Bis(3-amino-2-chloro­pyridine-κN)silver(I) perchlorate

In the title compound, [Ag(C₅H₅ClN₂)₂]ClO₄, the Ag^I atom is surrounded by two pyridyl N atoms [2.197 (4) and 2.199 (4) Å] in a linear AgN₂ geometry. Adjacent mononuclear [Ag(3-amino-2-chloro­pyridine)₂]⁺ species are interlinked through weak Ag...N(amine) and Ag...O(perchlorate) coordination contacts and extensive hydrogen-bonding and π–π interactions, resulting in a three-dimensional supramolecular network in the solid.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.043
• wR factor = 0.093
• Data-to-parameter ratio = 16.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N2     -   H2N2              ?

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      1
                   N3  -AG1 -N1  -C5    -25.20  1.10   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      2
                   N3  -AG1 -N1  -C1    156.10  0.80   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     17
                   N1  -AG1 -N3  -C10    16.20  1.10   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     18
                   N1  -AG1 -N3  -C6   -171.20  0.80   1.555   1.555   1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.849(10) ....       3.00 s.u-Ratio
                     N2   -H2N1    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.852(10) ....       3.00 s.u-Ratio
                     N2   -H2N2    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.84(3), Rep   0.840(10) ....       3.00 s.u-Ratio
                     N4   -H4N2    1.555   1.555

PLAT_732  Alert C Angle   Calc      110(5), Rep   109.7(17) ....       2.94 s.u-Ratio
                     H2N1 -N2   -H2N2    1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc      113(4), Rep   113.2(18) ....       2.22 s.u-Ratio
                     H4N1 -N4   -H4N2    1.555   1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.849(10) ....       3.00 s.u-Ratio
                     N2   -H2N1    1.555   1.555

PLAT_736  Alert C H...A   Calc     2.22(4), Rep   2.223(17) ....       2.35 s.u-Ratio
                     H2N1 -O3      1.555   4.666


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 12 Alert Level C = Please check

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S1. Comment

The synthesis of coordination polymers with large channels or cavities is currently an active field due to their intriguing structural diversity and potential functions as microporous solids for molecular adsorption, ion exchange, and heterogeneous catalysis (Batten et al., 1998; Fujita et al., 1994; Janiak, 1997; Tong Chen et al., 1999; Yaghi et al., 1998). We are interested in the preparation of one-, two- and three-dimensional coordination polymers with potential applications and report here the preparation and crystal structure of [Ag(2-Clnpy)₂](ClO₄), (I) (2-Clnpy is 3-amino-2-chloropyridine).

The crystal structure of (I) comprises discrete mononuclear [Ag(2-Clnpy)₂]⁺ cations and perchlorate counter-ions. As shown in Fig. 1, each Ag^I atom is coordinated in a linear geometry to two pyridyl N atoms from two different 2-Clnpy ligands (Table 1). The Ag—N(pyridyl) distances in (I) are comparable to those [2.186 (4)—2.199 (2) Å] found in the silver compounds of bipyridine (Tong et al., 1998; Tong & Chen, 2000; Tong, Chen & Ng, 2000), but are slightly longer than those [2.122 (3) Å] in bis(4-aminopyridine)silver(I) nitrate (Kristiansson, 2000). Adjacent [Ag(2-Clnpy)₂]⁺ cations are interlinked through weak Ag···N(amine) coordination [Ag···N(amine) = 2.762 (5) Å], resulting in a polymeric chain along the c axis direction (Fig. 2). The adjacent chains are further interlinked by perchlorate anions through weak Ag···O2 coordination [Ag···O2 = 2.833 (4) Å] and N2···O3 hydrogen bonds (Table 2). There are also strong interchain π–π interactions between the pyridyl rings of adjacent chains with the staggered face-to-face separation of ca 3.36–3.46 Å. Thus, the structure of (I) provides an interesting three-dimensional supramolecular architecture driven by the extensive supramolecular interactions (Fig. 3).

It should be also noted that non-classical hydrogen-bonding interactions play a role in consolidating the solid-state structure of (I). The perchlorate counter-ions are hydrogen bonded to the adjacent 2-Clnpy ligands (Table 2), which is also observed in other related compounds (Tong, Lee et al., 1999).

