Bis(acridine-κN)dibromidoplatinum(II)

Ha, K.

doi:10.1107/S160053681003309X

metal-organic compounds

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Volume 66| Part 9| September 2010| Page m1142

https://doi.org/10.1107/S160053681003309X

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Bis(acridine-κN)dibromidoplatinum(II)

Kwang Ha ^a ^*

^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 7 August 2010; accepted 17 August 2010; online 21 August 2010)

In the title complex, [PtBr₂(C₁₃H₉N)₂], the Pt^II ion is four-coordinated in a slightly distorted square-planar environment by two N atoms from two acridine ligands and two Br atoms. The Pt atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex and the PtN₂Br₂ unit is exactly planar. The dihedral angle between the PtN₂Br₂ unit and acridine ligand is 78.98 (9)°. In the crystal structure, the complex molecules are arranged in two distinct chains along [110] and [ $[\overline{1}]$ 10]. In the chains, intermolecular π–π interactions between the pyridyl and benzene rings connect the complex molecules, with a centroid–centroid distance of 3.631 (4) Å.

Related literature

For the crystal structure of [PtCl₂(acridine)₂], see: Ha (2010 ). For the formation of polymorphs of acridine using dicarboxylic acids, see: Mei & Wolf (2004 ).

Experimental

Crystal data

[PtBr₂(C₁₃H₉N)₂]
M_r = 713.33
Monoclinic, C 2/c
a = 16.0256 (9) Å
b = 8.6845 (5) Å
c = 17.0646 (10) Å
β = 115.017 (1)°
V = 2152.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 10.25 mm⁻¹
T = 200 K
0.35 × 0.06 × 0.04 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.601, T_max = 1.000
6467 measured reflections
2091 independent reflections
1672 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.070
S = 1.00
2091 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 2.19 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Table 1
Selected bond lengths (Å)

Pt1—N1	2.058 (4)
Pt1—Br1	2.4385 (7)

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681003309X/hy2340sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681003309X/hy2340Isup2.hkl

checkCIF report

Comment top

The title complex, [PtBr₂(acr)₂] (acr = acridine), is isomorphous with the chlorido analogue [PtCl₂(acr)₂] (Ha, 2010). In the complex, the Pt^II ion is four-coordinated in an essentially square-planar environment by two N atoms from two acridine ligands and two Br atoms (Table 1 and Fig. 1). The Pt atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex and the PtN₂Br₂ unit is exactly planar. The nearly planar acridine ligands, with a maximum deviation of 0.072 (6) Å (C11) from the least-squares plane, are parallel. The dihedral angle between the PtN₂Br₂ unit and acridine ligand is 78.98 (9)°. The Br atoms are in a trans arrangement and almost perpendicular to the acridine planes, with the bond angle N1—Pt1—Br1 = 88.65 (14)°. In the crystal structure, the complex molecules are arranged in two distinct chains along [1 1 0] and [1 1 0] (Fig. 2). In the chains, intermolecular π–π interactions between the pyridyl and benzene rings connect the complex molecules, with a centroid–centroid distance of 3.631 (4) Å, and the dihedral angle between the ring planes is 1.2 (3)°. The packing pattern is considerably similar to that of the most stable polymorph of acridine (Mei & Wolf, 2004).

Related literature top

For the crystal structure of [PtCl₂(acridine)₂], see: Ha (2010). For the formation of polymorphs of acridine using dicarboxylic acids, see: Mei & Wolf (2004).

Experimental top

To a solution of K₂PtBr₄ (0.203 g, 0.342 mmol) in H₂O (30 ml) was added acridine (0.131 g, 0.730 mmol) and the mixture was refluxed for 3 h. The precipitate was then separated by filtration, washed with H₂O and EtOH and dried under vacuum to give a yellow powder (0.186 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from an N,N-dimethylformamide solution at 323 K.

Structure description top

For the crystal structure of [PtCl₂(acridine)₂], see: Ha (2010). For the formation of polymorphs of acridine using dicarboxylic acids, see: Mei & Wolf (2004).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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

	Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry code: (i) 1-x, 1-y, 1-z.]
	Fig. 2. View of the unit-cell contents of the title complex. H atoms have been omitted for clarity.

Bis(acridine-κN)dibromidoplatinum(II) top

Crystal data top

[PtBr₂(C₁₃H₉N)₂]	F(000) = 1344
M_r = 713.33	D_x = 2.202 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3125 reflections
a = 16.0256 (9) Å	θ = 2.7–26.0°
b = 8.6845 (5) Å	µ = 10.25 mm⁻¹
c = 17.0646 (10) Å	T = 200 K
β = 115.017 (1)°	Rod, yellow
V = 2152.1 (2) Å³	0.35 × 0.06 × 0.04 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	2091 independent reflections
Radiation source: fine-focus sealed tube	1672 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
φ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −19→19
T_min = 0.601, T_max = 1.000	k = −10→10
6467 measured reflections	l = −14→21

Refinement top

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0286P)²] where P = (F_o² + 2F_c²)/3
2091 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 2.19 e Å⁻³
0 restraints	Δρ_min = −0.92 e Å⁻³

