catena-Poly­[[(di-2-pyridyl­amine)­silver(I)]-μ-nicotinato] and catena-poly­[[(di-2-pyridyl­amine)silver(I)]-μ-2,6-di­hydroxy­benzoato]

In catena-poly­[[(di-2-pyridyl­amine-κ²N,N′)silver(I)]-μ-nico­tinato-κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di-2-pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H...O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H...O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena-poly­[[(di-2-pyridyl­amine-κ²N,N′)silver(I)]-μ-2,6-di­hydroxy­benzoato-κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6-di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag-atom coordination is to one of the phenol O atoms [Ag...O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H...O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H...O hydrogen bonds and additional π–π interactions between inversion-related pairs of 2,6-di­hydroxy­benzoate ligands to generate a three-dimensional network.

S1. Comment

Silver(I) complexes with Ag—N bonds have been found to show effective antimicrobial activity (Spadaro et al., 1974; Nomiya et al., 1997) and silver compounds with pyridine or its derivatives have attracted attention recently (Zhu et al., 2001; Zhu et al., 2003; Bi et al., 2002; Kristiansson, 2000). Among the compounds containing a pyridine ring, nicotinic acid (3-pyridinecarboxylic acid; niacin; vitamin B; henceforth NA) plays important roles in metabolism. Dihydroxybenzoic acids are known to be strong antioxidants (Maoka et al., 1997). As one example, 2,6-dihydroxybenzoic acid (2,6-DHB) is known to have a cytotoxic effect on tumor cells at low pH values when mixed with acetylsalicylic acid (Kreutz, 1998). Moreover 2,6-DHB always shows versatile coordination modes in its complexes. We report here the structures of two complexes of Ag^I, viz. compound (I) with NA and a bidentate pyridine-based ligand, 2,2'-bipyridylamine (BPA) [Ag(NA)(BPA)]_n, and compound (II) with 2,6-DHB and BPA [Ag(2,6-DHB)(BPA)]_n.

In (I) there is a one-dimensional polymer chain (Fig. 1), with each Ag^I atom coordinated to two N atoms from a BPA ligand, one N atom from a nicotinate ligand and one carboxylate O atom from another nicotinate ligand [at (1 + x,y,z)] as shown in Fig. 1; geometric details are given in Table 1. The coordination geometry of the Ag^I ion is best described as distorted tetrahedral. The carboxyl atom (O1) that is not bonded to the Ag atom takes part in an intrachain C—H···O hydrogen bond, further stabilizing the chain (Table 2).

The coordination mode of (I) can be compared with some previous findings for the silver(I)–nicotinic acid system. In catena-[pyridine-3-carboxylato-(O,O')]silver(I) (Smith & Reddy, 1994), the Ag^I ion has a trigonal coordination geometry, being connected to three nicotinate residues, two via carboxylate O atoms and the third through the pyridine N atom [Ag—O = 2.258 (8) and 2.280 (8) Å, and Ag—N = 2.362 (10) Å]; in ammonium bis[pyridine-3-carboxylato-(O,N,N')]silver(I) monohydrate (Smith & Reddy, 1994), the Ag^I ion also has three-coordinate distorted trigonal planar geometry and is bonded to two pyridine N atoms and one carboxylate O atom from three independent nicotinate ligands [Ag—N = 2.248 (3) and 2.269 (3) Å, and Ag—O = 2.342 (2) Å]. The Ag^I coordination mode in (I) is also different from that reported in catena-bis[pyridine-3-carboxylato-(N,N')]silver(I) (Käll et al., 2001), where the Ag^I ion has distorted octahedral coordination geometry lies on an inversion centre with the N atoms in axial positions (Ag—N = 2.234 Å and N—Ag—N 180°) and is bonded weakly to four carboxylate O atoms from four independent nicotinate molecules (Ag—O = 2.803 and 2.821 Å). The Ag—N distances in (I) are slightly longer than those in silver complexes of other pyridine derivatives, such as bis(3-amino-2-chloropyridine-κN)silver(I) perchlorate [2.197 (4)–2.199 (4) Å; Li et al., 2002], bis(2-aminopyridine-κN¹)(benzoate-κO)silver(I) [2.205 (4)–2.230 (3) Å; Zhu et al., 2003] and catena-poly[silver(I)-µ-4,4'-bipyridine]nitrate [2.211 (4) Å; Bi et al., 2002].

In the nicotinate ligand, the carboxyl group plane (C3/C7/O1/O2) is rotated 10.7 (1)° around the exocyclic C3—C7 bond out of the N1/C2–C7 plane. The two pyridine rings in the BPA ligand have an interplanar angle of 9.7 (1)°, and the six-membered Ag1/N11/C12/N3/C22/N21 ring has a slightly deformed envelope conformation, with atom Ag1 as the flap.

In the crystal structure (Fig. 2), pairs of inversion related chains are linked by N—H···O hydrogen bonds (Table 2) to generate ribbons extending along [100]. Calculations with PLATON (Spek, 2003) show that there are only van der Waals interactions between the ribbons.

In complex (II) (Fig. 3), atom Ag^I has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand and one carboxylate O atom from the 2,6-dihydroxybenzoate group; the fourth, weaker, Ag-atom coordination is to one of the phenol O atoms (O61) of an adjacent moiety (Table 3), thus generating a polymeric chain along [100]. BPA atoms N11 and N12 together with carboxyl atom O2 are the atoms that are strongly bonded to atom Ag1; these atoms define a trigonal plane, with atom Ag1 0.319 (2) Å from the plane.

In the 2,6-DHB ligand, the carboxyl group plane (C3/C7/O1/O2) is rotated 2.4 (3)° around the exocyclic C1—C7 bond out of the C1–C7 plane. Both phenol OH groups form intramolecular O—H···O hydrogen bonds (Table 4) with adjacent carboxyl O atoms. The two pyridine rings in the BPA ligand have an interplanar angle of 5.2 (2)°, and as in (I), the six-membered Ag1/N11/C12/N3/C22/N21 ring has a slightly deformed envelope conformation, with atom Ag1 as the flap. With the participation of the BPA ligand, the Ag coordination environment in (II) is (as expected) completely different from the dimer-bridged coordination mode reported for the 2,6-DHB ligand in bis(µ₂-2,6-dihydroxybenzoato-O,O')disilver(I) (Smith et al., 1988).

In the crystal structure of (II), inversion-related chains are linked [as in (I)] by N—H···O hydrogen bonds involving the BPA N3/H3 group and carboxyl atom O1 of an adjacent moiety (Table 1), thus generating ribbons extending along [100], as shown in Fig. 4. Also present in these ribbons are π–π interactions between inversion-related BPA ligands. The distance between the ring centroids of the N11/c12–C16 and N21/c22–C26 BPA pyridine rings [at (1 − x,1 − y,1 − z)] is 3.616 Å and the shortest atom–atom separation is 3.466 (9) Å, between atoms C12 and C22 [at (1 − x,1 − y,1 − z)]. This ring overlap can be seen clearly in Fig. 5, which also shows that the ribbons are linked by an inter-ribbon C—H···O hydrogen bond involving the C25/H25 group and phenol atom O21(x,y − 1,z), which is not involved in any Ag contact (see Table 4). There are in addition a second set of π–π interactions between inversion-related 2,6-DHB ligands. The centroid of the C1–C6 aromatic ring at (x,y,z) is 3.763 Å from the centroid of the same ring at (2 − x,2 − y,-z); the distance between these parallel rings is 3.425 Å and the shortest C···C contact is 3.413 (3) Å, between atoms C2 and C6 [at (2 − x,2 − y,-z)]. The overall effect of all these interactions is to generate a three-dimensional network.

S2. Experimental

Thin colorless needle-shaped crystals of (I) were obtained by slow evaporation of an aqueous solution (containing a small amount of methanol) of a mixture of nicotinic acid acid, 2,2'-bipyridineamine and AgNO₃ (molar ratio 1:1:1) at room temperature. Colorless prismatic crystals of (II) were obtained by slow evaporation of a mixture of 2,6-dihydroxybenzoic acid, 2,2'-bipyridineamine and AgNO₃ (molar ratio 4:4:1) in methanol/water (80%) at room temperature.

S3. Refinement

For both (I) and (II), all H atoms were clearly visible in difference Fourier maps. H atoms were allowed for as riding atoms in the refinements, with C—H distances of 0.93 Å, N—H distance of 0.86 Å and O—H distances of 0.82 Å, and with U_iso(H) = 1.2U_eq(C,N) and 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2003) for (I); CrystalStructure (Rigaku/MSC, 2004) and CRYSTALS (Watkin et al., 1996) for (II). Cell refinement: RAPID-AUTO (Rigaku, 2003) for (I); Crystal Structure and CRYSTALS for (II). Data reduction: CrystalStructure (Rigaku/MSC, 2004) and CRYSTALS (Watkin et al., 1996) for (I); CrystalStructure and CRYSTALS for (II). For both compounds, program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: WORDPERFECT.

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of part of the polymeric chain in (I), with the atomic numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. [Symmetry codes: (a) x − 1,y,z; (b) 1 + x,y,z.]
	Fig. 2. A view of a pair of inversion-related chains linked by N—H···O hydrogen bonds to generate a ribbon extending in the a direction. Hydrogen bonds are indicated by broken lines. [Symmetry codes: (#) −x,-y,1 − z; (*) 1 + x,y,z.]
	Fig. 3. An ORTEP-3 (Farrugia, 1997) drawing of part of the polymeric chain in (II), with the atomic numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. [Symmetry codes: (a) x − 1,y,z; (b) 1 + x,y,z.]
	Fig. 4. A view of a pair of inversion-related chains linked by N—H···O hydrogen bonds to generate a ribbon extending in the a direction. The weak Ag···O contact and hydrogen bonds are indicated by broken lines. [Symmetry codes: (#) 1 − x,1 − y,1 − z; (*) 1 + x,y,z; (dollar) x − 1,y,z.]
	Fig. 5. A stereoview along the a direction of part of the structure of (II), showing π–π interactions between inversion-related pairs of BPA ligands and between inversion-related pairs of 2,6-DHB ligands.

(I) catena-Poly[[(di-2-pyridylamine-κ²N,N')silver(I)]-µ-nicotinato- κ²N:O]

Crystal data

[Ag(C6H4NO2)(C10H9N3)]	F(000) = 800
Mr = 401.17	Dx = 1.718 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12577 reflections
a = 7.9623 (1) Å	θ = 3.0–27.5°
b = 8.9487 (1) Å	µ = 1.31 mm^−1
c = 21.887 (1) Å	T = 296 K
β = 96.000 (1)°	Prism, colorless
V = 1550.95 (8) Å^3	0.30 × 0.10 × 0.10 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	3530 independent reflections
Radiation source: fine-focus sealed tube	2779 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.0 pixels mm^-1	θmax = 27.6°, θmin = 3.4°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
Tmin = 0.649, Tmax = 0.877	l = −28→28
15058 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H-atom parameters constrained
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0291P)^2] where P = (Fo^2 + 2Fc^2)/3
3530 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.233689 (19)	0.17553 (2)	0.385416 (8)	0.05460 (7)
O1	−0.58654 (18)	0.3494 (2)	0.29926 (7)	0.0700 (5)
O2	−0.47617 (17)	0.22560 (18)	0.38149 (7)	0.0622 (4)
N1	0.00773 (19)	0.29422 (18)	0.33394 (8)	0.0467 (4)
N3	0.3099 (2)	−0.06456 (17)	0.51457 (7)	0.0467 (4)
H3	0.3630	−0.1119	0.5449	0.056*
N11	0.1748 (3)	0.1666 (2)	0.48968 (8)	0.0602 (5)
N21	0.2491 (2)	−0.07973 (19)	0.40620 (8)	0.0514 (4)
C2	−0.1497 (2)	0.2719 (2)	0.34789 (9)	0.0423 (4)
H2	−0.1648	0.2061	0.3798	0.051*
C3	−0.2906 (2)	0.3390 (2)	0.31856 (8)	0.0359 (4)
C4	−0.2683 (2)	0.4402 (2)	0.27226 (10)	0.0493 (5)
H4	−0.3603	0.4885	0.2512	0.059*
C5	−0.1082 (3)	0.4676 (2)	0.25825 (10)	0.0561 (6)
H5	−0.0895	0.5369	0.2280	0.067*
C6	0.0257 (2)	0.3920 (2)	0.28912 (9)	0.0493 (5)
H6	0.1337	0.4101	0.2782	0.059*
C7	−0.4660 (2)	0.3029 (2)	0.33416 (9)	0.0403 (4)
C12	0.2511 (2)	0.0737 (2)	0.53106 (9)	0.0425 (4)
C13	0.2755 (3)	0.1092 (3)	0.59323 (11)	0.0627 (6)
H13	0.3331	0.0436	0.6210	0.075*
C14	0.2148 (4)	0.2403 (3)	0.61315 (12)	0.0811 (8)
H14	0.2296	0.2650	0.6546	0.097*
C15	0.1310 (4)	0.3362 (3)	0.57117 (14)	0.0843 (9)
H15	0.0860	0.4257	0.5836	0.101*
C16	0.1162 (4)	0.2960 (3)	0.51124 (13)	0.0807 (8)
H16	0.0619	0.3620	0.4829	0.097*
C22	0.3019 (2)	−0.1433 (2)	0.45989 (9)	0.0442 (5)
C23	0.3547 (3)	−0.2930 (2)	0.46413 (12)	0.0635 (6)
H23	0.3908	−0.3351	0.5021	0.076*
C24	0.3522 (4)	−0.3759 (3)	0.41163 (14)	0.0801 (8)
H24	0.3871	−0.4751	0.4135	0.096*
C25	0.2974 (4)	−0.3114 (3)	0.35561 (14)	0.0797 (8)
H25	0.2959	−0.3658	0.3193	0.096*
C26	0.2462 (3)	−0.1671 (3)	0.35497 (12)	0.0679 (7)
H26	0.2067	−0.1249	0.3174	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.04412 (10)	0.06451 (12)	0.05617 (12)	0.01111 (8)	0.01003 (7)	0.02146 (8)
O1	0.0346 (7)	0.1119 (14)	0.0626 (10)	0.0128 (8)	0.0011 (7)	0.0200 (10)
O2	0.0381 (8)	0.0809 (11)	0.0685 (10)	0.0042 (8)	0.0100 (7)	0.0295 (9)
N1	0.0337 (8)	0.0546 (10)	0.0520 (10)	0.0026 (7)	0.0049 (7)	0.0160 (8)
N3	0.0566 (10)	0.0436 (10)	0.0398 (9)	0.0098 (8)	0.0044 (8)	0.0071 (7)
N11	0.0784 (13)	0.0554 (12)	0.0482 (10)	0.0244 (10)	0.0131 (9)	0.0060 (9)
N21	0.0602 (11)	0.0498 (11)	0.0444 (10)	−0.0031 (8)	0.0063 (8)	−0.0002 (8)
C2	0.0372 (10)	0.0471 (11)	0.0431 (11)	−0.0006 (8)	0.0059 (8)	0.0133 (9)
C3	0.0347 (9)	0.0367 (10)	0.0365 (9)	0.0021 (8)	0.0040 (8)	−0.0026 (8)
C4	0.0416 (11)	0.0566 (13)	0.0485 (12)	0.0079 (10)	−0.0011 (9)	0.0121 (10)
C5	0.0496 (12)	0.0642 (14)	0.0545 (13)	−0.0011 (11)	0.0053 (10)	0.0270 (11)
C6	0.0377 (10)	0.0594 (13)	0.0515 (12)	−0.0046 (10)	0.0074 (9)	0.0131 (10)
C7	0.0358 (9)	0.0418 (11)	0.0435 (11)	0.0043 (8)	0.0050 (8)	−0.0072 (9)
C12	0.0429 (10)	0.0408 (11)	0.0450 (11)	0.0000 (9)	0.0094 (9)	0.0034 (9)
C13	0.0869 (18)	0.0531 (13)	0.0467 (12)	0.0054 (12)	0.0008 (12)	0.0002 (11)
C14	0.123 (2)	0.0655 (17)	0.0541 (16)	0.0063 (17)	0.0071 (15)	−0.0153 (13)
C15	0.117 (2)	0.0584 (17)	0.0791 (19)	0.0260 (15)	0.0191 (17)	−0.0127 (14)
C16	0.109 (2)	0.0640 (17)	0.0697 (18)	0.0372 (15)	0.0125 (16)	0.0073 (13)
C22	0.0436 (11)	0.0411 (11)	0.0493 (12)	−0.0001 (8)	0.0112 (9)	0.0018 (9)
C23	0.0767 (16)	0.0488 (13)	0.0663 (15)	0.0089 (12)	0.0142 (13)	0.0040 (12)
C24	0.099 (2)	0.0517 (15)	0.094 (2)	0.0061 (14)	0.0294 (17)	−0.0123 (15)
C25	0.098 (2)	0.0718 (19)	0.0720 (19)	−0.0135 (16)	0.0202 (16)	−0.0269 (15)
C26	0.0793 (17)	0.0761 (19)	0.0484 (14)	−0.0081 (14)	0.0066 (12)	−0.0058 (12)

