3,3′-{Ethane-1,2-diylbis[carbonylbis(azanediyl)]}dipyridinium tetra­chloridoplatinate(II)

Adarsh, N.N.; Krishna Kumar, D.; Dastidar, P.

doi:10.1107/S1600536810004253

metal-organic compounds

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Volume 66| Part 3| March 2010| Page m270

doi:10.1107/S1600536810004253

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3,3′-{Ethane-1,2-diylbis[carbonylbis(azanediyl)]}dipyridinium tetrachloridoplatinate(II)

N. N. Adarsh,^a D. Krishna Kumar ^b and Parthasarathi Dastidar ^a ^*

^aDepartment of Organic Chemistry, Indian Association for the Cultivation of Science, 2A & 2B Raja S C Mullick Road, Jadavpur, Kolkata 700 032, India, and ^bPresent address: Department of Chemistry, Imperial College, London SW7 2AZ, England
^*Correspondence e-mail: parthod123@rediffmail.com

(Received 16 January 2010; accepted 3 February 2010; online 6 February 2010)

In the crystal structure of the title compound, (C₁₄H₁₈N₆O₂)·[PtCl₄], the cation and square-planar anion are located on special positions (on a twofold axis and an inversion centre, respectively). In the crystal structure, N—H⋯Cl hydrogen bonds lead to a staircase-like motif. The central ethane backbone of the cation is disordered over two positions of equal occupancy.

Related literature

For organic–inorganic hybrid compounds displaying N—H⋯Cl—metal hydrogen bonds, see: Adams et al. (2007 ); Deifela & Cahill (2009 ). Orpen et al. (2004 ); Krishna Kumar et al. (2005 , 2006 ).

Experimental

Crystal data

(C₁₄H₁₈N₆O₂)[PtCl₄]
M_r = 639.23
Monoclinic, C 2/c
a = 17.8126 (13) Å
b = 7.0799 (5) Å
c = 15.5765 (12) Å
β = 103.332 (1)°
V = 1911.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 7.92 mm⁻¹
T = 100 K
0.22 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.275, T_max = 0.693
7045 measured reflections
1877 independent reflections
1693 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.064
S = 0.97
1877 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.51 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2ⁱ	0.76 (5)	2.55 (5)	3.259 (4)	156 (5)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 and SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97, publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004253/bt5171sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004253/bt5171Isup2.hkl

checkCIF report

Comment top

Suitable single crystals of the title compound were obtained by the resultant reaction of BPEBU and [K₂(PtCl₄)] in acidic medium (see experimental). The asymmetric unit consists of half of (PtCl₄) and one half molecule of bis-protonated BPEBU. The ORTEP diagram with 50% probability is given in Fig. 1. The metal center Pt(II) displayed a slight distorted square plannar geometry [Cl—Pt—Cl = 89.91 (4)–90.09 (4)°]. In the crystal structure, the bis-protonated ligand BPEBU displays syn–anti-syn conformation (scheme 1). N—H···Cl hydrogen bonds lead to a staircase like structure (Fig. 2).

Related literature top

For organic–inorganic hybrid compounds displaying N—H···Cl—metal hydrogen bonds, see: Adams et al. (2007); Deifela & Cahill (2009). Orpen et al. (2004); Krishna Kumar et al. (2005, 2006).

Experimental top

Synthesis: The title compound was synthesized by layering a methanolic solution of BPEBU (30 mg, 0.1 mmol) containing HCl (MeOH : HCl = 8 ml : 2 ml) over an aqueous solution of [K₂(PtCl₄)] (41.5 mg, 0.1 mmol) containings HCl (H₂O : HCl = 8 ml : 2 ml). After a period of two weeks, X-ray quality single crystals were obtained (yield = 30 mg, 47%). FT–IR (KBr, cm-1): 3325 (b, O—H, N—H stretch), 3082 (b, aromatic C—H stretch), 2965 (b, aliphatic C—H), 1686 (s, urea C═O stretch), 1612 (s, urea N—H bend), 1580, 1520, 1480, 1422, 1331, 1264,1238, 1191, 1111, 1024, 989, 864, 800, 694.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006) and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Ortep diagram of title compound with anisotropic displacement ellipsoids drawn at the 50% probability level. H atoms omitted for clarity.
	Fig. 2. Staircaise like hydrogen bonded network via N—H···Cl interactions

3,3'-{Ethane-1,2-diylbis[carbonylbis(azanediyl)]}dipyridinium tetrachloridoplatinate(II) top

Crystal data top

(C₁₄H₁₈N₆O₂)[PtCl₄]	F(000) = 1224
M_r = 639.23	D_x = 2.221 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.8126 (13) Å	Cell parameters from 566 reflections
b = 7.0799 (5) Å	θ = 2.4–27.8°
c = 15.5765 (12) Å	µ = 7.92 mm⁻¹
β = 103.332 (1)°	T = 100 K
V = 1911.4 (2) Å³	Plate, yellow
Z = 4	0.22 × 0.14 × 0.05 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1877 independent reflections
Radiation source: fine-focus sealed tube	1693 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ–ω scan	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −21→21
T_min = 0.275, T_max = 0.693	k = −8→8
7045 measured reflections	l = −19→19

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0343P)² + 6.3133P] where P = (F_o² + 2F_c²)/3
1877 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 1.51 e Å⁻³
0 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

(C₁₄H₁₈N₆O₂)[PtCl₄]	V = 1911.4 (2) Å³
M_r = 639.23	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.8126 (13) Å	µ = 7.92 mm⁻¹
b = 7.0799 (5) Å	T = 100 K
c = 15.5765 (12) Å	0.22 × 0.14 × 0.05 mm
β = 103.332 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1877 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1693 reflections with I > 2σ(I)
T_min = 0.275, T_max = 0.693	R_int = 0.044
7045 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 1.51 e Å⁻³
1877 reflections	Δρ_min = −0.89 e Å⁻³
132 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pt1	0.5000	0.5000	0.0000	0.01584 (10)
Cl1	0.39171 (5)	0.65021 (15)	−0.07921 (6)	0.0228 (2)
Cl2	0.50224 (6)	0.69911 (14)	0.11747 (7)	0.0226 (2)
N1	0.1742 (2)	−0.0639 (6)	−0.1087 (3)	0.0250 (8)
H1	0.139 (3)	−0.108 (7)	−0.096 (3)	0.030*
C2	0.2331 (3)	−0.0133 (5)	−0.0434 (3)	0.0193 (9)
H2	0.2297	−0.0254	0.0163	0.023*
C3	0.3001 (2)	0.0577 (6)	−0.0639 (2)	0.0160 (8)
C4	0.3007 (2)	0.0717 (7)	−0.1528 (3)	0.0223 (8)
H4	0.3455	0.1183	−0.1690	0.027*
C5	0.2379 (3)	0.0195 (6)	−0.2176 (3)	0.0305 (12)
H5	0.2391	0.0310	−0.2781	0.037*
C6	0.1730 (3)	−0.0497 (7)	−0.1941 (3)	0.0304 (10)
H6	0.1288	−0.0861	−0.2378	0.036*
N7	0.36384 (19)	0.1145 (5)	−0.0011 (2)	0.0176 (7)
C8	0.3757 (2)	0.0918 (6)	0.0896 (3)	0.0214 (9)
O9	0.3290 (2)	0.0132 (4)	0.1240 (3)	0.0367 (10)
N10	0.4417 (2)	0.1661 (6)	0.1358 (2)	0.0275 (9)
C11A	0.4643 (5)	0.2153 (13)	0.2283 (5)	0.0202 (16)*	0.50
H11A	0.4227	0.1819	0.2582	0.024*	0.50
H11B	0.4740	0.3528	0.2351	0.024*	0.50
C11B	0.4631 (5)	0.1063 (12)	0.2315 (5)	0.0185 (16)*	0.50
H11C	0.4728	−0.0314	0.2365	0.022*	0.50
H11D	0.4213	0.1381	0.2614	0.022*	0.50
H7	0.400 (3)	0.164 (6)	−0.020 (3)	0.022*
H10	0.467 (3)	0.219 (7)	0.116 (3)	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.01344 (14)	0.01733 (15)	0.01748 (14)	−0.00161 (7)	0.00507 (9)	−0.00225 (7)
Cl1	0.0172 (5)	0.0302 (5)	0.0211 (5)	0.0044 (4)	0.0046 (4)	0.0037 (4)
Cl2	0.0192 (5)	0.0254 (5)	0.0239 (5)	−0.0025 (4)	0.0062 (4)	−0.0096 (4)
N1	0.0220 (19)	0.0246 (19)	0.030 (2)	−0.0071 (16)	0.0105 (16)	−0.0072 (17)
C2	0.019 (2)	0.019 (2)	0.021 (2)	−0.0005 (14)	0.0066 (19)	−0.0024 (15)
C3	0.020 (2)	0.0134 (17)	0.0147 (19)	0.0009 (16)	0.0045 (16)	−0.0006 (16)
C4	0.020 (2)	0.030 (2)	0.018 (2)	−0.0010 (18)	0.0067 (17)	−0.0012 (18)
C5	0.023 (3)	0.050 (3)	0.018 (2)	0.0020 (19)	0.004 (2)	−0.0089 (18)
C6	0.023 (2)	0.040 (2)	0.026 (3)	−0.002 (2)	0.003 (2)	−0.017 (2)
N7	0.0184 (17)	0.0221 (18)	0.0135 (16)	−0.0055 (13)	0.0064 (14)	0.0016 (13)
C8	0.019 (2)	0.033 (2)	0.0128 (19)	0.0068 (17)	0.0043 (16)	0.0044 (17)
O9	0.028 (2)	0.063 (3)	0.0219 (18)	−0.0011 (14)	0.0108 (16)	0.0151 (14)
N10	0.022 (2)	0.046 (2)	0.0143 (18)	−0.0013 (16)	0.0037 (15)	−0.0045 (16)

Geometric parameters (Å, º) top

Pt1—Cl1ⁱ	2.2971 (9)	C6—H6	0.9500
Pt1—Cl1	2.2971 (9)	N7—C8	1.389 (5)
Pt1—Cl2ⁱ	2.3028 (9)	N7—H7	0.83 (5)
Pt1—Cl2	2.3028 (9)	C8—O9	1.223 (5)
N1—C6	1.330 (6)	C8—N10	1.337 (6)
N1—C2	1.331 (6)	N10—C11A	1.447 (8)
N1—H1	0.76 (5)	N10—C11B	1.511 (9)
C2—C3	1.397 (6)	N10—H10	0.71 (5)
C2—H2	0.9500	C11A—C11Bⁱⁱ	1.513 (10)
C3—N7	1.377 (5)	C11A—H11A	0.9900
C3—C4	1.392 (5)	C11A—H11B	0.9900
C4—C5	1.374 (7)	C11B—C11Aⁱⁱ	1.513 (10)
C4—H4	0.9500	C11B—H11C	0.9900
C5—C6	1.380 (7)	C11B—H11D	0.9900
C5—H5	0.9500

Cl1ⁱ—Pt1—Cl1	180.0	C3—N7—C8	126.6 (3)
Cl1ⁱ—Pt1—Cl2ⁱ	90.11 (4)	C3—N7—H7	116 (3)
Cl1—Pt1—Cl2ⁱ	89.89 (4)	C8—N7—H7	117 (3)
Cl1ⁱ—Pt1—Cl2	89.89 (4)	O9—C8—N10	123.1 (4)
Cl1—Pt1—Cl2	90.11 (4)	O9—C8—N7	122.6 (4)
Cl2ⁱ—Pt1—Cl2	180.0	N10—C8—N7	114.3 (4)
C6—N1—C2	124.9 (4)	C8—N10—C11A	129.8 (5)
C6—N1—H1	118 (4)	C8—N10—C11B	114.3 (4)
C2—N1—H1	117 (4)	C11A—N10—C11B	30.3 (4)
N1—C2—C3	119.0 (4)	C8—N10—H10	122 (4)
N1—C2—H2	120.5	C11A—N10—H10	105 (4)
C3—C2—H2	120.5	C11B—N10—H10	123 (4)
N7—C3—C4	119.4 (4)	N10—C11A—C11Bⁱⁱ	107.6 (6)
N7—C3—C2	123.4 (4)	N10—C11A—H11A	110.2
C4—C3—C2	117.2 (4)	C11Bⁱⁱ—C11A—H11A	110.2
C5—C4—C3	121.3 (4)	N10—C11A—H11B	110.2
C5—C4—H4	119.3	C11Bⁱⁱ—C11A—H11B	110.2
C3—C4—H4	119.3	H11A—C11A—H11B	108.5
C4—C5—C6	119.4 (5)	N10—C11B—C11Aⁱⁱ	105.2 (5)
C4—C5—H5	120.3	N10—C11B—H11C	110.7
C6—C5—H5	120.3	C11Aⁱⁱ—C11B—H11C	110.7
N1—C6—C5	118.1 (4)	N10—C11B—H11D	110.7
N1—C6—H6	121.0	C11Aⁱⁱ—C11B—H11D	110.7
C5—C6—H6	121.0	H11C—C11B—H11D	108.8

C6—N1—C2—C3	−1.1 (7)	C3—N7—C8—O9	1.0 (7)
N1—C2—C3—N7	179.7 (4)	C3—N7—C8—N10	−177.7 (4)
N1—C2—C3—C4	0.2 (6)	O9—C8—N10—C11A	−17.3 (8)
N7—C3—C4—C5	−178.9 (4)	N7—C8—N10—C11A	161.5 (6)
C2—C3—C4—C5	0.6 (6)	O9—C8—N10—C11B	13.7 (7)
C3—C4—C5—C6	−0.5 (7)	N7—C8—N10—C11B	−167.5 (5)
C2—N1—C6—C5	1.2 (7)	C8—N10—C11A—C11Bⁱⁱ	122.2 (6)
C4—C5—C6—N1	−0.3 (7)	C11B—N10—C11A—C11Bⁱⁱ	53.4 (10)
C4—C3—N7—C8	−172.8 (4)	C8—N10—C11B—C11Aⁱⁱ	−176.5 (5)
C2—C3—N7—C8	7.7 (6)	C11A—N10—C11B—C11Aⁱⁱ	−48.3 (10)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2ⁱⁱⁱ	0.76 (5)	2.55 (5)	3.259 (4)	156 (5)

Symmetry code: (iii) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	(C₁₄H₁₈N₆O₂)[PtCl₄]
M_r	639.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	17.8126 (13), 7.0799 (5), 15.5765 (12)
β (°)	103.332 (1)
V (Å³)	1911.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.92
Crystal size (mm)	0.22 × 0.14 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.275, 0.693
No. of measured, independent and observed [I > 2σ(I)] reflections	7045, 1877, 1693
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.064, 0.97
No. of reflections	1877
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.51, −0.89

Computer programs: , APEX2 (Bruker, 2006) and SAINT (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2ⁱ	0.76 (5)	2.55 (5)	3.259 (4)	156 (5)

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Acknowledgements

We thank the Department of Science and Technology (DST), New Delhi, India, for financial support. NNA thanks IACS for research fellowships.

References

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

3,3′-{Ethane-1,2-diylbis[carbonylbis(azanediyl)]}dipyridinium tetra­chloridoplatinate(II)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

3,3′-{Ethane-1,2-diylbis[carbonylbis(azanediyl)]}dipyridinium tetrachloridoplatinate(II)