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The title compound, {[Ag(C4H6NO4)(C4H5N3)]·H2O}n, was synthesized by the reaction of silver(I) nitrate with 2-am­ino­pyrimidine and imino­diacetic acid. X-ray analysis reveals that the crystal structure contains a one-dimensional ladder-like AgI coordination polymer and that N—H...O and O—H...O hydrogen bonding results in a three-dimensional network. The AgI centre is four-coordinated by three N atoms from three different 2-amino­pyrimidine ligands and one O atom from one imino­diacetate ligand. Comparison of the structural features with previous findings suggests that the existence of a second ligand plays an important role in the construction of such polymer frameworks.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010902695X/bm3083sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010902695X/bm3083Isup2.hkl
Contains datablock I

CCDC reference: 746045

Comment top

Pyrimidine and aminopyrimidine derivatives are biologically important compounds as they occur in nature as components of nucleic acids. Some aminopyrimidine derivatives are used as antifolate drugs (Hunt et al., 1980; Baker & Santi, 1965). They are also used in the development of polymeric metal–organic frameworks (MOFs), owing to their demonstrated ability to form very stable hydrogen-bonded chain arrays via their stereochemically associative amino groups and hetero-ring N atoms, and to coordinate to metal centres through various bonding modes (Aoki et al., 1994; Blake et al., 1999). As a soft acid, the AgI ion is a favourable and fashionable building block or connecting node for coordination polymers, not only due to its ready coordination by soft bases such as unsaturated N atoms (Carlucci et al., 1995), but also because closed-shell d10 Ag···Ag interactions can often give rise to intriguing supramolecular motifs (Blake et al., 2000; Melcer et al., 2001). Recently, we have undertaken a series of investigations into the assembly of AgI ions with different aminopyrimidine derivatives (Luo, Huang, Chen et al., 2008; Luo, Huang, Zhang et al., 2008; Luo et al., 2009), with the principal aim of obtaining supramolecular compounds or ordered coordination polymers, and found that in the resulting structures, aminopyrimidine derivatives often adopt mono- and bidentate coordination modes with AgI ions via their pyrimidyl N atoms. However, tridentate coordination by pyrimidyl and amino N atoms is still quite rare (Wang et al., 2006). The introduction of a second ligand such as a dicarboxylic acid dramatically alters the structures and properties of these complexes. Inspired by these results, we employed 2-aminopyrimidine as a tridentate ligand and incorporated iminodiacetic acid into the previously known AgI–2-aminopyrimidine system, and successfully obtained the title compound, (I), a novel one-dimensional ladder coordination polymer.

Single-crystal X-ray diffraction study reveals that compound (I) comprises one AgI centre, one 2-aminopyrimidine ligand, one iminodiacetate anion and one uncoordinated water molecule. As shown in Fig. 1, the four-coordinated AgI atom adopts a strongly distorted tetrahedral geometry (Table 1), which is coordinated by two pyrimidyl N atoms from two independent 2-aminopyrimidine ligands, one amino N atom from another 2-aminopyrimidine ligand and one O atom from an iminodiacetate anion. The widest N3i—Ag1—O1 angle is 133.95 (6)° and the remaining angles are in the range 89.22 (6)–126.98 (7)°. It is noteworthy that the Ag—Namino distance [Ag1—N1 = 2.604 (2) Å] is significantly longer than the Ag···Npyrimidyl distances [Ag1—N3i = 2.2872 (19) and Ag1—N2ii = 2.3312 (19) Å; symmetry codes: (i) 1 - x, y - 1/2, -z+ 1/2; (ii) 1 - x, y + 1/2, -z + 1/2]. This difference may be partly due to electronic effects between the amino N and pyrimidyl N atoms. A pair of lone electrons on the amino N atom is partially delocalized into the pyrimidyl ring, which makes the amino N atom less basic than the pyrimidyl N atoms. Interestingly, aminopyrimidine derivatives often adopt N-monodentate and N,N'-bidentate coordination modes with AgI via their pyrimidyl N atoms, and the only example adopting tridentate coordination was reported by Wang et al. (2006).

As shown in Fig. 2, the 2-aminopyrimidine ligands of (I) are coordinated to the AgI centres in this N,N',N''-coordination mode to form a one-dimensional ladder structure, in which the iminodiacetate anion adopts a bis-monodentate coordination mode to AgI, precluding the extension of the motif into two dimensions. It is noteworthy that the N atoms of the iminodiacetate anions are protonated, and so do not participate in coordination to any metal centre. All the carboxylate groups are deprotonated, fulfilling the requirement for overall charge neutrality.

