Crystal structure of catena-poly[silver(I)-μ-L-tyrosinato-κ²O:N]

The title compound, [Ag(C₉H₁₀NO₃)]_n, is a polymeric silver(I) complex of L-tyrosine. The Ag^I atom is connected to N and O atoms of two different L-tyrosine ligands in an almost linear arrangement, with an Nⁱ—Ag—O1 bond angle of 173.4 (2)° [symmetry code: (i) x + 1, y, z]. The Ag—Nⁱ and Ag—O bond lengths are 2.156 (5) and 2.162 (4) Å, respectively. The polymeric chains extend along the crystallographic a axis. Strong hydrogen bonds of the N—H...O and O—H...O types and additional C—H...O inter­actions connect these chains into a double-layer polymeric network in the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.022
• wR factor = 0.052
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

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Alert level C
PLAT090_ALERT_3_C Poor Data / Parameter Ratio (Zmax > 18) ........       7.50 Note
PLAT420_ALERT_2_C D-H Without Acceptor        N1     -   H1A    ..     Please Check
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O2      ..       2.63 Ang.

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT791_ALERT_4_G The Model has Chirality at C2      (Chiral SPGR)          S Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

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S1. Comment

Silver(I) complexes of amino acids are important from a medicinal point of view because of their effective biological activities against bacteria, yeasts and moulds (Ahmad et al. 2006; Kasuga et al. 2011; Nomiya et al. 2000; Nomiya & Yokoyama 2002). These complexes usually exist in the form of polymers and the Ag—O and Ag—N bonds play an important role in exhibiting a wide spectrum of antimicrobial activities. The Ag—O bonding complexes can readily undergo ligand replacement with sulfur containing biological ligands such as proteins (Ahmad et al. 2006; Kasuga et al. 2011; Nomiya et al. 2000; Nomiya & Yokoyama, 2002). The crystal structures of these complexes are also characterized by strong hydrogen bonding. The present report is concerned with the crystal structure of a new polymeric silver(I) complex of L-tyrosine (Fig. 1), which has been synthesized for various studies.

In (I) the part of acetate group A (C1/C2/O1/O2) is planar with r. m. s. deviation of 0.0065 Å. The attached N-atom is at a distance of 0.614 (9) Å from the plane A. The 4-methylphenol group B (C3—C9/O3) also attached at the same C-atom is planar with r. m. s. deviation of 0.0032 Å. The dihedral angle between A/B is 21.3 (3)°. Silver atoms are coordinted to L-tyrosine through the deprotonated O atom of the carboxyl group and the amino group of another amino acid residue. The Ag1–N1ⁱ [i = x + 1, y, z] and Ag1–O1 bond distances are almost equal and have values of 2.156 (5) and 2.162 (4) Å, respectively. The N1ⁱ–Ag1–O1 bond angle is 173.4 (2)° due to which the silver atoms are at a separation of 7.2944 (7) Å in this polymeric complex. The polymeric chains are oriented along the crystallographic a-axis. Polymeric chains are linked to layers in the ab plane by O—H···O hydrogen bonds and two of theses layers are additionally linked to a double layer structure by N—H···O hydrogen bonds. This arrangement is further stabilized by weak C—H···O hydrogen bonds (Table 1, Fig. 2). Additionally, C—H···π interactions between benzene rings are observed. Due to these interactions molecules are arranged in the form of a two-dimensional polymeric network with base vectors [1 0 0], [0 1 0] in the (001) plane.

Related literature

For related structures and related studies, see: Ahmad et al. (2006); Kasuga et al. (2011); Nomiya et al. (2000); Nomiya & Yokoyama (2002).

S2. Experimental

L-Tyrosine (0.18 g, 1.0 mmol) was disolved in 10 ml water by adding 10 drops of 1.0 M NaOH. AgNO₃ (0.17 g, 1.0 mmol) was disolved in 10 ml of acetonitrile. The L-tyrosine solution was slowly added to the AgNO₃ solution and the resulting mixture after filtration was kept in the refrigerator at 0°C for crystallization. After three days, colorless needles of (I) were obtained (yield: 20%, m.p = 547 K).

S3. Refinement

The coordinates of H-atoms of the NH₂ group were obtained from the Fourier map and refined isotropically. The other H-atoms were positioned geometrically (C–H = 0.93–0.98 Å, O—H = 0.82 Å) and refined as riding with U_iso(H) = xU_eq(C, N, O) with x = 1.5 for hydroxy and x = 1.2 for other H-atoms.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the asymmetric unit of the title compound. Thermal ellipsoids are drawn at the 50% probability level. H atoms are shown by small circles of arbitrary radii.
	Fig. 2. The partial packing (PLATON; Spek, 2009) showing the polymeric network due to C—H···O, N—H···O and O—H···O interactions. H atoms not involved in hydrogen-bonding interactions are omitted for clarity.

catena-Poly[silver(I)-µ-L-tyrosinato-κ²O:N]

Crystal data

[Ag(C9H10NO3)]	F(000) = 284
Mr = 288.05	Dx = 2.020 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.2944 (5) Å	Cell parameters from 1753 reflections
b = 7.1464 (5) Å	θ = 2.9–26.0°
c = 9.2736 (7) Å	µ = 2.11 mm^−1
β = 101.546 (4)°	T = 296 K
V = 473.64 (6) Å^3	Block, colorless
Z = 2	0.34 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	1816 independent reflections
Radiation source: fine-focus sealed tube	1752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.00 pixels mm^-1	θmax = 26.0°, θmin = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
Tmin = 0.538, Tmax = 0.701	l = −11→11
4086 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0222P)^2 + 0.0305P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
1816 reflections	Δρmax = 0.28 e Å^−3
134 parameters	Δρmin = −0.48 e Å^−3
1 restraint	Absolute structure: Flack x determined using 751 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

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	0.95099 (4)	0.57540 (7)	0.87242 (4)	0.04160 (14)
O1	0.6862 (5)	0.4646 (5)	0.9045 (4)	0.0364 (8)
O2	0.5870 (6)	0.7436 (5)	0.8171 (6)	0.0493 (10)
O3	−0.4102 (5)	0.0526 (9)	0.6482 (4)	0.0418 (12)
H3	−0.4074	−0.0285	0.7111	0.063*
N1	0.2293 (6)	0.6694 (6)	0.8634 (6)	0.0367 (10)
H1A	0.219 (9)	0.716 (8)	0.781 (7)	0.044*
H1B	0.282 (9)	0.725 (9)	0.945 (7)	0.044*
C1	0.5594 (5)	0.5852 (11)	0.8581 (4)	0.0270 (9)
C2	0.3595 (7)	0.5138 (6)	0.8509 (5)	0.0265 (11)
H2	0.3601	0.4267	0.9326	0.032*
C3	0.2963 (7)	0.4091 (7)	0.7071 (5)	0.0307 (10)
H3A	0.2921	0.4963	0.6264	0.037*
H3B	0.3892	0.3146	0.6989	0.037*
C4	0.1078 (7)	0.3152 (6)	0.6902 (5)	0.0273 (10)
C5	0.0880 (7)	0.1543 (6)	0.7700 (5)	0.0312 (10)
H5	0.1925	0.1052	0.8327	0.037*
C6	−0.0825 (6)	0.0651 (10)	0.7588 (5)	0.0312 (9)
H6	−0.0914	−0.0417	0.8143	0.037*
C7	−0.2405 (6)	0.1346 (6)	0.6650 (5)	0.0290 (11)
C8	−0.2230 (7)	0.2942 (7)	0.5838 (6)	0.0336 (11)
H8	−0.3272	0.3422	0.5200	0.040*
C9	−0.0515 (7)	0.3826 (7)	0.5972 (5)	0.0324 (11)
H9	−0.0429	0.4900	0.5423	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.01769 (18)	0.0458 (2)	0.0638 (3)	−0.0039 (2)	0.01412 (15)	−0.0078 (3)
O1	0.0186 (19)	0.044 (2)	0.047 (2)	0.0018 (16)	0.0080 (16)	0.0041 (17)
O2	0.034 (2)	0.038 (2)	0.077 (3)	−0.0093 (18)	0.015 (2)	0.0112 (19)
O3	0.0268 (16)	0.039 (3)	0.057 (2)	−0.009 (2)	0.0010 (14)	0.004 (2)
N1	0.020 (2)	0.039 (2)	0.052 (3)	−0.0001 (19)	0.010 (2)	−0.006 (2)
C1	0.0209 (19)	0.031 (2)	0.030 (2)	−0.006 (3)	0.0076 (15)	−0.007 (3)
C2	0.019 (3)	0.031 (3)	0.031 (3)	−0.0017 (16)	0.0073 (19)	0.0005 (16)
C3	0.025 (3)	0.037 (3)	0.032 (3)	−0.006 (2)	0.009 (2)	−0.003 (2)
C4	0.027 (2)	0.029 (2)	0.025 (2)	−0.0037 (19)	0.005 (2)	−0.0037 (18)
C5	0.027 (2)	0.027 (2)	0.036 (3)	0.0020 (19)	−0.002 (2)	0.0040 (19)
C6	0.035 (2)	0.024 (2)	0.034 (2)	−0.004 (3)	0.0055 (17)	0.000 (3)
C7	0.024 (2)	0.029 (3)	0.033 (3)	−0.0052 (17)	0.005 (2)	−0.0073 (17)
C8	0.025 (3)	0.038 (3)	0.035 (3)	−0.002 (2)	−0.001 (2)	0.001 (2)
C9	0.034 (3)	0.033 (2)	0.030 (3)	−0.003 (2)	0.004 (2)	0.0053 (19)

