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In the title centrosymmetric binuclear AgI complex, [Ag2(NO3)2(C12H10N4)2], each AgI center is coordinated by one pyridine and one benzotriazole N-donor atom of two inversion-related 2-(3-pyridylmeth­yl)-2H-benzotriazole (L) ligands, and an O atom of a coordinated NO3 anion in a distorted T-shaped geometry. This forms a unique box-like cyclic dimer with an intra­molecular non-bonding Ag...Ag separation of 6.327 (2) Å. Weak inter­molecular Ag...O(nitrate) inter­actions [2.728 (4) and 2.646 (3) Å] link the binuclear units, forming a two-dimensional network parallel to (100). Inter­molecular C—H...O hydrogen-bonding inter­actions, involving the L ligands and the coordinated NO3 anions, link the sheets, forming a three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680803479X/su2070sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680803479X/su2070Isup2.hkl
Contains datablock I

CCDC reference: 709563

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.036
  • wR factor = 0.072
  • Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level A DIFF020_ALERT_1_A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for N5
Alert level C Value of measurement temperature given = 293.000 Value of melting point given = 0.000 SHFSU01_ALERT_2_C Test not performed. _refine_ls_shift/su_max and _refine_ls_shift/esd_max not present. Absolute value of the parameter shift to su ratio given 0.001 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ag1 -- O3 .. 5.17 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ag1 -- O2_a .. 5.81 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ag1 -- N1_c .. 7.46 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O3 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The structures of five N-containing bis-heterocyclic ligands bearing 1-substituted benzotriazole subunits, such as 1-(2-pyridylmethyl)-1H-benzotriazole and its binuclear CuII, PdII, and AgI complexes, have been published previously (Richardson & Steel, 2003). As part of a study on the coordination possibilities of benzotriazole-based ligands with different N-substituted positions in the self-assembly process of coordination complexes, we synthesized a nonplanar flexible ligand based on a 2-substituted benzotriazole subunit and a pendant pyridyl group, namely 2-(3-pyridylmethyl)-2H-benzotriazole (L). Ligand L was then used to construct the title compound, (I), by the reaction of L with AgNO3.

The structure of compound (I) consists of a centrosymmetric binuclear unit compossed of two L ligands, two AgI centers, and two coordinated NO3- anions (Fig. 1). The intramolecular non-bonding Ag···Ag separation is 6.327 (2) Å. Each AgI center adopts a distorted T-shaped geometry (Table 1) formed by one O atom of a NO3- anion and two N-donor atoms; one from the benzotriazole ring system of one L ligand, and the other one from the pendant pyridine ring of another L ligand.

In this case the 16-membered dimetallocyclic ring is far from planar as a result of the presence of the tetrahedral methylene group of the L ligand. All the Ag—O and Ag—N bond distances are in the normal range found for similar complexes (Liu, Chen et al., 2006; Liu, Li et al., 2007).

In the crystal structure adjacent discrete binuclear [Ag(L)(NO3)]2 units are further assembled into one-dimensional chains by intermolecular Ag···O interactions [Ag1···O1ii = 2.728 (4) Å and Ag1···O2ii = 2.646 (3) Å; symmetry code ii: -x + 1, y - 1/2, -z + 1.5, see Table 1]. The net result is a two-dimensional network running parallel to the (100) plane (Fig. 2). In addition, the crystal structure of (I) also contains intermolecular C—H···O hydrogen-bonding interactions (Table 2) between the L ligands and the coordinated NO3- anions that interlink the two-dimensional sheets to form a three-dimensional framework.

We are currently exploring the extension of this study to other 2-substituted benzotriazole-based bis-heterocyclic ligands with bulky aromatic pendant groups, such as acridine and quinoline, and their metal-organic coordination complexes with may have potentially useful properties.

Related literature top

For similar structures, see: Liu, Chen et al. (2006); Liu, Li et al. (2007); Richardson & Steel (2003); For the synthesis of ligand L, see: Liu, Sun et al. (2008).

Experimental top

The ligand 2-(3-Pyridylmethyl)-2H-benzotriazole (L) was synthesized according to the modified method reported in the literature (Liu, Sun et al., 2008). Benzotriazole (0.26 g, 2.2 mmol), 3-(chloromethyl)pyridine hydrochloride (3-picolyl chloride hydrochloride) (0.33 g, 2 mmol), and potassium carbonate (1.52 g, 11 mmol) were added to 50 ml of CH3CN. The mixture was stirred at rt for ca 1 h before being heated at reflux for 24 h, with vigorous stirring. A beige precipitate was obtained, filtered off and rinsed with CH3CN. The solvent was removed from the filtrate, and the beige product obtained was taken up in CHCl3 and washed three times with H2O, before being dried over anhydrous MgSO4. Ligand (L) was obtained as a yellow powder and purified by recrystallization from CHCl3/hexane [Yield: ca 40% (based on 3-(chloromethyl)pyridine hydrochloride)]. Elemental analysis calculated for (C12H10N4): C 68.56, H 4.79, N 26.65%; found: C 68.61, H 4.8, N 26.55%. Complex (I) was prepared by adding a solution of AgNO3 (0.1 mmol) to a mixture of ligand L (0.1 mmol) in CH3OH (15 ml) and CH3CN (5 ml). A yellow solid formed which was filtered off and the resulting solution was kept at rt. Yellow crystals of complex (I), suitable for X-ray analysis, were obtained by slow evaporation of the solvent after several days. Yield: ~30%. Elemental analysis calculated for (C12H10AgN5O3): C 37.92, H 2.65, N 18.42%; found: C 37.81, H 2.70, N 18.34%.

Refinement top

H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and Uiso(H) = 1.2 or 1.5 Ueq(C). One reflection (100) was omitted from the refinement.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (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) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of complex (I). Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are generated by the symmetry operation (–x + 1, –y + 1, –z + 1).
[Figure 2] Fig. 2. A view of the two-dimensional network of compound (I), parallel to the (100) plane, formed by the intermolecular Ag···O (fine dashed lines) interactions (H atoms have been omitted for clarity).
Bis[µ-2-(3-pyridylmethyl)-2H-benzotriazole]bis[nitratosilver(I)] top
Crystal data top
[Ag2(NO3)2(C12H10N4)2]F(000) = 752
Mr = 760.24Dx = 1.901 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4027 reflections
a = 10.472 (2) Åθ = 2.3–28.0°
b = 8.6921 (17) ŵ = 1.54 mm1
c = 14.656 (3) ÅT = 293 K
β = 95.33 (3)°Block, yellow
V = 1328.3 (5) Å30.20 × 0.15 × 0.11 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2336 independent reflections
Radiation source: fine-focus sealed tube2256 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
h = 1212
Tmin = 0.749, Tmax = 0.849k = 1010
12799 measured reflectionsl = 1717
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0212P)2 + 2.3034P]
where P = (Fo2 + 2Fc2)/3
2335 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.96 e Å3
0 restraintsΔρmin = 0.70 e Å3
Crystal data top
[Ag2(NO3)2(C12H10N4)2]V = 1328.3 (5) Å3
Mr = 760.24Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.472 (2) ŵ = 1.54 mm1
b = 8.6921 (17) ÅT = 293 K
c = 14.656 (3) Å0.20 × 0.15 × 0.11 mm
β = 95.33 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2336 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
2256 reflections with I > 2σ(I)
Tmin = 0.749, Tmax = 0.849Rint = 0.027
12799 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.11Δρmax = 0.96 e Å3
2335 reflectionsΔρmin = 0.70 e Å3
190 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
xyzUiso*/Ueq
Ag10.44311 (3)0.21531 (4)0.62448 (2)0.05524 (13)
C10.6409 (3)0.4663 (4)0.5666 (2)0.0383 (8)
H10.60920.51970.61460.046*
C20.7353 (3)0.5350 (4)0.5209 (2)0.0377 (7)
C30.7781 (4)0.4566 (5)0.4484 (3)0.0568 (10)
H30.84120.49900.41550.068*
C40.7268 (5)0.3148 (5)0.4249 (3)0.0656 (12)
H40.75370.26130.37520.079*
C50.6361 (4)0.2536 (4)0.4753 (3)0.0527 (10)
H50.60340.15660.45990.063*
C60.7883 (4)0.6881 (4)0.5539 (2)0.0485 (9)
H610.72020.74830.57690.058*
H620.85380.67150.60430.058*
C70.9795 (3)0.8736 (4)0.4051 (2)0.0407 (8)
C81.0899 (4)0.9289 (5)0.3673 (3)0.0568 (10)
H81.17190.90700.39400.068*
C91.0709 (4)1.0148 (5)0.2908 (3)0.0590 (11)
H91.14171.05390.26460.071*
C100.9472 (4)1.0472 (5)0.2493 (3)0.0590 (11)
H100.93911.10650.19620.071*
C110.8387 (4)0.9950 (5)0.2840 (2)0.0505 (9)
H110.75731.01670.25600.061*
C120.8568 (3)0.9069 (4)0.3639 (2)0.0374 (7)
N10.7703 (3)0.8416 (3)0.41543 (19)0.0398 (7)
N20.8434 (3)0.7743 (3)0.48214 (19)0.0405 (7)
N30.9691 (3)0.7872 (4)0.4807 (2)0.0468 (7)
N40.5926 (3)0.3275 (3)0.5456 (2)0.0416 (7)
N50.4289 (3)0.4142 (4)0.8019 (2)0.0487 (8)
O10.5156 (4)0.4675 (5)0.7624 (2)0.0997 (13)
O20.4036 (3)0.4733 (4)0.8748 (2)0.0705 (8)
O30.3683 (3)0.3011 (4)0.7710 (2)0.0759 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.04179 (18)0.0525 (2)0.0734 (2)0.00689 (13)0.01612 (14)0.00621 (15)
C10.0340 (17)0.044 (2)0.0370 (17)0.0018 (15)0.0035 (14)0.0029 (15)
C20.0400 (18)0.0372 (18)0.0360 (17)0.0006 (15)0.0036 (14)0.0048 (15)
C30.065 (3)0.051 (2)0.058 (2)0.007 (2)0.029 (2)0.0018 (19)
C40.085 (3)0.054 (3)0.063 (3)0.008 (2)0.031 (2)0.015 (2)
C50.059 (2)0.040 (2)0.059 (2)0.0071 (18)0.0048 (19)0.0036 (18)
C60.060 (2)0.048 (2)0.0391 (19)0.0129 (18)0.0110 (17)0.0021 (17)
C70.0407 (19)0.0393 (19)0.0431 (19)0.0094 (15)0.0091 (15)0.0064 (16)
C80.041 (2)0.066 (3)0.065 (3)0.0151 (19)0.0127 (18)0.010 (2)
C90.058 (3)0.064 (3)0.059 (3)0.025 (2)0.024 (2)0.008 (2)
C100.081 (3)0.052 (2)0.045 (2)0.021 (2)0.017 (2)0.0025 (19)
C110.054 (2)0.053 (2)0.045 (2)0.0077 (18)0.0065 (17)0.0038 (18)
C120.0389 (18)0.0356 (18)0.0387 (18)0.0084 (14)0.0088 (14)0.0068 (15)
N10.0361 (15)0.0445 (16)0.0394 (15)0.0103 (13)0.0063 (12)0.0011 (13)
N20.0413 (16)0.0413 (16)0.0397 (15)0.0092 (13)0.0086 (13)0.0008 (13)
N30.0400 (17)0.0509 (18)0.0495 (18)0.0052 (14)0.0038 (13)0.0006 (15)
N40.0363 (15)0.0405 (16)0.0475 (17)0.0034 (13)0.0008 (13)0.0040 (14)
N50.0404 (17)0.0463 (18)0.060 (2)0.0007 (15)0.0081 (15)0.0028 (16)
O10.091 (3)0.124 (3)0.089 (2)0.053 (2)0.038 (2)0.001 (2)
O20.0648 (19)0.067 (2)0.081 (2)0.0013 (15)0.0153 (16)0.0275 (17)
O30.080 (2)0.071 (2)0.081 (2)0.0322 (18)0.0301 (17)0.0311 (17)
Geometric parameters (Å, º) top
Ag1—N42.253 (3)C7—N31.351 (5)
Ag1—N1i2.311 (3)C7—C121.399 (5)
Ag1—O32.468 (3)C7—C81.412 (5)
Ag1—O1ii2.728 (4)C8—C91.345 (6)
Ag1—O2ii2.646 (3)C8—H80.9300
C1—N41.333 (4)C9—C101.408 (6)
C1—C21.381 (5)C9—H90.9300
C1—H10.9300C10—C111.365 (5)
C2—C31.372 (5)C10—H100.9300
C2—C61.504 (5)C11—C121.397 (5)
C3—C41.376 (6)C11—H110.9300
C3—H30.9300C12—N11.356 (4)
C4—C51.364 (6)N1—N21.321 (4)
C4—H40.9300N1—Ag1i2.311 (3)
C5—N41.329 (5)N2—N31.324 (4)
C5—H50.9300N5—O11.214 (4)
C6—N21.454 (4)N5—O31.234 (4)
C6—H610.9700N5—O21.236 (4)
C6—H620.9700
N4—Ag1—N1i131.66 (10)C9—C8—H8121.5
N4—Ag1—O3127.43 (11)C7—C8—H8121.5
N1i—Ag1—O384.66 (11)C8—C9—C10122.0 (4)
N4—C1—C2123.6 (3)C8—C9—H9119.0
N4—C1—H1118.2C10—C9—H9119.0
C2—C1—H1118.2C11—C10—C9122.4 (4)
C3—C2—C1117.4 (3)C11—C10—H10118.8
C3—C2—C6123.4 (3)C9—C10—H10118.8
C1—C2—C6119.1 (3)C10—C11—C12116.2 (4)
C2—C3—C4119.4 (4)C10—C11—H11121.9
C2—C3—H3120.3C12—C11—H11121.9
C4—C3—H3120.3N1—C12—C11130.6 (3)
C5—C4—C3119.3 (4)N1—C12—C7107.9 (3)
C5—C4—H4120.4C11—C12—C7121.5 (3)
C3—C4—H4120.4N2—N1—C12103.1 (3)
N4—C5—C4122.5 (4)N2—N1—Ag1i125.0 (2)
N4—C5—H5118.8C12—N1—Ag1i129.0 (2)
C4—C5—H5118.8N1—N2—N3117.4 (3)
N2—C6—C2112.5 (3)N1—N2—C6121.5 (3)
N2—C6—H61109.1N3—N2—C6121.1 (3)
C2—C6—H61109.1N2—N3—C7102.5 (3)
N2—C6—H62109.1C5—N4—C1117.8 (3)
C2—C6—H62109.1C5—N4—Ag1119.5 (2)
H61—C6—H62107.8C1—N4—Ag1122.6 (2)
N3—C7—C12109.2 (3)O1—N5—O3120.7 (4)
N3—C7—C8130.0 (4)O1—N5—O2119.0 (4)
C12—C7—C8120.9 (3)O3—N5—O2120.3 (3)
C9—C8—C7116.9 (4)N5—O3—Ag1111.5 (2)
N4—C1—C2—C32.0 (5)C12—N1—N2—N30.2 (4)
N4—C1—C2—C6176.4 (3)Ag1i—N1—N2—N3161.7 (2)
C1—C2—C3—C40.4 (6)C12—N1—N2—C6179.6 (3)
C6—C2—C3—C4177.9 (4)Ag1i—N1—N2—C617.7 (4)
C2—C3—C4—C51.2 (7)C2—C6—N2—N174.0 (4)
C3—C4—C5—N41.6 (7)C2—C6—N2—N3105.4 (4)
C3—C2—C6—N225.6 (5)N1—N2—N3—C70.5 (4)
C1—C2—C6—N2156.1 (3)C6—N2—N3—C7179.9 (3)
N3—C7—C8—C9179.3 (4)C12—C7—N3—N20.7 (4)
C12—C7—C8—C90.3 (6)C8—C7—N3—N2179.0 (4)
C7—C8—C9—C100.7 (6)C4—C5—N4—C10.1 (6)
C8—C9—C10—C110.5 (7)C4—C5—N4—Ag1179.8 (3)
C9—C10—C11—C120.2 (6)C2—C1—N4—C51.7 (5)
C10—C11—C12—N1178.7 (4)C2—C1—N4—Ag1177.9 (2)
C10—C11—C12—C70.6 (5)N1i—Ag1—N4—C568.9 (3)
N3—C7—C12—N10.6 (4)O3—Ag1—N4—C5169.5 (3)
C8—C7—C12—N1179.0 (3)N1i—Ag1—N4—C1111.5 (3)
N3—C7—C12—C11179.9 (3)O3—Ag1—N4—C110.1 (3)
C8—C7—C12—C110.4 (5)O1—N5—O3—Ag11.8 (5)
C11—C12—N1—N2179.6 (4)O2—N5—O3—Ag1179.5 (3)
C7—C12—N1—N20.3 (4)N4—Ag1—O3—N53.8 (3)
C11—C12—N1—Ag1i19.5 (5)N1i—Ag1—O3—N5144.1 (3)
C7—C12—N1—Ag1i161.1 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2iii0.932.593.365 (3)141
C6—H61···O2iv0.972.483.416 (5)161
Symmetry codes: (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Ag2(NO3)2(C12H10N4)2]
Mr760.24
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)10.472 (2), 8.6921 (17), 14.656 (3)
β (°) 95.33 (3)
V3)1328.3 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.54
Crystal size (mm)0.20 × 0.15 × 0.11
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.749, 0.849
No. of measured, independent and
observed [I > 2σ(I)] reflections
12799, 2336, 2256
Rint0.027
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.072, 1.11
No. of reflections2335
No. of parameters190
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.96, 0.70

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Ag1—N42.253 (3)Ag1—O1ii2.728 (4)
Ag1—N1i2.311 (3)Ag1—O2ii2.646 (3)
Ag1—O32.468 (3)
N4—Ag1—N1i131.66 (10)N1i—Ag1—O384.66 (11)
N4—Ag1—O3127.43 (11)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2iii0.932.593.365 (3)141
C6—H61···O2iv0.972.483.416 (5)161
Symmetry codes: (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z+3/2.
 

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