In each one-dimensional ladder, AgI ions and 2-aminopyrimidine ligands are interlinked to form chair-like eight-membered M2L2 binuclear rings. Two kinds of intermolecular hydrogen bonds are observed in neighbouring ladders. N—H···O hydrogen bonds have N···O distances in the range 2.781 (3)–3.070 (3) Å. The N atoms of the amino group of the 2-aminopyrimidine ligands and protonated imino groups serve as donors, while the O atoms of the iminodiacetate anion and uncoordinated water molecule act as acceptors. O1W—H···O hydrogen bonds involve the O atoms of the iminodiacetate anion and uncoordinated water molecule, acting as acceptors and donors, respectively. These hydrogen bonds link the ladders into a three-dimensional framework, as shown in Fig. 3.

In conclusion, a new one-dimensional AgI coordination polymer with mixed N-donor and O-donor ligands shows rare N,N',N''-tridentate and O-monodentate coordination modes, respectively.

Experimental top

All reagents and solvents were obtained commercially and used without further purification. Silver nitrate (170 mg, 1 mmol) and 2-aminopyrimidine (95 mg, 1 mmol) were dissolved in water (5 ml). To this solution was added a methanolic solution (5 ml) of iminodiacetic acid (133 mg, 1 mmol) with stirring. The mixture was stirred for about 20 min at room temperature to give a clear colourless solution. The resulting solution was kept in darkness for 4 d, after which time well-formed colourless block-shaped crystals of (I) were obtained. The product is insoluble in water and methanol.

Refinement top

The aromatic and amino H atoms were generated geometrically (C—H = 0.93 Å and N—H = 0.90 Å) and were allowed to ride on their parent atoms in the riding-model approximations, with Uiso(H) = 1.2Ueq(C,N). The positions and Uiso values of the water H atoms were refined, with the O—H distances restrained to 0.85 (1) Å.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and the coordination environment at the AgI centre. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) 1 - x, y - 1/2, -z + 1/2; (ii) 1 - x, y + 1/2, -z + 1/2.]
[Figure 2] Fig. 2. A perspective view of the one-dimensional ladder of (I), which runs parallel to the b axis. H atoms have been omitted for clarity.
[Figure 3] Fig. 3. A schematic representation of the three-dimensional structure formed via hydrogen bonds (dashed lines), viewed down the b axis.
catena-Poly[[[(iminodiacetato-κO)silver(I)]-µ3-2- aminopyrimidine-κ3N1:N2:N3] monohydrate] top
Crystal data top
[Ag(C4H6NO4)(C4H5N3)]·H2OF(000) = 704
Mr = 353.09Dx = 2.061 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8629 reflections
a = 13.495 (3) Åθ = 6.1–54.9°
b = 6.5202 (13) ŵ = 1.79 mm1
c = 14.103 (3) ÅT = 298 K
β = 113.49 (3)°Block, colourless
V = 1138.1 (4) Å30.50 × 0.30 × 0.30 mm
Z = 4
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2230 independent reflections
Radiation source: sealed tube2013 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 16.1903 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = 1616
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 78
Tmin = 0.468, Tmax = 0.615l = 1617
9403 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0289P)2 + 0.7853P]
where P = (Fo2 + 2Fc2)/3
2230 reflections(Δ/σ)max = 0.036
171 parametersΔρmax = 0.84 e Å3
2 restraintsΔρmin = 0.67 e Å3
Crystal data top
[Ag(C4H6NO4)(C4H5N3)]·H2OV = 1138.1 (4) Å3
Mr = 353.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.495 (3) ŵ = 1.79 mm1
b = 6.5202 (13) ÅT = 298 K
c = 14.103 (3) Å0.50 × 0.30 × 0.30 mm
β = 113.49 (3)°
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2230 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
2013 reflections with I > 2σ(I)
Tmin = 0.468, Tmax = 0.615Rint = 0.037
9403 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0252 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.84 e Å3
2230 reflectionsΔρmin = 0.67 e Å3
171 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.505184 (17)0.05560 (3)0.363312 (16)0.03553 (10)
O10.31897 (15)0.0875 (3)0.29507 (14)0.0330 (4)
O20.30387 (16)0.2039 (3)0.20966 (15)0.0418 (5)
O30.11448 (18)0.5458 (3)0.11212 (16)0.0474 (5)
O40.05387 (17)0.5604 (3)0.23040 (16)0.0452 (5)
N10.55486 (17)0.0520 (3)0.20288 (15)0.0257 (4)
H1A0.59500.06010.20600.031*
H1B0.59550.16290.20530.031*
N20.42832 (16)0.2350 (3)0.06723 (14)0.0233 (4)
N30.42247 (16)0.1315 (3)0.07246 (14)0.0231 (4)
N40.11408 (15)0.2039 (3)0.18785 (15)0.0253 (4)
H4A0.16380.29950.19230.030*
H4B0.11300.19140.25100.030*
C10.3308 (2)0.1276 (4)0.01377 (18)0.0281 (5)
H10.29750.25130.04150.034*
C20.2844 (2)0.0514 (4)0.0626 (2)0.0313 (6)
H20.22050.05160.12160.038*
C30.3373 (2)0.2313 (4)0.01952 (18)0.0279 (5)
H30.30880.35490.05190.033*
C40.4667 (2)0.0517 (3)0.11073 (18)0.0206 (5)
C50.2670 (2)0.0402 (3)0.22768 (18)0.0253 (5)
C60.1489 (2)0.0054 (4)0.1599 (2)0.0285 (5)
H6A0.13930.00930.08800.034*
H6B0.10390.10380.16770.034*
C70.00698 (18)0.2783 (4)0.11535 (17)0.0274 (5)
H7A0.04780.17660.10880.033*
H7B0.00770.30030.04760.033*
C80.0195 (2)0.4798 (4)0.15619 (19)0.0294 (5)
O1W0.2232 (2)0.5509 (3)0.09963 (17)0.0448 (5)
H1WA0.247 (3)0.435 (3)0.126 (3)0.053 (10)*
H1WB0.186 (3)0.542 (6)0.0349 (10)0.081 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.03753 (15)0.01852 (13)0.04244 (15)0.00165 (7)0.00740 (10)0.00067 (7)
O10.0281 (10)0.0287 (9)0.0353 (9)0.0030 (7)0.0052 (8)0.0010 (7)
O20.0392 (11)0.0334 (10)0.0475 (11)0.0130 (8)0.0118 (9)0.0044 (8)
O30.0355 (12)0.0504 (13)0.0447 (12)0.0178 (9)0.0037 (9)0.0051 (9)
O40.0390 (12)0.0386 (11)0.0470 (12)0.0057 (8)0.0053 (10)0.0143 (9)
N10.0240 (11)0.0164 (10)0.0303 (10)0.0000 (7)0.0042 (9)0.0002 (7)
N20.0262 (10)0.0167 (9)0.0260 (9)0.0015 (7)0.0095 (8)0.0005 (8)
N30.0261 (10)0.0168 (9)0.0246 (9)0.0010 (8)0.0082 (8)0.0011 (8)
N40.0224 (10)0.0220 (10)0.0284 (10)0.0009 (8)0.0069 (8)0.0020 (8)
C10.0285 (13)0.0247 (12)0.0286 (12)0.0030 (10)0.0089 (10)0.0052 (10)
C20.0289 (14)0.0309 (14)0.0258 (12)0.0019 (10)0.0020 (10)0.0009 (10)
C30.0301 (13)0.0250 (12)0.0270 (11)0.0055 (10)0.0098 (10)0.0038 (9)
C40.0217 (11)0.0186 (12)0.0234 (11)0.0002 (8)0.0109 (9)0.0003 (8)
C50.0253 (13)0.0241 (12)0.0272 (12)0.0009 (9)0.0110 (10)0.0045 (9)
C60.0262 (13)0.0217 (11)0.0331 (12)0.0006 (10)0.0072 (10)0.0058 (10)
C70.0219 (12)0.0302 (12)0.0254 (11)0.0018 (9)0.0045 (10)0.0001 (10)
C80.0291 (14)0.0292 (13)0.0278 (12)0.0052 (10)0.0091 (11)0.0019 (10)
O1W0.0539 (14)0.0394 (12)0.0391 (12)0.0096 (9)0.0167 (11)0.0002 (9)
Geometric parameters (Å, º) top
Ag1—O12.4868 (19)C4—N31.348 (3)
Ag1—N12.604 (2)C4—N11.368 (3)
Ag1—N2i2.3312 (19)C3—N21.345 (3)
Ag1—N3ii2.2872 (19)C3—C21.381 (3)
C1—N31.345 (3)C3—H30.9300
C1—C21.373 (4)C6—N41.483 (3)
C1—H10.9300C6—H6A0.9700
C8—O41.235 (3)C6—H6B0.9700
C8—O31.257 (3)C2—H20.9300
C8—C71.533 (3)N1—H1A0.9000
C5—O21.246 (3)N1—H1B0.9000
C5—O11.248 (3)N4—H4A0.9000
C5—C61.526 (3)N4—H4B0.9000
C7—N41.480 (3)N3—Ag1i2.2872 (19)
C7—H7A0.9700N2—Ag1ii2.3312 (19)
C7—H7B0.9700O1W—H1WA0.844 (10)
C4—N21.349 (3)O1W—H1WB0.849 (10)
O1—Ag1—N1103.35 (7)N4—C6—H6A109.3
O1—Ag1—N2i89.22 (6)C5—C6—H6A109.3
O1—Ag1—N3ii133.95 (6)N4—C6—H6B109.3
N1—Ag1—N2i99.65 (6)C5—C6—H6B109.3
N1—Ag1—N3ii97.77 (6)H6A—C6—H6B108.0
N2i—Ag1—N3ii126.98 (7)C1—C2—C3116.7 (2)
N3—C1—C2122.7 (2)C1—C2—H2121.7
N3—C1—H1118.6C3—C2—H2121.7
C2—C1—H1118.6C4—N1—Ag1113.44 (16)
O4—C8—O3126.1 (3)C4—N1—H1A108.9
O4—C8—C7117.0 (2)Ag1—N1—H1A108.9
O3—C8—C7116.9 (2)C4—N1—H1B108.9
O2—C5—O1125.4 (2)Ag1—N1—H1B108.9
O2—C5—C6116.2 (2)H1A—N1—H1B107.7
O1—C5—C6118.5 (2)C6—N4—C7115.36 (18)
N4—C7—C8109.34 (18)C6—N4—H4A108.4
N4—C7—H7A109.8C7—N4—H4A108.4
C8—C7—H7A109.8C6—N4—H4B108.4
N4—C7—H7B109.8C7—N4—H4B108.4
C8—C7—H7B109.8H4A—N4—H4B107.5
H7A—C7—H7B108.3C1—N3—C4116.5 (2)
N2—C4—N3125.1 (2)C1—N3—Ag1i117.92 (15)
N2—C4—N1117.49 (19)C4—N3—Ag1i125.50 (16)
N3—C4—N1117.41 (19)C3—N2—C4116.4 (2)
N2—C3—C2122.7 (2)C3—N2—Ag1ii117.21 (15)
N2—C3—H3118.7C4—N2—Ag1ii126.14 (15)
C2—C3—H3118.7H1WA—O1W—H1WB111 (4)
N4—C6—C5111.47 (19)C5—O1—Ag1102.62 (15)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.902.092.904 (3)151
N1—H1B···O1ii0.902.002.896 (3)178
N4—H4A···O1Wiii0.902.032.781 (3)140
N4—H4B···O4iv0.902.523.070 (3)120
O1W—H1WA···O2v0.84 (1)1.88 (1)2.714 (3)168 (4)
O1W—H1WB···O30.85 (1)1.91 (1)2.753 (3)174 (5)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x, y+1, z; (iv) x, y1/2, z+1/2; (v) x, y, z.

