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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page m479
doi:10.1107/S1600536812011907

(Di-2-pyridyl­amine-κ2N2,N2′)di­iodidoplatinum(II)

Kwang Haa*

aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 10 March 2012; accepted 19 March 2012; online 24 March 2012)

The PtII ion in the title complex, [PtI2(C10H9N3)], is four-coordinated in a distorted square-planar environment defined by the two pyridine N atoms of the chelating di-2-pyridyl­amine (dpa) ligand and by two I− anions. The dpa ligand is not planar, the dihedral angle between the pyridine rings being 52.8 (3)°. Pairs of complex mol­ecules are assembled through inter­molecular N—H⋯I hydrogen bonds, forming a dimer-type species. The complexes are stacked in columns along the b axis and display several inter­molecular π–π inter­actions between the pyridine rings, with a shortest ring centroid–centroid distance of 3.997 (5) Å.

Related literature

For the crystal structure of the related chlorido PtII complex [PtCl2(dpa)], see: Li & Liu (2004[Li, D. & Liu, D. (2004). Cryst. Res. Technol. 39, 359-362.]); Tu et al. (2004[Tu, C., Wu, X., Liu, Q., Wang, X., Xu, Q. & Guo, Z. (2004). Inorg. Chim. Acta, 357, 95-102.]); Zhang et al. (2006[Zhang, F., Prokopchuk, E. M., Broczkowski, M. E., Jennings, M. C. & Puddephatt, R. J. (2006). Organometallics, 25, 1583-1591.]).

[Scheme 1]

Experimental

Crystal data

  • [PtI2(C10H9N3)]

  • Mr = 620.09

  • Monoclinic, P 21 /n

  • a = 8.2354 (6) Å

  • b = 9.7940 (7) Å

  • c = 16.4702 (12) Å

  • β = 102.148 (1)°

  • V = 1298.70 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 15.54 mm−1

  • T = 200 K

  • 0.16 × 0.12 × 0.08 mm
Data collection

  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.753, Tmax = 1.000

  • 7763 measured reflections

  • 2527 independent reflections

  • 2206 reflections with I > 2σ(I)

  • Rint = 0.028
Refinement

  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.077

  • S = 1.07

  • 2527 reflections

  • 145 parameters

  • H-atom parameters constrained

  • Δρmax = 1.47 e Å−3

  • Δρmin = −1.31 e Å−3

Table 1
Selected geometric parameters (Å, °)

Pt1—N1 2.033 (7)
Pt1—N3 2.055 (6)
Pt1—I2 2.5675 (7)
Pt1—I1 2.5934 (7)
N1—Pt1—N3 85.9 (3)
I2—Pt1—I1 90.85 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H2N⋯I1i 0.92 2.82 3.607 (7) 144
Symmetry code: (i) -x, -y+2, -z.

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812011907/wm2603sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011907/wm2603Isup2.hkl

checkCIF report


Comment top

The title complex, [PtI2(dpa)] (dpa = di-2-pyridylamine, C10H9N3), is closely related with the previously reported analogous chlorido PtII complex [PtCl2(dpa)] (Li & Liu, 2004; Tu et al., 2004; Zhang et al., 2006). The PtII ion is four-coordinated in a distorted square-planar environment by the two pyridine N atoms of the chelating dpa ligand and two I- anions (Fig. 1). In the crystal, the dpa ligand is not planar. The dihedral angle between the least-squares planes of the pyridine rings is 52.8 (3)°. The two Pt—N and the two Pt—I bond lengths, respectively, are nearly equivalent (Table 1). Two complex molecules are assembled through intermolecular N—H···I hydrogen bonds, forming a dimer-type species (Fig. 2 and Table 2). The complexes are stacked in columns along the b axis and display several intermolecular π—π interactions between the pyridine rings, with a shortest ring centroid to centroid distance of 3.997 (5) Å.

Related literature top

For the crystal structure of the related chlorido PtII complex [PtCl2(dpa)], see: Li & Liu (2004); Tu et al. (2004); Zhang et al. (2006).

Experimental top

To a solution of K2PtCl4 (0.2082 g, 0.502 mmol) in H2O (20 ml) and MeOH (10 ml) were added KI (0.7022 g, 4.230 mmol) and di-2-pyridylamine (0.0896 g, 0.523 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with H2O and MeOH, and dried at 373 K, to give a yellow powder (0.2614 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN/acetone solution.

Refinement top

Carbon-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)]. The nitrogen-bound H atom was located from Fourier difference maps and then allowed to ride on its parent atom in the final cycles of refinement with N—H = 0.92 Å and Uiso(H) = 1.5 Ueq(N). The highest peak (1.47 e Å-3) and the deepest hole (-1.31 e Å-3) in the difference Fourier map are located 0.56 Å and 0.67 Å from the atoms Pt1 and I1, respectively.

Structure description top

The title complex, [PtI2(dpa)] (dpa = di-2-pyridylamine, C10H9N3), is closely related with the previously reported analogous chlorido PtII complex [PtCl2(dpa)] (Li & Liu, 2004; Tu et al., 2004; Zhang et al., 2006). The PtII ion is four-coordinated in a distorted square-planar environment by the two pyridine N atoms of the chelating dpa ligand and two I- anions (Fig. 1). In the crystal, the dpa ligand is not planar. The dihedral angle between the least-squares planes of the pyridine rings is 52.8 (3)°. The two Pt—N and the two Pt—I bond lengths, respectively, are nearly equivalent (Table 1). Two complex molecules are assembled through intermolecular N—H···I hydrogen bonds, forming a dimer-type species (Fig. 2 and Table 2). The complexes are stacked in columns along the b axis and display several intermolecular π—π interactions between the pyridine rings, with a shortest ring centroid to centroid distance of 3.997 (5) Å.

For the crystal structure of the related chlorido PtII complex [PtCl2(dpa)], see: Li & Liu (2004); Tu et al. (2004); Zhang et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for all non-H atoms.
[Figure 2] Fig. 2. A view of the unit-cell content of the title complex. Intermolecular N—H···I hydrogen-bonding interactions are drawn with dashed lines.
(Di-2-pyridylamine-κ2N2,N2')diiodidoplatinum(II) top
Crystal data top
[PtI2(C10H9N3)]F(000) = 1096
Mr = 620.09Dx = 3.171 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4677 reflections
a = 8.2354 (6) Åθ = 2.4–26.0°
b = 9.7940 (7) ŵ = 15.54 mm−1
c = 16.4702 (12) ÅT = 200 K
β = 102.148 (1)°Block, yellow
V = 1298.70 (16) Å30.16 × 0.12 × 0.08 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		2527 independent reflections
Radiation source: fine-focus sealed tube2206 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→9
Tmin = 0.753, Tmax = 1.000k = −12→9
7763 measured reflectionsl = −20→20
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0328P)2 + 7.7728P]
where P = (Fo2 + 2Fc2)/3
2527 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 1.47 e Å−3
0 restraintsΔρmin = −1.31 e Å−3
Crystal data top
[PtI2(C10H9N3)]V = 1298.70 (16) Å3
Mr = 620.09Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2354 (6) ŵ = 15.54 mm−1
b = 9.7940 (7) ÅT = 200 K
c = 16.4702 (12) Å0.16 × 0.12 × 0.08 mm
β = 102.148 (1)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		2527 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2206 reflections with I > 2σ(I)
Tmin = 0.753, Tmax = 1.000Rint = 0.028
7763 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.07Δρmax = 1.47 e Å−3
2527 reflectionsΔρmin = −1.31 e Å−3
145 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
Pt10.06711 (4)0.84628 (3)0.151994 (17)0.02326 (11)
I10.24006 (8)1.04400 (6)0.23202 (3)0.04146 (18)
I2−0.14376 (8)0.86265 (7)0.24634 (4)0.04368 (18)
N10.2236 (8)0.8338 (7)0.0719 (4)0.0272 (15)
N2−0.0138 (9)0.8279 (7)−0.0353 (4)0.0289 (15)
H2N−0.05820.8189−0.09110.043*
N3−0.0752 (8)0.7046 (7)0.0769 (4)0.0239 (14)
C10.3928 (11)0.8266 (8)0.0968 (6)0.0326 (19)
H10.44030.81840.15430.039*
C20.4957 (11)0.8309 (9)0.0416 (6)0.035 (2)
H20.61260.82440.06050.042*
C30.4278 (12)0.8447 (8)−0.0417 (6)0.038 (2)
H30.49790.8505−0.08060.046*
C40.2564 (11)0.8501 (8)−0.0688 (5)0.0313 (19)
H40.20770.8616−0.12600.038*
C50.1575 (10)0.8384 (8)−0.0103 (5)0.0242 (17)
C6−0.0991 (9)0.7231 (8)−0.0054 (5)0.0232 (16)
C7−0.2111 (11)0.6449 (9)−0.0613 (5)0.035 (2)
H7−0.23270.6645−0.11910.041*
C8−0.2908 (11)0.5374 (9)−0.0309 (6)0.037 (2)
H8−0.36660.4810−0.06770.044*
C9−0.2582 (11)0.5140 (9)0.0534 (6)0.038 (2)
H9−0.31010.44000.07530.046*
C10−0.1502 (10)0.5980 (9)0.1058 (6)0.0315 (19)
H10−0.12780.58070.16380.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02847 (18)0.02197 (18)0.01700 (16)−0.00104 (12)−0.00054 (12)0.00125 (12)
I10.0546 (4)0.0355 (3)0.0275 (3)−0.0086 (3)−0.0067 (3)−0.0009 (3)
I20.0488 (4)0.0540 (4)0.0301 (3)0.0015 (3)0.0125 (3)−0.0015 (3)
N10.031 (4)0.023 (4)0.024 (3)−0.001 (3)−0.001 (3)0.001 (3)
N20.033 (4)0.031 (4)0.020 (3)−0.004 (3)−0.001 (3)0.001 (3)
N30.023 (3)0.023 (3)0.024 (3)0.003 (3)0.002 (3)0.002 (3)
C10.034 (5)0.026 (4)0.036 (5)−0.002 (4)0.002 (4)0.000 (4)
C20.030 (5)0.033 (5)0.043 (5)0.000 (4)0.006 (4)−0.002 (4)
C30.043 (5)0.023 (5)0.053 (6)0.000 (4)0.021 (5)0.003 (4)
C40.039 (5)0.030 (5)0.026 (4)0.000 (4)0.011 (4)−0.002 (4)
C50.034 (4)0.017 (4)0.023 (4)−0.001 (3)0.007 (3)−0.002 (3)
C60.025 (4)0.016 (4)0.026 (4)0.002 (3)0.000 (3)0.001 (3)
C70.036 (5)0.039 (5)0.027 (4)−0.002 (4)0.003 (4)−0.004 (4)
C80.033 (5)0.026 (5)0.048 (6)−0.005 (4)0.000 (4)−0.012 (4)
C90.042 (5)0.023 (4)0.048 (6)−0.011 (4)0.008 (4)−0.005 (4)
