2,2′-(p-Phenyl­ene)bis­(1,4,5,6-tetra­hydro­pyrimidinium) bis­[dicyanidoargentate(I)]

Jiang, Z.-Y.; Dong, H.-Z.; Zhang, G.; Cheng, L.

doi:10.1107/S1600536808015791

metal-organic compounds

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Volume 64| Part 7| July 2008| Page m858

doi:10.1107/S1600536808015791

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2,2′-(p-Phenylene)bis(1,4,5,6-tetrahydropyrimidinium) bis[dicyanidoargentate(I)]

Zhi-Yu Jiang,^a Hua-Ze Dong,^b Gong Zhang ^b and Lin Cheng ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 24 May 2008; accepted 26 May 2008; online 7 June 2008)

The asymmetric unit of the title compound, (C₁₄H₂₀N₄)[Ag(CN)₂]₂, contains one-half of a centrosymmetric 2,2′-(p-phenylene)bis(1,4,5,6-tetrahydropyrimidinium) (H₂btb) cation and one [Ag(CN)₂]⁻ anion. In the anions, the Ag^I atoms adopt near linear coordination modes with the two attached cyanide groups [C—Ag—C = 173.3 (2)°]. In the crystal structure, each H₂btb cation links four [Ag(CN)₂]⁻ anions via N—H⋯N hydrogen bonds into a one-dimensional ribbon.

Related literature

For related structures, see: Braga et al. (2000 ); Felix et al. (1998 ). For related literature, see: Burchell et al. (2004 ); Holliday & Mirkin (2001 ).

Experimental

Crystal data

(C₁₄H₂₀N₄)[Ag(CN)₂]₂
M_r = 564.16
Triclinic, $[P \overline 1]$
a = 6.6930 (9) Å
b = 7.276 (1) Å
c = 11.4982 (15) Å
α = 89.963 (2)°
β = 87.318 (2)°
γ = 68.066 (2)°
V = 518.76 (12) Å³
Z = 1
Mo Kα radiation
μ = 1.91 mm⁻¹
T = 273 (2) K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.702, T_max = 0.763
4040 measured reflections
2015 independent reflections
1769 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.093
S = 1.09
2015 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯N4ⁱ	0.78 (4)	2.13 (4)	2.903 (4)	175 (4)
N2—H2C⋯N3	0.79 (4)	2.13 (4)	2.905 (5)	168 (3)
Symmetry code: (i) x-1, y+1, z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); 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: 10.1107/S1600536808015791/bt2718sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015791/bt2718Isup2.hkl

checkCIF report

Comment top

Supramolecular chemistry has been a rapidly growing field concerning with the construction of supramolecular assemblies held together by non-classical chemical interactions in addition to covalent bonds (Holliday & Mirkin, 2001). A variety of weak forces, such as hydrogen bond, π–π stacking, and metal–ligand coordination, have been extensively used in this field (Burchell et al., 2004). Within the various types of organic ligands utilized in assembly of supramolecular structures, tetrahydropyrimidines have attracted considerable interest for their versatile coordination mode with the protonated or deprotonated moiety and potential to form supramolecular aggregates through hydrogen bonding (Braga et al., 2000; Felix et al., 1998).

Herein, we report the crystal structure of the title compound, (C₁₄H₂₀N₄).2(C₂AgN₂), based on a tetrahydropyrimidine ligand–1,4-bis(1,4,5,6-tetrahydropyrimidin-2-yl)benzene. The asymmetric unit of the title compound, (C₁₄H₂₀N₄).2(C₂AgN₂), contains half a H₂btb cation (btb = 1,4-bis(1,4,5,6-tetrahydropyrimidin-2-yl)benzene) and one Ag(CN)₂ anion. In the compound, each H₂btb cation links four Ag(CN)₂ anions by the N—H···N hydrogen bonds into an one-dimensional ribbon. Meanwhile, each pair of adjacent H₂btb cations are hydrogen-bonded by two parallel Ag(CN)₂ anions. The hydrogen-bonding distances are 2.904 (5) and 2.905 (6) Å. In one chain, the shortest Ag···Ag distance is 4.218 (2) Å. The distance of adjacent H₂btb cations seperated by Ag(CN)₂ anions is 13.655 (3) Å.

Related literature top

For related structures, see: Braga et al. (2000); Felix et al. (1998). For related literature, see: Burchell et al. (2004); Holliday & Mirkin (2001).

Experimental top

A mixture of btb (0.024 g, 0.1 mmol), k[Ag(CN)₂] (0.010 g, 0.05 mmol), and water (8 ml) was stirred for 1 h at room temperature, and then filtered. The filtrate was allowed to evaporate slowly at room temperature. After 3 weeks, colorless block crystals were obtained in 60% yield (0.034 g) based on btb.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. Perspective view of the title compound with 30% displacement ellipsoids. H atoms bonded to C atoms have been omitted for clarity. [Symmetry code (A): 3-x, -y, 1-z.]
	Fig. 2. The hydrogen-bonding pattern of the title compound.

2,2'-(p-Phenylene)bis(1,4,5,6-tetrahydropyrimidinium) bis[dicyanidoargentate(I)] top

Crystal data top

(C₁₄H₂₀N₄)[Ag(CN)₂]₂	Z = 1
M_r = 564.16	F(000) = 278
Triclinic, P1	D_x = 1.806 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6930 (9) Å	Cell parameters from 783 reflections
b = 7.276 (1) Å	θ = 2.5–28.0°
c = 11.4982 (15) Å	µ = 1.91 mm⁻¹
α = 89.963 (2)°	T = 273 K
β = 87.318 (2)°	Block, colourless
γ = 68.066 (2)°	0.20 × 0.18 × 0.15 mm
V = 518.76 (12) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2015 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→7
T_min = 0.702, T_max = 0.763	k = −8→8
4040 measured reflections	l = −14→14

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0523P)² + 0.1388P] where P = (F_o² + 2F_c²)/3
2015 reflections	(Δ/σ)_max < 0.001
135 parameters	Δρ_max = 1.07 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

(C₁₄H₂₀N₄)[Ag(CN)₂]₂	γ = 68.066 (2)°
M_r = 564.16	V = 518.76 (12) Å³
Triclinic, P1	Z = 1
a = 6.6930 (9) Å	Mo Kα radiation
b = 7.276 (1) Å	µ = 1.91 mm⁻¹
c = 11.4982 (15) Å	T = 273 K
α = 89.963 (2)°	0.20 × 0.18 × 0.15 mm
β = 87.318 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2015 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1769 reflections with I > 2σ(I)
T_min = 0.702, T_max = 0.763	R_int = 0.015
4040 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.07 e Å⁻³
2015 reflections	Δρ_min = −0.33 e Å⁻³
135 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

