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The dinuclear title complex, [Ag
2(NO
3)
2(3-PyOH)
4]·2H
2O (3-PyOH is 3-hydroxypyridine, C
5H
5NO), situated across a crystallographic inversion centre, can be described as a dimeric structure, in which two [Ag(3-PyOH)
2] groups are held together by the Ag
Ag interaction [3.317 (1) Å]. Each Ag atom is two-coordinate and exists in an approximately linear geometry. The two NO
3− ions interact with the Ag
I atoms in a bridging mode through very weak Ag
O interactions [Ag
O = 2.862 (2) and 2.877 (2) Å]. A three-dimensional supramolecular framework is formed by O—H
O hydrogen bonds.
Supporting information
CCDC reference: 287529
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.027
- wR factor = 0.068
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level C
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
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N3
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 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
3 ALERT type 4 Improvement, methodology, query or suggestion
The title complex, (II), was prepared by the addition of AgNO3 (2 mmol) to an aqueous solution of 3-hydroxypyridine (6 mmol). The resulting solution was protected from light and allowed to evaporate slowly at room temperature, whereupon colourless prismatic crystals of (I) were isolated after 5 d. Analysis calculated for C10H12N3O6Ag: C 31.77, H 3.20, N 11.11%; found: C 31.71, H 3.21, N 11.12%.
H atoms attached to O atoms were located in a difference Fourier map and refined with an O—H distance restraint of 0.85 (1) Å and Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions and were allowed to ride on their parent C atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2002); 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.
Di-µ-nitrato-
κ4O:
O'-bis[bis(3-hydroxypyridine-
κN)silver(I)] dihydrate
top
Crystal data top
[Ag2(NO3)2(C5H5NO)4]·2H2O | Z = 1 |
Mr = 756.19 | F(000) = 376 |
Triclinic, P1 | Dx = 1.892 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9912 (16) Å | Cell parameters from 5742 reflections |
b = 8.8615 (18) Å | θ = 3.1–27.5° |
c = 10.399 (2) Å | µ = 1.55 mm−1 |
α = 81.37 (3)° | T = 296 K |
β = 71.64 (3)° | Prism, colourless |
γ = 72.01 (3)° | 0.36 × 0.27 × 0.19 mm |
V = 663.6 (3) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 3011 independent reflections |
Radiation source: fine-focus sealed tube | 2533 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 10 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −9→10 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −11→11 |
Tmin = 0.610, Tmax = 0.747 | l = −13→13 |
6582 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0416P)2 + 0.0053P] where P = (Fo2 + 2Fc2)/3 |
3011 reflections | (Δ/σ)max = 0.001 |
193 parameters | Δρmax = 0.58 e Å−3 |
5 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
[Ag2(NO3)2(C5H5NO)4]·2H2O | γ = 72.01 (3)° |
Mr = 756.19 | V = 663.6 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.9912 (16) Å | Mo Kα radiation |
b = 8.8615 (18) Å | µ = 1.55 mm−1 |
c = 10.399 (2) Å | T = 296 K |
α = 81.37 (3)° | 0.36 × 0.27 × 0.19 mm |
β = 71.64 (3)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 3011 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2533 reflections with I > 2σ(I) |
Tmin = 0.610, Tmax = 0.747 | Rint = 0.017 |
6582 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 5 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.58 e Å−3 |
3011 reflections | Δρmin = −0.32 e Å−3 |
193 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ag1 | 0.69864 (3) | 0.54425 (2) | 0.43994 (2) | 0.05103 (9) | |
O1W | 1.0194 (3) | 0.1979 (4) | 1.0753 (2) | 0.0828 (7) | |
O1 | 0.2890 (3) | 1.0702 (2) | 0.2297 (2) | 0.0539 (4) | |
O2 | 0.9111 (4) | 0.4190 (3) | 0.8937 (2) | 0.0742 (6) | |
O3 | 0.3204 (3) | 0.7474 (3) | 0.6333 (2) | 0.0724 (6) | |
O4 | 0.5717 (3) | 0.7994 (2) | 0.6194 (2) | 0.0622 (5) | |
O5 | 0.3432 (3) | 0.8461 (3) | 0.7989 (2) | 0.0782 (7) | |
N1 | 0.5825 (3) | 0.6775 (2) | 0.2838 (2) | 0.0432 (4) | |
N2 | 0.8483 (3) | 0.3954 (2) | 0.5733 (2) | 0.0437 (4) | |
N3 | 0.4115 (3) | 0.7960 (2) | 0.6849 (2) | 0.0461 (5) | |
C1 | 0.4793 (3) | 0.8278 (3) | 0.3024 (2) | 0.0421 (5) | |
C2 | 0.3940 (3) | 0.9176 (3) | 0.2084 (2) | 0.0413 (5) | |
C3 | 0.4130 (4) | 0.8499 (3) | 0.0924 (3) | 0.0491 (6) | |
C4 | 0.5220 (4) | 0.6965 (3) | 0.0719 (3) | 0.0554 (7) | |
C5 | 0.6049 (4) | 0.6133 (3) | 0.1693 (3) | 0.0492 (6) | |
C6 | 0.8391 (3) | 0.4458 (3) | 0.6892 (3) | 0.0469 (6) | |
C7 | 0.9323 (3) | 0.3531 (3) | 0.7791 (3) | 0.0481 (6) | |
C8 | 1.0403 (3) | 0.2026 (3) | 0.7449 (3) | 0.0509 (6) | |
C9 | 1.0504 (4) | 0.1516 (3) | 0.6240 (3) | 0.0541 (6) | |
C10 | 0.9538 (4) | 0.2490 (3) | 0.5393 (3) | 0.0510 (6) | |
H1 | 0.4645 | 0.8735 | 0.3816 | 0.050* | |
H3 | 0.3535 | 0.9067 | 0.0290 | 0.059* | |
H4 | 0.5396 | 0.6490 | −0.0071 | 0.066* | |
H5 | 0.6784 | 0.5096 | 0.1547 | 0.059* | |
H6 | 0.7669 | 0.5481 | 0.7118 | 0.056* | |
H8 | 1.1049 | 0.1371 | 0.8023 | 0.061* | |
H9 | 1.1231 | 0.0503 | 0.5988 | 0.065* | |
H10 | 0.9622 | 0.2125 | 0.4576 | 0.061* | |
H11 | 0.335 (5) | 1.110 (4) | 0.274 (3) | 0.081* | |
H12 | 0.961 (5) | 0.346 (4) | 0.943 (4) | 0.111* | |
H1W1 | 1.087 (4) | 0.194 (6) | 1.125 (3) | 0.124* | |
H1W2 | 0.916 (3) | 0.189 (6) | 1.125 (3) | 0.124* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.05349 (13) | 0.04793 (12) | 0.05306 (13) | −0.00751 (9) | −0.02662 (9) | 0.00361 (8) |
O1W | 0.0701 (15) | 0.1093 (19) | 0.0705 (15) | −0.0225 (15) | −0.0371 (12) | 0.0221 (14) |
O1 | 0.0555 (11) | 0.0466 (9) | 0.0615 (12) | −0.0033 (8) | −0.0301 (9) | −0.0029 (8) |
O2 | 0.0901 (16) | 0.0682 (13) | 0.0550 (12) | 0.0067 (12) | −0.0325 (11) | −0.0116 (10) |
O3 | 0.0952 (17) | 0.0712 (13) | 0.0732 (14) | −0.0329 (12) | −0.0438 (13) | −0.0074 (11) |
O4 | 0.0598 (12) | 0.0608 (12) | 0.0601 (12) | −0.0073 (10) | −0.0111 (10) | −0.0191 (10) |
O5 | 0.0730 (15) | 0.1116 (19) | 0.0545 (12) | −0.0273 (14) | −0.0105 (11) | −0.0320 (13) |
N1 | 0.0453 (11) | 0.0423 (10) | 0.0427 (10) | −0.0089 (8) | −0.0170 (9) | −0.0019 (8) |
N2 | 0.0410 (10) | 0.0394 (10) | 0.0509 (12) | −0.0090 (8) | −0.0175 (9) | 0.0018 (9) |
N3 | 0.0626 (14) | 0.0329 (9) | 0.0456 (11) | −0.0036 (9) | −0.0274 (10) | −0.0051 (8) |
C1 | 0.0462 (13) | 0.0456 (12) | 0.0361 (11) | −0.0115 (10) | −0.0141 (10) | −0.0050 (10) |
C2 | 0.0378 (12) | 0.0453 (12) | 0.0421 (12) | −0.0121 (10) | −0.0140 (10) | 0.0006 (10) |
C3 | 0.0569 (15) | 0.0583 (15) | 0.0408 (13) | −0.0231 (12) | −0.0224 (11) | 0.0043 (11) |
C4 | 0.0732 (19) | 0.0588 (15) | 0.0389 (13) | −0.0241 (14) | −0.0135 (13) | −0.0102 (12) |
C5 | 0.0542 (15) | 0.0479 (13) | 0.0432 (13) | −0.0111 (11) | −0.0111 (11) | −0.0084 (11) |
C6 | 0.0434 (13) | 0.0399 (12) | 0.0511 (14) | −0.0031 (10) | −0.0144 (11) | 0.0002 (11) |
C7 | 0.0448 (13) | 0.0503 (13) | 0.0444 (13) | −0.0081 (11) | −0.0117 (11) | −0.0013 (11) |
C8 | 0.0426 (13) | 0.0467 (13) | 0.0596 (16) | −0.0055 (11) | −0.0201 (12) | 0.0053 (12) |
C9 | 0.0452 (14) | 0.0417 (12) | 0.0712 (18) | −0.0005 (11) | −0.0209 (13) | −0.0060 (12) |
C10 | 0.0482 (14) | 0.0458 (13) | 0.0588 (15) | −0.0076 (11) | −0.0195 (12) | −0.0055 (12) |
Geometric parameters (Å, º) top
Ag1—N1 | 2.142 (2) | N2—C10 | 1.339 (3) |
Ag1—N2 | 2.148 (2) | C1—C2 | 1.379 (3) |
Ag1—O3i | 2.862 (2) | C1—H1 | 0.93 |
Ag1—O4 | 2.877 (2) | C2—C3 | 1.373 (4) |
Ag1—Ag1i | 3.317 (1) | C3—C4 | 1.375 (4) |
O1W—H1W1 | 0.85 (4) | C3—H3 | 0.93 |
O1W—H1W2 | 0.85 (3) | C4—C5 | 1.380 (4) |
O1—C2 | 1.362 (3) | C4—H4 | 0.93 |
O1—H11 | 0.84 (4) | C5—H5 | 0.93 |
O2—C7 | 1.346 (4) | C6—C7 | 1.390 (4) |
O2—H12 | 0.84 (4) | C6—H6 | 0.93 |
O3—N3 | 1.230 (3) | C7—C8 | 1.374 (4) |
O4—N3 | 1.253 (3) | C8—C9 | 1.369 (4) |
O5—N3 | 1.226 (3) | C8—H8 | 0.93 |
N1—C5 | 1.334 (3) | C9—C10 | 1.380 (4) |
N1—C1 | 1.338 (3) | C9—H9 | 0.93 |
N2—C6 | 1.321 (3) | C10—H10 | 0.93 |
| | | |
O4—Ag1—N1 | 96.37 (7) | C2—O1—H11 | 107 (2) |
O4—Ag1—N2 | 90.05 (8) | C2—C1—H1 | 118.8 |
N1—Ag1—N2 | 171.79 (8) | C2—C3—C4 | 118.6 (2) |
N1—Ag1—O3i | 91.78 (2) | C2—C3—H3 | 120.7 |
N2—Ag1—O3i | 84.98 (2) | C3—C2—C1 | 119.0 (2) |
O4—Ag1—O3i | 151.50 (2) | C3—C4—C5 | 119.6 (2) |
N1—Ag1—Ag1i | 84.09 (6) | C3—C4—H4 | 120.2 |
N2—Ag1—Ag1i | 100.95 (6) | C4—C3—H3 | 120.7 |
O4—Ag1—Ag1i | 91.48 (2) | C4—C5—H5 | 119.1 |
O3i—Ag1—Ag1i | 62.10 (2) | C5—C4—H4 | 120.2 |
O1—C2—C3 | 119.6 (2) | C5—N1—C1 | 118.5 (2) |
O1—C2—C1 | 121.5 (2) | C5—N1—Ag1 | 121.9 (2) |
O2—C7—C8 | 124.6 (2) | C6—N2—C10 | 118.8 (2) |
O2—C7—C6 | 117.0 (2) | C6—N2—Ag1 | 121.1 (2) |
O3—N3—O4 | 120.2 (2) | C7—O2—H12 | 106 (3) |
O5—N3—O3 | 119.8 (2) | C7—C6—H6 | 118.5 |
O5—N3—O4 | 120.0 (2) | C7—C8—H8 | 120.9 |
N1—C1—C2 | 122.5 (2) | C8—C9—C10 | 120.7 (3) |
N1—C1—H1 | 118.8 | C8—C9—H9 | 119.7 |
N1—C5—C4 | 121.9 (2) | C8—C7—C6 | 118.4 (3) |
N1—C5—H5 | 119.1 | C9—C8—C7 | 118.2 (2) |
N2—C6—C7 | 123.0 (2) | C9—C10—H10 | 119.6 |
N2—C6—H6 | 118.5 | C9—C8—H8 | 120.9 |
N2—C10—C9 | 120.9 (3) | C10—C9—H9 | 119.7 |
N2—C10—H10 | 119.6 | C10—N2—Ag1 | 120.13 (18) |
C1—N1—Ag1 | 119.6 (2) | H1W1—O1W—H1W2 | 109 (3) |
| | | |
Ag1i—Ag1—N1—C5 | −90.6 (2) | O1—C2—C3—C4 | 179.1 (2) |
Ag1i—Ag1—N1—C1 | 87.1 (2) | O2—C7—C8—C9 | −179.4 (3) |
Ag1i—Ag1—N2—C6 | −88.4 (2) | C1—C2—C3—C4 | −2.3 (4) |
Ag1i—Ag1—N2—C10 | 91.9 (2) | C1—N1—C5—C4 | −1.3 (4) |
Ag1—N1—C5—C4 | 176.5 (2) | C2—C3—C4—C5 | 1.8 (4) |
Ag1—N1—C1—C2 | −177.1 (2) | C3—C4—C5—N1 | 0.1 (4) |
Ag1—N2—C6—C7 | 179.4 (2) | C5—N1—C1—C2 | 0.8 (4) |
Ag1—N2—C10—C9 | −179.8 (2) | C6—C7—C8—C9 | −0.1 (4) |
N1—C1—C2—O1 | 179.7 (2) | C6—N2—C10—C9 | 0.5 (4) |
N1—C1—C2—C3 | 1.1 (4) | C7—C8—C9—C10 | −0.2 (4) |
N2—C6—C7—O2 | 180.0 (2) | C8—C9—C10—N2 | 0.0 (4) |
N2—C6—C7—C8 | 0.6 (4) | C10—N2—C6—C7 | −0.8 (4) |
Symmetry code: (i) −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—H11···O4ii | 0.84 (4) | 1.89 (4) | 2.735 (3) | 177 (3) |
O1—H11···O5ii | 0.84 (4) | 2.58 (3) | 3.163 (3) | 128 (3) |
O2—H12···O1W | 0.84 (4) | 1.82 (4) | 2.650 (3) | 168 (4) |
O1W—H1W1···O1iii | 0.85 (4) | 2.16 (2) | 2.937 (3) | 153 (4) |
O1W—H1W2···O5iv | 0.85 (3) | 2.08 (3) | 2.901 (3) | 166 (4) |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x+1, y−1, z+1; (iv) −x+1, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | [Ag2(NO3)2(C5H5NO)4]·2H2O |
Mr | 756.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.9912 (16), 8.8615 (18), 10.399 (2) |
α, β, γ (°) | 81.37 (3), 71.64 (3), 72.01 (3) |
V (Å3) | 663.6 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.55 |
Crystal size (mm) | 0.36 × 0.27 × 0.19 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.610, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6582, 3011, 2533 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.068, 1.04 |
No. of reflections | 3011 |
No. of parameters | 193 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.32 |
Selected geometric parameters (Å, º) topAg1—N1 | 2.142 (2) | Ag1—O4 | 2.877 (2) |
Ag1—N2 | 2.148 (2) | Ag1—Ag1i | 3.317 (1) |
Ag1—O3i | 2.862 (2) | | |
| | | |
O4—Ag1—N1 | 96.37 (7) | N1—Ag1—O3i | 91.78 (2) |
O4—Ag1—N2 | 90.05 (8) | N2—Ag1—O3i | 84.98 (2) |
N1—Ag1—N2 | 171.79 (8) | O4—Ag1—O3i | 151.50 (2) |
Symmetry code: (i) −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—H11···O4ii | 0.84 (4) | 1.89 (4) | 2.735 (3) | 177 (3) |
O1—H11···O5ii | 0.84 (4) | 2.58 (3) | 3.163 (3) | 128 (3) |
O2—H12···O1W | 0.84 (4) | 1.82 (4) | 2.650 (3) | 168 (4) |
O1W—H1W1···O1iii | 0.85 (4) | 2.16 (2) | 2.937 (3) | 153 (4) |
O1W—H1W2···O5iv | 0.85 (3) | 2.08 (3) | 2.901 (3) | 166 (4) |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x+1, y−1, z+1; (iv) −x+1, −y+1, −z+2. |
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3-Hydroxypyridine (3-PyOH), when deprotonated, is a good building block in directing polymeric coordination architectures with interesting properties, such as magnetism (Castillo et al., 2000; Kawata et al., 1997) and fluorescence (Gao et al., 2005); in its neutral form, it is also useful in the synthesis of supramolecules and inorganic precursor compounds for solid-state materials, since it is not only capable of binding to metal centers but can also form regular hydrogen bonds by functioning as both a hydrogen-bond donor and an acceptor (Breeze & Wang, 1993). Recently, we have reported the chain and layer hydrogen-bonding architectures of two copper(II) complexes (Gao, Zhang et al., 2004; Gao, Lu et al., 2004), as well as the three-dimensional supramolecular framework structure of [Ag(3-PyOH)2]NO3, (I) (Lu et al., 2005). In continuation of our research in synthesis of supramolecular transition metal complexes with the 3-PyOH ligand, we have recently obtained the title compound, (II), from an aqueous solution of AgNO3 and 3-PyOH. We report here the crystal structure of (II).
The asymmetric unit of (II) consists of one-half of [Ag(3-PyOH)2NO3]2·2H2O, situated across a crystallographic inversion centre (Fig. 1). Each AgI atom is coordinated by two neutral 3-PyOH molecules through the N atoms [Ag—N = 2.142 (2) and 2.148 (2) Å] and shows a linear geometry with an N—Ag—N angle of 171.79 (8)°. The two NO3− ions interact with the AgI atoms in a bridging mode through very weak Ag···O interactions [Ag···O = 2.862 (2) and 2.877 (2) Å]. The fact that the N—Ag—N angle in (II) is wider than that in (I) [162.54 (9)°; Lu et al., 2005] may be ascribed to the bridging mode of the two NO3− ions, rather than the chelating coordination of just one NO3− ions in (I). The Ag···O distances in (II) (Table 1) are longer than those in (I) [2.760 (3) and 2.801 (3) Å; Lu et al., 2005]. The Ag···Ag distance of 3.317 (1) Å is within the sum of van der Waals radii for two AgI centers (3.44 Å; Bondi, 1964) and can be considered as an Ag···Ag interaction.
In the dinuclear unit, π–π interactions are observed between adjacent pyridine rings, with a centroid–centroid distance of 3.579 (2) Å. The dinuclear units are linked by O—H···O hydrogen bonds involving the water molecules, the hydroxy groups in the 3-PyOH ligands and the NO3− ions, into a three-dimensional hydrogen-bonded framework (Fig. 2 and Table 2).