S2. Experimental

To a solution of AgClO₄ (1.0 mmol) in 1:1 (v/v) MeCN/H₂O (10 ml), a solution of 2-Clnpy (1.0 mmol) in MeOH (5 ml) was added slowly with stirring for 15 min at 333 K. Colorless block crystals were deposited within five days (90% yield).

S3. Refinement

The carbon-bound H atoms were generated geometrically and ride on their parent C atoms; U_iso(H) = 1.2U_eq(C). The nitrogen-bound H-atoms were located and the N—H distance was restrained to 0.85 (1) Å.

Computing details

Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) plot (35% probability displacement ellipsoids) of the coordination environment in the title compound.
	Fig. 2. Perspective view of the polymeric chain in (I).
	Fig. 3. Three-dimensional supramolecular network of the title compound viewed along the c axis direction.

Bis(3-amino-2-chloropyridine-κN)silver(I) perchlorate

Crystal data

[Ag(C5H5ClN2)2]ClO4	F(000) = 912
Mr = 464.44	Dx = 2.037 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.777 (2) Å	Cell parameters from 25 reflections
b = 26.904 (8) Å	θ = 7–15°
c = 7.600 (2) Å	µ = 1.88 mm^−1
β = 107.72 (1)°	T = 298 K
V = 1514.7 (7) Å^3	Block, colorless
Z = 4	0.38 × 0.30 × 0.26 mm

Data collection

Siemens R3m four-circle diffractometer	2251 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ω scans	h = −10→9
Absorption correction: ψ scan (North et al., 1968)	k = −34→0
Tmin = 0.494, Tmax = 0.613	l = 0→9
3723 measured reflections	2 standard reflections every 150 reflections
3472 independent reflections	intensity decay: none

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0387P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3472 reflections	Δρmax = 0.42 e Å^−3
216 parameters	Δρmin = −0.43 e Å^−3
6 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (4)

