metal-organic compounds
Poly[[μ-ethane-1,2-diyl bis(pyridine-3-carboxylate)](μ-tetrafluoridoborato)silver(I)]
aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, bDepartamento de Física, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, and cInstitut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
*Correspondence e-mail: ivanbritob@yahoo.com
In the title compound, [Ag(BF4)(C14H12N2O4)]n, the coordination of the Ag+ ion is trigonal–bipyramidal with the N atoms of two ethane-1,2-diyl bis(pyridine-3-carboxylate) ligands in the apical positions and three F atoms belonging to different tetrafluoridoborate anions in the equatorial plane. The material consists of infinite chains of [Ag(C14H12N2O4)] units running along [001], held together by BF4− bridging anions.
Related literature
For the et al. (2010). For background to coordination chemistry, see: Blake et al. (1999); Brito et al. (2011).
of the ethane-1,2-diyl bis(pyridine-3-carboxylate) ligand, see: BritoExperimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812018399/ff2064sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812018399/ff2064Isup2.hkl
A solution of AgBF4 (19.4 mg, 0.1 mmol) in water was slowly added to a solution of the ligand (27.2 mg, 0.1 mmol) in THF (4 ml). Colorless single crystals suitable for X-ray were obtained after a few days (82%).The FT—IR (KBr, cm-1): 1724 s, 1609, 1434 m, 1280 s, 742 m.
All H-atoms were positioned geometrically with C—H in the range of 0.95 or 0.99 Å and refined using a riding model with Uiso(H)= 1.2 Ueq(C).
Data collection: X-AREA (Stoe & Cie, 2001); cell
X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Ag(BF4)(C14H12N2O4)] | F(000) = 1840 |
Mr = 466.94 | Dx = 1.960 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9495 reflections |
a = 15.2667 (11) Å | θ = 2.7–25.9° |
b = 6.7170 (4) Å | µ = 1.34 mm−1 |
c = 30.8598 (16) Å | T = 173 K |
V = 3164.6 (3) Å3 | Needle, colourless |
Z = 8 | 0.16 × 0.04 × 0.04 mm |
Stoe IPDS-II two-circle diffractometer | 2772 independent reflections |
Radiation source: fine-focus sealed tube | 1605 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.115 |
ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −18→18 |
Tmin = 0.814, Tmax = 0.948 | k = −7→7 |
27909 measured reflections | l = −36→36 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0668P)2] where P = (Fo2 + 2Fc2)/3 |
2772 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 1.75 e Å−3 |
0 restraints | Δρmin = −1.14 e Å−3 |
[Ag(BF4)(C14H12N2O4)] | V = 3164.6 (3) Å3 |
Mr = 466.94 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 15.2667 (11) Å | µ = 1.34 mm−1 |
b = 6.7170 (4) Å | T = 173 K |
c = 30.8598 (16) Å | 0.16 × 0.04 × 0.04 mm |
