Bis(μ-bis­{[4-(2-pyrid­yl)pyrimidin-2-yl]sulfan­yl}methane)­disilver(I) bis­(perchlorate)

Zhu, H.-B.

doi:10.1107/S160053681004924X

metal-organic compounds

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Volume 66| Part 12| December 2010| Page m1691

https://doi.org/10.1107/S160053681004924X

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Bis(μ-bis{[4-(2-pyridyl)pyrimidin-2-yl]sulfanyl}methane)disilver(I) bis(perchlorate)

Hai-Bin Zhu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhuhaibin@seu.edu.cn

(Received 20 November 2010; accepted 25 November 2010; online 30 November 2010)

In the macrocyclic centrosymmetric dinuclear complex, [Ag₂(C₁₉H₁₄N₆S₂)₂](ClO₄)₂, the Ag^I atom, bis{[4-(2-pyridyl)pyrimidin-2-yl]sulfanyl}methane (2-bppt) ligand and perchlorate anion each lie on a twofold rotation axis. The 2-bppt ligand chelates two four-coordinated Ag^I atoms through its two bipyridine-like arms. The O atoms of the perchlorate anion are disordered each over two positions of equal occupancy. Adjacent complex molecules are linked by π–π interactions between the pyridine and pyrimidine rings [centroid–centroid distance = 3.663 (8) Å].

Related literature

For Ag(I) coordination polymers, see: Chen et al. (2006 ). For the coordination chemistry of 4-(pyridin-n-yl)pyrimidin-2-thiol (n = 2, 3, 4) and their derivatives, see: Dong et al. (2009 ); Huang et al. (2007 ); Zhu et al. (2010 ).

Experimental

Crystal data

[Ag₂(C₁₉H₁₄N₆S₂)₂](ClO₄)₂
M_r = 1195.64
Orthorhombic, F d d d
a = 10.4382 (16) Å
b = 27.896 (4) Å
c = 30.089 (5) Å
V = 8761 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 298 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.832, T_max = 0.880
14503 measured reflections
2705 independent reflections
1640 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.172
S = 1.05
2705 reflections
169 parameters
24 restraints
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected bond lengths (Å)

Ag1—N1	2.277 (4)
Ag1—N2	2.398 (3)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681004924X/hy2383sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004924X/hy2383Isup2.hkl

checkCIF report

Comment top

The supramolecular chemistry of Ag(I) coordination polymers is being a dynamic and thriving research field, which has attracted considerable interest (Chen et. al, 2006). For a long time, we have focused on the coordination chemistry of 4-(pyridin-n-yl)pyrimidin-2-thiol (n = 2, 3, 4) and their derivatives (Dong et al., 2009; Huang et al., 2007; Zhu et al., 2010). Herein, we report a macrocyclic Ag(I) complex with bis[4-(2-pyridyl)pyrimidin-2-ylthio]methane (2-bppt) ligand.

The title compound shows a discrete macrocylic dinuclear structure, with perchlorate anions uncoordinated (Fig. 1). Each Ag^I ion is chelated by two sets of N,N-chelating donors from two 2-bppt ligands. The Ag—N bond distances are 2.277 (4) and 2.398 (3) Å (Table 1), while the N—Ag—N angles are in the range of 70.96 (13) to 158.7 (2)°. The Ag—Ag separation across the macrocycle is 8.167 (1) Å.

Related literature top

For Ag(I) coordination polymers, see: Chen et al. (2006). For the coordination chemistry of 4-(pyridin-n-yl)pyrimidin-2-thiol (n = 2, 3, 4) and their derivatives, see: Dong et al. (2009); Huang et al. (2007); Zhu et al. (2010).

Experimental top

A CH₃CN solution of AgClO₄ (0.1 mmol) was layered above a CH₂Cl₂ solution of 2-bppt (0.1 mmol). Colorless crystals were obtained after one week. The crystals were collected and dried under vacuum (yield: 46%).

Structure description top

For Ag(I) coordination polymers, see: Chen et al. (2006). For the coordination chemistry of 4-(pyridin-n-yl)pyrimidin-2-thiol (n = 2, 3, 4) and their derivatives, see: Dong et al. (2009); Huang et al. (2007); Zhu et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound, with the 30% probability displacement ellipsoids. [Symmetry codes: (A) 7/4 - x, 3/4 - y, z; (B) x, 3/4 - y, -1/4 - z; (C) 7/4 - x, y, -1/4 - z; (D) 9/4 - x, 1/4 - y, z.]

Bis(µ-bis{[4-(2-pyridyl)pyrimidin-2-yl]sulfanyl}methane)disilver(I) bis(perchlorate) top

Crystal data top

[Ag₂(C₁₉H₁₄N₆S₂)₂](ClO₄)₂	F(000) = 4768
M_r = 1195.64	D_x = 1.813 Mg m⁻³
Orthorhombic, Fddd	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vw	Cell parameters from 2705 reflections
a = 10.4382 (16) Å	θ = 2.3–25.5°
b = 27.896 (4) Å	µ = 1.27 mm⁻¹
c = 30.089 (5) Å	T = 298 K
V = 8761 (2) Å³	Block, colorless
Z = 8	0.15 × 0.12 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2705 independent reflections
Radiation source: fine-focus sealed tube	1640 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→12
T_min = 0.832, T_max = 0.880	k = −36→35
14503 measured reflections	l = −35→40