C100.035 (5)0.023 (4)0.036 (5)0.000 (4)0.005 (4)0.006 (4)
Geometric parameters (Å, º) top
Pt1—N12.033 (7)C2—H20.9500
Pt1—N32.055 (6)C3—C41.390 (13)
Pt1—I22.5675 (7)C3—H30.9500
Pt1—I12.5934 (7)C4—C51.391 (12)
N1—C51.349 (10)C4—H40.9500
N1—C11.369 (11)C6—C71.389 (11)
N2—C51.388 (10)C7—C81.388 (13)
N2—C61.390 (10)C7—H70.9500
N2—H2N0.9196C8—C91.377 (13)
N3—C61.340 (10)C8—H80.9500
N3—C101.349 (10)C9—C101.375 (12)
C1—C21.368 (13)C9—H90.9500
C1—H10.9500C10—H100.9500
C2—C31.374 (13)
N1—Pt1—N385.9 (3)C4—C3—H3120.1
N1—Pt1—I2176.88 (18)C3—C4—C5118.6 (8)
N3—Pt1—I291.94 (18)C3—C4—H4120.7
N1—Pt1—I191.11 (18)C5—C4—H4120.7
N3—Pt1—I1173.33 (18)N1—C5—N2117.7 (7)
I2—Pt1—I190.85 (2)N1—C5—C4121.7 (8)
C5—N1—C1118.2 (7)N2—C5—C4120.5 (7)
C5—N1—Pt1118.2 (5)N3—C6—C7122.1 (7)
C1—N1—Pt1123.6 (6)N3—C6—N2118.7 (7)
C5—N2—C6120.5 (6)C7—C6—N2119.1 (7)
C5—N2—H2N117.9C8—C7—C6118.5 (8)
C6—N2—H2N99.2C8—C7—H7120.7
C6—N3—C10118.8 (7)C6—C7—H7120.7
C6—N3—Pt1117.5 (5)C9—C8—C7118.9 (8)
C10—N3—Pt1123.7 (6)C9—C8—H8120.6
C2—C1—N1122.2 (8)C7—C8—H8120.6
C2—C1—H1118.9C10—C9—C8119.8 (8)
N1—C1—H1118.9C10—C9—H9120.1
C1—C2—C3119.2 (8)C8—C9—H9120.1
C1—C2—H2120.4N3—C10—C9121.7 (8)
C3—C2—H2120.4N3—C10—H10119.2
C2—C3—C4119.7 (9)C9—C10—H10119.2
C2—C3—H3120.1
N3—Pt1—N1—C546.4 (6)C6—N2—C5—N1−50.2 (10)
I1—Pt1—N1—C5−127.7 (6)C6—N2—C5—C4128.4 (8)
N3—Pt1—N1—C1−136.3 (6)C3—C4—C5—N15.8 (12)
I1—Pt1—N1—C149.6 (6)C3—C4—C5—N2−172.7 (7)
N1—Pt1—N3—C6−44.0 (6)C10—N3—C6—C76.6 (12)
I2—Pt1—N3—C6133.8 (5)Pt1—N3—C6—C7−170.9 (6)
N1—Pt1—N3—C10138.6 (7)C10—N3—C6—N2−176.1 (7)
I2—Pt1—N3—C10−43.6 (6)Pt1—N3—C6—N26.4 (9)
C5—N1—C1—C23.4 (12)C5—N2—C6—N352.8 (10)
Pt1—N1—C1—C2−173.9 (6)C5—N2—C6—C7−129.9 (8)
N1—C1—C2—C30.9 (13)N3—C6—C7—C8−5.1 (13)
C1—C2—C3—C4−1.9 (13)N2—C6—C7—C8177.6 (8)
C2—C3—C4—C5−1.3 (12)C6—C7—C8—C91.1 (13)
C1—N1—C5—N2171.8 (7)C7—C8—C9—C101.1 (14)
Pt1—N1—C5—N2−10.8 (9)C6—N3—C10—C9−4.2 (12)
C1—N1—C5—C4−6.7 (11)Pt1—N3—C10—C9173.1 (7)
Pt1—N1—C5—C4170.7 (6)C8—C9—C10—N30.5 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···I1i0.922.823.607 (7)144
Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula[PtI2(C10H9N3)]
Mr620.09
Crystal system, space groupMonoclinic, P21/n
Temperature (K)200
a, b, c (Å)8.2354 (6), 9.7940 (7), 16.4702 (12)
β (°) 102.148 (1)
V (Å3)1298.70 (16)
Z4
Radiation typeMo Kα
µ (mm−1)15.54
Crystal size (mm)0.16 × 0.12 × 0.08
Data collection
DiffractometerBruker SMART 1000 CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.753, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		7763, 2527, 2206
Rint0.028
(sin θ/λ)max (Å−1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.077, 1.07
No. of reflections2527
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.47, −1.31

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
Pt1—N12.033 (7)Pt1—I22.5675 (7)
Pt1—N32.055 (6)Pt1—I12.5934 (7)
N1—Pt1—N385.9 (3)I2—Pt1—I190.85 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···I1i0.922.823.607 (7)143.8
Symmetry code: (i) −x, −y+2, −z.
 

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011–0030747).

References

First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationLi, D. & Liu, D. (2004). Cryst. Res. Technol. 39, 359–362.  Web of Science CSD CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationTu, C., Wu, X., Liu, Q., Wang, X., Xu, Q. & Guo, Z. (2004). Inorg. Chim. Acta, 357, 95–102.  Web of Science CSD CrossRef CAS Google Scholar
 First citationZhang, F., Prokopchuk, E. M., Broczkowski, M. E., Jennings, M. C. & Puddephatt, R. J. (2006). Organometallics, 25, 1583–1591.  Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Page m479
doi:10.1107/S1600536812011907
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