Stoe IPDS-II two-circle diffractometer | 2772 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1605 reflections with I > 2σ(I) |
Tmin = 0.814, Tmax = 0.948 | Rint = 0.115 |
27909 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 0.93 | Δρmax = 1.75 e Å−3 |
2772 reflections | Δρmin = −1.14 e Å−3 |
235 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.32630 (5) | 0.68683 (11) | 0.122155 (18) | 0.0436 (2) | |
O1 | 0.1384 (4) | 0.6081 (9) | 0.27974 (18) | 0.0388 (14) | |
O2 | 0.2325 (3) | 0.4748 (8) | 0.32836 (16) | 0.0318 (13) | |
O3 | 0.1274 (4) | 0.7200 (9) | 0.46953 (18) | 0.0426 (15) | |
O4 | 0.2171 (3) | 0.6095 (9) | 0.41696 (16) | 0.0350 (13) | |
C1 | 0.2118 (6) | 0.5608 (13) | 0.2904 (2) | 0.0318 (19) | |
C2 | 0.1594 (5) | 0.4311 (13) | 0.3564 (2) | 0.0347 (19) | |
H2A | 0.1715 | 0.3060 | 0.3723 | 0.042* | |
H2B | 0.1065 | 0.4096 | 0.3385 | 0.042* | |
C3 | 0.1415 (5) | 0.5929 (15) | 0.3883 (2) | 0.038 (2) | |
H3A | 0.1317 | 0.7205 | 0.3730 | 0.046* | |
H3B | 0.0884 | 0.5611 | 0.4054 | 0.046* | |
C4 | 0.1992 (5) | 0.6804 (12) | 0.4566 (2) | 0.0305 (17) | |
N11 | 0.3421 (4) | 0.6597 (11) | 0.1910 (2) | 0.0385 (17) | |
C12 | 0.2759 (6) | 0.6318 (12) | 0.2184 (2) | 0.035 (2) | |
H12 | 0.2174 | 0.6408 | 0.2080 | 0.041* | |
C13 | 0.2907 (5) | 0.5899 (12) | 0.2618 (2) | 0.0287 (17) | |
C14 | 0.3766 (5) | 0.5786 (12) | 0.2780 (3) | 0.0310 (18) | |
H14 | 0.3881 | 0.5471 | 0.3074 | 0.037* | |
C15 | 0.4436 (5) | 0.6155 (12) | 0.2490 (3) | 0.036 (2) | |
H15 | 0.5027 | 0.6141 | 0.2586 | 0.044* | |
C16 | 0.4251 (6) | 0.6540 (14) | 0.2065 (3) | 0.042 (2) | |
H16 | 0.4723 | 0.6777 | 0.1871 | 0.050* | |
C21 | 0.2811 (5) | 0.7043 (13) | 0.4833 (2) | 0.0295 (17) | |
C22 | 0.2702 (6) | 0.7513 (12) | 0.5268 (2) | 0.032 (2) | |
H22 | 0.2126 | 0.7616 | 0.5382 | 0.039* | |
N23 | 0.3379 (5) | 0.7822 (10) | 0.5529 (2) | 0.0384 (17) | |
C24 | 0.4197 (6) | 0.7680 (13) | 0.5363 (3) | 0.041 (2) | |
H24 | 0.4682 | 0.7907 | 0.5549 | 0.049* | |
C25 | 0.4354 (6) | 0.7217 (14) | 0.4934 (3) | 0.040 (2) | |
H25 | 0.4936 | 0.7149 | 0.4827 | 0.048* | |
C26 | 0.3651 (5) | 0.6855 (13) | 0.4662 (2) | 0.0332 (17) | |
H26 | 0.3739 | 0.6490 | 0.4367 | 0.040* | |
B1 | 0.0651 (6) | 0.6709 (18) | 0.1252 (3) | 0.040 (2) | |
F1 | 0.0369 (5) | 0.8388 (12) | 0.1072 (3) | 0.107 (3) | |
F2 | 0.1447 (5) | 0.6209 (11) | 0.1101 (3) | 0.098 (3) | |
F3 | 0.0720 (6) | 0.7014 (14) | 0.1693 (2) | 0.110 (3) | |
F4 | 0.0034 (5) | 0.5200 (11) | 0.1204 (3) | 0.097 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0429 (4) | 0.0680 (5) | 0.0198 (3) | −0.0014 (4) | −0.0011 (3) | 0.0042 (3) |
O1 | 0.021 (3) | 0.065 (4) | 0.030 (3) | −0.002 (3) | −0.003 (2) | 0.007 (3) |