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2705 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.54 e Å⁻³
24 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Ag₂(C₁₉H₁₄N₆S₂)₂](ClO₄)₂	V = 8761 (2) Å³
M_r = 1195.64	Z = 8
Orthorhombic, Fddd	Mo Kα radiation
a = 10.4382 (16) Å	µ = 1.27 mm⁻¹
b = 27.896 (4) Å	T = 298 K
c = 30.089 (5) Å	0.15 × 0.12 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2705 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1640 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.880	R_int = 0.035
14503 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	24 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	Δρ_max = 0.54 e Å⁻³
2705 reflections	Δρ_min = −0.64 e Å⁻³
169 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ag1	0.8750	0.3750	0.010711 (18)	0.0724 (3)
S1	0.64901 (13)	0.37857 (5)	−0.07449 (5)	0.0703 (4)
Cl1	1.1250	0.1250	−0.08929 (11)	0.1119 (9)
C6	0.8563 (4)	0.27205 (15)	−0.03645 (15)	0.0602 (11)
N2	0.7995 (3)	0.31493 (12)	−0.03991 (12)	0.0577 (9)
N3	0.6715 (4)	0.28754 (15)	−0.10059 (13)	0.0708 (10)
C9	0.7124 (4)	0.32014 (15)	−0.07181 (14)	0.0598 (10)
C5	0.9565 (5)	0.26651 (16)	−0.00209 (16)	0.0652 (12)
C10	0.5575 (6)	0.3750	−0.1250	0.0715 (18)
H10A	0.5025	0.4030	−0.1267	0.086*	0.50
H10B	0.5025	0.3470	−0.1233	0.086*	0.50
N1	0.9792 (4)	0.30490 (14)	0.02472 (13)	0.0693 (10)
C8	0.7272 (6)	0.24468 (18)	−0.09552 (17)	0.0804 (15)
H8	0.7013	0.2199	−0.1141	0.096*
C7	0.8198 (6)	0.23519 (16)	−0.06458 (18)	0.0761 (14)
H7	0.8571	0.2050	−0.0625	0.091*
C3	1.1171 (7)	0.2208 (3)	0.0336 (3)	0.107 (2)
H3	1.1630	0.1924	0.0365	0.128*
C1	1.0704 (5)	0.3010 (2)	0.05571 (19)	0.0873 (15)
H1	1.0864	0.3268	0.0745	0.105*
C2	1.1432 (5)	0.2585 (3)	0.0605 (3)	0.105 (2)
H2	1.2078	0.2565	0.0817	0.125*
C4	1.0244 (6)	0.2245 (2)	0.0026 (2)	0.0892 (16)
H4	1.0062	0.1985	−0.0158	0.107*
O1	1.1499 (10)	0.1740 (3)	−0.0861 (3)	0.120 (3)	0.50
O2	1.2437 (12)	0.1043 (4)	−0.0898 (4)	0.142 (4)	0.50
O3	1.0656 (13)	0.1194 (5)	−0.0423 (5)	0.166 (5)	0.50
O4	1.0504 (13)	0.1200 (6)	−0.1265 (5)	0.176 (5)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0848 (4)	0.0529 (3)	0.0795 (4)	−0.0060 (2)	0.000	0.000
S1	0.0718 (8)	0.0712 (7)	0.0679 (8)	0.0074 (5)	−0.0057 (6)	−0.0091 (6)
Cl1	0.1036 (17)	0.0619 (12)	0.170 (3)	0.0054 (11)	0.000	0.000
C6	0.068 (3)	0.051 (2)	0.062 (3)	−0.0062 (19)	0.026 (2)	0.0064 (19)
N2	0.059 (2)	0.0522 (18)	0.062 (2)	−0.0070 (15)	0.0100 (18)	−0.0039 (15)
N3	0.074 (2)	0.071 (3)	0.067 (2)	−0.022 (2)	0.007 (2)	−0.0131 (19)
C9	0.058 (2)	0.063 (2)	0.059 (2)	−0.0073 (19)	0.012 (2)	−0.006 (2)
C5	0.065 (3)	0.062 (3)	0.069 (3)	0.002 (2)	0.023 (2)	0.013 (2)
C10	0.050 (3)	0.089 (5)	0.076 (4)	0.000	0.000	0.000 (3)
N1	0.066 (2)	0.068 (2)	0.074 (2)	−0.0072 (19)	0.004 (2)	0.0169 (19)
C8	0.095 (4)	0.075 (3)	0.071 (3)	−0.026 (3)	0.020 (3)	−0.020 (3)
C7	0.091 (4)	0.050 (2)	0.087 (4)	−0.008 (2)	0.034 (3)	−0.007 (2)
C3	0.092 (5)	0.102 (5)	0.126 (6)	0.029 (4)	0.023 (4)	0.036 (5)
C1	0.074 (3)	0.101 (4)	0.087 (4)	−0.006 (3)	−0.007 (3)	0.023 (3)
C2	0.065 (4)	0.129 (6)	0.120 (5)	0.007 (3)	−0.003 (3)	0.050 (5)
C4	0.087 (4)	0.081 (3)	0.099 (4)	0.022 (3)	0.027 (3)	0.019 (3)
O1	0.152 (7)	0.076 (5)	0.132 (7)	0.008 (5)	−0.029 (5)	−0.009 (4)
O2	0.133 (7)	0.105 (6)	0.188 (8)	0.044 (6)	−0.017 (6)	−0.012 (6)
O3	0.176 (9)	0.166 (8)	0.155 (8)	−0.016 (7)	0.028 (7)	0.007 (7)
O4	0.167 (8)	0.198 (9)	0.162 (8)	−0.025 (8)	−0.076 (7)	−0.041 (7)

Geometric parameters (Å, º) top

Ag1—N1	2.277 (4)	C5—C4	1.377 (6)
Ag1—N2	2.398 (3)	C10—S1ⁱ	1.798 (4)
S1—C9	1.761 (4)	C10—H10A	0.9700
S1—C10	1.798 (4)	C10—H10B	0.9700
Cl1—O4	1.370 (11)	N1—C1	1.337 (6)
Cl1—O2	1.367 (11)	C8—C7	1.368 (8)
Cl1—O1	1.395 (9)	C8—H8	0.9300
Cl1—O3	1.552 (13)	C7—H7	0.9300
C6—N2	1.339 (5)	C3—C2	1.355 (11)
C6—C7	1.385 (7)	C3—C4	1.348 (9)
C6—C5	1.479 (7)	C3—H3	0.9300
N2—C9	1.330 (5)	C1—C2	1.416 (9)
N3—C9	1.326 (5)	C1—H1	0.9300
N3—C8	1.338 (6)	C2—H2	0.9300
C5—N1	1.361 (6)	C4—H4	0.9300

N1—Ag1—N1ⁱⁱ	158.7 (2)	S1ⁱ—C10—H10A	108.3
N1—Ag1—N2	71.00 (14)	S1—C10—H10B	108.3
N1ⁱⁱ—Ag1—N2	124.11 (13)	S1ⁱ—C10—H10B	108.3
N1—Ag1—N2ⁱⁱ	124.11 (13)	H10A—C10—H10B	107.4
N1ⁱⁱ—Ag1—N2ⁱⁱ	71.00 (14)	C5—N1—C1	118.3 (5)
N2—Ag1—N2ⁱⁱ	101.13 (16)	C5—N1—Ag1	118.9 (3)
C9—S1—C10	100.78 (17)	C1—N1—Ag1	122.6 (4)
O4—Cl1—O4ⁱⁱⁱ	70.5 (13)	N3—C8—C7	123.9 (4)
O4—Cl1—O2	117.6 (10)	N3—C8—H8	118.1
O4ⁱⁱⁱ—Cl1—O2	61.2 (7)	C7—C8—H8	118.1
O4—Cl1—O2ⁱⁱⁱ	61.2 (7)	C8—C7—C6	117.8 (5)
O4ⁱⁱⁱ—Cl1—O2ⁱⁱⁱ	117.6 (10)	C8—C7—H7	121.1
O2—Cl1—O2ⁱⁱⁱ	178.7 (11)	C6—C7—H7	121.1
O4—Cl1—O1ⁱⁱⁱ	81.5 (8)	C2—C3—C4	119.8 (6)
O4ⁱⁱⁱ—Cl1—O1ⁱⁱⁱ	105.2 (8)	C2—C3—H3	120.1
O2—Cl1—O1ⁱⁱⁱ	75.8 (6)	C4—C3—H3	120.1
O2ⁱⁱⁱ—Cl1—O1ⁱⁱⁱ	104.3 (6)	N1—C1—C2	121.3 (6)
O4—Cl1—O1	105.2 (8)	N1—C1—H1	119.3
O4ⁱⁱⁱ—Cl1—O1	81.5 (8)	C2—C1—H1	119.3
O2—Cl1—O1	104.3 (6)	C3—C2—C1	118.9 (6)
O2ⁱⁱⁱ—Cl1—O1	75.8 (6)	C3—C2—H2	120.6
O1ⁱⁱⁱ—Cl1—O1	172.0 (9)	C1—C2—H2	120.6
O4—Cl1—O3ⁱⁱⁱ	168.9 (8)	C3—C4—C5	120.3 (6)
O4ⁱⁱⁱ—Cl1—O3ⁱⁱⁱ	120.5 (8)	C3—C4—H4	119.8
O2—Cl1—O3ⁱⁱⁱ	72.0 (7)	C5—C4—H4	119.8
O2ⁱⁱⁱ—Cl1—O3ⁱⁱⁱ	109.3 (9)	Cl1—O1—O2ⁱⁱⁱ	51.3 (4)
O1ⁱⁱⁱ—Cl1—O3ⁱⁱⁱ	96.3 (7)	Cl1—O1—O4ⁱⁱⁱ	48.6 (5)
O1—Cl1—O3ⁱⁱⁱ	76.3 (7)	O2ⁱⁱⁱ—O1—O4ⁱⁱⁱ	83.8 (7)
O4—Cl1—O3	120.5 (8)	Cl1—O1—O3ⁱⁱⁱ	55.7 (6)
O4ⁱⁱⁱ—Cl1—O3	168.9 (8)	O2ⁱⁱⁱ—O1—O3ⁱⁱⁱ	85.0 (7)
O2—Cl1—O3	109.3 (9)	O4ⁱⁱⁱ—O1—O3ⁱⁱⁱ	88.7 (8)
O2ⁱⁱⁱ—Cl1—O3	72.0 (7)	Cl1—O2—O4ⁱⁱⁱ	59.5 (7)
O1ⁱⁱⁱ—Cl1—O3	76.3 (7)	Cl1—O2—O1ⁱⁱⁱ	52.8 (5)
O1—Cl1—O3	96.3 (7)	O4ⁱⁱⁱ—O2—O1ⁱⁱⁱ	90.0 (9)
O3ⁱⁱⁱ—Cl1—O3	48.6 (10)	Cl1—O2—O3ⁱⁱⁱ	59.0 (6)
N2—C6—C7	119.6 (5)	O4ⁱⁱⁱ—O2—O3ⁱⁱⁱ	108.6 (10)
N2—C6—C5	117.4 (4)	O1ⁱⁱⁱ—O2—O3ⁱⁱⁱ	80.0 (8)
C7—C6—C5	123.0 (4)	O3ⁱⁱⁱ—O3—Cl1	65.7 (5)
C9—N2—C6	117.2 (4)	O3ⁱⁱⁱ—O3—O2ⁱⁱⁱ	104.2 (9)
C9—N2—Ag1	127.3 (3)	Cl1—O3—O2ⁱⁱⁱ	49.0 (5)
C6—N2—Ag1	115.4 (3)	O3ⁱⁱⁱ—O3—O1ⁱⁱⁱ	88.3 (12)
C9—N3—C8	113.5 (4)	Cl1—O3—O1ⁱⁱⁱ	48.0 (5)
N3—C9—N2	128.0 (4)	O2ⁱⁱⁱ—O3—O1ⁱⁱⁱ	75.8 (7)
N3—C9—S1	119.0 (4)	Cl1—O4—O2ⁱⁱⁱ	59.3 (7)
N2—C9—S1	113.0 (3)	Cl1—O4—O4ⁱⁱⁱ	54.8 (6)
N1—C5—C4	121.3 (5)	O2ⁱⁱⁱ—O4—O4ⁱⁱⁱ	103.6 (10)
N1—C5—C6	117.1 (4)	Cl1—O4—O1ⁱⁱⁱ	49.9 (6)
C4—C5—C6	121.6 (5)	O2ⁱⁱⁱ—O4—O1ⁱⁱⁱ	84.9 (9)
S1—C10—S1ⁱ	115.8 (4)	O4ⁱⁱⁱ—O4—O1ⁱⁱⁱ	80.6 (11)
S1—C10—H10A	108.3

Symmetry codes: (i) x, −y+3/4, −z−1/4; (ii) −x+7/4, −y+3/4, z; (iii) −x+9/4, −y+1/4, z.

Experimental details

Crystal data
Chemical formula	[Ag₂(C₁₉H₁₄N₆S₂)₂](ClO₄)₂
M_r	1195.64
Crystal system, space group	Orthorhombic, Fddd
Temperature (K)	298
a, b, c (Å)	10.4382 (16), 27.896 (4), 30.089 (5)
V (Å³)	8761 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.832, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	14503, 2705, 1640
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.172, 1.05
No. of reflections	2705
No. of parameters	169
No. of restraints	24
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.64

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ag1—N1

2.277 (4)

Ag1—N2

2.398 (3)

Acknowledgements

The author acknowledges financial support from the China Postdoctoral Research Fund (20070411010).

References

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