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Bis[
-1-(3-pyridyl)ethanone oxime-
2N:
N']bis[nitratosilver(I)], [Ag
2(NO
3)
2(C
7H
8N
2O)
2], crystallizes as a centrosymmetric binuclear macrocylic complex containing silver(I) ions bridged by the organic 1-(3-pyridyl)ethanone oxime ligand. The ligand coordinates
via the pyridine and the oxime N atoms. A similar metal-ligand arrangement was found in the copper(I) complex
catena-poly[[bis[
-1-(3-pyridyl)ethanone oxime-
2N:
N']dicopper(I)]-di-
-iodo], [Cu
2I
2(C
7H
8N
2O)
2]
n, but here the centrosymmetric macrocycles are connected by double anion bridges, resulting in the formation of a one-dimensional coordination polymer.
Supporting information
CCDC references: 231033; 231034
Compound (I) was synthesized by adding a solution of 1-pyridin-3-yl-ethanone oxime (10 mg, 0.073 mmol) in ethanol (10 ml) to an aqueous solution of silver(I) nitrate (12.5 mg, 0.073 mmol, 10 ml). Colourless transparent crystals were obtained by slow evaporation of the solvent at room temperature. Compound (II) was synthesized by adding 1-pyridin-3-yl-ethanone oxime (25 mg, 0.184 mmol) to a solution of copper(I) iodide (35 mg, 0.184 mmol) in acetonitrile (20 ml). After some days, brown crystals were obtained by slow evaporation of the solvent at room temperature.
H atoms attached to C atoms were all located from Fourier difference maps but were included in calulated positions and treated as riding atoms, with C—H distances of 0.95–0.98 Å and Uiso(H) values equal to 1.2Ueq(C aromatic) and 1.5Ueq(C methyl). In (I), the hydroxy H atom was included in a calculated position (AFIX 147), with an O—H distance of 0.84 Å and Uiso(H) equal to 1.5Ueq(O1). In (II), the hydroxy H atom was initially located from a Fourier difference map but in the final cycles of refinement its position was fixed [O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O1)]. Using the image-plate distance of 70 mm, to obtain maximum resolution for the triclinic system, only 90 [for (I)] and 92% [for II] of the full date set (θ = 25.85°) could be measured.
For both compounds, data collection: EXPOSE (Stoe & Cie, 2000); cell refinement: CELL (Stoe & Cie, 2000). Data reduction: INTEGRATE (Stoe Cie, 2000) for (I); INTEGRATE (Stoe & Cie, 2000) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
(I) Bis[µ-1-(3-pyridyl)ethanone oxime-
κ2N:
N']bis[nitratosilver(I)]
top
Crystal data top
[Ag2(NO3)2(C7H8NO)2] | Z = 1 |
Mr = 612.07 | F(000) = 300 |
Triclinic, P1 | Dx = 2.170 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.076 (1) Å | Cell parameters from 5158 reflections |
b = 8.084 (1) Å | θ = 2.9–25.9° |
c = 8.808 (1) Å | µ = 2.15 mm−1 |
α = 105.34 (2)° | T = 153 K |
β = 114.53 (2)° | Block, colourless |
γ = 102.51 (2)° | 0.35 × 0.30 × 0.20 mm |
V = 468.28 (18) Å3 | |
Data collection top
STOE IPDS diffractometer | 1622 independent reflections |
Radiation source: fine-focus sealed tube | 1579 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 0.81Å pixels mm-1 | θmax = 25.9°, θmin = 2.9° |
ϕ scans | h = −9→9 |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | k = −9→9 |
Tmin = 0.478, Tmax = 0.701 | l = −10→10 |
3502 measured reflections | |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0322P)2 + 0.2699P] where P = (Fo2 + 2Fc2)/3 |
1622 reflections | (Δ/σ)max = 0.002 |
138 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
Crystal data top
[Ag2(NO3)2(C7H8NO)2] | γ = 102.51 (2)° |
Mr = 612.07 | V = 468.28 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.076 (1) Å | Mo Kα radiation |
b = 8.084 (1) Å | µ = 2.15 mm−1 |
c = 8.808 (1) Å | T = 153 K |
α = 105.34 (2)° | 0.35 × 0.30 × 0.20 mm |
β = 114.53 (2)° | |
Data collection top
STOE IPDS diffractometer | 1622 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | 1579 reflections with I > 2σ(I) |
Tmin = 0.478, Tmax = 0.701 | Rint = 0.024 |
3502 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.56 e Å−3 |
1622 reflections | Δρmin = −0.75 e Å−3 |
138 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 | 0.29933 (2) | 0.13147 (2) | 0.54899 (2) | 0.01892 (9) | |
N1 | 0.4889 (3) | −0.0710 (3) | 0.2360 (3) | 0.0161 (4) | |
N2 | 0.2693 (3) | 0.3163 (3) | 0.4011 (3) | 0.0152 (4) | |
O1 | 0.2374 (3) | 0.4756 (2) | 0.4723 (2) | 0.0203 (4) | |
H1O | 0.2108 | 0.4692 | 0.5537 | 0.030* | |
C1 | 0.3216 (3) | 0.1380 (3) | 0.1819 (3) | 0.0155 (4) | |
C2 | 0.4625 (3) | 0.0874 (3) | 0.2949 (3) | 0.0158 (4) | |
H2 | 0.5442 | 0.1684 | 0.4197 | 0.019* | |
C3 | 0.3757 (3) | −0.1819 (3) | 0.0582 (3) | 0.0180 (5) | |
H3 | 0.3897 | −0.2961 | 0.0158 | 0.022* | |
C4 | 0.2398 (3) | −0.1374 (3) | −0.0661 (3) | 0.0195 (5) | |
H4 | 0.1665 | −0.2170 | −0.1917 | 0.023* | |
C5 | 0.2126 (3) | 0.0253 (3) | −0.0042 (3) | 0.0179 (5) | |
H5 | 0.1213 | 0.0598 | −0.0869 | 0.021* | |
C6 | 0.2852 (3) | 0.3042 (3) | 0.2594 (3) | 0.0164 (5) | |
C7 | 0.2653 (4) | 0.4381 (4) | 0.1725 (4) | 0.0240 (5) | |
H7A | 0.3954 | 0.5158 | 0.2030 | 0.036* | |
H7B | 0.2040 | 0.5160 | 0.2170 | 0.036* | |
H7C | 0.1835 | 0.3711 | 0.0402 | 0.036* | |
N11 | −0.0043 (3) | −0.2621 (3) | 0.3523 (3) | 0.0196 (4) | |
O11 | 0.0556 (3) | −0.1633 (3) | 0.5138 (3) | 0.0406 (5) | |
O12 | −0.1571 (3) | −0.4049 (3) | 0.2698 (3) | 0.0304 (4) | |
