Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013872/ta1379sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013872/ta1379Isup2.hkl |
CCDC reference: 195609
To a solution of AgNO3 (1.0 mmol) in MeCN/H2O [10 ml; 1:1 (v/v)], a solution of 2-Clnpy (1.0 mmol) in MeOH (5 ml) was slowly added and stirred for 15 min at 333 K. Colourless polyhedral crystals of (I) were deposited within 2 d (75% yield).
The amino H atoms were located and refined subject to N—H = 0.85 (1) Å and H···H = 1.39 (1) Å, with Uiso(H) = 1.2Ueq(N). The carbon-bound H atoms were generated geometrically, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ag(C5H5ClN2)]NO3 | F(000) = 576 |
Mr = 298.44 | Dx = 2.294 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 25 reflections |
a = 13.343 (5) Å | θ = 7–15° |
b = 7.832 (2) Å | µ = 2.62 mm−1 |
c = 8.270 (2) Å | T = 298 K |
V = 864.2 (4) Å3 | Polyhedral, colourless |
Z = 4 | 0.34 × 0.30 × 0.20 mm |
Siemens R3m four-circle diffractometer | 1080 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω scans | h = −1→17 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.427, Tmax = 0.593 | l = 0→10 |
1268 measured reflections | 2 standard reflections every 150 reflections |
1248 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0493P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1248 reflections | Δρmax = 0.44 e Å−3 |
124 parameters | Δρmin = −0.76 e Å−3 |
3 restraints | Absolute structure: Flack (1983) with 74 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.20 (8) |
[Ag(C5H5ClN2)]NO3 | V = 864.2 (4) Å3 |
Mr = 298.44 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 13.343 (5) Å | µ = 2.62 mm−1 |
b = 7.832 (2) Å | T = 298 K |
c = 8.270 (2) Å | 0.34 × 0.30 × 0.20 mm |
Siemens R3m four-circle diffractometer | 1080 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.018 |
Tmin = 0.427, Tmax = 0.593 | 2 standard reflections every 150 reflections |
1268 measured reflections | intensity decay: none |
1248 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | Δρmax = 0.44 e Å−3 |
S = 1.07 | Δρmin = −0.76 e Å−3 |
1248 reflections | Absolute structure: Flack (1983) with 74 Friedel pairs |
124 parameters | Absolute structure parameter: 0.20 (8) |
3 restraints |
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 | ||
Ag | 0.76829 (4) | 0.90000 (6) | 0.19699 (6) | 0.04304 (16) | |
Cl1 | 0.75176 (14) | 0.9794 (3) | 0.5906 (2) | 0.0561 (5) | |
O1 | 0.6048 (5) | 0.8701 (6) | −0.0330 (7) | 0.0621 (15) | |
O2 | 0.7137 (4) | 0.6722 (8) | 0.0026 (7) | 0.0710 (18) | |
O3 | 0.5947 (5) | 0.6321 (8) | −0.1625 (8) | 0.077 (2) | |
N1 | 0.6560 (4) | 1.0693 (6) | 0.3300 (6) | 0.0389 (13) | |
N2 | 0.6022 (4) | 1.2019 (8) | 0.7496 (7) | 0.0382 (13) | |
H2N1 | 0.619 (4) | 1.109 (5) | 0.797 (7) | 0.046* | |
H2N2 | 0.552 (3) | 1.244 (7) | 0.799 (7) | 0.046* | |
N3 | 0.6378 (4) | 0.7258 (8) | −0.0638 (7) | 0.0410 (13) | |
C1 | 0.5843 (6) | 1.1559 (10) | 0.2502 (9) | 0.0466 (18) | |
H1 | 0.5823 | 1.1480 | 0.1380 | 0.056* | |
C2 | 0.5134 (6) | 1.2562 (10) | 0.3268 (8) | 0.0513 (19) | |
H2 | 0.4652 | 1.3150 | 0.2678 | 0.062* | |
C3 | 0.5163 (5) | 1.2667 (10) | 0.4939 (9) | 0.0436 (16) | |
H3 | 0.4684 | 1.3307 | 0.5486 | 0.052* | |
C4 | 0.5896 (5) | 1.1829 (8) | 0.5793 (8) | 0.0331 (13) | |
C5 | 0.6575 (4) | 1.0849 (8) | 0.4903 (7) | 0.0330 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag | 0.0490 (3) | 0.0409 (2) | 0.0393 (2) | 0.0027 (2) | −0.0012 (2) | −0.0025 (2) |
Cl1 | 0.0584 (11) | 0.0625 (10) | 0.0475 (9) | 0.0315 (10) | −0.0048 (8) | −0.0042 (8) |
O1 | 0.087 (4) | 0.041 (3) | 0.059 (3) | 0.017 (3) | 0.008 (3) | −0.011 (3) |
O2 | 0.057 (3) | 0.090 (4) | 0.066 (3) | 0.031 (3) | −0.031 (3) | −0.022 (4) |
O3 | 0.064 (3) | 0.074 (4) | 0.092 (5) | 0.021 (3) | −0.043 (3) | −0.041 (4) |
N1 | 0.045 (3) | 0.033 (3) | 0.039 (3) | −0.001 (2) | −0.002 (2) | −0.009 (2) |
N2 | 0.040 (3) | 0.037 (3) | 0.037 (3) | 0.007 (3) | 0.009 (2) | 0.000 (3) |
N3 | 0.040 (3) | 0.045 (3) | 0.037 (3) | 0.003 (3) | −0.004 (2) | −0.002 (3) |
C1 | 0.053 (4) | 0.045 (4) | 0.042 (3) | 0.001 (3) | −0.014 (3) | −0.006 (3) |
C2 | 0.047 (4) | 0.050 (4) | 0.057 (4) | 0.010 (4) | −0.019 (4) | 0.002 (4) |
C3 | 0.032 (3) | 0.040 (4) | 0.059 (4) | 0.002 (3) | −0.002 (3) | −0.012 (4) |
C4 | 0.034 (3) | 0.026 (3) | 0.038 (3) | −0.006 (3) | −0.001 (3) | 0.000 (3) |
C5 | 0.029 (3) | 0.028 (3) | 0.042 (3) | 0.003 (3) | −0.003 (2) | 0.001 (3) |
Ag—N1 | 2.283 (5) | N2—C4 | 1.427 (9) |
Ag—N2i | 2.364 (6) | N2—H2N1 | 0.86 (5) |
Ag—O2 | 2.510 (6) | N2—H2N2 | 0.85 (5) |
Ag—O3ii | 2.594 (6) | C1—C2 | 1.383 (10) |
Cl1—C5 | 1.718 (6) | C1—H1 | 0.9300 |
O1—N3 | 1.240 (7) | C2—C3 | 1.385 (9) |
O2—N3 | 1.226 (7) | C2—H2 | 0.9300 |
O2—Agiii | 2.707 (6) | C3—C4 | 1.373 (10) |
O3—N3 | 1.239 (8) | C3—H3 | 0.9300 |
N1—C5 | 1.332 (8) | C4—C5 | 1.397 (9) |
N1—C1 | 1.346 (9) | ||
N1—Ag—N2i | 140.44 (18) | O2—N3—O1 | 120.9 (6) |
N1—Ag—O2 | 122.09 (18) | O2—N3—O3 | 118.4 (6) |
N2i—Ag—O2 | 82.25 (19) | O1—N3—O3 | 120.7 (6) |
N1—Ag—O3ii | 96.2 (2) | N1—C1—C2 | 123.2 (6) |
N2i—Ag—O3ii | 88.0 (2) | N1—C1—H1 | 118.4 |
O2—Ag—O3ii | 129.2 (2) | C2—C1—H1 | 118.4 |
N3—O2—Ag | 106.5 (5) | C3—C2—C1 | 118.2 (7) |
N3—O2—Agiii | 94.0 (4) | C3—C2—H2 | 120.9 |
Ag—O2—Agiii | 157.6 (2) | C1—C2—H2 | 120.9 |
N3—O3—Agiii | 99.2 (4) | C4—C3—C2 | 120.3 (7) |
C5—N1—C1 | 116.9 (6) | C4—C3—H3 | 119.9 |
C5—N1—Ag | 121.5 (4) | C2—C3—H3 | 119.9 |
C1—N1—Ag | 121.5 (4) | C3—C4—C5 | 117.0 (6) |
C4—N2—Agiv | 109.8 (4) | C3—C4—N2 | 122.8 (6) |
C4—N2—H2N1 | 113 (5) | C5—C4—N2 | 120.1 (6) |
Agiv—N2—H2N1 | 107 (5) | N1—C5—C4 | 124.4 (6) |
C4—N2—H2N2 | 115 (5) | N1—C5—Cl1 | 116.6 (5) |
Agiv—N2—H2N2 | 103 (5) | C4—C5—Cl1 | 119.0 (5) |
H2N1—N2—H2N2 | 108 (5) | ||
N1—Ag—O2—N3 | 33.8 (5) | Agiii—O3—N3—O1 | 168.0 (5) |
N2i—Ag—O2—N3 | −179.8 (5) | C5—N1—C1—C2 | −0.7 (11) |
O3ii—Ag—O2—N3 | −98.8 (5) | Ag—N1—C1—C2 | 178.3 (6) |
N1—Ag—O2—Agiii | −170.8 (7) | N1—C1—C2—C3 | −0.4 (13) |
N2i—Ag—O2—Agiii | −24.4 (7) | C1—C2—C3—C4 | 1.8 (13) |
O3ii—Ag—O2—Agiii | 56.6 (8) | C2—C3—C4—C5 | −1.8 (11) |
N2i—Ag—N1—C5 | 5.9 (7) | C2—C3—C4—N2 | 173.9 (7) |
O2—Ag—N1—C5 | 126.5 (5) | Agiv—N2—C4—C3 | −98.7 (7) |
O3ii—Ag—N1—C5 | −88.5 (5) | Agiv—N2—C4—C5 | 76.9 (7) |
N2i—Ag—N1—C1 | −173.1 (5) | C1—N1—C5—C4 | 0.6 (10) |
O2—Ag—N1—C1 | −52.5 (6) | Ag—N1—C5—C4 | −178.4 (5) |
O3ii—Ag—N1—C1 | 92.5 (5) | C1—N1—C5—Cl1 | −178.0 (5) |
Ag—O2—N3—O1 | 2.2 (8) | Ag—N1—C5—Cl1 | 3.0 (7) |
Agiii—O2—N3—O1 | −168.6 (6) | C3—C4—C5—N1 | 0.6 (10) |
Ag—O2—N3—O3 | −177.7 (5) | N2—C4—C5—N1 | −175.2 (6) |
Agiii—O2—N3—O3 | 11.4 (7) | C3—C4—C5—Cl1 | 179.2 (5) |
Agiii—O3—N3—O2 | −12.1 (7) | N2—C4—C5—Cl1 | 3.4 (9) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) −x+3/2, y+1/2, −z; (iii) −x+3/2, y−1/2, −z; (iv) −x+3/2, y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N1···O1v | 0.86 (5) | 2.35 (5) | 3.160 (8) | 159 (5) |
N2—H2N2···O3vi | 0.85 (5) | 2.20 (4) | 3.020 (8) | 160 (6) |
Symmetry codes: (v) x, y, z+1; (vi) −x+1, −y+2, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C5H5ClN2)]NO3 |
Mr | 298.44 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 298 |
a, b, c (Å) | 13.343 (5), 7.832 (2), 8.270 (2) |
V (Å3) | 864.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.62 |
Crystal size (mm) | 0.34 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Siemens R3m four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.427, 0.593 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1268, 1248, 1080 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.083, 1.07 |
No. of reflections | 1248 |
No. of parameters | 124 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.76 |
Absolute structure | Flack (1983) with 74 Friedel pairs |
Absolute structure parameter | 0.20 (8) |
Computer programs: XSCANS (Siemens, 1990), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Ag—N1 | 2.283 (5) | Ag—O3ii | 2.594 (6) |
Ag—N2i | 2.364 (6) | O2—Agiii | 2.707 (6) |
Ag—O2 | 2.510 (6) | ||
N1—Ag—N2i | 140.44 (18) | N1—Ag—O3ii | 96.2 (2) |
N1—Ag—O2 | 122.09 (18) | N2i—Ag—O3ii | 88.0 (2) |
N2i—Ag—O2 | 82.25 (19) | O2—Ag—O3ii | 129.2 (2) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) −x+3/2, y+1/2, −z; (iii) −x+3/2, y−1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N1···O1iv | 0.86 (5) | 2.35 (5) | 3.160 (8) | 159 (5) |
N2—H2N2···O3v | 0.85 (5) | 2.20 (4) | 3.020 (8) | 160 (6) |
Symmetry codes: (iv) x, y, z+1; (v) −x+1, −y+2, z+1. |
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The field of metal-organic coordination polymers has recently attracted great interest, because such supramolecular architectures have potential as smart optoelectronic, magnetic or microporous materials (Abrahams et al., 1994; Biradha et al., 1999; Braga et al., 1998; Fujita et al., 1994; Gardner et al., 1995; Kahn, 2000; Russell et al., 1997). The structures of coordination polymers are highly influenced by factors such as the coordination nature of the metal ion, the structural characteristics of the polydentate organic ligand, the metal-ligand ratio and possible counter-ion influence. A subtle alteration in any of these factors can lead to new extended network structures. Thus, a great variety of supramolecular architectures have been ingeniously constructed. These not only have aesthetic appeal, but occasionally exhibit interesting functions. We are interested in the preparation of one-, two- and three-dimensional coordination polymers with potential applications in optoelectronics and adsorption (Tong et al., 1999; Zheng, Tong, Fu et al., 2001; Zheng, Tong, Tan et al., 2001 Is this the correct place to cite both these references?). We report here the preparation and crystal structure of a chiral two-dimensional coordination polymer constructed from an achiral building block, [Ag(µ-2-Clnpy)(µ-NO3)], (I) (2-Clnpy is 3-amino-2-chloropyridine). \sch
The crystal structure of (I) comprises a chiral two-dimensional coordination network. As shown in Fig. 1, each AgI atom is coordinated in an irregular geometry, with one pyridyl N atom and one amine N atom from two different 2-Clnpy ligands and three O atoms from different nitrate ions (Table 1). The Ag—N(pyridyl) distances in (I) are slightly longer than those in bis(3-amino-2-chloropyridine)silver(I) perchlorate [2.179 (4)–2.199 (4) Å; Li et al., 2002] and that in bis(4-aminopyridine)silver(I) nitrate [2.122 (3) Å; Kristiansson, 2000]. The AgI atoms are bridged by µ-2-Clnpy ligands to form polymeric helical motifs along the c axis direction. Adjacent uniform infinite helical motifs are further interlinked through the µ-NO3 bridges into chiral two-dimensional layers (Fig. 2). Within each layer, there are hydrogen-bonding interactions between adjacent NO3- and amine groups (Table 2).
It should be also noted that π···π stacking interactions play a role in consolidating the solid state structure of (I). Adjacent coordination layers are stacked via interlayer pyridyl groups with a face-to-face separation of 3.38–3.58 Å, resulting in a three-dimensional supramolecular architecture (Fig. 3).