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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): m858.
Published online 2008 June 7. doi:  10.1107/S1600536808015791
PMCID: PMC2961762

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

Abstract

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 AgI 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 [triangle]); Felix et al. (1998 [triangle]). For related literature, see: Burchell et al. (2004 [triangle]); Holliday & Mirkin (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m858-scheme1.jpg

Experimental

Crystal data

  • (C14H20N4)[Ag(CN)2]2
  • M r = 564.16
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m858-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.093
  • S = 1.09
  • 2015 reflections
  • 135 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.07 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015791/bt2718sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms bonded to N atoms were located in a difference map and they were freely refined. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.97 Å and with Uiso(H) = 1.2Ueq(C).

Figures

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.

Crystal data

(C14H20N4)[Ag(CN)2]2Z = 1
Mr = 564.16F000 = 278
Triclinic, P1Dx = 1.806 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.6930 (9) ÅCell parameters from 783 reflections
b = 7.2760 (10) Åθ = 2.5–28.0º
c = 11.4982 (15) ŵ = 1.91 mm1
α = 89.963 (2)ºT = 273 (2) K
β = 87.318 (2)ºBlock, colourless
γ = 68.066 (2)º0.20 × 0.18 × 0.15 mm
V = 518.76 (12) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2015 independent reflections
Radiation source: fine-focus sealed tube1769 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 273(2) Kθmax = 26.0º
[var phi] and ω scansθmin = 3.0º
Absorption correction: multi-scan(SADABS; Bruker, 1998)h = −8→7
Tmin = 0.702, Tmax = 0.763k = −8→8
4040 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093  w = 1/[σ2(Fo2) + (0.0523P)2 + 0.1388P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2015 reflectionsΔρmax = 1.07 e Å3
135 parametersΔρmin = −0.33 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Ag11.75049 (5)−0.46673 (5)−0.11338 (2)0.06556 (17)
C10.7736 (6)0.2925 (7)0.3110 (3)0.0600 (10)
H1A0.76720.41290.27220.072*
H1B0.64010.32080.35720.072*
C20.8010 (7)0.1333 (8)0.2228 (4)0.0702 (12)
H2A0.68620.17990.16880.084*
H2B0.79080.01850.26170.084*
C31.0154 (6)0.0746 (6)0.1567 (3)0.0589 (10)
H3A1.0439−0.04700.11270.071*
H3B1.01250.17730.10230.071*
C41.1503 (5)0.1093 (5)0.3465 (3)0.0385 (7)
C51.3309 (5)0.0529 (5)0.4257 (3)0.0370 (6)
C61.3411 (5)0.1879 (5)0.5078 (3)0.0416 (7)
H6A1.23460.31450.51280.050*
C71.4921 (5)−0.1357 (5)0.4178 (3)0.0432 (7)
H7A1.4869−0.22650.36230.052*
C81.6530 (7)−0.3227 (7)0.0448 (4)0.0652 (11)
C91.8252 (6)−0.5801 (6)−0.2799 (3)0.0536 (9)
N10.9572 (4)0.2250 (5)0.3863 (3)0.0459 (7)
H1C0.934 (5)0.254 (5)0.452 (3)0.040 (9)*
N21.1869 (5)0.0453 (5)0.2384 (2)0.0456 (7)
H2C1.303 (6)−0.023 (5)0.214 (3)0.036 (9)*
N31.5816 (7)−0.2314 (7)0.1250 (3)0.0828 (12)
N41.8570 (5)−0.6394 (5)−0.3728 (3)0.0616 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ag10.0783 (3)0.0661 (2)0.0430 (2)−0.01739 (17)0.00644 (14)−0.01324 (14)
C10.0390 (18)0.078 (3)0.052 (2)−0.0090 (17)−0.0110 (16)0.0055 (19)
C20.059 (2)0.084 (3)0.067 (3)−0.024 (2)−0.028 (2)0.005 (2)
C30.067 (2)0.068 (2)0.0389 (19)−0.0198 (19)−0.0212 (17)−0.0030 (17)
C40.0378 (16)0.0433 (17)0.0334 (15)−0.0137 (13)−0.0051 (12)0.0008 (13)
C50.0361 (15)0.0434 (16)0.0314 (15)−0.0144 (13)−0.0035 (12)−0.0011 (12)
C60.0396 (16)0.0402 (16)0.0383 (17)−0.0071 (13)−0.0021 (13)−0.0050 (13)
C70.0440 (17)0.0429 (17)0.0391 (17)−0.0119 (14)−0.0053 (13)−0.0119 (13)
C80.064 (2)0.074 (3)0.047 (2)−0.015 (2)0.0055 (18)−0.010 (2)
C90.055 (2)0.056 (2)0.047 (2)−0.0178 (16)0.0016 (16)−0.0061 (17)
N10.0383 (14)0.0607 (18)0.0327 (15)−0.0112 (12)−0.0053 (11)−0.0030 (13)
N20.0430 (15)0.0557 (17)0.0335 (14)−0.0126 (13)−0.0065 (12)−0.0061 (12)
N30.085 (3)0.097 (3)0.052 (2)−0.020 (2)0.0103 (19)−0.023 (2)
N40.0624 (19)0.071 (2)0.048 (2)−0.0220 (17)0.0042 (15)−0.0109 (16)

