Download citation
Download citation
link to html
The title compound, [Ag2(C9H9N3)2](NO3)2, is a 14-membered metallamacrocycle formed by two Ag atoms bridging two N-(2-pyridylmeth­yl)imidazole (pymim) mol­ecules. The asymmetric unit consists of one-half of the cation and one nitrate anion. The metallamacrocycle complex lies on an inversion centre. The nitrate anions are in close contact with the Ag centres of two neighbouring cations, which link the metallamacrocyclic units into a double-chain structure along the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040032/er2033sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040032/er2033Isup2.hkl
Contains datablock I

CCDC reference: 660129

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.029
  • wR factor = 0.084
  • Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N4
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1 (9) 0.40
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The synthesis and properties of self-assembled hybrid organic–inorganic macrocyclic or polymeric compounds involving suitably designed ligands and transition-metal ions have drawn an ever-increasing level of attention (Yue et al., 2005; Zheng et al., 2003). There has been much progress recently in the study of crystal engineering of supramolecular architectures using N-donor ligands (Telfer et al., 2006; Peng et al., 2006). The cation of the title compound, Ag2(pymim)2(NO3)2 is a fourteen-membered metallomacrocycle formed by the two Ag atoms bridging two pymim molecules. The asymmetric unit consists of one-half of the molecular cation and one nitrate anion. The full cation and the other nitrate anion are generated by the symmetry operation of a crystallographic inversion centre. As shown Fig. 1 and Fig. 2, The ligands are arranged in a head-to-tail fashion. The macrocycle lie on an inversion centre and the silver atoms are coordinated by a pyridine and a imidazole moiety. The Ag···Ag distance of 5.040 (6) Å is much longer than the sum of van der Waals radii of two Ag atoms (3.40 Å, Bondi, 1964) and can be regarded as noninteracting. Each pyridine ring is highly twisted from its trans imidazole ring with an interplanar angle of 74.55 (11)°. The overall geometry of the metallomacrocycle is slightly twisted with the N1—Ag1···Ag1A—N3 dihedral angle of 1.37 (3)°. The O atoms of nitrate anions are in close contact with the silver centers of two neighboring cations having nonbonding distances of 2.715 (3)–2.918 (3) Å, which are shorter than the sum of van der Waals radii for the Ag and O atoms (3.24 Å, Bondi, 1964) and consistent with those reported for other silver nitrate complexes in the literature (Yue et al., 2005; Zhang et al., 2005; Lin et al., 2004). These bridging nitrate interactions pull the silver centers in the metallomacrocyclic units away from each other resulting in very long Ag···Ag distance and a one-dimensional double-chain structure along the a axis.

Related literature top

For related literature, see: Bondi (1964); Chiu et al. (2005); Lin et al. (2004); Peng et al. (2006); Telfer et al. (2006); Yue et al. (2005); Zhang et al. (2005); Zheng et al. (2003).

Experimental top

All reagents were of analytical grade and used without further purification. Pymim was prepared by the general procedure of Chiu et al. (2005). A solution of pymim (0.4 mmol, 64 mg) in MeOH (4 ml) was added to a stirring solution of AgNO3 (0.4 mmol, 68 mg) in MeOH (8 ml). The white precipitate that formed immediately was collected, washed with MeOH and dried. Colorless single crystals were grown from diffusion of dithyl ether into a DMF solution containing the silver complexes. Yield: 35%. Analysis found: C 33.01, H 2.79, N 16.93%.; calculated for Ag2(C9H9N3)2(NO3)2: C 32.85, H 2.76, N 17.03%.

Refinement top

C-bound H atoms were positioned geometrically and treated as riding with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).

Structure description top

The synthesis and properties of self-assembled hybrid organic–inorganic macrocyclic or polymeric compounds involving suitably designed ligands and transition-metal ions have drawn an ever-increasing level of attention (Yue et al., 2005; Zheng et al., 2003). There has been much progress recently in the study of crystal engineering of supramolecular architectures using N-donor ligands (Telfer et al., 2006; Peng et al., 2006). The cation of the title compound, Ag2(pymim)2(NO3)2 is a fourteen-membered metallomacrocycle formed by the two Ag atoms bridging two pymim molecules. The asymmetric unit consists of one-half of the molecular cation and one nitrate anion. The full cation and the other nitrate anion are generated by the symmetry operation of a crystallographic inversion centre. As shown Fig. 1 and Fig. 2, The ligands are arranged in a head-to-tail fashion. The macrocycle lie on an inversion centre and the silver atoms are coordinated by a pyridine and a imidazole moiety. The Ag···Ag distance of 5.040 (6) Å is much longer than the sum of van der Waals radii of two Ag atoms (3.40 Å, Bondi, 1964) and can be regarded as noninteracting. Each pyridine ring is highly twisted from its trans imidazole ring with an interplanar angle of 74.55 (11)°. The overall geometry of the metallomacrocycle is slightly twisted with the N1—Ag1···Ag1A—N3 dihedral angle of 1.37 (3)°. The O atoms of nitrate anions are in close contact with the silver centers of two neighboring cations having nonbonding distances of 2.715 (3)–2.918 (3) Å, which are shorter than the sum of van der Waals radii for the Ag and O atoms (3.24 Å, Bondi, 1964) and consistent with those reported for other silver nitrate complexes in the literature (Yue et al., 2005; Zhang et al., 2005; Lin et al., 2004). These bridging nitrate interactions pull the silver centers in the metallomacrocyclic units away from each other resulting in very long Ag···Ag distance and a one-dimensional double-chain structure along the a axis.

For related literature, see: Bondi (1964); Chiu et al. (2005); Lin et al. (2004); Peng et al. (2006); Telfer et al. (2006); Yue et al. (2005); Zhang et al. (2005); Zheng et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) and parts of adjacent units, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry code (A): -x + 2,-y + 1,-z + 1]
[Figure 2] Fig. 2. Bridging nitrate interactions in (I) along the a axis. Hydrogen atoms are omitted for clarity.
Bis[µ-1-(4-pyridylmethyl)-1H-imidazole]disilver(I) dinitrate top
Crystal data top
[Ag2(C9H9N3)2](NO3)2F(000) = 648
Mr = 658.14Dx = 1.983 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3520 reflections
a = 5.4170 (9) Åθ = 2.6–27.7°
b = 13.020 (2) ŵ = 1.83 mm1
c = 15.648 (3) ÅT = 291 K
β = 92.915 (2)°Block, colourless
V = 1102.2 (3) Å30.33 × 0.28 × 0.19 mm
Z = 2
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2024 independent reflections
Radiation source: fine-focus sealed tube1809 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 10 pixels mm-1θmax = 25.5°, θmin = 2.6°
φ and ω scansh = 56
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 1515
Tmin = 0.587, Tmax = 0.720l = 1818
6892 measured reflections
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0546P)2 + 0.4881P]
where P = (Fo2 + 2Fc2)/3
2024 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.85 e Å3
0 restraintsΔρmin = 0.50 e Å3
Crystal data top
[Ag2(C9H9N3)2](NO3)2V = 1102.2 (3) Å3
Mr = 658.14Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.4170 (9) ŵ = 1.83 mm1
b = 13.020 (2) ÅT = 291 K
c = 15.648 (3) Å0.33 × 0.28 × 0.19 mm
β = 92.915 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2024 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1809 reflections with I > 2σ(I)
Tmin = 0.587, Tmax = 0.720Rint = 0.022
6892 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.05Δρmax = 0.85 e Å3
2024 reflectionsΔρmin = 0.50 e Å3
154 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. Highest peak 0.85 at 0.2188 0.3146 0.5020 [0.90 A from AG1] Deepest hole -0.50 at 0.0726 0.3653 0.5062 [0.80 A from AG1]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag11.08496 (5)0.313742 (18)0.533996 (15)0.04668 (14)
O10.5896 (5)0.2907 (3)0.5539 (2)0.0823 (10)
O20.3913 (6)0.2095 (3)0.6460 (2)0.0767 (9)
O30.7815 (5)0.2392 (2)0.6697 (2)0.0716 (8)
N11.0499 (6)0.19166 (19)0.43290 (18)0.0445 (7)
N20.8319 (5)0.37732 (19)0.36086 (15)0.0396 (6)
N30.9081 (5)0.5376 (2)0.40039 (16)0.0442 (6)
N40.5879 (5)0.2460 (2)0.62429 (17)0.0439 (6)
C11.1948 (8)0.1093 (3)0.4469 (3)0.0606 (10)
H11.31740.11230.49060.073*
C21.1706 (9)0.0201 (3)0.3995 (3)0.0713 (12)
H21.27520.03540.41080.086*
C30.9894 (9)0.0152 (3)0.3354 (3)0.0724 (12)
H30.96560.04450.30340.087*
C40.8433 (8)0.1000 (3)0.3193 (2)0.0622 (10)
H40.72160.09870.27520.075*
C50.8776 (7)0.1871 (2)0.3686 (2)0.0415 (7)
C60.7082 (6)0.2779 (3)0.3527 (2)0.0480 (8)
H6A0.63130.27220.29560.058*
H6B0.57800.27520.39300.058*
C70.7586 (6)0.4584 (2)0.40715 (19)0.0438 (7)
H70.61990.45830.43980.053*
C81.0864 (7)0.5054 (3)0.34738 (19)0.0454 (7)
H81.21880.54520.33130.054*
C91.0426 (7)0.4081 (3)0.3220 (2)0.0459 (8)
H91.13570.36940.28540.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0523 (2)0.04178 (19)0.04488 (19)0.00715 (10)0.00753 (13)0.01113 (9)
O10.057 (2)0.136 (3)0.0540 (16)0.0109 (18)0.0005 (13)0.0275 (18)
O20.0523 (18)0.098 (2)0.079 (2)0.0163 (16)0.0053 (15)0.0353 (17)
O30.0530 (17)0.0734 (19)0.0855 (19)0.0112 (14)0.0239 (15)0.0270 (15)
N10.0514 (18)0.0358 (15)0.0454 (16)0.0011 (11)0.0047 (13)0.0084 (10)
N20.0450 (16)0.0357 (14)0.0373 (13)0.0038 (11)0.0044 (11)0.0037 (10)
N30.0555 (17)0.0381 (14)0.0382 (13)0.0077 (12)0.0053 (12)0.0049 (10)
N40.0425 (16)0.0399 (14)0.0487 (15)0.0027 (12)0.0018 (13)0.0013 (12)
C10.069 (3)0.042 (2)0.070 (2)0.0093 (17)0.0122 (19)0.0104 (16)
C20.090 (3)0.0379 (19)0.086 (3)0.015 (2)0.002 (3)0.0105 (19)
C30.100 (4)0.039 (2)0.077 (3)0.004 (2)0.002 (3)0.0259 (19)
C40.074 (3)0.056 (2)0.055 (2)0.009 (2)0.0098 (19)0.0175 (17)
C50.047 (2)0.0380 (17)0.0395 (17)0.0067 (13)0.0017 (14)0.0046 (12)
C60.047 (2)0.0481 (18)0.0484 (19)0.0061 (16)0.0068 (15)0.0028 (15)
C70.0440 (18)0.0486 (18)0.0383 (16)0.0096 (15)0.0024 (13)0.0076 (13)
C80.0498 (19)0.0407 (17)0.0455 (17)0.0032 (14)0.0018 (15)0.0005 (14)
C90.054 (2)0.0422 (17)0.0422 (16)0.0056 (15)0.0062 (15)0.0046 (13)
Geometric parameters (Å, º) top
Ag1—N3i2.190 (3)C1—H10.9300
Ag1—N12.244 (3)C2—C31.368 (6)
O1—N41.246 (4)C2—H20.9300
O2—N41.230 (4)C3—C41.375 (6)
O3—N41.240 (4)C3—H30.9300
N1—C51.338 (5)C4—C51.379 (5)
N1—C11.341 (4)C4—H40.9300
N2—C71.351 (4)C5—C61.509 (5)
N2—C91.380 (4)C6—H6A0.9700
N2—C61.460 (4)C6—H6B0.9700
N3—C71.319 (4)C7—H70.9300
N3—C81.370 (4)C8—C91.345 (5)
N3—Ag1i2.190 (3)C8—H80.9300
C1—C21.380 (5)C9—H90.9300
N3i—Ag1—N1162.80 (10)C3—C4—C5119.9 (4)
C5—N1—C1117.9 (3)C3—C4—H4120.1
C5—N1—Ag1126.3 (2)C5—C4—H4120.1
C1—N1—Ag1115.1 (2)N1—C5—C4121.7 (3)
C7—N2—C9106.3 (3)N1—C5—C6119.0 (3)
C7—N2—C6126.4 (3)C4—C5—C6119.2 (3)
C9—N2—C6127.3 (3)N2—C6—C5114.0 (3)
C7—N3—C8105.3 (3)N2—C6—H6A108.7
C7—N3—Ag1i130.5 (2)C5—C6—H6A108.7
C8—N3—Ag1i123.9 (2)N2—C6—H6B108.7
O2—N4—O3122.2 (3)C5—C6—H6B108.7
O2—N4—O1118.1 (3)H6A—C6—H6B107.6
O3—N4—O1119.8 (3)N3—C7—N2111.7 (3)
N1—C1—C2123.1 (4)N3—C7—H7124.1
N1—C1—H1118.5N2—C7—H7124.1
C2—C1—H1118.5C9—C8—N3110.4 (3)
C3—C2—C1118.6 (4)C9—C8—H8124.8
C3—C2—H2120.7N3—C8—H8124.8
C1—C2—H2120.7C8—C9—N2106.3 (3)
C2—C3—C4118.8 (3)C8—C9—H9126.8
C2—C3—H3120.6N2—C9—H9126.8
C4—C3—H3120.6
N3i—Ag1—N1—C541.1 (5)C7—N2—C6—C5130.2 (3)
N3i—Ag1—N1—C1149.0 (4)C9—N2—C6—C551.1 (4)
C5—N1—C1—C21.4 (6)N1—C5—C6—N241.2 (4)
Ag1—N1—C1—C2169.3 (4)C4—C5—C6—N2141.9 (3)
N1—C1—C2—C30.4 (7)C8—N3—C7—N20.3 (4)
C1—C2—C3—C41.8 (7)Ag1i—N3—C7—N2174.26 (19)
C2—C3—C4—C51.4 (7)C9—N2—C7—N30.2 (4)
C1—N1—C5—C41.8 (5)C6—N2—C7—N3179.1 (3)
Ag1—N1—C5—C4167.8 (3)C7—N3—C8—C90.6 (4)
C1—N1—C5—C6178.6 (3)Ag1i—N3—C8—C9175.1 (2)
Ag1—N1—C5—C69.0 (4)N3—C8—C9—N20.7 (4)
C3—C4—C5—N10.4 (6)C7—N2—C9—C80.6 (3)
C3—C4—C5—C6177.2 (4)C6—N2—C9—C8179.4 (3)
Symmetry code: (i) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Ag2(C9H9N3)2](NO3)2
Mr658.14
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)5.4170 (9), 13.020 (2), 15.648 (3)
β (°) 92.915 (2)
V3)1102.2 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.83
Crystal size (mm)0.33 × 0.28 × 0.19
Data collection
DiffractometerBruker SMART 1K CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.587, 0.720
No. of measured, independent and
observed [I > 2σ(I)] reflections
6892, 2024, 1809
Rint0.022
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.084, 1.05
No. of reflections2024
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.85, 0.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL.

Selected geometric parameters (Å, º) top
Ag1—N3i2.190 (3)Ag1—N12.244 (3)
N3i—Ag1—N1162.80 (10)C7—N3—Ag1i130.5 (2)
C5—N1—Ag1126.3 (2)C8—N3—Ag1i123.9 (2)
C1—N1—Ag1115.1 (2)N2—C6—C5114.0 (3)
Symmetry code: (i) x+2, y+1, z+1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds