Bis[2-(1H-imidazol-2-yl-κN3)-1H-imidazol-3-ium]silver(I) trinitrate

Finch, S.R.; Harper, J.P.; Choudhury, A.; Sinn, E.; Collier, H.L.

doi:10.1107/S1600536811021799

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m909

doi:10.1107/S1600536811021799

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Bis[2-(1H-imidazol-2-yl-κN³)-1H-imidazol-3-ium]silver(I) trinitrate

Shelonda R. Finch,^a Johnathan P. Harper,^a Amitava Choudhury,^a Ekkehard Sinn ^b and Harvest L. Collier ^a ^*

^aChemistry Department, Missouri University of Science and Technology, Rolla MO 65409, USA, and ^bWestern Michigan University, Chemistry Department, 1903 West Michigan Avenue MS 5413, Kalamazoo MI 49008, USA
^*Correspondence e-mail: hcollier@mst.edu

(Received 31 March 2011; accepted 6 June 2011; online 11 June 2011)

The synthesis of the title salt, [Ag(C₆H₇N₄)₂](NO₃)₃, was carried out employing a 1:2 molar ratio of 2,2′-biimidazole and silver nitrate respectively. The cation has crystallographically-imposed C2 symmetry with the metal atom in an almost linear coordination environment [N—Ag—N = 177.01 (17)°]. The crystal structure displays N—H⋯O and C—H⋯O hydrogen-bonding interactions.

Related literature

The synthesis of the complex is described by Hester et al. (1997 ). 2,2′-Biimidazole was prepared in a manner similar to Debus (1858 ).

Experimental

Crystal data

[Ag(C₆H₇N₄)₂](NO₃)₃
M_r = 564.21
Monoclinic, C 2/c
a = 24.095 (6) Å
b = 12.037 (3) Å
c = 6.8262 (18) Å
β = 91.319 (6)°
V = 1979.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.735, T_max = 0.811
9412 measured reflections
2275 independent reflections
1723 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.104
S = 0.99
2275 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O4ⁱ	0.86	1.94	2.792 (4)	173
N3—H3⋯O1ⁱⁱ	0.86	1.92	2.765 (4)	166
N4—H4⋯O4	0.86	1.93	2.758 (4)	160
C1—H1⋯O3ⁱⁱ	0.93	2.49	3.179 (5)	131
C2—H2⋯O5ⁱⁱⁱ	0.93	2.60	3.331 (5)	136
C5—H5⋯O3^iv	0.93	2.55	3.340 (6)	144
C6—H6⋯O2^v	0.93	2.55	3.376 (6)	148
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y, z-{\script{1\over 2}}]$ ; (v) x, y-1, z.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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/S1600536811021799/mw2006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021799/mw2006Isup2.hkl

checkCIF report

Comment top

The compound, silver bis (1H-imidazolium) trinitrate [Ag(biimH)₂(NO₃)₃] crystallizes in the monoclinic crystal system in space group C2/c. The Ag atom is coordinated to N atoms on two different 2,2'-biimidazole entities in an almost linear geometry where the biimidazole acts as a monodentate ligand. The Ag—N distance is 2.118 (3) Å and the N—Ag—N bond angle is 177.01 (17)°. There are one and one half crystallographically independent nitrate anions in the asymmetric unit (Figure 1). The nearest contacts of Ag with O atoms from one of the nitrate groups are in the range 3.026 (3)–3.070 (3) Å. The other nitrate is hydrogen-bonded to the other side of the uncoordinated ring of 2,2'-bimidazole (Figure 2). The two imidazole rings in 2,2'-biimidazole are no longer in one plane when coordinated to Ag as in [Ag(biimH)₂(NO₃)₃] but are twisted with a N1—C3—C4—N4 torsion angle of 33.5 (6)°. A very similar torsion angle [34.30 (7)°] has been observed in another silver complex of 2,2'-biimidazole (Hester et al. (1997)) where such a torsion angle between the imidazole rings is responsible for the helicity of the complex. However, in contrast to the present structure, in the Ag-biimidazole complex reported by Hester the biimidazole binds to Ag atoms in a bis-monodentate fashion bridging two Ag atoms with a very close Ag—Ag contact distance of 3.003 (3)Å and an N—Ag—N bond angle of 162.36 (2)°. This contrasts with the nearest Ag—Ag contact distance in the present complex which is considerably greater at 3.5473 (9) Å.