O2 | 0.030 (3) | 0.046 (4) | 0.019 (3) | −0.002 (2) | 0.003 (2) | 0.003 (2) |
O3 | 0.026 (3) | 0.068 (4) | 0.033 (3) | 0.005 (3) | 0.003 (3) | −0.012 (3) |
O4 | 0.029 (3) | 0.059 (4) | 0.018 (3) | −0.002 (2) | −0.002 (2) | −0.002 (2) |
C1 | 0.035 (5) | 0.040 (5) | 0.020 (4) | −0.003 (4) | −0.003 (3) | −0.001 (4) |
C2 | 0.032 (5) | 0.054 (5) | 0.017 (4) | −0.009 (4) | 0.006 (3) | −0.001 (4) |
C3 | 0.024 (4) | 0.067 (6) | 0.024 (4) | −0.003 (4) | −0.004 (3) | −0.010 (4) |
C4 | 0.040 (5) | 0.033 (4) | 0.018 (3) | −0.004 (4) | 0.000 (3) | −0.006 (4) |
N11 | 0.036 (4) | 0.053 (5) | 0.026 (3) | −0.002 (4) | 0.004 (3) | 0.000 (3) |
C12 | 0.030 (4) | 0.050 (6) | 0.024 (4) | 0.004 (4) | −0.002 (3) | −0.003 (4) |
C13 | 0.025 (4) | 0.040 (5) | 0.021 (4) | −0.002 (3) | 0.003 (3) | −0.004 (3) |
C14 | 0.032 (5) | 0.039 (5) | 0.022 (4) | −0.001 (4) | −0.002 (3) | 0.001 (4) |
C15 | 0.030 (5) | 0.054 (5) | 0.025 (4) | −0.001 (3) | −0.002 (4) | −0.002 (4) |
C16 | 0.029 (4) | 0.069 (7) | 0.027 (4) | −0.001 (4) | 0.006 (3) | −0.002 (4) |
C21 | 0.025 (4) | 0.044 (5) | 0.019 (3) | 0.002 (4) | 0.001 (3) | 0.000 (4) |
C22 | 0.031 (5) | 0.047 (6) | 0.018 (4) | −0.001 (3) | 0.001 (3) | 0.002 (3) |
N23 | 0.034 (4) | 0.051 (4) | 0.030 (3) | 0.001 (3) | 0.000 (3) | 0.002 (3) |
C24 | 0.030 (5) | 0.065 (7) | 0.029 (4) | −0.003 (4) | −0.005 (4) | −0.001 (4) |
C25 | 0.028 (5) | 0.063 (7) | 0.030 (5) | 0.004 (4) | −0.004 (4) | −0.006 (4) |
C26 | 0.040 (4) | 0.042 (5) | 0.017 (4) | 0.001 (4) | 0.001 (3) | −0.002 (4) |
B1 | 0.028 (4) | 0.058 (6) | 0.034 (5) | 0.011 (5) | 0.006 (4) | −0.003 (5) |
F1 | 0.071 (5) | 0.122 (7) | 0.127 (7) | 0.029 (5) | 0.007 (5) | 0.055 (5) |
F2 | 0.057 (4) | 0.103 (6) | 0.136 (7) | 0.016 (4) | 0.042 (4) | 0.000 (4) |
F3 | 0.118 (6) | 0.166 (7) | 0.044 (4) | −0.038 (6) | 0.003 (4) | −0.018 (5) |
F4 | 0.079 (5) | 0.118 (6) | 0.095 (5) | −0.046 (4) | 0.005 (4) | −0.025 (5) |
Ag1—N11 | 2.145 (6) | C13—C14 | 1.405 (11) |
Ag1—N23i | 2.155 (6) | C14—C15 | 1.382 (11) |
Ag1—F1ii | 3.168 (9) | C14—H14 | 0.9500 |
Ag1—F2 | 2.832 (8) | C15—C16 | 1.365 (11) |
Ag1—F2iii | 2.972 (7) | C15—H15 | 0.9500 |
O1—C1 | 1.210 (9) | C16—H16 | 0.9500 |
O2—C1 | 1.345 (9) | C21—C22 | 1.389 (10) |
O2—C2 | 1.443 (9) | C21—C26 | 1.394 (11) |
O3—C4 | 1.196 (9) | C22—N23 | 1.327 (10) |
O4—C4 | 1.341 (9) | C22—H22 | 0.9500 |
O4—C3 | 1.458 (9) | N23—C24 | 1.352 (11) |
C1—C13 | 1.504 (11) | N23—Ag1iv | 2.155 (6) |
C2—C3 | 1.492 (12) | C24—C25 | 1.382 (12) |
C2—H2A | 0.9900 | C24—H24 | 0.9500 |
C2—H2B | 0.9900 | C25—C26 | 1.383 (12) |
C3—H3A | 0.9900 | C25—H25 | 0.9500 |
C3—H3B | 0.9900 | C26—H26 | 0.9500 |
C4—C21 | 1.506 (10) | B1—F1 | 1.329 (13) |
N11—C12 | 1.332 (10) | B1—F2 | 1.344 (11) |
N11—C16 | 1.356 (11) | B1—F3 | 1.379 (12) |
C12—C13 | 1.389 (11) | B1—F4 | 1.391 (13) |
C12—H12 | 0.9500 | ||
N11—Ag1—N23i | 168.8 (3) | C13—C14—H14 | 121.5 |
C1—O2—C2 | 115.4 (6) | C16—C15—C14 | 120.1 (8) |
C4—O4—C3 | 114.7 (6) | C16—C15—H15 | 119.9 |
O1—C1—O2 | 124.5 (7) | C14—C15—H15 | 119.9 |
O1—C1—C13 | 123.3 (7) | N11—C16—C15 | 122.6 (8) |
O2—C1—C13 | 112.2 (7) | N11—C16—H16 | 118.7 |
O2—C2—C3 | 112.9 (7) | C15—C16—H16 | 118.7 |
O2—C2—H2A | 109.0 | C22—C21—C26 | 119.8 (7) |
C3—C2—H2A | 109.0 | C22—C21—C4 | 117.0 (7) |
O2—C2—H2B | 109.0 | C26—C21—C4 | 123.2 (6) |
C3—C2—H2B | 109.0 | N23—C22—C21 | 121.9 (8) |
H2A—C2—H2B | 107.8 | N23—C22—H22 | 119.0 |
O4—C3—C2 | 108.1 (7) | C21—C22—H22 | 119.0 |
O4—C3—H3A | 110.1 | C22—N23—C24 | 118.6 (7) |
C2—C3—H3A | 110.1 | C22—N23—Ag1iv | 123.5 (6) |
O4—C3—H3B | 110.1 | C24—N23—Ag1iv | 117.3 (5) |
C2—C3—H3B | 110.1 | N23—C24—C25 | 122.7 (8) |
H3A—C3—H3B | 108.4 | N23—C24—H24 | 118.7 |
O3—C4—O4 | 124.8 (7) | C25—C24—H24 | 118.7 |
O3—C4—C21 | 123.7 (7) | C24—C25—C26 | 119.1 (8) |
O4—C4—C21 | 111.6 (6) | C24—C25—H25 | 120.4 |
C12—N11—C16 | 118.7 (7) | C26—C25—H25 | 120.4 |
C12—N11—Ag1 | 123.7 (5) | C25—C26—C21 | 117.9 (7) |
C16—N11—Ag1 | 117.3 (5) | C25—C26—H26 | 121.1 |
N11—C12—C13 | 121.2 (8) | C21—C26—H26 | 121.1 |
N11—C12—H12 | 119.4 | F1—B1—F2 | 111.1 (9) |
C13—C12—H12 | 119.4 | F1—B1—F3 | 108.1 (10) |
C12—C13—C14 | 120.3 (7) | F2—B1—F3 | 108.0 (9) |
C12—C13—C1 | 117.5 (7) | F1—B1—F4 | 110.8 (9) |
C14—C13—C1 | 122.2 (7) | F2—B1—F4 | 113.1 (9) |
C15—C14—C13 | 116.9 (7) | F3—B1—F4 | 105.3 (8) |
C15—C14—H14 | 121.5 | ||
C2—O2—C1—O1 | 2.8 (11) | C13—C14—C15—C16 | −2.1 (13) |
C2—O2—C1—C13 | −176.4 (6) | C12—N11—C16—C15 | 1.8 (14) |
C1—O2—C2—C3 | −93.6 (8) | Ag1—N11—C16—C15 | −172.7 (7) |
C4—O4—C3—C2 | −152.9 (7) | C14—C15—C16—N11 | 0.6 (14) |
O2—C2—C3—O4 | −63.9 (9) | O3—C4—C21—C22 | 8.2 (13) |
C3—O4—C4—O3 | 3.4 (12) | O4—C4—C21—C22 | −171.7 (7) |
C3—O4—C4—C21 | −176.7 (7) | O3—C4—C21—C26 | −170.4 (9) |
N23i—Ag1—N11—C12 | −177.4 (12) | O4—C4—C21—C26 | 9.7 (12) |
N23i—Ag1—N11—C16 | −3.2 (18) | C26—C21—C22—N23 | 1.0 (13) |
C16—N11—C12—C13 | −2.5 (12) | C4—C21—C22—N23 | −177.7 (8) |
Ag1—N11—C12—C13 | 171.6 (6) | C21—C22—N23—C24 | 0.2 (12) |
N11—C12—C13—C14 | 0.9 (13) | C21—C22—N23—Ag1iv | −170.8 (6) |
N11—C12—C13—C1 | 179.9 (8) | C22—N23—C24—C25 | −0.3 (13) |
O1—C1—C13—C12 | −14.4 (12) | Ag1iv—N23—C24—C25 | 171.3 (7) |
O2—C1—C13—C12 | 164.9 (7) | N23—C24—C25—C26 | −1.0 (14) |
O1—C1—C13—C14 | 164.7 (8) | C24—C25—C26—C21 | 2.1 (14) |
O2—C1—C13—C14 | −16.1 (11) | C22—C21—C26—C25 | −2.2 (13) |
C12—C13—C14—C15 | 1.4 (12) | C4—C21—C26—C25 | 176.4 (8) |