Geometric parameters (Å, °)

Ag1—C92.050 (4)C4—N11.312 (4)
Ag1—C82.052 (4)C4—C51.481 (4)
C1—N11.466 (4)C5—C61.385 (4)
C1—C21.493 (7)C5—C71.393 (4)
C1—H1A0.9700C6—C7i1.376 (4)
C1—H1B0.9700C6—H6A0.9300
C2—C31.503 (6)C7—C6i1.376 (4)
C2—H2A0.9700C7—H7A0.9300
C2—H2B0.9700C8—N31.115 (6)
C3—N21.471 (4)C9—N41.133 (5)
C3—H3A0.9700N1—H1C0.78 (4)
C3—H3B0.9700N2—H2C0.79 (4)
C4—N21.307 (4)
C9—Ag1—C8173.24 (15)N2—C4—C5119.5 (3)
N1—C1—C2108.6 (3)N1—C4—C5119.0 (3)
N1—C1—H1A110.0C6—C5—C7119.6 (3)
C2—C1—H1A110.0C6—C5—C4120.1 (3)
N1—C1—H1B110.0C7—C5—C4120.3 (3)
C2—C1—H1B110.0C7i—C6—C5120.3 (3)
H1A—C1—H1B108.3C7i—C6—H6A119.8
C1—C2—C3111.0 (4)C5—C6—H6A119.8
C1—C2—H2A109.4C6i—C7—C5120.1 (3)
C3—C2—H2A109.4C6i—C7—H7A120.0
C1—C2—H2B109.4C5—C7—H7A120.0
C3—C2—H2B109.4N3—C8—Ag1172.6 (4)
H2A—C2—H2B108.0N4—C9—Ag1177.0 (4)
N2—C3—C2109.8 (3)C4—N1—C1121.6 (3)
N2—C3—H3A109.7C4—N1—H1C121 (3)
C2—C3—H3A109.7C1—N1—H1C117 (3)
N2—C3—H3B109.7C4—N2—C3123.5 (3)
C2—C3—H3B109.7C4—N2—H2C122 (2)
H3A—C3—H3B108.2C3—N2—H2C114 (2)
N2—C4—N1121.5 (3)

Symmetry codes: (i) −x+3, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···N4ii0.78 (4)2.13 (4)2.903 (4)175 (4)
N2—H2C···N30.79 (4)2.13 (4)2.905 (5)168 (3)

Symmetry codes: (ii) x−1, y+1, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2718).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography