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

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μ3-Chlorido-tris­­(bis­­{1-[2-(di­methyl­amino)­eth­yl]-3-methyl­imidazol-2-yl­­idene}silver(I)) dichloride

aJohannes Kepler Universität Linz, Institut für Anorganische Chemie, Altenbergerstrasse 69, A-4040 Linz, Austria
*Correspondence e-mail: uwe.monkowius@jku.at

(Received 31 January 2012; accepted 2 February 2012; online 10 February 2012)

In the crystal structure of the title compound, [Ag3Cl(C8H15N3)6]Cl2, the AgI ion, which is located on a twofold rotation axis, exists in a T-shape coordination environment. Two carbene C atoms of the N-heterocyclic carbene (NHC) ligands are bonded tightly forming a slightly bent [Ag(NHC)2]+ cation [C—Ag—C angle = 162.80 (18)°]. Three of these complex cations are further aggregated by one bridging chloride anion, which is lying on a threefold rotoinversion axis and is only loosely binding to the Ag+ ions. The N atom of the amine group is not engaged in any coordinative bond.

Related literature

For related literature concerning similar N-heterocyclic carbenes, see: Topf, Hirtenlehner, Fleck et al. (2011[Topf, C., Hirtenlehner, C., Fleck, M., List, M. & Monkowius, U. (2011). Z. Anorg. Allg. Chem. 637, 2129-2134.]); Topf, Hirtenlehner & Monkowius (2011[Topf, C., Hirtenlehner, C. & Monkowius, U. (2011). J. Organomet. Chem. 696, 3274-3278.]); Leitner et al. (2011[Leitner, S., List, M. & Monkowius, U. (2011). Z. Naturforsch. Teil B, 66, 1255-1260.]). For related structures, see: Hirtenlehner et al. (2011[Hirtenlehner, C., Krims, C., Hölbling, J., List, M., Zabel, M., Fleck, M., Berger, R. J. F., Schoefberger, W. & Monkowius, U. (2011). Dalton Trans. 40, 9899-9910.]); Wang et al. (2006[Wang, X., Liu, S., Wenig, L.-H. & Jin, G.-X. (2006). Organometallics, 25, 3565-3569.]). For details of the preparation, see: Topf, Hirtenlehner, Zabel et al. (2011[Topf, C., Hirtenlehner, C., Zabel, M., List, M., Fleck, M. & Monkowius, U. (2011). Organometallics, pp. 2755-2764.]).

[Scheme 1]

Experimental

Crystal data
  • [Ag3Cl(C8H15N3)6]Cl2

  • Mr = 1349.34

  • Trigonal, [R \overline 3c ]

  • a = 12.7300 (16) Å

  • c = 66.789 (12) Å

  • V = 9373 (2) Å3

  • Z = 6

  • Mo Kα radiation

  • μ = 1.11 mm−1

  • T = 200 K

  • 0.50 × 0.36 × 0.31 mm

Data collection
  • Bruker SMART X2S diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, GIS, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.61, Tmax = 0.73

  • 18593 measured reflections

  • 1859 independent reflections

  • 1590 reflections with I > 2σ(I)

  • Rint = 0.060

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.095

  • S = 1.03

  • 1859 reflections

  • 113 parameters

  • H-atom parameters constrained

  • Δρmax = 1.28 e Å−3

  • Δρmin = −0.46 e Å−3

Data collection: APEX2 and GIS (Bruker, 2009[Bruker (2009). APEX2, GIS, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, GIS, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

In the course of our studies on gold- and silver-complexes bearing functionalized N-heterocyclic carbenes (NHCs), we became interested in examples with amino groups containing side arms at a nitrogen atom of the NHC ligands (Topf, Hirtenlehner, Fleck et al. (2011); Topf, Hirtenlehner & Monkowius (2011); Leitner et al., 2011; Hirtenlehner et al., 2011). Just recently, we published the multifarious coordination patterns of such silver complexes (Topf, Hirtenlehner, Zabel et al., 2011): E.g., in the ionic compound [(C8H15N3)2Ag][AgCl2], which is formed from the respective imidazolium chloride and Ag2O in dichloromethane, the ions are aggregated to infinite chains with short silver-silver contacts. Treatment of this complex with HBF4 yields the cluster (C8H15N3)4Ag10Cl10 with the carbene carbon atom binding in a unusual µ2-fashion to two silver atoms. In an attempt to prepare this cluster, crystals of the title compound were formed representing the third silver chloride complex in the series of this ligand. The formation of this complex is easily rationalized by the precipitation of AgCl from [(C8H15N3)2Ag][AgCl2] in solution.

The silver atom is in a slightly bent linear coordination with an Ag1—C1 bond length of 2.099 (3) Å and an angle C1—Ag1—C1i of 162.8 (2)°. Perpendicular to the C1—Ag1—C1i vector, a chloride anion is loosely binding with an Ag1—Cl1 bond length of 2.981 (1) Å. The chloride Cl1 is linking three [(C8H15N3)2Ag]+ units in a µ3-fashion forming a D3 symmteric trimeric aggregate. The net 2+ charge is balanced by two non-interacting chloride ions. Within other cationic species of the type [(NHC)2Ag]+, the imidazole ring planes are usually found in a coplanar arrangement due to a higher π-backbonding contribution compared to a perpendicular orientation. Presumably because of steric reasons, the [(C8H15N3)2Ag]+ moiety features an arrangement with both imidazole ring planes approaching a perpendicular orientation [N1—C1—C1i—N1i 89.8°]. The distance between two silver atoms within the trimer is 5.164 Å, which is well beyond the range of argentophilic interactions. It should be noted, that this aggregation pattern is very rare and to the best of our knowledge reported only for {[(NHC)2Ag]33-I)}I2 (NHC = 1-methyl-3-picolyl-imidazol-2-ylidene) (Wang et al., 2006) and {[(NHC)2Au]33-Br)}Br2 (NHC= 1-methyl-3-benzyl-imidazol-2-ylidene) (Hirtenlehner et al., 2011).

Related literature top

For related literature, see: Topf, Hirtenlehner, Fleck et al. (2011); Topf, Hirtenlehner & Monkowius (2011); Leitner et al. (2011). For related structures, see: Hirtenlehner et al. (2011); Wang et al. (2006). For details of the preparation, see: Topf, Hirtenlehner, Zabel et al. (2011).

Experimental top

Crystals of the title compound were formed in an attempt to synthesize the silver cluster (C8H15N3)4Ag10Cl10 according to a literature procedure (Topf, Hirtenlehner, Zabel et al., 2011).

Refinement top

The hydrogen atoms were placed in calculated positions with C—H = 0.95–0.99 Å and refined using a riding model with Uiso(H) = 1.5 Ueq(C) for methyl groups and Uiso(H) = 1.2 Ueq(C) for methylen and aromatic hydrogen atoms. The highest residual electron density peak is located 1.28 Å from H9A and the deepest hole is located 0.53 Å from C9.

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of the title compound with the atom numbering scheme (symmetry code: (i) x-y + 1/3, -y + 2/3, -z + 1/6). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. [Ag3Cl]2+ cation in the crystals of the title compound. The H atoms and the methyl and 2-dimethyl-amino-ethyl groups are omitted for the sake of clarity (symmetry codes: (ii) -y + 1, x-y, z; (iv) y + 1/3, x - 1/3, -z + 1/6).
µ3-Chlorido-tris(bis{1-[2-(dimethylamino)ethyl]-3-methylimidazol-2- ylidene}silver(I)) dichloride top
Crystal data top
[Ag3Cl(C8H15N3)2]Cl2F(000) = 4176
Mr = 1349.34Dx = 1.434 Mg m3
Trigonal, R3cMo Kα radiation, λ = 0.71073 Å
a = 12.7300 (16) ŵ = 1.11 mm1
c = 66.789 (12) ÅT = 200 K
V = 9373 (2) Å3Prism, colourless
Z = 60.50 × 0.36 × 0.31 mm
Data collection top
Bruker SMART X2S
diffractometer
1859 independent reflections
Radiation source: sealed MicroFocus tube1590 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromatorRint = 0.060
ω scansθmax = 25.1°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1514
Tmin = 0.61, Tmax = 0.73k = 1515
18593 measured reflectionsl = 7979
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0504P)2 + 47.4314P]
where P = (Fo2 + 2Fc2)/3
1859 reflections(Δ/σ)max = 0.001
113 parametersΔρmax = 1.28 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
[Ag3Cl(C8H15N3)2]Cl2Z = 6
Mr = 1349.34Mo Kα radiation
Trigonal, R3cµ = 1.11 mm1
a = 12.7300 (16) ÅT = 200 K
c = 66.789 (12) Å0.50 × 0.36 × 0.31 mm
V = 9373 (2) Å3
Data collection top
Bruker SMART X2S
diffractometer
1859 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
1590 reflections with I > 2σ(I)
Tmin = 0.61, Tmax = 0.73Rint = 0.060
18593 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0504P)2 + 47.4314P]
where P = (Fo2 + 2Fc2)/3
1859 reflectionsΔρmax = 1.28 e Å3
113 parametersΔρmin = 0.46 e Å3
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
xyzUiso*/Ueq
Ag10.90085 (3)0.33330.08330.03038 (16)
C61.1504 (3)0.5164 (4)0.05466 (6)0.0422 (9)
H6A1.13740.57640.06170.063*
H6B1.21840.5580.04530.063*
H6C1.16890.47030.06440.063*
C10.9354 (3)0.3530 (3)0.05243 (5)0.0257 (7)
N20.8610 (3)0.2965 (3)0.03679 (4)0.0284 (6)
C50.7252 (4)0.0798 (4)0.03044 (7)0.0543 (11)
H5A0.63940.01460.03150.065*
H5B0.74710.09090.01610.065*
N11.0411 (2)0.4340 (2)0.04359 (4)0.0271 (6)
C40.7366 (3)0.1961 (4)0.03843 (6)0.0388 (9)
H4A0.6820.21580.03080.047*
H4B0.71120.18480.05260.047*
C30.9192 (3)0.3417 (3)0.01870 (6)0.0358 (9)
H30.88530.31630.00570.043*
C21.0327 (3)0.4284 (3)0.02306 (5)0.0341 (8)
H21.0950.47660.01380.041*
N30.8016 (3)0.0410 (3)0.04089 (6)0.0475 (9)
C80.7953 (7)0.0580 (6)0.02927 (11)0.101 (2)
H8A0.8420.08980.0360.151*
H8B0.8290.02860.01590.151*
H8C0.71040.12260.0280.151*
C90.7645 (7)0.0065 (6)0.06074 (11)0.114 (3)
H9A0.7720.07610.06820.172*
H9B0.81570.02170.0670.172*
H9C0.67970.05910.06090.172*
Cl10.66670.33330.08330.0307 (4)
Cl20.33330.66670.00857 (2)0.0344 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0353 (2)0.0290 (2)0.0247 (2)0.01451 (11)0.00056 (7)0.00112 (14)
C60.032 (2)0.035 (2)0.048 (2)0.0078 (17)0.0022 (17)0.0035 (17)
C10.0288 (17)0.0288 (17)0.0267 (18)0.0197 (15)0.0005 (14)0.0007 (13)
N20.0256 (14)0.0345 (16)0.0289 (16)0.0180 (13)0.0007 (12)0.0018 (12)
C50.040 (2)0.053 (3)0.057 (3)0.013 (2)0.003 (2)0.005 (2)
N10.0246 (14)0.0259 (14)0.0314 (15)0.0131 (12)0.0013 (11)0.0016 (12)
C40.0238 (18)0.046 (2)0.044 (2)0.0161 (17)0.0016 (15)0.0062 (18)
C30.040 (2)0.048 (2)0.0245 (19)0.0255 (18)0.0000 (15)0.0000 (15)
C20.039 (2)0.039 (2)0.0290 (19)0.0233 (17)0.0095 (15)0.0072 (15)
N30.0411 (19)0.0327 (18)0.061 (2)0.0126 (15)0.0096 (17)0.0030 (16)
C80.108 (5)0.066 (4)0.121 (6)0.039 (4)0.011 (4)0.010 (4)
C90.132 (7)0.081 (5)0.069 (4)0.007 (4)0.034 (4)0.012 (3)
Cl10.0299 (6)0.0299 (6)0.0323 (10)0.0150 (3)00
Cl20.0356 (5)0.0356 (5)0.0319 (7)0.0178 (3)00
Geometric parameters (Å, º) top
Ag1—C1i2.099 (3)N1—C21.374 (5)
Ag1—C12.099 (3)C4—H4A0.99
C6—N11.458 (5)C4—H4B0.99
C6—H6A0.98C3—C21.340 (5)
C6—H6B0.98C3—H30.95
C6—H6C0.98C2—H20.95
C1—N21.350 (5)N3—C91.402 (8)
C1—N11.355 (4)N3—C81.447 (7)
N2—C31.383 (5)C8—H8A0.98
N2—C41.459 (5)C8—H8B0.98
C5—N31.469 (6)C8—H8C0.98
C5—C41.511 (6)C9—H9A0.98
C5—H5A0.99C9—H9B0.98
C5—H5B0.99C9—H9C0.98
C1i—Ag1—C1162.80 (18)N2—C4—H4B109.4
N1—C6—H6A109.5C5—C4—H4B109.4
N1—C6—H6B109.5H4A—C4—H4B108.0
H6A—C6—H6B109.5C2—C3—N2106.6 (3)
N1—C6—H6C109.5C2—C3—H3126.7
H6A—C6—H6C109.5N2—C3—H3126.7
H6B—C6—H6C109.5C3—C2—N1106.5 (3)
N2—C1—N1103.5 (3)C3—C2—H2126.8
N2—C1—Ag1130.4 (3)N1—C2—H2126.8
N1—C1—Ag1126.0 (2)C9—N3—C8111.8 (5)
C1—N2—C3111.5 (3)C9—N3—C5112.2 (5)
C1—N2—C4125.0 (3)C8—N3—C5106.3 (4)
C3—N2—C4123.4 (3)N3—C8—H8A109.5
N3—C5—C4114.0 (3)N3—C8—H8B109.5
N3—C5—H5A108.8H8A—C8—H8B109.5
C4—C5—H5A108.8N3—C8—H8C109.5
N3—C5—H5B108.8H8A—C8—H8C109.5
C4—C5—H5B108.8H8B—C8—H8C109.5
H5A—C5—H5B107.7N3—C9—H9A109.5
C1—N1—C2111.9 (3)N3—C9—H9B109.5
C1—N1—C6123.7 (3)H9A—C9—H9B109.5
C2—N1—C6124.4 (3)N3—C9—H9C109.5
N2—C4—C5111.3 (3)H9A—C9—H9C109.5
N2—C4—H4A109.4H9B—C9—H9C109.5
C5—C4—H4A109.4
Symmetry code: (i) xy+1/3, y+2/3, z+1/6.

Experimental details

Crystal data
Chemical formula[Ag3Cl(C8H15N3)2]Cl2
Mr1349.34
Crystal system, space groupTrigonal, R3c
Temperature (K)200
a, c (Å)12.7300 (16), 66.789 (12)
V3)9373 (2)
Z6
Radiation typeMo Kα
µ (mm1)1.11
Crystal size (mm)0.50 × 0.36 × 0.31
Data collection
DiffractometerBruker SMART X2S
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.61, 0.73
No. of measured, independent and
observed [I > 2σ(I)] reflections
18593, 1859, 1590
Rint0.060
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.095, 1.03
No. of reflections1859
No. of parameters113
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0504P)2 + 47.4314P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.28, 0.46

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).

 

Acknowledgements

We thank Professor Günther Knör for fruitful discussion and generous support of the experimental work.

References

First citationBruker (2009). APEX2, GIS, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHirtenlehner, C., Krims, C., Hölbling, J., List, M., Zabel, M., Fleck, M., Berger, R. J. F., Schoefberger, W. & Monkowius, U. (2011). Dalton Trans. 40, 9899–9910.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationLeitner, S., List, M. & Monkowius, U. (2011). Z. Naturforsch. Teil B, 66, 1255–1260.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTopf, C., Hirtenlehner, C., Fleck, M., List, M. & Monkowius, U. (2011). Z. Anorg. Allg. Chem. 637, 2129–2134.  Web of Science CSD CrossRef CAS Google Scholar
First citationTopf, C., Hirtenlehner, C. & Monkowius, U. (2011). J. Organomet. Chem. 696, 3274–3278.  Web of Science CSD CrossRef CAS Google Scholar
First citationTopf, C., Hirtenlehner, C., Zabel, M., List, M., Fleck, M. & Monkowius, U. (2011). Organometallics, pp. 2755–2764.  Web of Science CSD CrossRef CAS Google Scholar
First citationWang, X., Liu, S., Wenig, L.-H. & Jin, G.-X. (2006). Organometallics, 25, 3565–3569.  Web of Science CSD CrossRef CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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