(2-Amino-4,6-dimethyl­pyrimidine-κN1)(2-amino-4-methyl­pyrimidine-κN1)silver(I) perchlorate

Yang, H.

doi:10.1107/S1600536809035193

metal-organic compounds

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Volume 65| Part 10| October 2009| Page m1176

doi:10.1107/S1600536809035193

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(2-Amino-4,6-dimethylpyrimidine-κN¹)(2-amino-4-methylpyrimidine-κN¹)silver(I) perchlorate

Hua Yang ^a ^*

^aDepartment of Chemistry, Mudanjiang Teachers College, Mudanjiang 157012, People's Republic of China
^*Correspondence e-mail: youngflower7799@yahoo.com.cn

(Received 1 August 2009; accepted 1 September 2009; online 5 September 2009)

Colourless crystals of the title mixed ligand complex, [Ag(C₅H₇N₃)(C₆H₉N₃)]ClO₄, were obtained from a solution of 2-amino-4-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine and silver perchlorate in water and methanol. The crystal structure is stabilized by intermolecular N—H⋯O and N—H⋯N hydrogen bonds and π–π stacking interactions of the aromatic rings of the two ligands [interplanar distance = 3.652 (10) Å]. The Ag^I atom shows a linear coordination [N—Ag—N = 174.6 (1)°].

Related literature

For N—Ag—N geometry, see: Greenwood & Earnshaw (1997 ). For π–π stacking, see: Munakata et al. (2000 ). For silver coordination networks, see: Shimizu et al. (1999 ); Seward et al. (2004 ).

Experimental

Crystal data

[Ag(C₅H₇N₃)(C₆H₉N₃)]ClO₄
M_r = 439.62
Monoclinic, P 2₁ /n
a = 12.3952 (5) Å
b = 7.8324 (4) Å
c = 15.9956 (5) Å
β = 94.339 (3)°
V = 1548.47 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.50 mm⁻¹
T = 120 K
0.40 × 0.40 × 0.25 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.553, T_max = 0.678
8880 measured reflections
2678 independent reflections
2254 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.100
S = 1.07
2678 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5C⋯O4ⁱ	0.86	2.32	3.131 (5)	158
N5—H5B⋯N3ⁱⁱ	0.86	2.20	3.050 (5)	172
N2—H2B⋯O2	0.86	2.50	3.077 (5)	126
N2—H2A⋯N6ⁱⁱⁱ	0.86	2.30	3.147 (5)	169
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035193/ng2621sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035193/ng2621Isup2.hkl

checkCIF report

Comment top

The structure of the title compound (I) comprises of uncoordinated ClO₄^- anions and [Ag(2-amino-4-methylpyrimidine)(2-amino-4,6-dimethylpyrimidine)]⁺ cations. The central silver(I) ion, possessing its vacant s and p orbitals, coordinated to two nitrogen atoms from those two different pyrimidine derivative ligands, presenting nearly linear N-Ag-N geometry Greenwood et al., 1997). An one dimensional framework was built by multiple intermolecular N–H–N hydrogen bonds along one of the diagonals of a and c axial plane, while pi–pi stacking interaction of the aromatic rings with an interplane distance 3.65 Å stabilized the whole crystal structure (Munakata et al., 2000).

Related literature top

For N—Ag—N geometry, see: Greenwood & Earnshaw et al. (1997). For π–π stacking, see: Munakata et al. (2000). For related literature [on what subject?], see: Shimizu et al. (1999); Seward et al. (2004).

Experimental top

A solution of 108 mg (1 mmol) 2-amino-4-methylpyrimidine and 123 mg (1 mmol) of 2-amino-4,6-dimethylpyrimidine in distilled water-CH₃OH (1:1 v/v, 10 mL) was added to an aqueous solution of AgClO₄ 208 mg (1 mmol) in 3 ml distilled water at 333 K. A small amount of white precipitate was removed from the resulting solution. Prism colorless crystals were obtained by slow evaporation at room temperature over a period of 3 days.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing diagram of molecules, viewed down the b axis, with the weak interactions shown as dashed lines.