Crystal data top

[PtBr₂(C₁₃H₉N)₂]	V = 2152.1 (2) Å³
M_r = 713.33	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.0256 (9) Å	µ = 10.25 mm⁻¹
b = 8.6845 (5) Å	T = 200 K
c = 17.0646 (10) Å	0.35 × 0.06 × 0.04 mm
β = 115.017 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2091 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1672 reflections with I > 2σ(I)
T_min = 0.601, T_max = 1.000	R_int = 0.048
6467 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.00	Δρ_max = 2.19 e Å⁻³
2091 reflections	Δρ_min = −0.92 e Å⁻³
142 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pt1	0.5000	0.5000	0.5000	0.02062 (12)
Br1	0.51478 (4)	0.44407 (8)	0.36640 (5)	0.03216 (18)
N1	0.3748 (3)	0.3887 (5)	0.4493 (3)	0.0218 (11)
C1	0.3686 (4)	0.2391 (6)	0.4712 (4)	0.0215 (13)
C2	0.4437 (4)	0.1654 (6)	0.5371 (4)	0.0267 (15)
H2	0.4997	0.2201	0.5666	0.032*
C3	0.4373 (4)	0.0170 (6)	0.5592 (5)	0.0326 (16)
H3	0.4891	−0.0305	0.6036	0.039*
C4	0.3550 (4)	−0.0683 (7)	0.5172 (4)	0.0299 (15)
H4	0.3519	−0.1725	0.5328	0.036*
C5	0.2809 (4)	−0.0004 (6)	0.4549 (5)	0.0300 (15)
H5	0.2252	−0.0569	0.4275	0.036*
C6	0.2850 (4)	0.1547 (7)	0.4295 (4)	0.0256 (14)
C7	0.2099 (4)	0.2251 (6)	0.3653 (4)	0.0243 (14)
H7	0.1546	0.1688	0.3358	0.029*
C8	0.2149 (4)	0.3780 (7)	0.3437 (4)	0.0232 (14)
C9	0.1382 (4)	0.4572 (7)	0.2798 (5)	0.0339 (17)
H9	0.0824	0.4031	0.2483	0.041*
C10	0.1441 (4)	0.6080 (7)	0.2638 (4)	0.0334 (16)
H10	0.0921	0.6598	0.2220	0.040*
C11	0.2273 (4)	0.6896 (7)	0.3088 (5)	0.0347 (16)
H11	0.2305	0.7956	0.2968	0.042*
C12	0.3023 (4)	0.6182 (7)	0.3687 (4)	0.0283 (15)
H12	0.3574	0.6750	0.3984	0.034*
C13	0.2995 (4)	0.4596 (6)	0.3878 (4)	0.0232 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.01485 (17)	0.02395 (18)	0.0197 (2)	−0.00426 (13)	0.00406 (14)	−0.00171 (15)
Br1	0.0278 (3)	0.0431 (4)	0.0263 (4)	−0.0104 (3)	0.0121 (3)	−0.0085 (3)
N1	0.017 (2)	0.024 (3)	0.023 (3)	−0.0023 (19)	0.007 (2)	−0.004 (2)
C1	0.019 (3)	0.026 (3)	0.020 (4)	0.001 (2)	0.009 (3)	−0.002 (3)
C2	0.022 (3)	0.030 (3)	0.024 (4)	−0.005 (3)	0.005 (3)	−0.002 (3)
C3	0.029 (3)	0.033 (4)	0.033 (4)	0.004 (3)	0.011 (3)	0.002 (3)
C4	0.034 (4)	0.024 (3)	0.034 (4)	−0.003 (3)	0.016 (3)	0.000 (3)
C5	0.031 (3)	0.030 (3)	0.035 (4)	−0.005 (3)	0.020 (3)	−0.003 (3)
C6	0.021 (3)	0.030 (3)	0.028 (4)	−0.001 (3)	0.012 (3)	−0.004 (3)
C7	0.015 (3)	0.032 (3)	0.024 (4)	−0.005 (2)	0.005 (3)	−0.004 (3)
C8	0.017 (3)	0.031 (3)	0.020 (4)	0.002 (2)	0.006 (3)	−0.004 (3)
C9	0.022 (3)	0.039 (4)	0.032 (4)	0.002 (3)	0.003 (3)	−0.002 (3)
C10	0.028 (4)	0.044 (4)	0.022 (4)	0.004 (3)	0.004 (3)	0.005 (3)
C11	0.039 (4)	0.033 (4)	0.028 (4)	0.000 (3)	0.010 (3)	0.003 (3)
C12	0.019 (3)	0.033 (3)	0.027 (4)	−0.003 (3)	0.003 (3)	0.004 (3)
C13	0.016 (3)	0.030 (4)	0.020 (4)	−0.005 (2)	0.005 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Pt1—N1	2.058 (4)	C6—C7	1.380 (8)
Pt1—Br1	2.4385 (7)	C7—C8	1.389 (8)
N1—C13	1.366 (7)	C7—H7	0.9500
N1—C1	1.367 (7)	C8—C9	1.428 (8)
C1—C2	1.406 (8)	C8—C13	1.430 (7)
C1—C6	1.426 (7)	C9—C10	1.349 (9)
C2—C3	1.359 (8)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.415 (8)
C3—C4	1.415 (9)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.355 (8)
C4—C5	1.349 (9)	C11—H11	0.9500
C4—H4	0.9500	C12—C13	1.420 (8)
C5—C6	1.425 (8)	C12—H12	0.9500
C5—H5	0.9500

N1—Pt1—N1ⁱ	180.00 (16)	C7—C6—C5	121.6 (5)
N1—Pt1—Br1ⁱ	91.35 (14)	C7—C6—C1	119.2 (5)
N1ⁱ—Pt1—Br1ⁱ	88.65 (14)	C5—C6—C1	119.2 (5)
N1—Pt1—Br1	88.65 (14)	C6—C7—C8	120.3 (5)
N1ⁱ—Pt1—Br1	91.35 (14)	C6—C7—H7	119.8
Br1ⁱ—Pt1—Br1	180.0	C8—C7—H7	119.8
C13—N1—C1	119.7 (5)	C7—C8—C9	122.4 (5)
C13—N1—Pt1	119.9 (4)	C7—C8—C13	118.8 (5)
C1—N1—Pt1	120.1 (4)	C9—C8—C13	118.8 (5)
N1—C1—C2	120.9 (5)	C10—C9—C8	120.7 (6)
N1—C1—C6	120.9 (5)	C10—C9—H9	119.7
C2—C1—C6	118.1 (5)	C8—C9—H9	119.7
C3—C2—C1	120.9 (6)	C9—C10—C11	120.4 (6)
C3—C2—H2	119.5	C9—C10—H10	119.8
C1—C2—H2	119.5	C11—C10—H10	119.8
C2—C3—C4	121.3 (6)	C12—C11—C10	120.8 (6)
C2—C3—H3	119.3	C12—C11—H11	119.6
C4—C3—H3	119.3	C10—C11—H11	119.6
C5—C4—C3	119.4 (6)	C11—C12—C13	120.9 (5)
C5—C4—H4	120.3	C11—C12—H12	119.6
C3—C4—H4	120.3	C13—C12—H12	119.6
C4—C5—C6	121.0 (6)	N1—C13—C12	120.7 (5)
C4—C5—H5	119.5	N1—C13—C8	120.9 (5)
C6—C5—H5	119.5	C12—C13—C8	118.3 (5)

Br1ⁱ—Pt1—N1—C13	104.3 (4)	C5—C6—C7—C8	178.0 (6)
Br1—Pt1—N1—C13	−75.7 (4)	C1—C6—C7—C8	−2.1 (9)
Br1ⁱ—Pt1—N1—C1	−81.7 (4)	C6—C7—C8—C9	−177.9 (6)
Br1—Pt1—N1—C1	98.3 (4)	C6—C7—C8—C13	1.2 (9)
C13—N1—C1—C2	−177.0 (6)	C7—C8—C9—C10	176.4 (6)
Pt1—N1—C1—C2	8.9 (8)	C13—C8—C9—C10	−2.7 (10)
C13—N1—C1—C6	1.2 (8)	C8—C9—C10—C11	1.4 (10)
Pt1—N1—C1—C6	−172.8 (4)	C9—C10—C11—C12	−0.1 (11)
N1—C1—C2—C3	179.6 (6)	C10—C11—C12—C13	0.2 (10)
C6—C1—C2—C3	1.3 (9)	C1—N1—C13—C12	175.2 (6)
C1—C2—C3—C4	−0.4 (10)	Pt1—N1—C13—C12	−10.8 (8)
C2—C3—C4—C5	−1.0 (10)	C1—N1—C13—C8	−2.1 (9)
C3—C4—C5—C6	1.3 (10)	Pt1—N1—C13—C8	171.9 (4)
C4—C5—C6—C7	179.5 (6)	C11—C12—C13—N1	−178.9 (6)
C4—C5—C6—C1	−0.4 (10)	C11—C12—C13—C8	−1.5 (9)
N1—C1—C6—C7	0.9 (9)	C7—C8—C13—N1	1.0 (9)
C2—C1—C6—C7	179.2 (6)	C9—C8—C13—N1	−179.9 (6)
N1—C1—C6—C5	−179.2 (6)	C7—C8—C13—C12	−176.4 (6)
C2—C1—C6—C5	−0.9 (9)	C9—C8—C13—C12	2.7 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[PtBr₂(C₁₃H₉N)₂]
M_r	713.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	16.0256 (9), 8.6845 (5), 17.0646 (10)
β (°)	115.017 (1)
V (Å³)	2152.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.25
Crystal size (mm)	0.35 × 0.06 × 0.04

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.601, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6467, 2091, 1672
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.070, 1.00
No. of reflections	2091
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.19, −0.92

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Pt1—N1

2.058 (4)

Pt1—Br1

2.4385 (7)

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 (2009–0094056).

References

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