Geometric parameters (Å, º)

Ag1—N1^i	2.156 (4)	C3—C4	1.510 (6)
Ag1—O1	2.162 (4)	C3—H3A	0.9700
O1—C1	1.275 (7)	C3—H3B	0.9700
O2—C1	1.224 (9)	C4—C9	1.388 (7)
O3—C7	1.350 (6)	C4—C5	1.390 (6)
O3—H3	0.8200	C5—C6	1.383 (7)
N1—C2	1.482 (6)	C5—H5	0.9300
N1—Ag1^ii	2.156 (4)	C6—C7	1.390 (7)
N1—H1A	0.83 (6)	C6—H6	0.9300
N1—H1B	0.87 (7)	C7—C8	1.386 (6)
C1—C2	1.534 (6)	C8—C9	1.385 (7)
C2—C3	1.518 (7)	C8—H8	0.9300
C2—H2	0.9800	C9—H9	0.9300
N1^i—Ag1—O1	173.41 (18)	C4—C3—H3B	108.6
C1—O1—Ag1	108.3 (3)	C2—C3—H3B	108.6
C7—O3—H3	109.5	H3A—C3—H3B	107.5
C2—N1—Ag1^ii	113.1 (3)	C9—C4—C5	117.0 (4)
C2—N1—H1A	100 (4)	C9—C4—C3	122.8 (4)
Ag1^ii—N1—H1A	105 (4)	C5—C4—C3	120.1 (4)
C2—N1—H1B	103 (4)	C6—C5—C4	122.0 (5)
Ag1^ii—N1—H1B	111 (4)	C6—C5—H5	119.0
H1A—N1—H1B	124 (6)	C4—C5—H5	119.0
O2—C1—O1	125.2 (4)	C5—C6—C7	120.2 (5)
O2—C1—C2	120.6 (5)	C5—C6—H6	119.9
O1—C1—C2	114.2 (6)	C7—C6—H6	119.9
N1—C2—C3	110.6 (4)	O3—C7—C8	118.5 (5)
N1—C2—C1	111.4 (5)	O3—C7—C6	122.9 (5)
C3—C2—C1	108.7 (4)	C8—C7—C6	118.6 (5)
N1—C2—H2	108.7	C9—C8—C7	120.4 (5)
C3—C2—H2	108.7	C9—C8—H8	119.8
C1—C2—H2	108.7	C7—C8—H8	119.8
C4—C3—C2	114.8 (4)	C8—C9—C4	121.8 (4)
C4—C3—H3A	108.6	C8—C9—H9	119.1
C2—C3—H3A	108.6	C4—C9—H9	119.1
Ag1—O1—C1—O2	−7.0 (6)	C2—C3—C4—C5	−73.4 (6)
Ag1—O1—C1—C2	170.8 (3)	C9—C4—C5—C6	−0.5 (7)
Ag1^ii—N1—C2—C3	63.8 (5)	C3—C4—C5—C6	179.3 (5)
Ag1^ii—N1—C2—C1	−175.2 (3)	C4—C5—C6—C7	0.6 (7)
O2—C1—C2—N1	−28.0 (7)	C5—C6—C7—O3	179.2 (5)
O1—C1—C2—N1	154.2 (4)	C5—C6—C7—C8	−0.1 (7)
O2—C1—C2—C3	94.2 (6)	O3—C7—C8—C9	−179.8 (5)
O1—C1—C2—C3	−83.6 (5)	C6—C7—C8—C9	−0.4 (7)
N1—C2—C3—C4	−62.6 (5)	C7—C8—C9—C4	0.5 (7)
C1—C2—C3—C4	174.7 (5)	C5—C4—C9—C8	0.0 (7)
C2—C3—C4—C9	106.5 (5)	C3—C4—C9—C8	−179.8 (4)

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
O3—H3···O2^iii	0.82	1.91	2.710 (7)	166
N1—H1B···O1^iv	0.87 (7)	2.19 (7)	2.988 (6)	152 (5)
C2—H2···O2^v	0.98	2.63	3.589 (7)	168
C3—H3B···O3^i	0.97	2.48	3.441 (7)	171

Symmetry codes: (i) x+1, y, z; (iii) x−1, y−1, z; (iv) −x+1, y+1/2, −z+2; (v) −x+1, y−1/2, −z+2.