O13 | 0.0863 (3) | −0.2166 (3) | 0.2770 (3) | 0.0297 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.02279 (13) | 0.01993 (13) | 0.01986 (13) | 0.01219 (9) | 0.01133 (9) | 0.01169 (9) |
N1 | 0.0165 (9) | 0.0157 (9) | 0.0174 (9) | 0.0058 (7) | 0.0092 (8) | 0.0074 (8) |
N2 | 0.0150 (9) | 0.0131 (9) | 0.0171 (9) | 0.0073 (7) | 0.0066 (7) | 0.0064 (8) |
O1 | 0.0284 (9) | 0.0159 (8) | 0.0232 (9) | 0.0124 (7) | 0.0160 (7) | 0.0088 (7) |
C1 | 0.0151 (10) | 0.0142 (10) | 0.0173 (11) | 0.0042 (8) | 0.0084 (9) | 0.0070 (9) |
C2 | 0.0151 (10) | 0.0164 (11) | 0.0147 (10) | 0.0041 (8) | 0.0075 (8) | 0.0061 (9) |
C3 | 0.0197 (11) | 0.0161 (10) | 0.0180 (11) | 0.0055 (9) | 0.0109 (9) | 0.0054 (10) |
C4 | 0.0196 (11) | 0.0199 (12) | 0.0151 (10) | 0.0036 (9) | 0.0084 (9) | 0.0048 (10) |
C5 | 0.0151 (10) | 0.0216 (11) | 0.0161 (11) | 0.0056 (9) | 0.0064 (9) | 0.0097 (10) |
C6 | 0.0133 (10) | 0.0148 (10) | 0.0163 (11) | 0.0039 (8) | 0.0041 (8) | 0.0059 (9) |
C7 | 0.0334 (14) | 0.0201 (12) | 0.0219 (12) | 0.0123 (11) | 0.0136 (11) | 0.0118 (11) |
N11 | 0.0182 (10) | 0.0204 (10) | 0.0199 (10) | 0.0091 (8) | 0.0089 (8) | 0.0074 (9) |
O11 | 0.0354 (11) | 0.0412 (12) | 0.0226 (10) | −0.0068 (9) | 0.0161 (9) | −0.0049 (9) |
O12 | 0.0277 (10) | 0.0267 (10) | 0.0230 (9) | −0.0022 (8) | 0.0106 (8) | 0.0037 (8) |
O13 | 0.0307 (10) | 0.0354 (10) | 0.0299 (10) | 0.0100 (8) | 0.0199 (8) | 0.0169 (9) |
Geometric parameters (Å, º) top
Ag1—N2 | 2.217 (2) | C3—C4 | 1.383 (4) |
Ag1—N1i | 2.217 (2) | C3—H3 | 0.9500 |
Ag1—O11 | 2.593 (2) | C4—C5 | 1.387 (3) |
N1—C3 | 1.344 (3) | C4—H4 | 0.9500 |
N1—C2 | 1.346 (3) | C5—H5 | 0.9500 |
N1—Ag1i | 2.217 (2) | C6—C7 | 1.481 (4) |
N2—C6 | 1.288 (3) | C7—H7A | 0.9800 |
N2—O1 | 1.403 (2) | C7—H7B | 0.9800 |
O1—H1O | 0.8400 | C7—H7C | 0.9800 |
C1—C2 | 1.389 (3) | N11—O13 | 1.235 (3) |
C1—C5 | 1.399 (3) | N11—O11 | 1.247 (3) |
C1—C6 | 1.487 (3) | N11—O12 | 1.256 (3) |
C2—H2 | 0.9500 | | |
| | | |
N2—Ag1—N1i | 144.35 (7) | C3—C4—C5 | 118.8 (2) |
N2—Ag1—O11 | 133.60 (8) | C3—C4—H4 | 120.6 |
N1i—Ag1—O11 | 81.93 (8) | C5—C4—H4 | 120.6 |
C3—N1—C2 | 117.7 (2) | C4—C5—C1 | 119.0 (2) |
C3—N1—Ag1i | 126.66 (16) | C4—C5—H5 | 120.5 |
C2—N1—Ag1i | 115.39 (15) | C1—C5—H5 | 120.5 |
C6—N2—O1 | 113.1 (2) | N2—C6—C7 | 124.9 (2) |
C6—N2—Ag1 | 129.26 (16) | N2—C6—C1 | 114.4 (2) |
O1—N2—Ag1 | 117.57 (13) | C7—C6—C1 | 120.7 (2) |
N2—O1—H1O | 109.5 | C6—C7—H7A | 109.5 |
C2—C1—C5 | 118.0 (2) | C6—C7—H7B | 109.5 |
C2—C1—C6 | 120.4 (2) | H7A—C7—H7B | 109.5 |
C5—C1—C6 | 121.6 (2) | C6—C7—H7C | 109.5 |
N1—C2—C1 | 123.1 (2) | H7A—C7—H7C | 109.5 |
N1—C2—H2 | 118.4 | H7B—C7—H7C | 109.5 |
C1—C2—H2 | 118.4 | O13—N11—O11 | 119.5 (2) |