Related literature top

The synthesis of the complex is described by Hester et al. (1997). 2,2'-Biimidazole was prepared in a manner similar to Debus (1858).

Experimental top

2,2'-Biimidazole was prepared in a manner similar to Debus (1858), using equal portions of 40% glyoxal and concentrated ammonium hydroxide (28–30%). Silver nitrate was used as received and concentrated nitric acid was diluted to 0.1 M. The synthesis of silver bis(1H-imidazolium) trinitrate used a procedure similar to that reported by Hester et al. (1997), using 0.1 M HNO₃. A mass of 1.343 g (1.001 x 10 ^-2 mol) of 2,2'-biimidazole was dissolved in 15 ml of 0.1M HNO₃ using heat. Silver nitrate (3.410 g, 2.007 x 10 ^-2 mol) was then added to the solution as a solid. A precipitate formed upon mixing and a few drops of 0.1 M HNO₃ were added to resolubilize the precipitate. Colourless crystals formed as the solution was allowed to slowly evaporate.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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. Asymmetric unit of silver bis(1H-imidazolium) trinitrate. Thermal ellipsoids are drawn at the 40% probability level.
	Fig. 2. Unit cell packing of silver bis(1H-imidazolium) trinitrate shown along the c-axis. Dotted lines indicate N—H···O and C—H···O hydrogen-bonding interactions.

Bis[2-(1H-imidazol-2-yl-κN³)-1H-imidazol-3-ium]silver(I) trinitrate top

Crystal data top

[Ag(C₆H₇N₄)₂](NO₃)₃	F(000) = 1128
M_r = 564.21	D_x = 1.893 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2422 reflections
a = 24.095 (6) Å	θ = 3.1–24.0°
b = 12.037 (3) Å	µ = 1.09 mm⁻¹
c = 6.8262 (18) Å	T = 298 K
β = 91.319 (6)°	Needle, colourless
V = 1979.3 (9) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2275 independent reflections
Radiation source: fine-focus sealed tube	1723 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −31→31
T_min = 0.735, T_max = 0.811	k = −15→15
9412 measured reflections	l = −8→8

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0505P)²] where P = (F_o² + 2F_c²)/3
2275 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Ag(C₆H₇N₄)₂](NO₃)₃	V = 1979.3 (9) Å³
M_r = 564.21	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.095 (6) Å	µ = 1.09 mm⁻¹
b = 12.037 (3) Å	T = 298 K
c = 6.8262 (18) Å	0.30 × 0.20 × 0.20 mm
β = 91.319 (6)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2275 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1723 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.811	R_int = 0.065
9412 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.99	Δρ_max = 0.46 e Å⁻³
2275 reflections	Δρ_min = −0.34 e Å⁻³
151 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	0.5000	0.45986 (4)	0.2500	0.04700 (17)
N1	0.58789 (12)	0.4553 (3)	0.2547 (4)	0.0405 (7)
C1	0.61871 (16)	0.5520 (3)	0.2559 (6)	0.0459 (9)
H1	0.6044	0.6235	0.2442	0.055*
C2	0.67332 (17)	0.5259 (3)	0.2768 (6)	0.0510 (10)
H2	0.7029	0.5755	0.2832	0.061*
N2	0.67642 (13)	0.4139 (3)	0.2867 (5)	0.0468 (8)
H2N	0.7063	0.3753	0.2994	0.056*
C3	0.62405 (14)	0.3734 (3)	0.2730 (5)	0.0379 (8)
C4	0.61183 (14)	0.2557 (3)	0.2817 (5)	0.0378 (8)
N3	0.57064 (13)	0.2026 (3)	0.1904 (5)	0.0440 (8)
H3	0.5456	0.2331	0.1165	0.053*
C6	0.57421 (18)	0.0915 (3)	0.2320 (6)	0.0527 (10)
H6	0.5506	0.0358	0.1856	0.063*
C5	0.6184 (2)	0.0791 (4)	0.3527 (7)	0.0590 (12)
H5	0.6310	0.0126	0.4068	0.071*
N4	0.64157 (14)	0.1813 (3)	0.3822 (5)	0.0487 (8)
H4	0.6706	0.1952	0.4538	0.058*
O1	0.50331 (14)	0.6989 (3)	0.4067 (5)	0.0721 (10)
N5	0.5000	0.7527 (5)	0.2500	0.0511 (12)
O2	0.5000	0.8540 (4)	0.2500	0.0879 (16)
O3	0.64511 (13)	0.1930 (3)	0.8363 (5)	0.0738 (10)
N6	0.69447 (15)	0.1706 (3)	0.8314 (6)	0.0541 (9)
O4	0.72151 (11)	0.1948 (3)	0.6770 (4)	0.0579 (8)
O5	0.71807 (15)	0.1225 (4)	0.9651 (5)	0.0968 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0336 (2)	0.0475 (3)	0.0597 (3)	0.000	−0.00185 (17)	0.000
N1	0.0385 (16)	0.0417 (17)	0.0412 (17)	−0.0022 (14)	−0.0010 (13)	0.0016 (14)
C1	0.047 (2)	0.042 (2)	0.049 (2)	−0.0031 (17)	0.0005 (17)	−0.0007 (18)
C2	0.048 (2)	0.053 (3)	0.052 (2)	−0.0141 (19)	−0.0009 (18)	0.002 (2)
N2	0.0330 (16)	0.056 (2)	0.051 (2)	−0.0003 (14)	−0.0034 (14)	0.0038 (16)
C3	0.0326 (17)	0.045 (2)	0.0365 (19)	0.0007 (15)	−0.0030 (14)	−0.0024 (16)
C4	0.0351 (18)	0.042 (2)	0.036 (2)	0.0031 (15)	0.0022 (15)	0.0011 (16)
N3	0.0427 (18)	0.0475 (19)	0.0416 (18)	−0.0023 (14)	−0.0009 (14)	−0.0004 (14)
C6	0.061 (3)	0.042 (2)	0.056 (3)	−0.006 (2)	0.016 (2)	−0.007 (2)
C5	0.071 (3)	0.041 (2)	0.066 (3)	0.008 (2)	0.012 (2)	0.007 (2)
N4	0.0499 (19)	0.049 (2)	0.047 (2)	0.0066 (15)	−0.0035 (15)	0.0055 (16)
O1	0.090 (2)	0.073 (2)	0.0526 (19)	−0.0163 (19)	−0.0198 (17)	0.0118 (16)
N5	0.047 (3)	0.052 (3)	0.054 (3)	0.000	−0.005 (2)	0.000
O2	0.095 (4)	0.046 (3)	0.122 (5)	0.000	−0.009 (3)	0.000
O3	0.053 (2)	0.078 (2)	0.091 (3)	0.0165 (17)	0.0225 (17)	0.0085 (19)
N6	0.049 (2)	0.054 (2)	0.059 (2)	0.0017 (17)	0.0028 (18)	0.0014 (18)
O4	0.0448 (16)	0.076 (2)	0.0532 (18)	0.0034 (14)	0.0059 (13)	0.0107 (15)
O5	0.074 (2)	0.149 (4)	0.067 (2)	0.007 (3)	−0.0109 (19)	0.039 (2)

Geometric parameters (Å, º) top

Ag1—N1ⁱ	2.118 (3)	N3—C6	1.370 (5)
Ag1—N1	2.118 (3)	N3—H3	0.8600
N1—C3	1.319 (4)	C6—C5	1.340 (6)
N1—C1	1.381 (5)	C6—H6	0.9300
C1—C2	1.357 (6)	C5—N4	1.365 (5)
C1—H1	0.9300	C5—H5	0.9300
C2—N2	1.351 (5)	N4—H4	0.8600
C2—H2	0.9300	O1—N5	1.251 (4)
N2—C3	1.354 (5)	N5—O2	1.220 (7)
N2—H2N	0.8600	N5—O1ⁱ	1.251 (4)
C3—C4	1.449 (5)	O3—N6	1.221 (4)
C4—N3	1.324 (5)	N6—O5	1.211 (5)
C4—N4	1.328 (5)	N6—O4	1.285 (4)

N1ⁱ—Ag1—N1	177.01 (17)	C4—N3—C6	109.3 (3)
C3—N1—C1	106.0 (3)	C4—N3—H3	125.3
C3—N1—Ag1	132.8 (2)	C6—N3—H3	125.3
C1—N1—Ag1	121.0 (2)	C5—C6—N3	106.4 (4)
C2—C1—N1	109.0 (4)	C5—C6—H6	126.8
C2—C1—H1	125.5	N3—C6—H6	126.8
N1—C1—H1	125.5	C6—C5—N4	107.8 (4)
N2—C2—C1	106.8 (4)	C6—C5—H5	126.1
N2—C2—H2	126.6	N4—C5—H5	126.1
C1—C2—H2	126.6	C4—N4—C5	108.6 (3)
C2—N2—C3	107.8 (3)	C4—N4—H4	125.7
C2—N2—H2N	126.1	C5—N4—H4	125.7
C3—N2—H2N	126.1	O2—N5—O1ⁱ	121.2 (3)
N1—C3—N2	110.5 (3)	O2—N5—O1	121.2 (3)
N1—C3—C4	126.9 (3)	O1ⁱ—N5—O1	117.6 (5)
N2—C3—C4	122.6 (3)	O5—N6—O3	121.7 (4)
N3—C4—N4	107.9 (3)	O5—N6—O4	119.2 (4)
N3—C4—C3	127.1 (3)	O3—N6—O4	119.0 (4)
N4—C4—C3	125.0 (3)

C3—N1—C1—C2	−0.5 (4)	N2—C3—C4—N3	−147.8 (4)
Ag1—N1—C1—C2	174.5 (3)	N1—C3—C4—N4	−148.0 (4)
N1—C1—C2—N2	0.6 (5)	N2—C3—C4—N4	30.8 (6)
C1—C2—N2—C3	−0.4 (4)	N4—C4—N3—C6	−0.4 (4)
C1—N1—C3—N2	0.3 (4)	C3—C4—N3—C6	178.3 (4)
Ag1—N1—C3—N2	−173.9 (2)	C4—N3—C6—C5	0.6 (5)
C1—N1—C3—C4	179.2 (4)	N3—C6—C5—N4	−0.6 (5)
Ag1—N1—C3—C4	5.0 (6)	N3—C4—N4—C5	0.0 (4)
C2—N2—C3—N1	0.0 (4)	C3—C4—N4—C5	−178.7 (4)
C2—N2—C3—C4	−178.9 (3)	C6—C5—N4—C4	0.3 (5)
N1—C3—C4—N3	33.5 (6)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O4ⁱⁱ	0.86	1.94	2.792 (4)	173
N3—H3···O1ⁱⁱⁱ	0.86	1.92	2.765 (4)	166
N4—H4···O4	0.86	1.93	2.758 (4)	160
C1—H1···O3ⁱⁱⁱ	0.93	2.49	3.179 (5)	131
C2—H2···O5^iv	0.93	2.60	3.331 (5)	136
C5—H5···O3^v	0.93	2.55	3.340 (6)	144
C6—H6···O2^vi	0.93	2.55	3.376 (6)	148

Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1; (iii) x, −y+1, z−1/2; (iv) −x+3/2, y+1/2, −z+3/2; (v) x, −y, z−1/2; (vi) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Ag(C₆H₇N₄)₂](NO₃)₃
M_r	564.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.095 (6), 12.037 (3), 6.8262 (18)
β (°)	91.319 (6)
V (Å³)	1979.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.735, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	9412, 2275, 1723
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.104, 0.99
No. of reflections	2275
No. of parameters	151
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.34

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2008), 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
N2—H2N···O4ⁱ	0.86	1.94	2.792 (4)	173
N3—H3···O1ⁱⁱ	0.86	1.92	2.765 (4)	166
N4—H4···O4	0.86	1.93	2.758 (4)	160
C1—H1···O3ⁱⁱ	0.93	2.49	3.179 (5)	131
C2—H2···O5ⁱⁱⁱ	0.93	2.60	3.331 (5)	136
C5—H5···O3^iv	0.93	2.55	3.340 (6)	144
C6—H6···O2^v	0.93	2.55	3.376 (6)	148

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, −y+1, z−1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x, −y, z−1/2; (v) x, y−1, z.

References

Bruker (2002). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Debus, H. (1858). Justus Liebigs Ann. Chem. 107, 199–208. CrossRef Google Scholar
Hester, C. A., Collier, H. L. & Baughman, R. G. (1997). Polyhedron, 16, 2893–2895. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar