5B
C4—C5—H5C
H5A—C5—H5C
H5B—C5—H5C
O2—C6—H6A
109.5
109.5
120.6
109.5
121.6 (5)
119.2
109.5
109.5
119.2
109.5
119.7 (5)
Acta Cryst. (2012). C68, m300–m302
sup-5

supplementary materials
O2—C6—H6B
H6A—C6—H6B
O2—C6—H6C
H6A—C6—H6C
H6B—C6—H6C
C1—O1—C3
109.5
C21—C22—H22
C23—C22—H22
C22—C23—C24
C22—C23—H23
C24—C23—H23
C19—C24—C23
C19—C24—H24
C23—C24—H24
120.1
109.5
120.1
109.5
120.2 (5)
119.9
109.5
109.5
119.9
119.4 (4)
119.7 (4)
118.4 (4)
121.9 (3)
119.5 (3)
120.0 (5)
120.0
C4—O2—C6
C12—C7—C8
C12—C7—P1
C8—C7—P1
120.0
H1W—O1W—H2W
100 (7)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1W—H2W···Cl2
N2—H2···Cl2
0.92 (2)
0.87 (4)
0.85 (4)
0.96
2.44 (2)
2.45 (4)
2.43 (4)
2.76
3.337 (5)
3.293 (3)
3.262 (4)
3.627 (5)
3.688 (5)
3.772 (5)
3.416 (5)
167 (6)
166 (4)
168 (4)
150
N1—H1···Cl2i
C2—H2A···Cl2i
C5—H5C···Cl2ii
C16—H16···Cl2iii
O1W—H1W···Cl1
0.96
2.79
156
0.93
2.89
160
0.95 (2)
2.48 (2)
168 (6)
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z.
Acta Cryst. (2012). C68, m300–m302
sup-6