N1—C3—C4 | 123.1 (2) | O13—N11—O12 | 121.7 (2) |
N1—C3—H3 | 118.5 | O11—N11—O12 | 118.8 (2) |
C4—C3—H3 | 118.5 | N11—O11—Ag1 | 99.22 (15) |
| | | |
N1i—Ag1—N2—C6 | 85.8 (2) | C6—C1—C5—C4 | −173.8 (2) |
O11—Ag1—N2—C6 | −88.5 (2) | O1—N2—C6—C7 | −2.1 (3) |
N1i—Ag1—N2—O1 | −90.85 (17) | Ag1—N2—C6—C7 | −178.94 (18) |
O11—Ag1—N2—O1 | 94.86 (16) | O1—N2—C6—C1 | 179.26 (18) |
C3—N1—C2—C1 | 1.7 (3) | Ag1—N2—C6—C1 | 2.5 (3) |
Ag1i—N1—C2—C1 | −173.39 (16) | C2—C1—C6—N2 | −46.5 (3) |
C5—C1—C2—N1 | −5.0 (3) | C5—C1—C6—N2 | 131.6 (2) |
C6—C1—C2—N1 | 173.1 (2) | C2—C1—C6—C7 | 134.9 (2) |
C2—N1—C3—C4 | 2.2 (3) | C5—C1—C6—C7 | −47.1 (3) |
Ag1i—N1—C3—C4 | 176.73 (16) | O13—N11—O11—Ag1 | 14.4 (3) |
N1—C3—C4—C5 | −2.7 (3) | O12—N11—O11—Ag1 | −164.94 (19) |
C3—C4—C5—C1 | −0.7 (3) | N2—Ag1—O11—N11 | 56.86 (19) |
C2—C1—C5—C4 | 4.3 (3) | N1i—Ag1—O11—N11 | −119.79 (17) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O12ii | 0.84 | 1.94 | 2.767 (3) | 168 |
O1—H1O···O11ii | 0.84 | 2.64 | 3.130 (3) | 119 |
O1—H1O···N11ii | 0.84 | 2.63 | 3.365 (3) | 146 |
Symmetry code: (ii) −x, −y, −z+1. |
(II)
catena-poly[[bis[µ-1-(3-pyridyl)ethanone oxime-
κ2N:
N']dicopper(I)]-di-µ-iodo]
top
Crystal data top
[Cu2I2(C7H8NO)2] | Z = 2 |
Mr = 326.60 | F(000) = 308 |
Triclinic, P1 | Dx = 2.425 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.512 (1) Å | Cell parameters from 8000 reflections |
b = 8.015 (1) Å | θ = 2.2–25.1° |
c = 8.886 (1) Å | µ = 5.84 mm−1 |
α = 111.88 (2)° | T = 153 K |
β = 101.38 (2)° | Plate, pale yellow |
γ = 106.57 (2)° | 0.40 × 0.40 × 0.25 mm |
V = 447.28 (17) Å3 | |
Data collection top
STOE IPDS diffractometer | 1588 independent reflections |
Radiation source: fine-focus sealed tube | 1522 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 0.81Å pixels mm-1 | θmax = 25.8°, θmin = 2.9° |
ϕ scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) refined from ΔF: DELABS in PLATON (Spek, 2003) | k = −9→9 |
Tmin = 0.225, Tmax = 0.689 | l = −10→10 |
3418 measured reflections | |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0291P)2 + 0.3665P] where P = (Fo2 + 2Fc2)/3 |
1588 reflections | (Δ/σ)max = 0.001 |
110 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
Crystal data top
[Cu2I2(C7H8NO)2] | γ = 106.57 (2)° |
Mr = 326.60 | V = 447.28 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.512 (1) Å | Mo Kα radiation |
b = 8.015 (1) Å | µ = 5.84 mm−1 |
c = 8.886 (1) Å | T = 153 K |
α = 111.88 (2)° | 0.40 × 0.40 × 0.25 mm |
β = 101.38 (2)° | |
Data collection top
STOE IPDS diffractometer | 1588 independent reflections |
Absorption correction: empirical (using intensity measurements) refined from ΔF: DELABS in PLATON (Spek, 2003) | 1522 reflections with I > 2σ(I) |
Tmin = 0.225, Tmax = 0.689 | Rint = 0.028 |
3418 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.67 e Å−3 |
1588 reflections | Δρmin = −0.65 e Å−3 |
110 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 | |
I1 | 0.66521 (3) | 0.45728 (2) | 0.71603 (2) | 0.01718 (9) | |
Cu1 | 0.68233 (6) | 0.56643 (5) | 0.46985 (4) | 0.01797 (11) | |
O1 | 1.2643 (4) | 0.0298 (3) | 0.4614 (3) | 0.0254 (5) | |
H1O | 1.3728 | 0.1203 | 0.5366 | 0.038* | |
N1 | 0.7466 (4) | 0.3641 (3) | 0.2925 (3) | 0.0168 (5) | |
N2 | 1.1649 (4) | 0.1353 (3) | 0.4103 (3) | 0.0167 (5) | |
C1 | 0.8788 (4) | 0.1151 (4) | 0.2265 (4) | 0.0146 (5) | |
C2 | 0.8458 (4) | 0.2684 (4) | 0.3421 (4) | 0.0154 (5) | |
H2 | 0.8965 | 0.3063 | 0.4618 | 0.018* | |
C3 | 0.6805 (4) | 0.3120 (4) | 0.1225 (4) | 0.0178 (6) | |
H3 | 0.6160 | 0.3835 | 0.0862 | 0.021* | |
C4 | 0.7020 (4) | 0.1592 (4) | −0.0019 (4) | 0.0188 (6) | |
H4 | 0.6518 | 0.1259 | −0.1206 | 0.023* | |
C5 | 0.7984 (4) | 0.0558 (4) | 0.0508 (4) | 0.0172 (6) | |
H5 | 0.8094 | −0.0538 | −0.0318 | 0.021* | |
C6 | 0.9983 (4) | 0.0200 (4) | 0.2906 (3) | 0.0152 (6) | |
C7 | 0.9181 (5) | −0.1990 (4) | 0.2110 (4) | 0.0201 (6) | |
H7A | 1.0239 | −0.2407 | 0.2434 | 0.030* | |
H7B | 0.8660 | −0.2536 | 0.0851 | 0.030* | |
H7C | 0.8119 | −0.2458 | 0.2523 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01757 (14) | 0.01965 (12) | 0.01496 (12) | 0.00823 (9) | 0.00416 (9) | 0.00856 (9) |
Cu1 | 0.0215 (2) | 0.01443 (18) | 0.01678 (19) | 0.00864 (16) | 0.00496 (17) | 0.00560 (15) |
O1 | 0.0250 (13) | 0.0188 (10) | 0.0292 (11) | 0.0105 (10) | 0.0015 (10) | 0.0102 (9) |
N1 | 0.0154 (13) | 0.0147 (11) | 0.0160 (11) | 0.0041 (10) | 0.0043 (11) | 0.0048 (9) |
N2 | 0.0210 (15) | 0.0159 (11) | 0.0157 (11) | 0.0101 (11) | 0.0063 (12) | 0.0077 (10) |
C1 | 0.0127 (14) | 0.0123 (12) | 0.0160 (13) | 0.0018 (11) | 0.0061 (12) | 0.0053 (11) |
C2 | 0.0143 (15) | 0.0126 (12) | 0.0139 (12) | 0.0023 (12) | 0.0026 (12) | 0.0040 (11) |
C3 | 0.0172 (16) | 0.0197 (13) | 0.0184 (14) | 0.0068 (12) | 0.0053 (13) | 0.0113 (12) |
C4 | 0.0167 (16) | 0.0228 (14) | 0.0151 (13) | 0.0048 (13) | 0.0049 (13) | 0.0094 (12) |
C5 | 0.0164 (16) | 0.0148 (13) | 0.0161 (13) | 0.0039 (12) | 0.0070 (13) | 0.0037 (11) |
C6 | 0.0194 (17) | 0.0148 (13) | 0.0137 (13) | 0.0068 (13) | 0.0095 (13) | 0.0067 (11) |
C7 | 0.0256 (17) | 0.0144 (13) | 0.0170 (13) | 0.0061 (13) | 0.0074 (13) | 0.0051 (11) |
Geometric parameters (Å, º) top
I1—Cu1 | 2.6535 (5) | C1—C6 | 1.491 (4) |
Cu1—N1 | 2.047 (2) | C2—H2 | 0.9500 |
Cu1—N2i | 2.055 (3) | C3—C4 | 1.387 (4) |
Cu1—I1ii | 2.7134 (7) | C3—H3 | 0.9500 |
O1—N2 | 1.412 (3) | C4—C5 | 1.388 (4) |
O1—H1O | 0.8504 | C4—H4 | 0.9500 |
N1—C2 | 1.337 (4) | C5—H5 | 0.9500 |
N1—C3 | 1.348 (4) | C6—C7 | 1.499 (4) |
N2—C6 | 1.278 (4) | C7—H7A | 0.9800 |
C1—C5 | 1.392 (4) | C7—H7B | 0.9800 |
C1—C2 | 1.400 (4) | C7—H7C | 0.9800 |
| | | |
Cu1—I1—Cu1ii | 64.769 (19) | N1—C2—C1 | 123.3 (3) |
N1—Cu1—N2i | 126.41 (9) | N1—C2—H2 | 118.4 |
N1—Cu1—I1 | 105.72 (7) | C1—C2—H2 | 118.4 |
N2i—Cu1—I1 | 107.13 (7) | N1—C3—C4 | 123.3 (3) |
N1—Cu1—I1ii | 103.48 (8) | N1—C3—H3 | 118.4 |
N2i—Cu1—I1ii | 99.27 (7) | C4—C3—H3 | 118.4 |
I1—Cu1—I1ii | 115.231 (19) | C3—C4—C5 | 118.6 (3) |
N1—Cu1—Cu1ii | 118.03 (7) | C3—C4—H4 | 120.7 |
N2i—Cu1—Cu1ii | 115.08 (7) | C5—C4—H4 | 120.7 |
I1—Cu1—Cu1ii | 58.622 (19) | C4—C5—C1 | 119.1 (2) |
I1ii—Cu1—Cu1ii | 56.608 (17) | C4—C5—H5 | 120.5 |
N2—O1—H1O | 102.4 | C1—C5—H5 | 120.5 |
C2—N1—C3 | 117.6 (2) | N2—C6—C1 | 116.0 (2) |
C2—N1—Cu1 | 119.91 (18) | N2—C6—C7 | 125.1 (3) |
C3—N1—Cu1 | 122.37 (19) | C1—C6—C7 | 118.8 (3) |
C6—N2—O1 | 111.2 (2) | C6—C7—H7A | 109.5 |
C6—N2—Cu1i | 133.4 (2) | C6—C7—H7B | 109.5 |
O1—N2—Cu1i | 115.35 (18) | H7A—C7—H7B | 109.5 |
C5—C1—C2 | 118.1 (3) | C6—C7—H7C | 109.5 |
C5—C1—C6 | 121.3 (2) | H7A—C7—H7C | 109.5 |
C2—C1—C6 | 120.7 (2) | H7B—C7—H7C | 109.5 |
| | | |
Cu1ii—I1—Cu1—N1 | −113.59 (8) | C2—N1—C3—C4 | 3.3 (4) |
Cu1ii—I1—Cu1—N2i | 109.36 (8) | Cu1—N1—C3—C4 | −172.0 (2) |
Cu1ii—I1—Cu1—I1ii | 0.0 | N1—C3—C4—C5 | −0.8 (4) |
N2i—Cu1—N1—C2 | 98.9 (2) | C3—C4—C5—C1 | −3.3 (4) |
I1—Cu1—N1—C2 | −27.1 (2) | C2—C1—C5—C4 | 4.7 (4) |
I1ii—Cu1—N1—C2 | −148.6 (2) | C6—C1—C5—C4 | −174.8 (3) |
Cu1ii—Cu1—N1—C2 | −89.5 (2) | O1—N2—C6—C1 | 179.7 (2) |
N2i—Cu1—N1—C3 | −85.8 (3) | Cu1i—N2—C6—C1 | −4.0 (4) |
I1—Cu1—N1—C3 | 148.2 (2) | O1—N2—C6—C7 | −1.0 (3) |
I1ii—Cu1—N1—C3 | 26.6 (2) | Cu1i—N2—C6—C7 | 175.27 (19) |
Cu1ii—Cu1—N1—C3 | 85.7 (2) | C5—C1—C6—N2 | 130.3 (3) |
C3—N1—C2—C1 | −1.8 (4) | C2—C1—C6—N2 | −49.2 (3) |
Cu1—N1—C2—C1 | 173.7 (2) | C5—C1—C6—C7 | −49.1 (4) |
C5—C1—C2—N1 | −2.2 (4) | C2—C1—C6—C7 | 131.5 (3) |
C6—C1—C2—N1 | 177.3 (3) | | |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···I1iii | 0.85 | 2.59 | 3.402 (3) | 161 |
Symmetry code: (iii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Ag2(NO3)2(C7H8NO)2] | [Cu2I2(C7H8NO)2] |
Mr | 612.07 | 326.60 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 153 | 153 |
a, b, c (Å) | 8.076 (1), 8.084 (1), 8.808 (1) | 7.512 (1), 8.015 (1), 8.886 (1) |
α, β, γ (°) | 105.34 (2), 114.53 (2), 102.51 (2) | 111.88 (2), 101.38 (2), 106.57 (2) |
V (Å3) | 468.28 (18) | 447.28 (17) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.15 | 5.84 |
Crystal size (mm) | 0.35 × 0.30 × 0.20 | 0.40 × 0.40 × 0.25 |
|
Data collection |
Diffractometer | STOE IPDS diffractometer | STOE IPDS diffractometer |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 2003) | Empirical (using intensity measurements) refined from ΔF: DELABS in PLATON (Spek, 2003) |
Tmin, Tmax | 0.478, 0.701 | 0.225, 0.689 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3502, 1622, 1579 | 3418, 1588, 1522 |
Rint | 0.024 | 0.028 |
(sin θ/λ)max (Å−1) | 0.613 | 0.613 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.053, 1.09 | 0.020, 0.050, 1.07 |
No. of reflections | 1622 | 1588 |
No. of parameters | 138 | 110 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.75 | 0.67, −0.65 |
Selected geometric parameters (Å, º) for (I) topAg1—N2 | 2.217 (2) | N2—O1 | 1.403 (2) |
Ag1—N1i | 2.217 (2) | C1—C6 | 1.487 (3) |
Ag1—O11 | 2.593 (2) | C6—C7 | 1.481 (4) |
N2—C6 | 1.288 (3) | | |
| | | |
N2—Ag1—N1i | 144.35 (7) | C6—N2—Ag1 | 129.26 (16) |
N2—Ag1—O11 | 133.60 (8) | O1—N2—Ag1 | 117.57 (13) |
N1i—Ag1—O11 | 81.93 (8) | N11—O11—Ag1 | 99.22 (15) |
C6—N2—O1 | 113.1 (2) | | |
| | | |
O1—N2—C6—C1 | 179.26 (18) | C2—C1—C6—N2 | −46.5 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O12ii | 0.84 | 1.94 | 2.767 (3) | 168 |
Symmetry code: (ii) −x, −y, −z+1. |
Selected bond lengths (Å) for (II) topI1—Cu1 | 2.6535 (5) | Cu1—N2i | 2.055 (3) |
Cu1—N1 | 2.047 (2) | Cu1—I1ii | 2.7134 (7) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···I1iii | 0.85 | 2.59 | 3.402 (3) | 161 |
Symmetry code: (iii) x+1, y, z. |
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For the design of supramolecular architectures, it is necessary to use versatile molecular synthons as connectors, for example, for the assembly of metal-containing networks. Predictable assembly of some metal complexes has been obtained through the synthesis of coordination polymers. Porous solids with channels and cavities have been obtained with 3 d metals and, for example, 4,4'-bipyridine or pyrazine (Moulton & Zaworotko, 2001). In crystal engineering, the use of hydrogen bonding as a steering force has also emerged as an important strategy (Aakeröy et al., 2000). It has been shown that oxime–pyridine derivatives can be used in assembling coordination complexes into extended hydrogen-bonded networks (Aakeröy et al., 1998; Aakeröy et al., 1999). We present here two new coordination compounds formed with the ligand 1-pyridin-3-yl-ethanone oxime (commonly known as 3-acetyloximepyridine) using silver(I) nitrate and copper(I) iodide.