Geometric parameters (Å, º)

Ag1—N1	2.2827 (15)	C4—H4	0.93
Ag1—N11	2.3785 (18)	C5—C6	1.378 (3)
Ag1—N21	2.3298 (18)	C5—H5	0.93
Ag1—O2^i	2.3636 (14)	C6—H6	0.93
O1—C7	1.235 (2)	C12—C13	1.391 (3)
O2—C7	1.255 (2)	C13—C14	1.358 (4)
O2—Ag1^ii	2.3636 (14)	C13—H13	0.93
N1—C6	1.334 (2)	C14—C15	1.378 (4)
N1—C2	1.336 (2)	C14—H14	0.93
N3—C12	1.384 (2)	C15—C16	1.353 (4)
N3—C22	1.385 (2)	C15—H15	0.93
N3—H3	0.86	C16—H16	0.93
N11—C12	1.329 (2)	C22—C23	1.405 (3)
N11—C16	1.351 (3)	C23—C24	1.366 (3)
N21—C22	1.333 (3)	C23—H23	0.93
N21—C26	1.365 (3)	C24—C25	1.384 (4)
C2—C3	1.372 (3)	C24—H24	0.93
C2—H2	0.93	C25—C26	1.354 (3)
C3—C4	1.385 (3)	C25—H25	0.93
C3—C7	1.507 (3)	C26—H26	0.93
C4—C5	1.364 (3)
N1—Ag1—N21	125.12 (6)	O1—C7—O2	125.66 (19)
N1—Ag1—O2^i	128.08 (5)	O1—C7—C3	117.81 (18)
N21—Ag1—O2^i	99.28 (6)	O2—C7—C3	116.52 (17)
N1—Ag1—N11	105.36 (6)	N11—C12—N3	121.65 (18)
N21—Ag1—N11	77.97 (6)	N11—C12—C13	122.08 (19)
O2^i—Ag1—N11	109.43 (6)	N3—C12—C13	116.27 (18)
C7—O2—Ag1^ii	106.39 (12)	C14—C13—C12	119.6 (2)
C6—N1—C2	116.24 (16)	C14—C13—H13	120.2
C6—N1—Ag1	121.92 (12)	C12—C13—H13	120.2
C2—N1—Ag1	121.83 (13)	C13—C14—C15	119.2 (2)
C12—N3—C22	133.95 (17)	C13—C14—H14	120.4
C12—N3—H3	113.0	C15—C14—H14	120.4
C22—N3—H3	113.0	C16—C15—C14	117.9 (2)
C12—N11—C16	116.6 (2)	C16—C15—H15	121.1
C12—N11—Ag1	123.57 (14)	C14—C15—H15	121.1
C16—N11—Ag1	114.61 (15)	N11—C16—C15	124.6 (2)
C22—N21—C26	117.15 (19)	N11—C16—H16	117.7
C22—N21—Ag1	126.55 (14)	C15—C16—H16	117.7
C26—N21—Ag1	113.90 (15)	N21—C22—N3	121.78 (17)
N1—C2—C3	124.66 (17)	N21—C22—C23	122.0 (2)
N1—C2—H2	117.7	N3—C22—C23	116.22 (19)
C3—C2—H2	117.7	C24—C23—C22	119.0 (2)
C2—C3—C4	117.90 (17)	C24—C23—H23	120.5
C2—C3—C7	122.16 (17)	C22—C23—H23	120.5
C4—C3—C7	119.93 (16)	C23—C24—C25	119.6 (3)
C5—C4—C3	118.44 (18)	C23—C24—H24	120.2
C5—C4—H4	120.8	C25—C24—H24	120.2
C3—C4—H4	120.8	C26—C25—C24	118.3 (3)
C4—C5—C6	119.69 (19)	C26—C25—H25	120.9
C4—C5—H5	120.2	C24—C25—H25	120.9
C6—C5—H5	120.2	C25—C26—N21	124.0 (2)
N1—C6—C5	123.04 (18)	C25—C26—H26	118.0
N1—C6—H6	118.5	N21—C26—H26	118.0
C5—C6—H6	118.5

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2^iii	0.86	2.03	2.894 (2)	177
C6—H6···O1^i	0.93	2.29	3.096 (2)	144

Symmetry codes: (i) x+1, y, z; (iii) −x, −y, −z+1.

(II) catena-poly[[(di-2-pyridylamine-κ²N,N')silver(I)]-µ-2,6-dihydroxybenzoato- κ²O¹:O²]

