(4-Chloro­benzoato)bis(5-methyl-2-pyridylamine)silver(I)

The title compound, [Ag(C₇H₄ClO₂)(C₆H₈N₂)₂], is a mononuclear silver(I) complex. The Ag^I atom is three-coordinated by two pyridine N atoms from two 5-methyl­pyridin-2-ylamine ligands and by one O atom of a 4-chloro­benzoate ligand, forming a distorted T-shaped coordination. In the crystal structure, the mol­ecules are linked through inter­molecular N—H...O hydrogen bonds, forming chains running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.087
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ag1    -   O1      ..       7.57 su

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C19 H20 Ag1 Cl1 N4 O2
            Atom count from _chemical_formula_moiety:
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Silver(I) complexes with carboxylate ligands and amine compounds have been widely investigated due to their versatile structures (Odoko et al., 2007; Li et al., 2007; Jones et al., 2006; Bi et al., 2002). We report herein the crystal structure of the title silver(I) complex.

The title compound is a mononuclear silver(I) complex (Fig. 1). The Ag^I atom is three-coordinated by two pyridine N atoms from two 5-methylpyridin-2-ylamine ligands and by one O atom of a 4-chlorobenzoate ligand, forming a distorted T-shaped coordination, the distortion being caused by the weak coordination of the carboxylate O atom (Ag1—O1 = 2.647 (2) Å, Table 1). The Ag—N bond lengths (Table 1) are comparable with the values observed in other silver(I) complexes (Kristiansson, 2000; Wang & Okabe, 2004; Sailaja et al., 2001; Khan et al., 2005; Deng et al., 2004).

In the crystal structure, the molecules are linked through intermolecular N—H···O hydrogen bonds (Table 2), forming chains running along the b axis (Fig. 2).

Related literature

For related literature, see: Bi et al. (2002); Deng et al. (2004); Jones et al. (2006); Khan et al. (2005); Kristiansson (2000); Li et al. (2007); Odoko et al. (2007); Sailaja et al. (2001); Wang & Okabe (2004).

S2. Experimental

Ag₂O (0.1 mmol, 23.2 mg) and 4-chlorobenzoic acid (0.1 mmol, 15.6 mg) were dissolved in an ammonia solution (10 ml, 30%), and the mixture was stirred for 20 min at room temperature. To the above mixture was added with stirring a methanol solution (3 ml) of 5-methylpyridin-2-ylamine (0.2 mmol, 21.6 mg). The final mixture was stirred for 30 min at room temperature. The resulting clear colourless solution was kept in dark for 12 d, yielding colourless block-shaped crystals.

S3. Refinement

Atoms H2A, H2B, H4A and H4B were located in a difference Fourier map and refined isotropically, with N—H and H···H distances restrained to 0.90 (1) Å and 1.43 (2) Å, respectively. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 5.1; Sheldrick, 2008).

Figures

	Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

(4-Chlorobenzoato)bis(5-methyl-2-pyridylamine)silver(I)

Crystal data

[Ag(C7H4ClO2)(C6H8N2)2]	F(000) = 968
Mr = 479.71	Dx = 1.617 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3734 reflections
a = 15.983 (3) Å	θ = 2.5–24.9°
b = 5.7428 (9) Å	µ = 1.18 mm^−1
c = 21.703 (4) Å	T = 298 K
β = 98.460 (2)°	Block, colourless
V = 1970.4 (6) Å^3	0.37 × 0.35 × 0.32 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4064 independent reflections
Radiation source: fine-focus sealed tube	3277 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 26.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→20
Tmin = 0.669, Tmax = 0.704	k = −7→7
13465 measured reflections	l = −26→27