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	0.37799 (5)	0.347139 (13)	0.73581 (6)	0.04964 (15)
Cl1	0.58803 (16)	0.24775 (5)	0.94521 (18)	0.0552 (3)
N1	0.2817 (5)	0.26995 (13)	0.6987 (5)	0.0376 (9)
N2	0.4274 (7)	0.14677 (16)	0.8916 (7)	0.0543 (11)
C1	0.1211 (6)	0.25929 (17)	0.5762 (6)	0.0421 (11)
H1	0.0486	0.2849	0.5117	0.051*
C2	0.0623 (6)	0.21079 (18)	0.5449 (7)	0.0476 (12)
H2	−0.0458	0.2037	0.4543	0.057*
C3	0.1626 (6)	0.17327 (17)	0.6468 (7)	0.0458 (12)
H3	0.1202	0.1408	0.6291	0.055*
C4	0.3270 (6)	0.18333 (16)	0.7764 (6)	0.0400 (10)
C5	0.3791 (6)	0.23243 (17)	0.7916 (6)	0.0372 (10)
Cl2	0.71420 (17)	0.37370 (5)	1.09506 (18)	0.0549 (3)
N3	0.4992 (5)	0.42085 (13)	0.8142 (5)	0.0371 (8)
N4	0.9015 (6)	0.4714 (2)	1.1513 (6)	0.0539 (11)
C6	0.4387 (6)	0.46070 (17)	0.7083 (6)	0.0422 (11)
H6	0.3349	0.4580	0.6078	0.051*
C7	0.5266 (6)	0.50549 (18)	0.7448 (7)	0.0459 (12)
H7	0.4819	0.5329	0.6701	0.055*
C8	0.6797 (6)	0.50977 (17)	0.8907 (7)	0.0451 (12)
H8	0.7399	0.5401	0.9139	0.054*
C9	0.7468 (6)	0.46962 (17)	1.0051 (6)	0.0386 (10)
C10	0.6475 (6)	0.42570 (16)	0.9579 (6)	0.0355 (10)
Cl3	−0.06074 (14)	0.39819 (4)	0.61996 (16)	0.0446 (3)
O1	0.0491 (5)	0.40646 (16)	0.8040 (5)	0.0762 (12)
O2	0.0520 (5)	0.38878 (16)	0.5066 (5)	0.0721 (11)
O3	−0.1727 (6)	0.35651 (17)	0.6168 (7)	0.0970 (16)
O4	−0.1670 (6)	0.44024 (16)	0.5542 (6)	0.0949 (15)
H2N1	0.541 (2)	0.1483 (17)	0.942 (8)	0.09 (2)*
H2N2	0.397 (6)	0.1169 (8)	0.860 (7)	0.075 (19)*
H4N1	0.927 (7)	0.5011 (6)	1.180 (6)	0.059 (17)*
H4N2	0.919 (7)	0.4525 (12)	1.243 (4)	0.07 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0470 (2)	0.0346 (2)	0.0599 (3)	−0.00668 (18)	0.00528 (17)	−0.00435 (19)
Cl1	0.0416 (6)	0.0548 (7)	0.0593 (8)	−0.0069 (6)	0.0004 (6)	0.0036 (6)
N1	0.036 (2)	0.0326 (19)	0.043 (2)	0.0002 (16)	0.0101 (17)	0.0002 (17)
N2	0.058 (3)	0.035 (3)	0.068 (3)	0.010 (2)	0.016 (2)	0.008 (2)
C1	0.039 (2)	0.045 (3)	0.042 (3)	0.004 (2)	0.012 (2)	0.005 (2)
C2	0.043 (3)	0.050 (3)	0.045 (3)	−0.012 (2)	0.006 (2)	−0.009 (2)
C3	0.049 (3)	0.031 (2)	0.057 (3)	−0.008 (2)	0.016 (2)	−0.007 (2)
C4	0.041 (3)	0.036 (2)	0.047 (3)	0.003 (2)	0.019 (2)	0.002 (2)
C5	0.033 (2)	0.042 (2)	0.037 (2)	−0.0033 (19)	0.011 (2)	−0.006 (2)
Cl2	0.0541 (7)	0.0463 (7)	0.0550 (8)	0.0012 (6)	0.0029 (6)	0.0035 (6)
N3	0.0336 (19)	0.037 (2)	0.040 (2)	−0.0045 (16)	0.0111 (17)	−0.0088 (17)
N4	0.039 (2)	0.060 (3)	0.056 (3)	−0.011 (2)	0.005 (2)	−0.010 (3)
C6	0.039 (2)	0.041 (3)	0.045 (3)	0.002 (2)	0.009 (2)	−0.002 (2)
C7	0.045 (3)	0.043 (3)	0.053 (3)	0.001 (2)	0.019 (2)	0.000 (2)
C8	0.048 (3)	0.038 (3)	0.056 (3)	−0.009 (2)	0.026 (3)	−0.005 (2)
C9	0.033 (2)	0.046 (3)	0.041 (3)	−0.009 (2)	0.018 (2)	−0.014 (2)
C10	0.037 (2)	0.037 (2)	0.036 (2)	0.0007 (19)	0.017 (2)	−0.0059 (19)
Cl3	0.0367 (6)	0.0431 (6)	0.0457 (7)	0.0032 (5)	0.0003 (5)	−0.0034 (5)
O1	0.081 (3)	0.088 (3)	0.043 (2)	−0.019 (2)	−0.0057 (19)	−0.004 (2)
O2	0.054 (2)	0.098 (3)	0.064 (2)	0.013 (2)	0.0170 (19)	−0.018 (2)
O3	0.071 (3)	0.093 (3)	0.116 (4)	−0.042 (3)	0.012 (3)	−0.010 (3)
O4	0.107 (3)	0.087 (3)	0.087 (3)	0.054 (3)	0.025 (3)	0.023 (3)

Geometric parameters (Å, º)