Crystal data

[Ag(C7H5O4)(C10H9N3)]	Z = 2
Mr = 432.18	F(000) = 432
Triclinic, P1	Dx = 1.822 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.56 (1) Å	Cell parameters from 6495 reflections
b = 9.23 (1) Å	θ = 3.1–27.6°
c = 12.01 (2) Å	µ = 1.31 mm^−1
α = 71.29 (5)°	T = 296 K
β = 82.87 (5)°	Block, colorless
γ = 87.44 (5)°	0.30 × 0.15 × 0.10 mm
V = 787.6 (19) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3567 independent reflections
Radiation source: fine-focus sealed tube	2402 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 10.00 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
Tmin = 0.672, Tmax = 0.878	l = −15→15
7753 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0754P)^2] where P = (Fo^2 + 2Fc^2)/3
3567 reflections	(Δ/σ)max = 0.002
228 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −1.28 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.39227 (5)	0.77082 (4)	0.27238 (4)	0.0583 (2)
O1	0.7839 (5)	0.8451 (4)	0.2814 (3)	0.0560 (10)
O2	0.5810 (4)	0.9525 (4)	0.1610 (3)	0.0530 (9)
O21	0.6521 (4)	1.1868 (4)	−0.0185 (3)	0.0538 (9)
H21	0.5887	1.1226	0.0320	0.065*
O61	1.0975 (5)	0.9485 (5)	0.2350 (3)	0.0539 (9)
H61	1.0108	0.9008	0.2760	0.065*
N3	0.2798 (6)	0.4296 (4)	0.5126 (3)	0.0466 (10)
H3	0.2744	0.3490	0.5738	0.056*
N11	0.2361 (5)	0.7001 (4)	0.4604 (3)	0.0412 (9)
N21	0.3765 (5)	0.5133 (5)	0.3060 (4)	0.0442 (10)
C1	0.8659 (6)	1.0629 (5)	0.1166 (4)	0.0334 (10)
C2	0.8178 (6)	1.1811 (5)	0.0155 (4)	0.0384 (10)
C3	0.9351 (7)	1.2925 (6)	−0.0495 (5)	0.0508 (13)
H3A	0.9001	1.3703	−0.1141	0.061*
C4	1.1044 (7)	1.2905 (6)	−0.0201 (5)	0.0550 (14)
H4	1.1833	1.3683	−0.0635	0.066*
C5	1.1586 (6)	1.1733 (6)	0.0738 (5)	0.0474 (12)
H5	1.2753	1.1705	0.0915	0.057*
C6	1.0421 (6)	1.0615 (5)	0.1407 (4)	0.0368 (10)
C7	0.7341 (7)	0.9444 (5)	0.1910 (4)	0.0403 (11)
C12	0.2176 (6)	0.5590 (5)	0.5400 (4)	0.0372 (10)
C13	0.1382 (7)	0.5354 (6)	0.6549 (4)	0.0529 (14)
H13	0.1260	0.4368	0.7081	0.063*
C14	0.0788 (8)	0.6563 (7)	0.6891 (5)	0.0605 (15)
H14	0.0253	0.6418	0.7658	0.073*
C15	0.0985 (8)	0.8027 (6)	0.6082 (5)	0.0574 (15)
H15	0.0605	0.8883	0.6296	0.069*
C16	0.1752 (7)	0.8163 (6)	0.4970 (4)	0.0481 (13)
H16	0.1859	0.9141	0.4424	0.058*
C22	0.3491 (6)	0.3994 (5)	0.4090 (4)	0.0369 (10)
C23	0.3820 (7)	0.2460 (6)	0.4187 (5)	0.0501 (13)
H23	0.3575	0.1699	0.4912	0.060*
C24	0.4492 (8)	0.2099 (7)	0.3226 (6)	0.0626 (16)
H24	0.4735	0.1084	0.3281	0.075*
C25	0.4822 (8)	0.3231 (8)	0.2158 (6)	0.0630 (16)
H25	0.5291	0.2996	0.1483	0.076*
C26	0.4447 (7)	0.4705 (7)	0.2108 (5)	0.0533 (14)
H26	0.4671	0.5465	0.1381	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0601 (3)	0.0467 (3)	0.0552 (3)	−0.0118 (2)	0.0100 (2)	−0.0027 (2)
O1	0.063 (2)	0.047 (2)	0.044 (2)	−0.0049 (18)	0.0059 (18)	0.0013 (16)
O2	0.0394 (19)	0.050 (2)	0.061 (2)	−0.0119 (15)	0.0042 (17)	−0.0072 (17)
O21	0.0390 (18)	0.061 (2)	0.052 (2)	−0.0015 (16)	−0.0109 (17)	−0.0032 (18)
O61	0.051 (2)	0.065 (2)	0.041 (2)	0.0104 (18)	−0.0134 (17)	−0.0081 (17)
N3	0.065 (3)	0.033 (2)	0.033 (2)	0.0002 (19)	0.0001 (19)	0.0004 (16)
N11	0.049 (2)	0.036 (2)	0.034 (2)	−0.0022 (17)	−0.0029 (18)	−0.0049 (16)
N21	0.047 (2)	0.043 (2)	0.037 (2)	−0.0033 (18)	−0.0014 (18)	−0.0065 (18)
C1	0.036 (2)	0.036 (2)	0.028 (2)	−0.0008 (18)	0.0012 (18)	−0.0102 (18)
C2	0.041 (2)	0.040 (3)	0.033 (2)	0.003 (2)	−0.005 (2)	−0.0095 (19)
C3	0.053 (3)	0.048 (3)	0.040 (3)	0.000 (2)	−0.002 (2)	0.001 (2)
C4	0.049 (3)	0.057 (3)	0.049 (3)	−0.017 (3)	0.006 (3)	−0.005 (3)
C5	0.036 (2)	0.063 (3)	0.050 (3)	−0.004 (2)	−0.006 (2)	−0.025 (3)
C6	0.039 (2)	0.046 (3)	0.027 (2)	0.004 (2)	−0.0060 (19)	−0.0140 (19)
C7	0.050 (3)	0.032 (2)	0.036 (2)	−0.003 (2)	0.008 (2)	−0.0107 (19)
C12	0.039 (2)	0.037 (2)	0.034 (2)	−0.0029 (19)	−0.005 (2)	−0.0080 (19)
C13	0.073 (4)	0.043 (3)	0.033 (3)	−0.005 (3)	0.009 (3)	−0.004 (2)
C14	0.071 (4)	0.066 (4)	0.039 (3)	0.000 (3)	0.008 (3)	−0.014 (3)
C15	0.075 (4)	0.052 (3)	0.051 (3)	0.018 (3)	−0.016 (3)	−0.022 (3)
C16	0.067 (3)	0.033 (3)	0.040 (3)	0.005 (2)	−0.013 (2)	−0.004 (2)
C22	0.037 (2)	0.040 (2)	0.033 (2)	−0.0028 (19)	−0.0058 (19)	−0.0088 (19)
C23	0.060 (3)	0.042 (3)	0.047 (3)	−0.001 (2)	−0.006 (3)	−0.013 (2)
C24	0.065 (4)	0.061 (4)	0.071 (4)	0.002 (3)	−0.009 (3)	−0.033 (3)
C25	0.059 (4)	0.078 (4)	0.063 (4)	0.000 (3)	−0.001 (3)	−0.040 (3)
C26	0.054 (3)	0.069 (4)	0.031 (3)	−0.002 (3)	−0.006 (2)	−0.009 (2)

Geometric parameters (Å, º)

Ag1—N11	2.320 (5)	C3—H3A	0.93
Ag1—N21	2.286 (5)	C4—C5	1.378 (8)
Ag1—O2	2.222 (4)	C4—H4	0.93
Ag1—O61^i	2.703 (4)	C5—C6	1.364 (7)
O1—C7	1.262 (6)	C5—H5	0.93
O2—C7	1.247 (6)	C12—C13	1.388 (7)
O21—C2	1.358 (6)	C13—C14	1.348 (8)
O21—H21	0.82	C13—H13	0.93
O61—C6	1.366 (6)	C14—C15	1.390 (8)
O61—H61	0.82	C14—H14	0.93
N3—C12	1.385 (6)	C15—C16	1.358 (7)
N3—C22	1.396 (6)	C15—H15	0.93
N3—H3	0.86	C16—H16	0.93
N11—C16	1.327 (6)	C22—C23	1.396 (7)
N11—C12	1.346 (6)	C23—C24	1.337 (8)
N21—C22	1.342 (6)	C23—H23	0.93
N21—C26	1.361 (7)	C24—C25	1.372 (9)
C1—C6	1.396 (7)	C24—H24	0.93
C1—C2	1.422 (6)	C25—C26	1.361 (8)
C1—C7	1.496 (6)	C25—H25	0.93
C2—C3	1.359 (7)	C26—H26	0.93
C3—C4	1.367 (8)
O2—Ag1—N21	133.99 (15)	O61—C6—C1	119.4 (4)
O2—Ag1—N11	138.13 (16)	O2—C7—O1	124.3 (4)
N11—Ag1—N21	80.97 (15)	O2—C7—C1	117.7 (4)
O2—Ag1—O61^i	95.21 (16)	O1—C7—C1	117.9 (5)
N21—Ag1—O61^i	120.49 (15)	N11—C12—N3	122.1 (4)
N11—Ag1—O61^i	78.52 (14)	N11—C12—C13	121.8 (5)
C7—O2—Ag1	116.2 (3)	N3—C12—C13	116.2 (4)
C2—O21—H21	109.5	C14—C13—C12	119.6 (5)
C6—O61—H61	109.5	C14—C13—H13	120.2
C12—N3—C22	134.9 (4)	C12—C13—H13	120.2
C12—N3—H3	112.5	C13—C14—C15	119.2 (5)
C22—N3—H3	112.5	C13—C14—H14	120.4
C16—N11—C12	117.0 (4)	C15—C14—H14	120.4
C16—N11—Ag1	114.6 (3)	C16—C15—C14	117.7 (5)
C12—N11—Ag1	128.0 (3)	C16—C15—H15	121.2
C22—N21—C26	115.6 (4)	C14—C15—H15	121.2
C22—N21—Ag1	129.2 (3)	N11—C16—C15	124.7 (5)
C26—N21—Ag1	113.2 (3)	N11—C16—H16	117.6
C6—C1—C2	116.7 (4)	C15—C16—H16	117.6
C6—C1—C7	122.2 (4)	N21—C22—N3	120.7 (4)
C2—C1—C7	121.1 (4)	N21—C22—C23	122.8 (4)
O21—C2—C3	118.0 (4)	N3—C22—C23	116.4 (4)
O21—C2—C1	120.9 (4)	C24—C23—C22	119.2 (5)
C3—C2—C1	121.2 (5)	C24—C23—H23	120.4
C2—C3—C4	120.2 (5)	C22—C23—H23	120.4
C2—C3—H3A	119.9	C23—C24—C25	119.8 (6)
C4—C3—H3A	119.9	C23—C24—H24	120.1
C3—C4—C5	120.2 (5)	C25—C24—H24	120.1
C3—C4—H4	119.9	C26—C25—C24	118.6 (5)
C5—C4—H4	119.9	C26—C25—H25	120.7
C6—C5—C4	120.4 (5)	C24—C25—H25	120.7
C6—C5—H5	119.8	N21—C26—C25	123.9 (5)
C4—C5—H5	119.8	N21—C26—H26	118.1
C5—C6—O61	119.4 (5)	C25—C26—H26	118.1
C5—C6—C1	121.2 (4)
N21—Ag1—O2—C7	−67.5 (4)	C6—C1—C7—O2	−178.2 (4)
N11—Ag1—O2—C7	71.1 (4)	C2—C1—C7—O2	0.4 (7)
O61^i—Ag1—O2—C7	149.7 (4)	C6—C1—C7—O1	3.3 (7)
O2—Ag1—N11—C16	36.7 (5)	C2—C1—C7—O1	−178.1 (4)
N21—Ag1—N11—C16	−172.1 (4)	C16—N11—C12—N3	−178.5 (5)
O61^i—Ag1—N11—C16	−48.2 (4)	Ag1—N11—C12—N3	−6.7 (7)
O2—Ag1—N11—C12	−135.3 (4)	C16—N11—C12—C13	0.2 (7)
N21—Ag1—N11—C12	15.9 (4)	Ag1—N11—C12—C13	172.0 (4)
O61^i—Ag1—N11—C12	139.8 (4)	C22—N3—C12—N11	−9.0 (9)
O2—Ag1—N21—C22	132.2 (4)	C22—N3—C12—C13	172.2 (5)
N11—Ag1—N21—C22	−21.3 (4)	N11—C12—C13—C14	−0.6 (8)
O61^i—Ag1—N21—C22	−92.2 (4)	N3—C12—C13—C14	178.2 (5)
O2—Ag1—N21—C26	−31.2 (4)	C12—C13—C14—C15	−0.1 (9)
N11—Ag1—N21—C26	175.3 (4)	C13—C14—C15—C16	1.0 (9)
O61^i—Ag1—N21—C26	104.5 (4)	C12—N11—C16—C15	0.8 (8)
C6—C1—C2—O21	176.5 (4)	Ag1—N11—C16—C15	−172.1 (5)
C7—C1—C2—O21	−2.1 (7)	C14—C15—C16—N11	−1.4 (9)
C6—C1—C2—C3	−4.1 (7)	C26—N21—C22—N3	179.9 (5)
C7—C1—C2—C3	177.3 (5)	Ag1—N21—C22—N3	16.9 (7)
O21—C2—C3—C4	−178.9 (5)	C26—N21—C22—C23	−2.1 (7)
C1—C2—C3—C4	1.7 (8)	Ag1—N21—C22—C23	−165.1 (4)
C2—C3—C4—C5	1.7 (9)	C12—N3—C22—N21	3.8 (8)
C3—C4—C5—C6	−2.4 (8)	C12—N3—C22—C23	−174.3 (5)
C4—C5—C6—O61	−178.5 (5)	N21—C22—C23—C24	2.2 (8)
C4—C5—C6—C1	−0.3 (8)	N3—C22—C23—C24	−179.7 (5)
C2—C1—C6—C5	3.4 (7)	C22—C23—C24—C25	−1.0 (9)
C7—C1—C6—C5	−178.0 (4)	C23—C24—C25—C26	−0.1 (9)
C2—C1—C6—O61	−178.4 (4)	C22—N21—C26—C25	0.9 (8)
C7—C1—C6—O61	0.2 (7)	Ag1—N21—C26—C25	166.7 (5)
Ag1—O2—C7—O1	−2.9 (6)	C24—C25—C26—N21	0.2 (9)
Ag1—O2—C7—C1	178.7 (3)

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O2	0.82	1.81	2.538 (6)	146
O61—H61···O1	0.82	1.80	2.525 (6)	147
N3—H3···O1^ii	0.86	2.08	2.927 (6)	170
C25—H25···O21^iii	0.93	2.60	3.519 (8)	171

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z.