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0422P)^2 + 0.4221P] where P = (Fo^2 + 2Fc^2)/3
4064 reflections	(Δ/σ)max = 0.001
258 parameters	Δρmax = 0.53 e Å^−3
6 restraints	Δρmin = −0.34 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	0.291478 (15)	0.09298 (4)	0.077611 (11)	0.05012 (11)
Cl1	0.69700 (7)	0.65902 (19)	0.36548 (5)	0.0793 (3)
O1	0.35007 (14)	0.2179 (4)	0.19330 (10)	0.0573 (6)
O2	0.45197 (17)	0.0110 (5)	0.16007 (13)	0.0760 (8)
N1	0.34955 (14)	0.3452 (4)	0.02193 (11)	0.0388 (5)
N2	0.39194 (19)	0.5847 (5)	0.10583 (14)	0.0556 (7)
N3	0.20646 (14)	−0.2005 (4)	0.08709 (11)	0.0432 (6)
N4	0.2241 (2)	−0.1612 (6)	0.19393 (13)	0.0605 (8)
C1	0.6161 (2)	0.5050 (6)	0.31981 (14)	0.0507 (8)
C2	0.5373 (2)	0.6012 (6)	0.30750 (15)	0.0542 (8)
H2	0.5258	0.7432	0.3251	0.065*
C3	0.4749 (2)	0.4848 (6)	0.26869 (14)	0.0491 (7)
H3	0.4210	0.5489	0.2602	0.059*
C4	0.49170 (19)	0.2737 (5)	0.24224 (13)	0.0427 (7)
C5	0.5713 (2)	0.1802 (6)	0.25682 (16)	0.0554 (8)
H5	0.5831	0.0371	0.2400	0.066*
C6	0.6338 (2)	0.2935 (7)	0.29568 (17)	0.0631 (9)
H6	0.6873	0.2277	0.3054	0.076*
C7	0.4262 (2)	0.1546 (6)	0.19559 (14)	0.0481 (8)
C8	0.38570 (17)	0.5444 (5)	0.04449 (15)	0.0417 (7)
C9	0.41727 (18)	0.7050 (5)	0.00414 (17)	0.0501 (8)
H9	0.4412	0.8445	0.0198	0.060*
C10	0.41269 (19)	0.6557 (6)	−0.05702 (17)	0.0525 (8)
H10	0.4337	0.7613	−0.0834	0.063*
C11	0.37643 (19)	0.4460 (6)	−0.08121 (15)	0.0465 (7)
C12	0.34602 (17)	0.3021 (5)	−0.03981 (13)	0.0414 (7)
H12	0.3209	0.1636	−0.0551	0.050*
C13	0.3731 (2)	0.3791 (7)	−0.14840 (16)	0.0674 (11)
H13A	0.3471	0.2288	−0.1553	0.101*
H13B	0.4295	0.3734	−0.1586	0.101*
H13C	0.3406	0.4923	−0.1743	0.101*
C14	0.19164 (17)	−0.2802 (6)	0.14244 (14)	0.0438 (7)
C15	0.1459 (2)	−0.4866 (6)	0.14600 (16)	0.0535 (8)
H15	0.1354	−0.5405	0.1845	0.064*
C16	0.1171 (2)	−0.6072 (6)	0.09412 (17)	0.0548 (8)
H16	0.0872	−0.7447	0.0970	0.066*
C17	0.13206 (19)	−0.5268 (6)	0.03557 (15)	0.0493 (8)
C18	0.17643 (19)	−0.3242 (6)	0.03562 (15)	0.0477 (7)
H18	0.1868	−0.2669	−0.0026	0.057*
C19	0.1021 (3)	−0.6605 (7)	−0.02362 (18)	0.0726 (11)
H19A	0.1096	−0.5667	−0.0590	0.109*
H19B	0.0433	−0.6984	−0.0253	0.109*
H19C	0.1344	−0.8013	−0.0241	0.109*
