The Ag
I atom in the polycationic salt, {[Ag(C
11H
11N
3O)]NO
3}
n, shows a linear coordination [N—Ag—N = 175.0 (2)°]; the polymeric nature arises from bridging by the pyrazine portion of the ligand, resulting in chains extending parallel to [100]. The NO
3− counter-ions surround the polymeric chain and interact only weakly with it [Ag
O = 2.701 (4) and 2.810 (5) Å]. Adjacent chains are linked into a three-dimensional network by O—H
O and N—H
O hydrogen bonds.
Supporting information
CCDC reference: 899579
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.043
- wR factor = 0.125
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of N4
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 6.690
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2
Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension . 1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............ 2
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.14 Ratio
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 18
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
7 ALERT level G = General information/check it is not something unexpected
2 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
3 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
3 ALERT type 5 Informative message, check
An acetonitrile solution (10 ml) of silver nitrate (1 mmol) was added to a
methanol solution (5 ml) of 2-[(pyrazin-2-ylamino)methyl]phenol (1 mmol). The
solution was filtered and then side aside, away from light, for the growth of
crystals. Colorless crystals were obtained after several days.
Hydrogen atoms were placed in calculated positions (C–H 0.93–0.97, N–H 0.88,
O–H 0.84 Å) and were included in the refinement in the riding model
approximation, with U(H) set to 1.2–1.5U(C,N,O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
catena-Poly[[silver(I)-µ-2-[(pyrazin-2-yl-
κ2N1:
N4)aminomethyl]phenol] nitrate]
top
Crystal data top
[Ag(C11H11N3O)]NO3 | F(000) = 736 |
Mr = 371.11 | Dx = 1.962 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5867 reflections |
a = 7.1265 (9) Å | θ = 3.1–27.5° |
b = 9.5249 (14) Å | µ = 1.63 mm−1 |
c = 18.654 (2) Å | T = 293 K |
β = 97.240 (4)° | Prism, colorless |
V = 1256.1 (3) Å3 | 0.27 × 0.18 × 0.13 mm |
Z = 4 | |
Data collection top
Rigaku R-AXIS RAPID IP diffractometer | 2864 independent reflections |
Radiation source: fine-focus sealed tube | 2038 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scan | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→8 |
Tmin = 0.668, Tmax = 0.817 | k = −12→12 |
11969 measured reflections | l = −24→24 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0508P)2 + 4.1394P] where P = (Fo2 + 2Fc2)/3 |
2864 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
Crystal data top
[Ag(C11H11N3O)]NO3 | V = 1256.1 (3) Å3 |
Mr = 371.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1265 (9) Å | µ = 1.63 mm−1 |
b = 9.5249 (14) Å | T = 293 K |
c = 18.654 (2) Å | 0.27 × 0.18 × 0.13 mm |
β = 97.240 (4)° | |
Data collection top
Rigaku R-AXIS RAPID IP diffractometer | 2864 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2038 reflections with I > 2σ(I) |
Tmin = 0.668, Tmax = 0.817 | Rint = 0.042 |
11969 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.64 e Å−3 |
2864 reflections | Δρmin = −0.77 e Å−3 |
182 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ag1 | 0.06666 (5) | 0.59659 (5) | 0.58246 (2) | 0.05110 (18) | |
O1 | 0.3023 (5) | 0.4649 (5) | 0.8136 (2) | 0.0571 (10) | |
H1 | 0.2582 | 0.5291 | 0.8375 | 0.086* | |
O2 | −0.0170 (6) | 0.6917 (5) | 0.4458 (2) | 0.0575 (11) | |
O3 | 0.1837 (5) | 0.8322 (5) | 0.4064 (2) | 0.0574 (11) | |
O4 | −0.0257 (6) | 0.7272 (6) | 0.3321 (2) | 0.0658 (12) | |
N1 | 0.3716 (5) | 0.5848 (4) | 0.5842 (2) | 0.0316 (8) | |
N2 | 0.7616 (5) | 0.5983 (4) | 0.5896 (2) | 0.0361 (9) | |
N3 | 0.4029 (6) | 0.4097 (5) | 0.6707 (2) | 0.0434 (10) | |
H3 | 0.2785 | 0.4081 | 0.6661 | 0.052* | |
N4 | 0.0450 (6) | 0.7509 (5) | 0.3943 (2) | 0.0414 (10) | |
C1 | 0.4556 (6) | 0.6685 (5) | 0.5406 (3) | 0.0352 (10) | |
H1A | 0.3804 | 0.7245 | 0.5078 | 0.042* | |
C2 | 0.6473 (7) | 0.6755 (5) | 0.5421 (3) | 0.0397 (11) | |
H2 | 0.6993 | 0.7341 | 0.5100 | 0.048* | |
C3 | 0.6828 (6) | 0.5159 (6) | 0.6338 (3) | 0.0368 (11) | |
H3A | 0.7599 | 0.4648 | 0.6683 | 0.044* | |
C4 | 0.4845 (6) | 0.5027 (5) | 0.6304 (2) | 0.0328 (10) | |
C5 | 0.5036 (8) | 0.3108 (6) | 0.7217 (3) | 0.0442 (12) | |
H5A | 0.6001 | 0.2642 | 0.6980 | 0.053* | |
H5B | 0.4151 | 0.2395 | 0.7333 | 0.053* | |
C6 | 0.5967 (7) | 0.3745 (5) | 0.7914 (3) | 0.0371 (11) | |
C7 | 0.7896 (7) | 0.3554 (6) | 0.8134 (3) | 0.0451 (12) | |
H7 | 0.8625 | 0.3062 | 0.7839 | 0.054* | |
C8 | 0.8733 (8) | 0.4086 (6) | 0.8783 (3) | 0.0510 (14) | |
H8 | 1.0016 | 0.3941 | 0.8926 | 0.061* | |
C9 | 0.7677 (8) | 0.4832 (7) | 0.9221 (3) | 0.0529 (14) | |
H9 | 0.8247 | 0.5192 | 0.9658 | 0.063* | |
C10 | 0.5791 (8) | 0.5042 (6) | 0.9013 (3) | 0.0472 (13) | |
H10 | 0.5082 | 0.5552 | 0.9308 | 0.057* | |
C11 | 0.4926 (7) | 0.4498 (6) | 0.8363 (3) | 0.0404 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.0201 (2) | 0.0684 (3) | 0.0657 (3) | 0.00250 (18) | 0.00874 (18) | 0.0059 (2) |
O1 | 0.039 (2) | 0.071 (3) | 0.062 (3) | 0.008 (2) | 0.0080 (19) | −0.008 (2) |
O2 | 0.050 (2) | 0.066 (3) | 0.059 (2) | 0.000 (2) | 0.018 (2) | 0.015 (2) |
O3 | 0.039 (2) | 0.064 (3) | 0.067 (3) | −0.0142 (19) | −0.0030 (19) | 0.011 (2) |
O4 | 0.048 (2) | 0.102 (4) | 0.047 (2) | −0.010 (2) | 0.0027 (19) | −0.012 (2) |
N1 | 0.0186 (16) | 0.038 (2) | 0.038 (2) | 0.0005 (15) | 0.0023 (15) | 0.0005 (17) |
N2 | 0.0183 (16) | 0.044 (2) | 0.046 (2) | −0.0003 (16) | 0.0028 (16) | 0.0007 (19) |
N3 | 0.028 (2) | 0.059 (3) | 0.043 (2) | −0.006 (2) | 0.0052 (18) | 0.010 (2) |
N4 | 0.028 (2) | 0.046 (3) | 0.050 (3) | −0.0013 (18) | 0.0086 (19) | −0.002 (2) |
C1 | 0.024 (2) | 0.035 (3) | 0.047 (3) | 0.0019 (19) | 0.005 (2) | 0.004 (2) |
C2 | 0.029 (2) | 0.041 (3) | 0.050 (3) | −0.002 (2) | 0.012 (2) | 0.008 (2) |
C3 | 0.022 (2) | 0.048 (3) | 0.041 (3) | 0.005 (2) | 0.0058 (19) | 0.002 (2) |
C4 | 0.025 (2) | 0.041 (3) | 0.034 (2) | −0.0041 (19) | 0.0101 (18) | −0.007 (2) |
C5 | 0.042 (3) | 0.046 (3) | 0.045 (3) | 0.002 (2) | 0.010 (2) | 0.003 (2) |
C6 | 0.038 (2) | 0.036 (3) | 0.039 (3) | −0.001 (2) | 0.009 (2) | 0.007 (2) |
C7 | 0.038 (3) | 0.047 (3) | 0.051 (3) | 0.005 (2) | 0.013 (2) | 0.014 (3) |
C8 | 0.035 (3) | 0.049 (3) | 0.067 (4) | 0.002 (2) | −0.002 (3) | 0.014 (3) |
C9 | 0.052 (3) | 0.053 (4) | 0.051 (3) | −0.008 (3) | −0.005 (3) | 0.003 (3) |
C10 | 0.052 (3) | 0.046 (3) | 0.044 (3) | −0.002 (3) | 0.010 (3) | −0.006 (2) |
C11 | 0.035 (2) | 0.040 (3) | 0.047 (3) | 0.001 (2) | 0.007 (2) | 0.005 (2) |
Geometric parameters (Å, º) top
Ag1—N1 | 2.172 (4) | C1—H1A | 0.9300 |
Ag1—N2i | 2.195 (4) | C2—H2 | 0.9300 |
Ag1—O2 | 2.701 (4) | C3—C4 | 1.412 (6) |
Ag1—O2ii | 2.810 (5) | C3—H3A | 0.9300 |
O1—C11 | 1.376 (6) | C5—C6 | 1.511 (7) |
O1—H1 | 0.8400 | C5—H5A | 0.9700 |
O2—N4 | 1.242 (6) | C5—H5B | 0.9700 |
O3—N4 | 1.254 (6) | C6—C7 | 1.396 (7) |
O4—N4 | 1.225 (6) | C6—C11 | 1.386 (7) |
N1—C1 | 1.333 (6) | C7—C8 | 1.377 (8) |
N1—C4 | 1.352 (6) | C7—H7 | 0.9300 |
N2—C3 | 1.314 (6) | C8—C9 | 1.376 (9) |
N2—C2 | 1.344 (6) | C8—H8 | 0.9300 |
N2—Ag1iii | 2.195 (4) | C9—C10 | 1.366 (8) |
N3—C4 | 1.342 (6) | C9—H9 | 0.9300 |
N3—C5 | 1.461 (7) | C10—C11 | 1.390 (8) |
N3—H3 | 0.8800 | C10—H10 | 0.9300 |
C1—C2 | 1.364 (6) | | |
| | | |
N1—Ag1—N2i | 175.01 (15) | C4—C3—H3A | 119.0 |
N1—Ag1—O2 | 97.63 (13) | N1—C4—N3 | 118.3 (4) |
N2i—Ag1—O2 | 87.27 (14) | N1—C4—C3 | 119.3 (4) |
N1—Ag1—O2ii | 93.12 (13) | N3—C4—C3 | 122.4 (5) |
N2i—Ag1—O2ii | 85.21 (14) | N3—C5—C6 | 115.3 (4) |
O2—Ag1—O2ii | 98.24 (12) | N3—C5—H5A | 108.5 |
C11—O1—H1 | 109.5 | C6—C5—H5A | 108.5 |
N4—O2—Ag1 | 145.6 (3) | N3—C5—H5B | 108.5 |
C1—N1—C4 | 117.2 (4) | C6—C5—H5B | 108.5 |
C1—N1—Ag1 | 119.1 (3) | H5A—C5—H5B | 107.5 |
C4—N1—Ag1 | 123.6 (3) | C7—C6—C11 | 118.1 (5) |
C3—N2—C2 | 117.9 (4) | C7—C6—C5 | 120.7 (5) |
C3—N2—Ag1iii | 122.6 (3) | C11—C6—C5 | 121.2 (5) |
C2—N2—Ag1iii | 119.1 (3) | C6—C7—C8 | 120.8 (5) |
C4—N3—C5 | 125.3 (4) | C6—C7—H7 | 119.6 |
C4—N3—H3 | 117.3 | C8—C7—H7 | 119.6 |
C5—N3—H3 | 117.3 | C9—C8—C7 | 120.2 (5) |
O4—N4—O2 | 120.3 (5) | C9—C8—H8 | 119.9 |
O4—N4—O3 | 120.3 (5) | C7—C8—H8 | 119.9 |
O2—N4—O3 | 119.4 (5) | C8—C9—C10 | 120.0 (5) |
N1—C1—C2 | 122.9 (5) | C8—C9—H9 | 120.0 |
N1—C1—H1A | 118.6 | C10—C9—H9 | 120.0 |
C2—C1—H1A | 118.6 | C9—C10—C11 | 120.3 (5) |
C1—C2—N2 | 120.6 (4) | C9—C10—H10 | 119.8 |
C1—C2—H2 | 119.7 | C11—C10—H10 | 119.8 |
N2—C2—H2 | 119.7 | C6—C11—C10 | 120.5 (5) |
N2—C3—C4 | 121.9 (4) | C6—C11—O1 | 116.7 (5) |
N2—C3—H3A | 119.0 | C10—C11—O1 | 122.7 (5) |
| | | |
N1—Ag1—O2—N4 | −19.9 (6) | C5—N3—C4—N1 | 178.2 (5) |
N2i—Ag1—O2—N4 | 161.0 (6) | C5—N3—C4—C3 | −0.7 (8) |
O2ii—Ag1—O2—N4 | −114.2 (6) | N2—C3—C4—N1 | −5.1 (7) |
O2—Ag1—N1—C1 | 26.1 (4) | N2—C3—C4—N3 | 173.8 (5) |
O2ii—Ag1—N1—C1 | 124.9 (4) | C4—N3—C5—C6 | 73.9 (6) |
O2ii—Ag1—N1—C4 | −59.3 (4) | N3—C5—C6—C7 | −124.6 (5) |
Ag1—O2—N4—O4 | 152.0 (5) | N3—C5—C6—C11 | 57.3 (6) |
Ag1—O2—N4—O3 | −26.1 (9) | C11—C6—C7—C8 | 0.7 (8) |
C4—N1—C1—C2 | −1.2 (7) | C5—C6—C7—C8 | −177.4 (5) |
Ag1—N1—C1—C2 | 174.9 (4) | C6—C7—C8—C9 | −0.8 (8) |
N1—C1—C2—N2 | −1.3 (8) | C7—C8—C9—C10 | 0.2 (9) |
C3—N2—C2—C1 | 0.5 (7) | C8—C9—C10—C11 | 0.5 (9) |
Ag1iii—N2—C2—C1 | 173.7 (4) | C7—C6—C11—C10 | −0.1 (8) |
C2—N2—C3—C4 | 2.6 (7) | C5—C6—C11—C10 | 178.1 (5) |
Ag1iii—N2—C3—C4 | −170.3 (4) | C7—C6—C11—O1 | −179.0 (5) |
C1—N1—C4—N3 | −174.8 (4) | C5—C6—C11—O1 | −0.9 (7) |
Ag1—N1—C4—N3 | 9.2 (6) | C9—C10—C11—C6 | −0.6 (8) |
C1—N1—C4—C3 | 4.2 (7) | C9—C10—C11—O1 | 178.4 (5) |
Ag1—N1—C4—C3 | −171.8 (3) | | |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1; (iii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3iv | 0.84 | 1.96 | 2.795 (6) | 171 |
N3—H3···O4ii | 0.88 | 2.22 | 2.982 (6) | 145 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iv) x, −y+3/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Ag(C11H11N3O)]NO3 |
Mr | 371.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.1265 (9), 9.5249 (14), 18.654 (2) |
β (°) | 97.240 (4) |
V (Å3) | 1256.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.63 |
Crystal size (mm) | 0.27 × 0.18 × 0.13 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID IP diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.668, 0.817 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11969, 2864, 2038 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.125, 1.02 |
No. of reflections | 2864 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.77 |
Selected bond lengths (Å) topAg1—N1 | 2.172 (4) | Ag1—N2i | 2.195 (4) |
Symmetry code: (i) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3ii | 0.84 | 1.96 | 2.795 (6) | 171 |
N3—H3···O4iii | 0.88 | 2.22 | 2.982 (6) | 145 |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x, −y+1, −z+1. |
A recent study reports 2-[(pyrazin-2-ylamino)methyl]phenol, a reduced Schiff-base that possesses an acidic phenolic group (Gao & Ng, 2012). The reaction with silver nitrate yields polycationic [Ag(C11H11N3O)]n nNO3 (Scheme I). The polymeric nature arises from bridging by the pyrazine portion of the ligand. The counterions surround the chain and interact only weakly with it [Ag···O 2.701 (4), 2.810 (5) Å] (Fig. 1). Adjacent chains are linked into a three-dimensional network by O–H···O and N–H···O hydrogen bonds (Table 1).