	x	y	z	U_iso*/U_eq
Ag1	1.75049 (5)	−0.46673 (5)	−0.11338 (2)	0.06556 (17)
C1	0.7736 (6)	0.2925 (7)	0.3110 (3)	0.0600 (10)
H1A	0.7672	0.4129	0.2722	0.072*
H1B	0.6401	0.3208	0.3572	0.072*
C2	0.8010 (7)	0.1333 (8)	0.2228 (4)	0.0702 (12)
H2A	0.6862	0.1799	0.1688	0.084*
H2B	0.7908	0.0185	0.2617	0.084*
C3	1.0154 (6)	0.0746 (6)	0.1567 (3)	0.0589 (10)
H3A	1.0439	−0.0470	0.1127	0.071*
H3B	1.0125	0.1773	0.1023	0.071*
C4	1.1503 (5)	0.1093 (5)	0.3465 (3)	0.0385 (7)
C5	1.3309 (5)	0.0529 (5)	0.4257 (3)	0.0370 (6)
C6	1.3411 (5)	0.1879 (5)	0.5078 (3)	0.0416 (7)
H6A	1.2346	0.3145	0.5128	0.050*
C7	1.4921 (5)	−0.1357 (5)	0.4178 (3)	0.0432 (7)
H7A	1.4869	−0.2265	0.3623	0.052*
C8	1.6530 (7)	−0.3227 (7)	0.0448 (4)	0.0652 (11)
C9	1.8252 (6)	−0.5801 (6)	−0.2799 (3)	0.0536 (9)
N1	0.9572 (4)	0.2250 (5)	0.3863 (3)	0.0459 (7)
H1C	0.934 (5)	0.254 (5)	0.452 (3)	0.040 (9)*
N2	1.1869 (5)	0.0453 (5)	0.2384 (2)	0.0456 (7)
H2C	1.303 (6)	−0.023 (5)	0.214 (3)	0.036 (9)*
N3	1.5816 (7)	−0.2314 (7)	0.1250 (3)	0.0828 (12)
N4	1.8570 (5)	−0.6394 (5)	−0.3728 (3)	0.0616 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0783 (3)	0.0661 (2)	0.0430 (2)	−0.01739 (17)	0.00644 (14)	−0.01324 (14)
C1	0.0390 (18)	0.078 (3)	0.052 (2)	−0.0090 (17)	−0.0110 (16)	0.0055 (19)
C2	0.059 (2)	0.084 (3)	0.067 (3)	−0.024 (2)	−0.028 (2)	0.005 (2)
C3	0.067 (2)	0.068 (2)	0.0389 (19)	−0.0198 (19)	−0.0212 (17)	−0.0030 (17)
C4	0.0378 (16)	0.0433 (17)	0.0334 (15)	−0.0137 (13)	−0.0051 (12)	0.0008 (13)
C5	0.0361 (15)	0.0434 (16)	0.0314 (15)	−0.0144 (13)	−0.0035 (12)	−0.0011 (12)
C6	0.0396 (16)	0.0402 (16)	0.0383 (17)	−0.0071 (13)	−0.0021 (13)	−0.0050 (13)
C7	0.0440 (17)	0.0429 (17)	0.0391 (17)	−0.0119 (14)	−0.0053 (13)	−0.0119 (13)
C8	0.064 (2)	0.074 (3)	0.047 (2)	−0.015 (2)	0.0055 (18)	−0.010 (2)
C9	0.055 (2)	0.056 (2)	0.047 (2)	−0.0178 (16)	0.0016 (16)	−0.0061 (17)
N1	0.0383 (14)	0.0607 (18)	0.0327 (15)	−0.0112 (12)	−0.0053 (11)	−0.0030 (13)
N2	0.0430 (15)	0.0557 (17)	0.0335 (14)	−0.0126 (13)	−0.0065 (12)	−0.0061 (12)
N3	0.085 (3)	0.097 (3)	0.052 (2)	−0.020 (2)	0.0103 (19)	−0.023 (2)
N4	0.0624 (19)	0.071 (2)	0.048 (2)	−0.0220 (17)	0.0042 (15)	−0.0109 (16)

Geometric parameters (Å, º) top

Ag1—C9	2.050 (4)	C4—N1	1.312 (4)
Ag1—C8	2.052 (4)	C4—C5	1.481 (4)
C1—N1	1.466 (4)	C5—C6	1.385 (4)
C1—C2	1.493 (7)	C5—C7	1.393 (4)
C1—H1A	0.9700	C6—C7ⁱ	1.376 (4)
C1—H1B	0.9700	C6—H6A	0.9300
C2—C3	1.503 (6)	C7—C6ⁱ	1.376 (4)
C2—H2A	0.9700	C7—H7A	0.9300
C2—H2B	0.9700	C8—N3	1.115 (6)
C3—N2	1.471 (4)	C9—N4	1.133 (5)
C3—H3A	0.9700	N1—H1C	0.78 (4)
C3—H3B	0.9700	N2—H2C	0.79 (4)
C4—N2	1.307 (4)

