In the title centrosymmetric binuclear Ag
I complex, [Ag
2(NO
3)
2(C
12H
10N
4)
2], each Ag
I center is coordinated by one pyridine and one benzotriazole N-donor atom of two inversion-related 2-(3-pyridylmethyl)-2
H-benzotriazole (
L) ligands, and an O atom of a coordinated NO
3− 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 NO
3− anions, link the sheets, forming a three-dimensional framework.
Supporting information
CCDC reference: 709563
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(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
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%.
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.
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).
Bis[µ-2-(3-pyridylmethyl)-2
H-benzotriazole]bis[nitratosilver(I)]
top
Crystal data top
[Ag2(NO3)2(C12H10N4)2] | F(000) = 752 |
Mr = 760.24 | Dx = 1.901 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4027 reflections |
a = 10.472 (2) Å | θ = 2.3–28.0° |
b = 8.6921 (17) Å | µ = 1.54 mm−1 |
c = 14.656 (3) Å | T = 293 K |
β = 95.33 (3)° | Block, yellow |
V = 1328.3 (5) Å3 | 0.20 × 0.15 × 0.11 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2336 independent reflections |
Radiation source: fine-focus sealed tube | 2256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −12→12 |
Tmin = 0.749, Tmax = 0.849 | k = −10→10 |
12799 measured reflections | l = −17→17 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-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 parameters | Δρmax = 0.96 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
[Ag2(NO3)2(C12H10N4)2] | V = 1328.3 (5) Å3 |
Mr = 760.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.472 (2) Å | µ = 1.54 mm−1 |
b = 8.6921 (17) Å | T = 293 K |
c = 14.656 (3) Å | 0.20 × 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 = 0.849 | Rint = 0.027 |
12799 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.96 e Å−3 |
2335 reflections | Δρmin = −0.70 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Ag1 | 0.44311 (3) | 0.21531 (4) | 0.62448 (2) | 0.05524 (13) | |
C1 | 0.6409 (3) | 0.4663 (4) | 0.5666 (2) | 0.0383 (8) | |
H1 | 0.6092 | 0.5197 | 0.6146 | 0.046* | |
C2 | 0.7353 (3) | 0.5350 (4) | 0.5209 (2) | 0.0377 (7) | |
C3 | 0.7781 (4) | 0.4566 (5) | 0.4484 (3) | 0.0568 (10) | |
H3 | 0.8412 | 0.4990 | 0.4155 | 0.068* | |
C4 | 0.7268 (5) | 0.3148 (5) | 0.4249 (3) | 0.0656 (12) | |
H4 | 0.7537 | 0.2613 | 0.3752 | 0.079* | |
C5 | 0.6361 (4) | 0.2536 (4) | 0.4753 (3) | 0.0527 (10) | |
H5 | 0.6034 | 0.1566 | 0.4599 | 0.063* | |
C6 | 0.7883 (4) | 0.6881 (4) | 0.5539 (2) | 0.0485 (9) | |
H61 | 0.7202 | 0.7483 | 0.5769 | 0.058* | |
H62 | 0.8538 | 0.6715 | 0.6043 | 0.058* | |
C7 | 0.9795 (3) | 0.8736 (4) | 0.4051 (2) | 0.0407 (8) | |
C8 | 1.0899 (4) | 0.9289 (5) | 0.3673 (3) | 0.0568 (10) | |
H8 | 1.1719 | 0.9070 | 0.3940 | 0.068* | |
C9 | 1.0709 (4) | 1.0148 (5) | 0.2908 (3) | 0.0590 (11) | |
H9 | 1.1417 | 1.0539 | 0.2646 | 0.071* | |
C10 | 0.9472 (4) | 1.0472 (5) | 0.2493 (3) | 0.0590 (11) | |
H10 | 0.9391 | 1.1065 | 0.1962 | 0.071* | |
C11 | 0.8387 (4) | 0.9950 (5) | 0.2840 (2) | 0.0505 (9) | |
H11 | 0.7573 | 1.0167 | 0.2560 | 0.061* | |
C12 | 0.8568 (3) | 0.9069 (4) | 0.3639 (2) | 0.0374 (7) | |
N1 | 0.7703 (3) | 0.8416 (3) | 0.41543 (19) | 0.0398 (7) | |
N2 | 0.8434 (3) | 0.7743 (3) | 0.48214 (19) | 0.0405 (7) | |
N3 | 0.9691 (3) | 0.7872 (4) | 0.4807 (2) | 0.0468 (7) | |
N4 | 0.5926 (3) | 0.3275 (3) | 0.5456 (2) | 0.0416 (7) | |
N5 | 0.4289 (3) | 0.4142 (4) | 0.8019 (2) | 0.0487 (8) | |
O1 | 0.5156 (4) | 0.4675 (5) | 0.7624 (2) | 0.0997 (13) | |
O2 | 0.4036 (3) | 0.4733 (4) | 0.8748 (2) | 0.0705 (8) | |
O3 | 0.3683 (3) | 0.3011 (4) | 0.7710 (2) | 0.0759 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.04179 (18) | 0.0525 (2) | 0.0734 (2) | −0.00689 (13) | 0.01612 (14) | 0.00621 (15) |
C1 | 0.0340 (17) | 0.044 (2) | 0.0370 (17) | 0.0018 (15) | 0.0035 (14) | 0.0029 (15) |
C2 | 0.0400 (18) | 0.0372 (18) | 0.0360 (17) | −0.0006 (15) | 0.0036 (14) | 0.0048 (15) |
C3 | 0.065 (3) | 0.051 (2) | 0.058 (2) | −0.007 (2) | 0.029 (2) | −0.0018 (19) |
C4 | 0.085 (3) | 0.054 (3) | 0.063 (3) | −0.008 (2) | 0.031 (2) | −0.015 (2) |
C5 | 0.059 (2) | 0.040 (2) | 0.059 (2) | −0.0071 (18) | 0.0048 (19) | −0.0036 (18) |
C6 | 0.060 (2) | 0.048 (2) | 0.0391 (19) | −0.0129 (18) | 0.0110 (17) | 0.0021 (17) |
C7 | 0.0407 (19) | 0.0393 (19) | 0.0431 (19) | −0.0094 (15) | 0.0091 (15) | −0.0064 (16) |
C8 | 0.041 (2) | 0.066 (3) | 0.065 (3) | −0.0151 (19) | 0.0127 (18) | −0.010 (2) |
C9 | 0.058 (3) | 0.064 (3) | 0.059 (3) | −0.025 (2) | 0.024 (2) | −0.008 (2) |
C10 | 0.081 (3) | 0.052 (2) | 0.045 (2) | −0.021 (2) | 0.017 (2) | 0.0025 (19) |
C11 | 0.054 (2) | 0.053 (2) | 0.045 (2) | −0.0077 (18) | 0.0065 (17) | 0.0038 (18) |
C12 | 0.0389 (18) | 0.0356 (18) | 0.0387 (18) | −0.0084 (14) | 0.0088 (14) | −0.0068 (15) |
N1 | 0.0361 (15) | 0.0445 (16) | 0.0394 (15) | −0.0103 (13) | 0.0063 (12) | 0.0011 (13) |
N2 | 0.0413 (16) | 0.0413 (16) | 0.0397 (15) | −0.0092 (13) | 0.0086 (13) | 0.0008 (13) |
N3 | 0.0400 (17) | 0.0509 (18) | 0.0495 (18) | −0.0052 (14) | 0.0038 (13) | 0.0006 (15) |
N4 | 0.0363 (15) | 0.0405 (16) | 0.0475 (17) | −0.0034 (13) | 0.0008 (13) | 0.0040 (14) |
N5 | 0.0404 (17) | 0.0463 (18) | 0.060 (2) | −0.0007 (15) | 0.0081 (15) | −0.0028 (16) |
O1 | 0.091 (3) | 0.124 (3) | 0.089 (2) | −0.053 (2) | 0.038 (2) | −0.001 (2) |
O2 | 0.0648 (19) | 0.067 (2) | 0.081 (2) | −0.0013 (15) | 0.0153 (16) | −0.0275 (17) |
O3 | 0.080 (2) | 0.071 (2) | 0.081 (2) | −0.0322 (18) | 0.0301 (17) | −0.0311 (17) |
Geometric parameters (Å, º) top
Ag1—N4 | 2.253 (3) | C7—N3 | 1.351 (5) |
Ag1—N1i | 2.311 (3) | C7—C12 | 1.399 (5) |
Ag1—O3 | 2.468 (3) | C7—C8 | 1.412 (5) |
Ag1—O1ii | 2.728 (4) | C8—C9 | 1.345 (6) |
Ag1—O2ii | 2.646 (3) | C8—H8 | 0.9300 |
C1—N4 | 1.333 (4) | C9—C10 | 1.408 (6) |
C1—C2 | 1.381 (5) | C9—H9 | 0.9300 |
C1—H1 | 0.9300 | C10—C11 | 1.365 (5) |
C2—C3 | 1.372 (5) | C10—H10 | 0.9300 |
C2—C6 | 1.504 (5) | C11—C12 | 1.397 (5) |
C3—C4 | 1.376 (6) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—N1 | 1.356 (4) |
C4—C5 | 1.364 (6) | N1—N2 | 1.321 (4) |
C4—H4 | 0.9300 | N1—Ag1i | 2.311 (3) |
C5—N4 | 1.329 (5) | N2—N3 | 1.324 (4) |
C5—H5 | 0.9300 | N5—O1 | 1.214 (4) |
C6—N2 | 1.454 (4) | N5—O3 | 1.234 (4) |
C6—H61 | 0.9700 | N5—O2 | 1.236 (4) |
C6—H62 | 0.9700 | | |
| | | |
N4—Ag1—N1i | 131.66 (10) | C9—C8—H8 | 121.5 |
N4—Ag1—O3 | 127.43 (11) | C7—C8—H8 | 121.5 |
N1i—Ag1—O3 | 84.66 (11) | C8—C9—C10 | 122.0 (4) |
N4—C1—C2 | 123.6 (3) | C8—C9—H9 | 119.0 |
N4—C1—H1 | 118.2 | C10—C9—H9 | 119.0 |
C2—C1—H1 | 118.2 | C11—C10—C9 | 122.4 (4) |
C3—C2—C1 | 117.4 (3) | C11—C10—H10 | 118.8 |
C3—C2—C6 | 123.4 (3) | C9—C10—H10 | 118.8 |
C1—C2—C6 | 119.1 (3) | C10—C11—C12 | 116.2 (4) |
C2—C3—C4 | 119.4 (4) | C10—C11—H11 | 121.9 |
C2—C3—H3 | 120.3 | C12—C11—H11 | 121.9 |
C4—C3—H3 | 120.3 | N1—C12—C11 | 130.6 (3) |
C5—C4—C3 | 119.3 (4) | N1—C12—C7 | 107.9 (3) |
C5—C4—H4 | 120.4 | C11—C12—C7 | 121.5 (3) |
C3—C4—H4 | 120.4 | N2—N1—C12 | 103.1 (3) |
N4—C5—C4 | 122.5 (4) | N2—N1—Ag1i | 125.0 (2) |
N4—C5—H5 | 118.8 | C12—N1—Ag1i | 129.0 (2) |
C4—C5—H5 | 118.8 | N1—N2—N3 | 117.4 (3) |
N2—C6—C2 | 112.5 (3) | N1—N2—C6 | 121.5 (3) |
N2—C6—H61 | 109.1 | N3—N2—C6 | 121.1 (3) |
C2—C6—H61 | 109.1 | N2—N3—C7 | 102.5 (3) |
N2—C6—H62 | 109.1 | C5—N4—C1 | 117.8 (3) |
C2—C6—H62 | 109.1 | C5—N4—Ag1 | 119.5 (2) |
H61—C6—H62 | 107.8 | C1—N4—Ag1 | 122.6 (2) |
N3—C7—C12 | 109.2 (3) | O1—N5—O3 | 120.7 (4) |
N3—C7—C8 | 130.0 (4) | O1—N5—O2 | 119.0 (4) |
C12—C7—C8 | 120.9 (3) | O3—N5—O2 | 120.3 (3) |
C9—C8—C7 | 116.9 (4) | N5—O3—Ag1 | 111.5 (2) |
| | | |
N4—C1—C2—C3 | 2.0 (5) | C12—N1—N2—N3 | −0.2 (4) |
N4—C1—C2—C6 | −176.4 (3) | Ag1i—N1—N2—N3 | 161.7 (2) |
C1—C2—C3—C4 | −0.4 (6) | C12—N1—N2—C6 | −179.6 (3) |
C6—C2—C3—C4 | 177.9 (4) | Ag1i—N1—N2—C6 | −17.7 (4) |
C2—C3—C4—C5 | −1.2 (7) | C2—C6—N2—N1 | 74.0 (4) |
C3—C4—C5—N4 | 1.6 (7) | C2—C6—N2—N3 | −105.4 (4) |
C3—C2—C6—N2 | 25.6 (5) | N1—N2—N3—C7 | 0.5 (4) |
C1—C2—C6—N2 | −156.1 (3) | C6—N2—N3—C7 | 179.9 (3) |
N3—C7—C8—C9 | −179.3 (4) | C12—C7—N3—N2 | −0.7 (4) |
C12—C7—C8—C9 | 0.3 (6) | C8—C7—N3—N2 | 179.0 (4) |
C7—C8—C9—C10 | −0.7 (6) | C4—C5—N4—C1 | −0.1 (6) |
C8—C9—C10—C11 | 0.5 (7) | C4—C5—N4—Ag1 | −179.8 (3) |
C9—C10—C11—C12 | 0.2 (6) | C2—C1—N4—C5 | −1.7 (5) |
C10—C11—C12—N1 | 178.7 (4) | C2—C1—N4—Ag1 | 177.9 (2) |
C10—C11—C12—C7 | −0.6 (5) | N1i—Ag1—N4—C5 | −68.9 (3) |
N3—C7—C12—N1 | 0.6 (4) | O3—Ag1—N4—C5 | 169.5 (3) |
C8—C7—C12—N1 | −179.0 (3) | N1i—Ag1—N4—C1 | 111.5 (3) |
N3—C7—C12—C11 | −179.9 (3) | O3—Ag1—N4—C1 | −10.1 (3) |
C8—C7—C12—C11 | 0.4 (5) | O1—N5—O3—Ag1 | −1.8 (5) |
C11—C12—N1—N2 | −179.6 (4) | O2—N5—O3—Ag1 | 179.5 (3) |
C7—C12—N1—N2 | −0.3 (4) | N4—Ag1—O3—N5 | −3.8 (3) |
C11—C12—N1—Ag1i | 19.5 (5) | N1i—Ag1—O3—N5 | −144.1 (3) |
C7—C12—N1—Ag1i | −161.1 (2) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2iii | 0.93 | 2.59 | 3.365 (3) | 141 |
C6—H61···O2iv | 0.97 | 2.48 | 3.416 (5) | 161 |
Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | [Ag2(NO3)2(C12H10N4)2] |
Mr | 760.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.472 (2), 8.6921 (17), 14.656 (3) |
β (°) | 95.33 (3) |
V (Å3) | 1328.3 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.20 × 0.15 × 0.11 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.749, 0.849 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12799, 2336, 2256 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.072, 1.11 |
No. of reflections | 2335 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.70 |
Selected geometric parameters (Å, º) topAg1—N4 | 2.253 (3) | Ag1—O1ii | 2.728 (4) |
Ag1—N1i | 2.311 (3) | Ag1—O2ii | 2.646 (3) |
Ag1—O3 | 2.468 (3) | | |
| | | |
N4—Ag1—N1i | 131.66 (10) | N1i—Ag1—O3 | 84.66 (11) |
N4—Ag1—O3 | 127.43 (11) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2iii | 0.93 | 2.59 | 3.365 (3) | 141 |
C6—H61···O2iv | 0.97 | 2.48 | 3.416 (5) | 161 |
Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+3/2. |
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.