Ag
I-containing coordination complexes have attracted attention because of their photoluminescence properties and antimicrobial activities and, in principle, these properties depend on the nature of the structural topologies. A novel two-dimensional silver(I) complex with the anti-inflammatory diclofenac molecule, namely bis{μ-2-[2-(2,6-dichloroanilino)phenyl]acetato-κ
3O,
O′:
O}bis(μ-2,5-dimethylpyrazine-κ
2N:
N′)silver(I), [Ag
2(C
14H
10Cl
2NO
2)
2(C
6H
8N
2)]
n, (I), has been synthesized and characterized by single-crystal X-ray diffraction, revealing that the Ag
I ions are chelated by the carboxylate groups of the anionic 2-[2-(2,6-dichloroanilino)phenyl]acetate (dicl) ligand in a μ
3-η
1:η
2 coordination mode. Each dicl ligand links three Ag
I atoms to generate a one-dimensional infinite chain. Adjacent chains are connected through 2,5-dimethylpyrazine (dmpyz) ligands to form a two-dimensional layer structure parallel to the crystallographic
bc plane. The layers are further connected by C—H
π interactions to generate a three-dimensional supramolecular structure. Additionally, the most striking feature is that the structure contains an intramolecular C—H
Ag anagostic interaction. Furthermore, the title complex has been tested for its
in vitro antibacterial activity and is determined to be highly effective on the studied microorganisms.
Supporting information
CCDC reference: 1500645
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: [Program(s) for molecular graphics?]; software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Bis{µ-2-[2-(2,6-dichloroanilino)phenyl]acetato-
κ3O,
O':
O}bis(µ-2,5-dimethylpyrazine-
κ2N:
N')silver(I)
top
Crystal data top
[Ag2(C14H10Cl2NO2)2(C6H8N2)] | F(000) = 1816 |
Mr = 914.14 | Dx = 1.825 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 36.3376 (18) Å | Cell parameters from 3828 reflections |
b = 9.6778 (3) Å | θ = 2.2–28.1° |
c = 9.4818 (5) Å | µ = 1.55 mm−1 |
β = 93.860 (4)° | T = 296 K |
V = 3326.9 (3) Å3 | Needle, colourless |
Z = 4 | 0.40 × 0.21 × 0.08 mm |
Data collection top
Stoe IPDS 2 diffractometer | 2948 reflections with I > 2σ(I) |
w–scan rotation method | Rint = 0.096 |
Absorption correction: integration | θmax = 27.6°, θmin = 2.2° |
Tmin = 0.683, Tmax = 0.896 | h = −47→47 |
15896 measured reflections | k = −12→12 |
3828 independent reflections | l = −12→12 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0399P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max = 0.046 |
3828 reflections | Δρmax = 1.04 e Å−3 |
218 parameters | Δρmin = −1.01 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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 | |
C1 | 0.34208 (9) | 0.5797 (3) | 0.0806 (3) | 0.0370 (6) | |
C2 | 0.31875 (11) | 0.4894 (3) | 0.0058 (4) | 0.0460 (8) | |
H2 | 0.3283 | 0.4187 | −0.0473 | 0.055* | |
C3 | 0.28122 (11) | 0.5050 (3) | 0.0105 (4) | 0.0504 (8) | |
H3 | 0.2652 | 0.4479 | −0.0436 | 0.060* | |
C4 | 0.26731 (9) | 0.6052 (3) | 0.0952 (4) | 0.0434 (7) | |
H4 | 0.2420 | 0.6138 | 0.1014 | 0.052* | |
C5 | 0.29137 (8) | 0.6935 (3) | 0.1715 (3) | 0.0340 (6) | |
C6 | 0.32961 (8) | 0.6891 (3) | 0.1610 (3) | 0.0321 (6) | |
C7 | 0.34965 (7) | 0.9234 (3) | 0.2401 (3) | 0.0302 (5) | |
C8 | 0.32558 (8) | 0.9944 (3) | 0.1463 (3) | 0.0346 (6) | |
H8 | 0.3122 | 0.9463 | 0.0752 | 0.042* | |
C9 | 0.32130 (9) | 1.1360 (3) | 0.1571 (4) | 0.0428 (7) | |
H9 | 0.3051 | 1.1826 | 0.0938 | 0.051* | |
C10 | 0.34122 (10) | 1.2077 (3) | 0.2622 (4) | 0.0470 (8) | |
H10 | 0.3380 | 1.3025 | 0.2716 | 0.056* | |
C11 | 0.36591 (9) | 1.1380 (3) | 0.3535 (4) | 0.0419 (7) | |
H11 | 0.3796 | 1.1874 | 0.4230 | 0.050* | |
C12 | 0.37092 (7) | 0.9962 (3) | 0.3444 (3) | 0.0315 (6) | |
C13 | 0.39949 (8) | 0.9258 (3) | 0.4423 (3) | 0.0368 (6) | |
H13A | 0.3905 | 0.8357 | 0.4688 | 0.044* | |
H13B | 0.4039 | 0.9803 | 0.5277 | 0.044* | |
C14 | 0.43534 (7) | 0.9092 (3) | 0.3701 (3) | 0.0313 (6) | |
C15 | 0.51952 (9) | 0.5612 (3) | 0.1048 (4) | 0.0439 (7) | |
H15 | 0.5338 | 0.6022 | 0.1784 | 0.053* | |
C16 | 0.47711 (9) | 0.5805 (3) | −0.0836 (4) | 0.0414 (7) | |
C17 | 0.45276 (11) | 0.6686 (4) | −0.1798 (4) | 0.0557 (9) | |
H17A | 0.4560 | 0.7639 | −0.1536 | 0.083* | |
H17B | 0.4275 | 0.6426 | −0.1721 | 0.083* | |
H17C | 0.4592 | 0.6561 | −0.2755 | 0.083* | |
Cl1 | 0.38949 (3) | 0.55424 (9) | 0.07567 (11) | 0.0564 (2) | |
Cl2 | 0.27174 (2) | 0.80471 (8) | 0.28764 (9) | 0.04399 (18) | |
N1 | 0.35427 (7) | 0.7785 (2) | 0.2321 (3) | 0.0360 (5) | |
H1 | 0.3738 | 0.7434 | 0.2744 | 0.043* | |
N2 | 0.49669 (8) | 0.6406 (3) | 0.0239 (3) | 0.0433 (6) | |
O1 | 0.43415 (6) | 0.8361 (2) | 0.2602 (2) | 0.0396 (5) | |
O2 | 0.46352 (6) | 0.9689 (2) | 0.4205 (3) | 0.0459 (5) | |