C1—C13—C14—C15 | −177.6 (8) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1/2, y−1/2, z; (iii) −x+1/2, y+1/2, z; (iv) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag(BF4)(C14H12N2O4)] |
Mr | 466.94 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 15.2667 (11), 6.7170 (4), 30.8598 (16) |
V (Å3) | 3164.6 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.16 × 0.04 × 0.04 |
Data collection | |
Diffractometer | Stoe IPDS-II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.814, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27909, 2772, 1605 |
Rint | 0.115 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.144, 0.93 |
No. of reflections | 2772 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.75, −1.14 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).
Ag1—N11 | 2.145 (6) | Ag1—F2 | 2.832 (8) |
Ag1—N23i | 2.155 (6) | Ag1—F2iii | 2.972 (7) |
Ag1—F1ii | 3.168 (9) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1/2, y−1/2, z; (iii) −x+1/2, y+1/2, z. |
Acknowledgements
Thanks are given to the Consejo Superior de Investigaciones Científicas (CSIC) of Spain for the award of a licence for the use of the Cambridge Structural Database (CSD). JV thanks the Universidad de Antofagasta for a PhD fellowship.
References
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The design of polymeric organic-inorganic materials with novel topologies and structural motifs is of current interest in the field of coordination chemistry (Blake et al., 1999). This paper forms part of our continuing study of the synthesis, structural characterization and physical properties of coordination polymers (Brito et al., 2011). We report here the crystal structure of the title compound (Fig.1). It crystallizes as colorless needles, which were found to be stable to air and light. In the title compound, the coordination of the AgI atom is a trigonal bipyramid with the N atoms of two 1,2-diyl-bis(pyridine-3-carboxylate)ethane ligands in the apical positions and three F atoms belonging to different tetrafluoroborate anions in the equatorial plane. The Ag–N distances are 2.145 (6) and 2.155 (6) Å and the Ag–F distances are 2.832 (8) Å, 2.972 (7) Å and 3.168 (9) Å. The N–Ag–N angle [168.8 (3)°] is not far from being linear and the Ag—N vectors are almost perpendicular to the Ag—F vectors [76.7 (3)° to 103.1 (3)°]. The F–Ag–F angles are 106.4 (2)°, 120.7 (2)° and 127.4 (2)°. The molecular dimensions of the 1,2-bis(3-pyridyl)ethane ligand are within normal ranges and the ethylene moiety retains the gauche conformation (Brito et al., 2010). The material consists of infinite chains of [Ag(C14H12N2O4)] moieties running along [001] held together by BF4- bridging anions (Fig. 2).