C9—Ag1—C8	173.24 (15)	N2—C4—C5	119.5 (3)
N1—C1—C2	108.6 (3)	N1—C4—C5	119.0 (3)
N1—C1—H1A	110.0	C6—C5—C7	119.6 (3)
C2—C1—H1A	110.0	C6—C5—C4	120.1 (3)
N1—C1—H1B	110.0	C7—C5—C4	120.3 (3)
C2—C1—H1B	110.0	C7ⁱ—C6—C5	120.3 (3)
H1A—C1—H1B	108.3	C7ⁱ—C6—H6A	119.8
C1—C2—C3	111.0 (4)	C5—C6—H6A	119.8
C1—C2—H2A	109.4	C6ⁱ—C7—C5	120.1 (3)
C3—C2—H2A	109.4	C6ⁱ—C7—H7A	120.0
C1—C2—H2B	109.4	C5—C7—H7A	120.0
C3—C2—H2B	109.4	N3—C8—Ag1	172.6 (4)
H2A—C2—H2B	108.0	N4—C9—Ag1	177.0 (4)
N2—C3—C2	109.8 (3)	C4—N1—C1	121.6 (3)
N2—C3—H3A	109.7	C4—N1—H1C	121 (3)
C2—C3—H3A	109.7	C1—N1—H1C	117 (3)
N2—C3—H3B	109.7	C4—N2—C3	123.5 (3)
C2—C3—H3B	109.7	C4—N2—H2C	122 (2)
H3A—C3—H3B	108.2	C3—N2—H2C	114 (2)
N2—C4—N1	121.5 (3)

Symmetry code: (i) −x+3, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···N4ⁱⁱ	0.78 (4)	2.13 (4)	2.903 (4)	175 (4)
N2—H2C···N3	0.79 (4)	2.13 (4)	2.905 (5)	168 (3)

Symmetry code: (ii) x−1, y+1, z+1.

Experimental details

Crystal data
Chemical formula	(C₁₄H₂₀N₄)[Ag(CN)₂]₂
M_r	564.16
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	6.6930 (9), 7.276 (1), 11.4982 (15)
α, β, γ (°)	89.963 (2), 87.318 (2), 68.066 (2)
V (Å³)	518.76 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.91
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.702, 0.763
No. of measured, independent and observed [I > 2σ(I)] reflections	4040, 2015, 1769
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.093, 1.09
No. of reflections	2015
No. of parameters	135
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.33

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···N4ⁱ	0.78 (4)	2.13 (4)	2.903 (4)	175 (4)
N2—H2C···N3	0.79 (4)	2.13 (4)	2.905 (5)	168 (3)

Symmetry code: (i) x−1, y+1, z+1.

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

Braga, D., Maini, L., Grepioni, F., De Cian, A., Felix, O., Fischer, J. & Hosseini, M. W. (2000). New J. Chem. 24, 547–553. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burchell, T. J., Eisler, D. J. & Puddephatt, R. J. (2004). Chem. Commun. pp. 944–945. Web of Science CSD CrossRef Google Scholar
Felix, O., Hosseini, M. W., De Cian, A. & Fischer, J. (1998). New J. Chem. 22, 1389–1393. Web of Science CrossRef CAS Google Scholar
Holliday, B. J. & Mirkin, C. A. (2001). Angew. Chem. Int. Ed. 40, 2022–2043. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m858

doi:10.1107/S1600536808015791

Open

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

2,2′-(p-Phenyl­ene)bis­­(1,4,5,6-tetra­hydro­pyrimidinium) bis­­[dicyanidoargentate(I)]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

2,2′-(p-Phenylene)bis(1,4,5,6-tetrahydropyrimidinium) bis[dicyanidoargentate(I)]