Ag1—N1	2.197 (4)	N3—C10	1.332 (5)
Ag1—N3	2.199 (4)	N3—C6	1.337 (5)
Cl1—C5	1.737 (4)	N4—C9	1.367 (6)
N1—C5	1.329 (5)	N4—H4N1	0.837 (10)
N1—C1	1.342 (5)	N4—H4N2	0.840 (10)
N2—C4	1.388 (6)	C6—C7	1.372 (6)
N2—H2N1	0.849 (10)	C6—H6	0.9300
N2—H2N2	0.852 (10)	C7—C8	1.363 (6)
C1—C2	1.379 (6)	C7—H7	0.9300
C1—H1	0.9300	C8—C9	1.385 (6)
C2—C3	1.364 (6)	C8—H8	0.9300
C2—H2	0.9300	C9—C10	1.397 (6)
C3—C4	1.382 (6)	Cl3—O4	1.401 (4)
C3—H3	0.9300	Cl3—O3	1.415 (4)
C4—C5	1.376 (6)	Cl3—O1	1.417 (4)
Cl2—C10	1.727 (5)	Cl3—O2	1.426 (4)
N1—Ag1—N3	171.43 (13)	C9—N4—H4N1	109 (3)
C5—N1—C1	117.8 (4)	C9—N4—H4N2	122 (4)
C5—N1—Ag1	122.2 (3)	H4N1—N4—H4N2	113.2 (18)
C1—N1—Ag1	120.0 (3)	N3—C6—C7	121.3 (4)
C4—N2—H2N1	124 (4)	N3—C6—H6	119.3
C4—N2—H2N2	116 (3)	C7—C6—H6	119.3
H2N1—N2—H2N2	109.7 (17)	C8—C7—C6	119.8 (5)
N1—C1—C2	120.8 (4)	C8—C7—H7	120.1
N1—C1—H1	119.6	C6—C7—H7	120.1
C2—C1—H1	119.6	C7—C8—C9	120.9 (4)
C3—C2—C1	120.0 (4)	C7—C8—H8	119.5
C3—C2—H2	120.0	C9—C8—H8	119.5
C1—C2—H2	120.0	N4—C9—C8	123.6 (4)
C2—C3—C4	120.3 (4)	N4—C9—C10	121.3 (5)
C2—C3—H3	119.8	C8—C9—C10	115.2 (4)
C4—C3—H3	119.8	N3—C10—C9	124.5 (4)
C5—C4—C3	115.6 (4)	N3—C10—Cl2	116.2 (3)
C5—C4—N2	122.2 (4)	C9—C10—Cl2	119.3 (3)
C3—C4—N2	122.1 (4)	O4—Cl3—O3	109.9 (3)
N1—C5—C4	125.4 (4)	O4—Cl3—O1	109.8 (3)
N1—C5—Cl1	116.2 (3)	O3—Cl3—O1	108.9 (3)
C4—C5—Cl1	118.4 (3)	O4—Cl3—O2	109.4 (3)
C10—N3—C6	118.3 (4)	O3—Cl3—O2	109.7 (3)
C10—N3—Ag1	120.2 (3)	O1—Cl3—O2	109.1 (2)
C6—N3—Ag1	121.1 (3)
N3—Ag1—N1—C5	−25.2 (11)	N1—Ag1—N3—C10	16.2 (11)
N3—Ag1—N1—C1	156.1 (8)	N1—Ag1—N3—C6	−171.2 (8)
C5—N1—C1—C2	−1.8 (6)	C10—N3—C6—C7	0.4 (7)
Ag1—N1—C1—C2	176.9 (3)	Ag1—N3—C6—C7	−172.3 (3)
N1—C1—C2—C3	4.0 (7)	N3—C6—C7—C8	0.5 (7)
C1—C2—C3—C4	−2.7 (7)	C6—C7—C8—C9	−1.0 (7)
C2—C3—C4—C5	−0.5 (7)	C7—C8—C9—N4	178.7 (4)
C2—C3—C4—N2	175.5 (5)	C7—C8—C9—C10	0.5 (7)
C1—N1—C5—C4	−1.7 (7)	C6—N3—C10—C9	−0.9 (6)
Ag1—N1—C5—C4	179.6 (4)	Ag1—N3—C10—C9	171.9 (3)
C1—N1—C5—Cl1	178.7 (3)	C6—N3—C10—Cl2	177.5 (3)
Ag1—N1—C5—Cl1	0.0 (5)	Ag1—N3—C10—Cl2	−9.7 (4)
C3—C4—C5—N1	2.9 (7)	N4—C9—C10—N3	−177.8 (4)
N2—C4—C5—N1	−173.1 (4)	C8—C9—C10—N3	0.5 (6)
C3—C4—C5—Cl1	−177.6 (3)	N4—C9—C10—Cl2	3.9 (6)
N2—C4—C5—Cl1	6.4 (6)	C8—C9—C10—Cl2	−177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N1···O3^i	0.85 (1)	2.22 (2)	3.061 (6)	169 (6)
C3—H3···O1^ii	0.93	2.68	3.279 (6)	122
C7—H7···O4^iii	0.93	2.62	3.352 (6)	135

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