The silver(I) compound, (I), was revealed to be a centrosymmetric binuclear macrocylic complex containing silver(I) ions bridged by the organic oxime ligand (Fig. 1). Selected geometric parameters for (I) are listed in Table 1. Both the pyridine and oxime N atoms are involved in coordination. Each Ag atom is in a planar trigonal environment, having, in addition to the two ligand molecules in its coordination sphere, a nitrate anion coordinating in a monodentate fashion. The Ag1—N1(pyridine) and Ag—N2(oxime) distances are both 2.217 (2) Å, while the Ag1—O11(nitrate) distance [2.593 (2) Å], is relatively long. The Ag atom is displaced 0.042 (1) Å from the plane defined by atoms N1i, N2 and O11 [symmetry code: (i) 1 − x, −y, 1 − z]. The formation of the macrocyclic structure results in the C(CH3)NOH group being twisted out of plane of the pyridine ring by 46.7 (1)°. The intramolecular metal–metal distance in the macrocycle is 4.484 (1) Å.
The formation of a strong intermolecular hydrogen bond between the OH function of the oxime ligand and a neighboring nitrate anion results in the formation of a hydrogen-bonded macrocycle, which in turn leads to the formation of a one-dimensional polymer (Fig. 2 and Table 2). The Ag atoms are separated by only 4.444 (1) Å. The structure of (I) is very different to the known mononuclear silver(I) compounds bis(3-acetyloximepyridine)silver(I) hexafluorophosphate and bis(3-acetyloximepyridine)silver(I) perchlorate, synthesized by Aakeröy et al. (1998). In those compounds, only the pyridine N atom coordinates to the Ag atom, and the Ag—N distances [2.13–2.16 Å] are shorter than those in (I). The coordinated ligand molecules are also more planar, with dihedral angles between the pyridine and C(CH3)NOH groups of 10.2–18.7°, compared with 46.7 (1)° in (I). In the free ligand (Aakeröy et al., 2000), the corresponding dihedral angle is only 9.1°.
The copper(I) complex, (II), is simlar to (I) but, in addition to the binuclear macrocyclic arrangement, the Cu atoms are bridged by iodide anions, thus linking these units to form a one-dimensional polymer (Fig. 3). Selected geometric parameters for (II) are listed in Table 3. Two ligand molecules, one involving the pyridine N atom [Cu1—N1 = 2.047 (2) Å], the other the oxime N atom [Cu1—N2ii = 2.055 (2) Å; symmetry code: (ii) 2 − x, 1 − y, 1 − z], are coordinated to the copper(I) ion. The tetrahedral coordination sphere of atom Cu1 is completed by two iodide anions [Cu1—I1,I1i = 2.6535 (5) and 2.7133 (7) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z]. In the chains, the intramolecular metal–metal distances are 5.149 (1) Å for the double ligand bridge and 2.8748 (8) Å for the double anion bridge. As in complex (I), the C(CH3)NOH group is twisted out of the plane of the pyridine ring by 49.8 (1)°. There exists within the polymer chains a hydrogen bond involving the oxime OH group and the briding iodine atom I1i (see Table 4 and Fig. 4).
Structures (I) and (II) show a new coordination mode of the ligand 1-pyridin-3-yl-ethanone oxime. The use of two nitrogen donor atoms of the same ligand molecule results in the formation of metallomacrocycles. These are are in turn connected by an N—OH···anion hydrogen bond [in (I)] or anion bridges [in (II)], to form zigzag one-dimensional polymeric arrangements.