Ag1 | 0.47925 (2) | 0.86905 (2) | 0.11173 (3) | 0.04030 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0435 (17) | 0.0306 (13) | 0.0371 (16) | 0.0013 (12) | 0.0045 (13) | 0.0042 (12) |
C2 | 0.066 (2) | 0.0311 (14) | 0.0413 (17) | −0.0032 (14) | 0.0033 (16) | −0.0048 (13) |
C3 | 0.061 (2) | 0.0373 (16) | 0.051 (2) | −0.0138 (15) | −0.0074 (17) | −0.0048 (15) |
C4 | 0.0374 (16) | 0.0396 (16) | 0.0521 (19) | −0.0115 (13) | −0.0047 (14) | 0.0036 (14) |
C5 | 0.0339 (14) | 0.0319 (13) | 0.0357 (15) | −0.0039 (11) | −0.0016 (12) | 0.0027 (12) |
C6 | 0.0341 (15) | 0.0274 (12) | 0.0341 (15) | −0.0025 (11) | −0.0029 (11) | 0.0033 (11) |
C7 | 0.0246 (13) | 0.0320 (13) | 0.0339 (14) | −0.0018 (10) | 0.0012 (11) | −0.0004 (11) |
C8 | 0.0284 (14) | 0.0367 (14) | 0.0384 (16) | −0.0037 (11) | −0.0007 (12) | −0.0004 (12) |
C9 | 0.0388 (16) | 0.0408 (15) | 0.0490 (18) | 0.0035 (13) | 0.0052 (14) | 0.0074 (15) |
C10 | 0.053 (2) | 0.0318 (15) | 0.057 (2) | −0.0029 (14) | 0.0099 (17) | −0.0043 (14) |
C11 | 0.0392 (16) | 0.0397 (15) | 0.0474 (18) | −0.0110 (13) | 0.0073 (14) | −0.0123 (14) |
C12 | 0.0207 (12) | 0.0402 (14) | 0.0339 (14) | −0.0045 (10) | 0.0049 (10) | −0.0037 (12) |
C13 | 0.0243 (13) | 0.0544 (17) | 0.0317 (15) | −0.0055 (12) | 0.0018 (11) | −0.0077 (13) |
C14 | 0.0230 (12) | 0.0356 (13) | 0.0350 (15) | 0.0004 (10) | −0.0014 (11) | −0.0002 (11) |
C15 | 0.0423 (17) | 0.0436 (17) | 0.0457 (19) | −0.0020 (13) | 0.0028 (14) | −0.0127 (15) |
C16 | 0.0360 (16) | 0.0416 (15) | 0.0478 (18) | −0.0002 (12) | 0.0108 (14) | −0.0096 (14) |
C17 | 0.051 (2) | 0.0512 (19) | 0.064 (2) | 0.0076 (16) | −0.0025 (18) | −0.0053 (17) |
Cl1 | 0.0472 (5) | 0.0473 (4) | 0.0756 (6) | 0.0134 (4) | 0.0114 (4) | −0.0004 (4) |
Cl2 | 0.0365 (4) | 0.0443 (4) | 0.0521 (5) | −0.0013 (3) | 0.0099 (3) | −0.0032 (3) |
N1 | 0.0268 (12) | 0.0314 (11) | 0.0483 (15) | 0.0013 (9) | −0.0088 (10) | −0.0022 (11) |
N2 | 0.0439 (14) | 0.0373 (13) | 0.0490 (16) | −0.0004 (11) | 0.0053 (12) | −0.0106 (12) |
O1 | 0.0294 (10) | 0.0492 (12) | 0.0403 (12) | −0.0048 (9) | 0.0042 (9) | −0.0121 (9) |
O2 | 0.0221 (10) | 0.0551 (13) | 0.0599 (14) | −0.0025 (9) | −0.0012 (10) | −0.0218 (11) |
Ag1 | 0.03129 (12) | 0.04507 (14) | 0.04485 (15) | 0.00259 (10) | 0.00490 (9) | 0.00503 (11) |
Geometric parameters (Å, º) top
C1—C2 | 1.380 (5) | C12—C13 | 1.508 (4) |
C1—C6 | 1.398 (4) | C13—C14 | 1.520 (4) |
C1—Cl1 | 1.744 (3) | C14—O2 | 1.243 (3) |
C2—C3 | 1.376 (5) | C14—O1 | 1.258 (4) |
C3—C4 | 1.377 (5) | C15—N2 | 1.335 (5) |
C4—C5 | 1.390 (4) | C15—C16i | 1.392 (4) |
C5—C6 | 1.400 (4) | C16—N2 | 1.337 (4) |
C5—Cl2 | 1.728 (3) | C16—C15i | 1.392 (4) |
C6—N1 | 1.387 (4) | C16—C17 | 1.495 (5) |
C7—C8 | 1.387 (4) | N2—Ag1 | 2.460 (2) |
C7—C12 | 1.403 (4) | O1—Ag1 | 2.254 (2) |
C7—N1 | 1.415 (4) | O2—Ag1ii | 2.332 (2) |
C8—C9 | 1.384 (4) | O2—Ag1iii | 2.436 (2) |
C9—C10 | 1.379 (5) | Ag1—O2ii | 2.332 (2) |
C10—C11 | 1.380 (5) | Ag1—O2iv | 2.436 (2) |
C11—C12 | 1.387 (4) | Ag1—Ag1ii | 2.9356 (5) |
| | | |
C2—C1—C6 | 123.3 (3) | O2—C14—C13 | 119.1 (2) |
C2—C1—Cl1 | 118.1 (2) | O1—C14—C13 | 116.7 (2) |
C6—C1—Cl1 | 118.6 (2) | N2—C15—C16i | 122.8 (3) |
C3—C2—C1 | 119.3 (3) | N2—C16—C15i | 119.4 (3) |
C2—C3—C4 | 120.0 (3) | N2—C16—C17 | 118.6 (3) |
C3—C4—C5 | 119.6 (3) | C15i—C16—C17 | 121.9 (3) |
C4—C5—C6 | 122.5 (3) | C6—N1—C7 | 124.7 (2) |
C4—C5—Cl2 | 116.3 (2) | C15—N2—C16 | 117.7 (3) |
C6—C5—Cl2 | 121.2 (2) | C15—N2—Ag1 | 119.2 (2) |
N1—C6—C1 | 121.0 (3) | C16—N2—Ag1 | 120.9 (2) |
N1—C6—C5 | 124.0 (3) | C14—O1—Ag1 | 116.88 (17) |
C1—C6—C5 | 114.9 (3) | C14—O2—Ag1ii | 118.44 (18) |
C8—C7—C12 | 119.8 (3) | C14—O2—Ag1iii | 136.99 (19) |
C8—C7—N1 | 121.9 (3) | Ag1ii—O2—Ag1iii | 101.40 (8) |
C12—C7—N1 | 118.3 (2) | O1—Ag1—O2ii | 146.39 (8) |
C9—C8—C7 | 120.8 (3) | O1—Ag1—O2iv | 114.32 (8) |
C10—C9—C8 | 119.7 (3) | O2ii—Ag1—O2iv | 78.60 (8) |
C9—C10—C11 | 119.7 (3) | O1—Ag1—N2 | 107.40 (8) |
C10—C11—C12 | 121.8 (3) | O2ii—Ag1—N2 | 94.33 (9) |
C11—C12—C7 | 118.2 (3) | O2iv—Ag1—N2 | 112.30 (9) |
C11—C12—C13 | 119.8 (3) | O1—Ag1—Ag1ii | 78.08 (6) |
C7—C12—C13 | 122.1 (3) | O2ii—Ag1—Ag1ii | 73.02 (6) |
C12—C13—C14 | 110.2 (2) | O2iv—Ag1—Ag1ii | 138.20 (6) |
O2—C14—O1 | 124.1 (3) | N2—Ag1—Ag1ii | 100.00 (7) |
| | | |
C6—C1—C2—C3 | −0.8 (5) | C8—C7—C12—C13 | −175.5 (3) |
Cl1—C1—C2—C3 | 178.5 (3) | N1—C7—C12—C13 | 3.0 (4) |
C1—C2—C3—C4 | −3.5 (5) | C11—C12—C13—C14 | −95.7 (3) |
C2—C3—C4—C5 | 2.4 (5) | C7—C12—C13—C14 | 82.4 (3) |
C3—C4—C5—C6 | 3.0 (5) | C12—C13—C14—O2 | 117.1 (3) |
C3—C4—C5—Cl2 | −174.0 (2) | C12—C13—C14—O1 | −61.9 (3) |
C2—C1—C6—N1 | −178.7 (3) | C1—C6—N1—C7 | 138.9 (3) |
Cl1—C1—C6—N1 | 2.0 (4) | C5—C6—N1—C7 | −46.1 (4) |
C2—C1—C6—C5 | 5.8 (4) | C8—C7—N1—C6 | −18.4 (4) |
Cl1—C1—C6—C5 | −173.5 (2) | C12—C7—N1—C6 | 163.2 (3) |
C4—C5—C6—N1 | 177.8 (3) | C16i—C15—N2—C16 | −1.7 (5) |
Cl2—C5—C6—N1 | −5.3 (4) | C16i—C15—N2—Ag1 | 161.7 (2) |
C4—C5—C6—C1 | −6.8 (4) | C15i—C16—N2—C15 | 1.6 (5) |
Cl2—C5—C6—C1 | 170.0 (2) | C17—C16—N2—C15 | −177.0 (3) |
C12—C7—C8—C9 | −2.2 (4) | C15i—C16—N2—Ag1 | −161.4 (2) |
N1—C7—C8—C9 | 179.4 (3) | C17—C16—N2—Ag1 | 19.9 (4) |
C7—C8—C9—C10 | 0.1 (5) | O2—C14—O1—Ag1 | −19.9 (4) |
C8—C9—C10—C11 | 1.6 (5) | C13—C14—O1—Ag1 | 159.1 (2) |
C9—C10—C11—C12 | −1.2 (5) | O1—C14—O2—Ag1ii | −30.4 (4) |
C10—C11—C12—C7 | −0.9 (4) | C13—C14—O2—Ag1ii | 150.7 (2) |
C10—C11—C12—C13 | 177.2 (3) | O1—C14—O2—Ag1iii | 174.1 (2) |
C8—C7—C12—C11 | 2.6 (4) | C13—C14—O2—Ag1iii | −4.8 (5) |
N1—C7—C12—C11 | −179.0 (3) | | |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y, −z+1/2; (iii) x, −y+2, z+1/2; (iv) x, −y+2, z−1/2. |
Hydrogen-bond geometry (Å, º) topCg is the centre of the aromatic ring, Cg3 is the centre of the
dmpyz ring and Cg5 is the centre of the C7–C12 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1ii | 0.93 | 2.59 | 3.356 (4) | 140 |
N1—H1···O1 | 0.86 | 2.38 | 2.950 (3) | 124 |
C17—H17A···Ag1 | 0.96 | 2.79 | 3.460 | 127 |
C17—H17C···Cg3v | 0.96 | 3.07 | 3.9408 | 151 |
C13—H13B···Cg5vi | 0.97 | 3.12 | 3.6237 | 114 |
C8—H8···Cg5vii | 0.93 | 3.39 | 3.9145 | 118 |
Symmetry codes: (ii) −x+1, y, −z+1/2; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, y+3/2, −z−1/2; (vii) −x+1/2, y+3/2, −z+1/2. |
Selected IR spectral dataa for the dicl ligand and (I) topAssignment | Nadicl | (I) |
ν (NH) | 3250 (m) | 3273 (m) |
νar(CH) | 3060 (vw) | 3090–3022 (vw) |
νal(CH) | 2980 (vw) | 2963–2910 (vw) |
νas(COO) | 1572 (vs) | 1579 (vs) |
νs(COO) | 1399 (w) | 1451 (vs), 1380 (vs) |
ν(CCl) | 768 (s) | 746 (vs) |
Frequencies are in cm-1; w = weak, m = medium, s =
strong, vs = very strong and vw = ???. |
Antimicrobial activities of (I) as MIC values (µg ml-1) topMicroorganism | Nadicl | (I) | Vancomycin | Ciprofloxacin | Amphotericine-B |
Gram (+) bacteria | | | | | |
MRSA | >1024 | 32 | 8 | 1 | - |
S. aureus | 256 | 16 | 2 | 0,125 | - |
E. feacalis | 256 | 16 | 2 | 0,25 | - |
B. cereus | 256 | 16 | 2 | 2 | - |
L. monocytogenes | 256 | 32 | 1 | 0,5 | - |
| | | | | |
Gram (-) bacteria | | | | | |
E. coli | >1024 | 32 | - | 0,0625 | - |
S. typhi | >1024 | 32 | - | 0,0625 | - |
| | | | | |
Yeast | | | | | |
C. albicans | 1024 | 1 | - | - | 0,025 |