Experimental details

Crystal data
Chemical formula[Ag(C4H6NO4)(C4H5N3)]·H2O
Mr353.09
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)13.495 (3), 6.5202 (13), 14.103 (3)
β (°) 113.49 (3)
V3)1138.1 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.79
Crystal size (mm)0.50 × 0.30 × 0.30
Data collection
DiffractometerOxford Diffraction Gemini S Ultra
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.468, 0.615
No. of measured, independent and
observed [I > 2σ(I)] reflections
9403, 2230, 2013
Rint0.037
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.064, 1.08
No. of reflections2230
No. of parameters171
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.84, 0.67

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top
Ag1—O12.4868 (19)Ag1—N2i2.3312 (19)
Ag1—N12.604 (2)Ag1—N3ii2.2872 (19)
O1—Ag1—N1103.35 (7)N1—Ag1—N2i99.65 (6)
O1—Ag1—N2i89.22 (6)N1—Ag1—N3ii97.77 (6)
O1—Ag1—N3ii133.95 (6)N2i—Ag1—N3ii126.98 (7)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.902.092.904 (3)151
N1—H1B···O1ii0.902.002.896 (3)178
N4—H4A···O1Wiii0.902.032.781 (3)140
N4—H4B···O4iv0.902.523.070 (3)120
O1W—H1WA···O2v0.844 (10)1.883 (13)2.714 (3)168 (4)
O1W—H1WB···O30.849 (10)1.908 (12)2.753 (3)174 (5)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x, y+1, z; (iv) x, y1/2, z+1/2; (v) x, y, z.
 

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