(2-Amino-4,6-dimethylpyrimidine-κN¹)(2-amino-4-methylpyrimidine- κN¹)silver(I) perchlorate top

Crystal data top

[Ag(C₅H₇N₃)(C₆H₉N₃)]ClO₄	F(000) = 880
M_r = 439.62	D_x = 1.886 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2795 reflections
a = 12.3952 (5) Å	θ = 2.6–32.8°
b = 7.8324 (4) Å	µ = 1.50 mm⁻¹
c = 15.9956 (5) Å	T = 120 K
β = 94.339 (3)°	Prism, colourless
V = 1548.47 (11) Å³	0.40 × 0.40 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2678 independent reflections
Radiation source: fine-focus sealed tube	2254 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
T_min = 0.553, T_max = 0.678	k = −8→9
8880 measured reflections	l = −19→19

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0544P)² + 2.3112P] where P = (F_o² + 2F_c²)/3
2678 reflections	(Δ/σ)_max = 0.001
211 parameters	Δρ_max = 1.36 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Ag(C₅H₇N₃)(C₆H₉N₃)]ClO₄	V = 1548.47 (11) Å³
M_r = 439.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.3952 (5) Å	µ = 1.50 mm⁻¹
b = 7.8324 (4) Å	T = 120 K
c = 15.9956 (5) Å	0.40 × 0.40 × 0.25 mm
β = 94.339 (3)°

Data collection top

Bruker APEXII diffractometer	2678 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2254 reflections with I > 2σ(I)
T_min = 0.553, T_max = 0.678	R_int = 0.028
8880 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.07	Δρ_max = 1.36 e Å⁻³
2678 reflections	Δρ_min = −0.53 e Å⁻³
211 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.19079 (3)	0.45483 (5)	0.720510 (19)	0.04423 (15)
C1	0.1554 (4)	0.3648 (7)	0.3245 (3)	0.0544 (12)
H1A	0.1108	0.2682	0.3087	0.082*
H1B	0.2261	0.3487	0.3051	0.082*
H1C	0.1235	0.4663	0.2998	0.082*
C2	0.1644 (3)	0.3818 (5)	0.4169 (3)	0.0373 (9)
C3	0.0929 (3)	0.3330 (5)	0.5423 (2)	0.0332 (9)
C4	0.2530 (4)	0.4782 (6)	0.5433 (3)	0.0398 (10)
H4A	0.3106	0.5345	0.5720	0.048*
C5	0.2516 (4)	0.4648 (6)	0.4585 (3)	0.0410 (10)
H5A	0.3073	0.5097	0.4294	0.049*
C6	0.3056 (3)	0.4035 (5)	0.8973 (2)	0.0316 (8)
C7	0.1481 (3)	0.5552 (5)	0.9020 (3)	0.0369 (9)
C8	0.0587 (4)	0.6489 (7)	0.8581 (3)	0.0566 (13)
H8A	0.0871	0.7365	0.8240	0.085*
H8B	0.0149	0.7000	0.8983	0.085*
H8C	0.0153	0.5717	0.8231	0.085*
C9	0.1577 (4)	0.5429 (6)	0.9877 (3)	0.0419 (10)
H9A	0.1075	0.5953	1.0197	0.050*
C10	0.2424 (4)	0.4521 (5)	1.0253 (3)	0.0380 (9)
C11	0.2548 (5)	0.4273 (8)	1.1177 (3)	0.0606 (14)
H11A	0.3269	0.4582	1.1384	0.091*
H11B	0.2420	0.3097	1.1307	0.091*
H11C	0.2037	0.4979	1.1437	0.091*
N1	0.2212 (3)	0.4824 (4)	0.8553 (2)	0.0319 (7)
N2	0.3831 (3)	0.3336 (4)	0.8522 (2)	0.0383 (8)
H2A	0.4366	0.2798	0.8774	0.046*
H2B	0.3785	0.3430	0.7985	0.046*
N3	0.3176 (3)	0.3841 (5)	0.9803 (2)	0.0365 (8)
N4	0.1743 (3)	0.4133 (4)	0.5875 (2)	0.0350 (8)
N5	0.0136 (3)	0.2635 (5)	0.5824 (2)	0.0455 (9)
H5B	−0.0386	0.2113	0.5545	0.055*
H5C	0.0144	0.2708	0.6360	0.055*
N6	0.0857 (3)	0.3161 (4)	0.4580 (2)	0.0361 (8)
Cl1	0.50494 (9)	0.64276 (14)	0.68793 (6)	0.0412 (3)
O1	0.4928 (3)	0.6816 (5)	0.6012 (2)	0.0629 (10)
O2	0.4001 (3)	0.6130 (5)	0.7187 (2)	0.0617 (9)
O3	0.5697 (3)	0.4961 (5)	0.7031 (3)	0.0666 (10)
O4	0.5523 (4)	0.7822 (6)	0.7327 (3)	0.0775 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0420 (2)	0.0623 (3)	0.02780 (19)	−0.00167 (16)	−0.00078 (13)	−0.00457 (14)
C1	0.062 (3)	0.071 (3)	0.030 (2)	−0.007 (3)	0.003 (2)	0.006 (2)
C2	0.044 (2)	0.037 (2)	0.031 (2)	0.0077 (19)	0.0058 (18)	0.0064 (17)
C3	0.036 (2)	0.035 (2)	0.0282 (19)	0.0065 (17)	0.0038 (16)	0.0023 (16)
C4	0.035 (2)	0.043 (2)	0.041 (2)	0.0017 (19)	−0.0023 (18)	0.0003 (19)
C5	0.041 (2)	0.045 (2)	0.038 (2)	−0.001 (2)	0.0064 (19)	0.0027 (19)
C6	0.036 (2)	0.032 (2)	0.0266 (19)	−0.0052 (17)	0.0030 (16)	−0.0023 (15)
C7	0.038 (2)	0.031 (2)	0.041 (2)	−0.0037 (18)	0.0006 (18)	−0.0006 (17)
C8	0.060 (3)	0.062 (3)	0.047 (3)	0.008 (3)	0.001 (2)	0.007 (2)
C9	0.049 (3)	0.038 (2)	0.041 (2)	−0.005 (2)	0.018 (2)	−0.0107 (19)
C10	0.045 (2)	0.037 (2)	0.032 (2)	−0.004 (2)	0.0037 (18)	−0.0054 (17)
C11	0.074 (4)	0.078 (4)	0.031 (2)	0.008 (3)	0.009 (2)	−0.006 (2)
N1	0.0344 (17)	0.0330 (17)	0.0285 (16)	−0.0038 (14)	0.0044 (14)	−0.0037 (13)
N2	0.0432 (19)	0.047 (2)	0.0250 (16)	0.0066 (16)	0.0074 (14)	0.0008 (14)
N3	0.0381 (18)	0.0430 (19)	0.0288 (17)	−0.0001 (16)	0.0050 (14)	−0.0035 (15)
N4	0.0326 (17)	0.0402 (19)	0.0318 (17)	0.0028 (15)	−0.0010 (14)	0.0000 (14)
N5	0.047 (2)	0.063 (2)	0.0269 (17)	−0.0130 (19)	0.0049 (15)	−0.0005 (17)
N6	0.0416 (19)	0.0403 (19)	0.0264 (16)	0.0019 (16)	0.0011 (14)	0.0031 (14)
Cl1	0.0467 (6)	0.0444 (6)	0.0331 (5)	−0.0052 (5)	0.0068 (4)	0.0038 (4)
O1	0.064 (2)	0.090 (3)	0.0356 (17)	−0.004 (2)	0.0119 (16)	0.0148 (17)
O2	0.053 (2)	0.086 (3)	0.049 (2)	−0.0050 (19)	0.0193 (16)	0.0121 (18)
O3	0.067 (2)	0.058 (2)	0.074 (3)	0.0125 (18)	0.000 (2)	0.0080 (19)
O4	0.092 (3)	0.077 (3)	0.063 (2)	−0.031 (2)	−0.001 (2)	−0.007 (2)

Geometric parameters (Å, º) top

Ag1—N4	2.146 (3)	C7—C8	1.465 (7)
Ag1—N1	2.171 (3)	C8—H8A	0.9600
C1—C2	1.479 (6)	C8—H8B	0.9600
C1—H1A	0.9600	C8—H8C	0.9600
C1—H1B	0.9600	C9—C10	1.370 (7)
C1—H1C	0.9600	C9—H9A	0.9300
C2—N6	1.322 (6)	C10—N3	1.330 (6)
C2—C5	1.387 (6)	C10—C11	1.487 (6)
C3—N5	1.330 (6)	C11—H11A	0.9600
C3—N6	1.351 (5)	C11—H11B	0.9600
C3—N4	1.352 (5)	C11—H11C	0.9600
C4—N4	1.347 (6)	N2—H2A	0.8600
C4—C5	1.360 (6)	N2—H2B	0.8600
C4—H4A	0.9300	N5—H5B	0.8600
C5—H5A	0.9300	N5—H5C	0.8600
C6—N3	1.334 (5)	Cl1—O4	1.409 (4)
C6—N1	1.350 (5)	Cl1—O3	1.412 (4)
C6—N2	1.359 (5)	Cl1—O1	1.417 (3)
C7—N1	1.344 (6)	Cl1—O2	1.443 (4)
C7—C9	1.370 (6)

N4—Ag1—N1	174.61 (13)	C7—C9—H9A	120.6
C2—C1—H1A	109.5	C10—C9—H9A	120.6
C2—C1—H1B	109.5	N3—C10—C9	121.0 (4)
H1A—C1—H1B	109.5	N3—C10—C11	117.4 (4)
C2—C1—H1C	109.5	C9—C10—C11	121.5 (4)
H1A—C1—H1C	109.5	C10—C11—H11A	109.5
H1B—C1—H1C	109.5	C10—C11—H11B	109.5
N6—C2—C5	121.4 (4)	H11A—C11—H11B	109.5
N6—C2—C1	117.3 (4)	C10—C11—H11C	109.5
C5—C2—C1	121.3 (4)	H11A—C11—H11C	109.5
N5—C3—N6	116.4 (4)	H11B—C11—H11C	109.5
N5—C3—N4	118.8 (4)	C7—N1—C6	116.6 (3)
N6—C3—N4	124.7 (4)	C7—N1—Ag1	121.4 (3)
N4—C4—C5	122.7 (4)	C6—N1—Ag1	121.2 (3)
N4—C4—H4A	118.6	C6—N2—H2A	120.0
C5—C4—H4A	118.6	C6—N2—H2B	120.0
C4—C5—C2	117.7 (4)	H2A—N2—H2B	120.0
C4—C5—H5A	121.1	C10—N3—C6	117.6 (4)
C2—C5—H5A	121.1	C4—N4—C3	115.8 (4)
N3—C6—N1	124.8 (4)	C4—N4—Ag1	116.4 (3)
N3—C6—N2	116.9 (4)	C3—N4—Ag1	127.7 (3)
N1—C6—N2	118.2 (3)	C3—N5—H5B	120.0
N1—C7—C9	121.1 (4)	C3—N5—H5C	120.0
N1—C7—C8	117.6 (4)	H5B—N5—H5C	120.0
C9—C7—C8	121.3 (4)	C2—N6—C3	117.6 (4)
C7—C8—H8A	109.5	O4—Cl1—O3	109.5 (3)
C7—C8—H8B	109.5	O4—Cl1—O1	109.9 (2)
H8A—C8—H8B	109.5	O3—Cl1—O1	111.1 (3)
C7—C8—H8C	109.5	O4—Cl1—O2	107.6 (3)
H8A—C8—H8C	109.5	O3—Cl1—O2	109.0 (3)
H8B—C8—H8C	109.5	O1—Cl1—O2	109.6 (2)
C7—C9—C10	118.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5C···O4ⁱ	0.86	2.32	3.131 (5)	158
N5—H5B···N3ⁱⁱ	0.86	2.20	3.050 (5)	172
N2—H2B···O2	0.86	2.50	3.077 (5)	126
N2—H2A···N6ⁱⁱⁱ	0.86	2.30	3.147 (5)	169
C1—H1C···O4^iv	0.96	2.38	3.339 (7)	177
C4—H4A···O1	0.93	2.55	3.437 (6)	160
C4—H4A···O2	0.93	2.59	3.396 (6)	145
C8—H8C···O4ⁱ	0.96	2.55	3.456 (7)	157

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Ag(C₅H₇N₃)(C₆H₉N₃)]ClO₄
M_r	439.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	12.3952 (5), 7.8324 (4), 15.9956 (5)
β (°)	94.339 (3)
V (Å³)	1548.47 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.50
Crystal size (mm)	0.40 × 0.40 × 0.25

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.553, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	8880, 2678, 2254
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.07
No. of reflections	2678
No. of parameters	211
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.36, −0.53

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5C···O4ⁱ	0.86	2.32	3.131 (5)	158
N5—H5B···N3ⁱⁱ	0.86	2.20	3.050 (5)	172
N2—H2B···O2	0.86	2.50	3.077 (5)	126
N2—H2A···N6ⁱⁱⁱ	0.86	2.30	3.147 (5)	169

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The author thanks the Natural Science Foundation of Heilongjiang Province for financial support.

References

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