H4B	0.209 (2)	−0.185 (6)	0.2308 (9)	0.080*
H4A	0.255 (2)	−0.032 (4)	0.1940 (16)	0.080*
H2B	0.407 (2)	0.720 (3)	0.1241 (14)	0.080*
H2A	0.374 (2)	0.489 (5)	0.1330 (13)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.05372 (17)	0.04898 (17)	0.04972 (16)	−0.01056 (11)	0.01445 (11)	0.00527 (11)
Cl1	0.0798 (7)	0.0821 (7)	0.0669 (6)	−0.0191 (5)	−0.0192 (5)	−0.0079 (5)
O1	0.0522 (13)	0.0746 (17)	0.0462 (13)	−0.0174 (12)	0.0110 (10)	−0.0097 (12)
O2	0.0837 (18)	0.0637 (16)	0.0788 (18)	−0.0047 (14)	0.0062 (14)	−0.0372 (15)
N1	0.0404 (13)	0.0345 (13)	0.0426 (14)	−0.0033 (10)	0.0100 (10)	0.0007 (11)
N2	0.0648 (18)	0.0463 (17)	0.0552 (18)	−0.0051 (14)	0.0075 (14)	−0.0123 (14)
N3	0.0432 (13)	0.0454 (15)	0.0419 (14)	−0.0063 (11)	0.0090 (11)	0.0021 (12)
N4	0.0729 (19)	0.070 (2)	0.0420 (16)	−0.0249 (16)	0.0199 (14)	−0.0044 (15)
C1	0.060 (2)	0.054 (2)	0.0359 (16)	−0.0103 (17)	−0.0015 (14)	0.0007 (15)
C2	0.066 (2)	0.052 (2)	0.0465 (18)	−0.0065 (17)	0.0145 (16)	−0.0162 (15)
C3	0.0491 (18)	0.0522 (19)	0.0472 (18)	−0.0026 (15)	0.0113 (14)	−0.0094 (15)
C4	0.0540 (17)	0.0401 (17)	0.0349 (15)	−0.0079 (14)	0.0098 (13)	0.0005 (13)
C5	0.070 (2)	0.0414 (18)	0.053 (2)	0.0066 (17)	0.0023 (16)	−0.0042 (16)
C6	0.062 (2)	0.057 (2)	0.065 (2)	0.0071 (18)	−0.0105 (17)	0.0010 (19)
C7	0.063 (2)	0.0435 (18)	0.0385 (17)	−0.0144 (15)	0.0093 (15)	−0.0058 (14)
C8	0.0382 (15)	0.0341 (17)	0.0530 (18)	0.0034 (12)	0.0073 (13)	−0.0022 (14)
C9	0.0438 (17)	0.0309 (17)	0.076 (2)	0.0001 (13)	0.0093 (15)	0.0040 (16)
C10	0.0420 (17)	0.049 (2)	0.069 (2)	0.0037 (14)	0.0166 (15)	0.0233 (17)
C11	0.0390 (16)	0.054 (2)	0.0481 (18)	0.0057 (14)	0.0115 (13)	0.0076 (15)
C12	0.0390 (15)	0.0392 (17)	0.0466 (17)	−0.0012 (13)	0.0079 (12)	−0.0022 (14)
C13	0.061 (2)	0.097 (3)	0.046 (2)	0.001 (2)	0.0159 (17)	0.0094 (19)
C14	0.0403 (15)	0.0489 (19)	0.0448 (17)	−0.0016 (14)	0.0147 (13)	0.0035 (15)
C15	0.058 (2)	0.0520 (19)	0.054 (2)	−0.0088 (16)	0.0204 (15)	0.0091 (17)
C16	0.0476 (18)	0.047 (2)	0.072 (2)	−0.0092 (15)	0.0146 (16)	−0.0004 (17)
C17	0.0412 (16)	0.0497 (19)	0.057 (2)	−0.0005 (14)	0.0065 (14)	−0.0085 (16)
C18	0.0474 (17)	0.055 (2)	0.0409 (17)	−0.0020 (15)	0.0085 (13)	0.0045 (15)
C19	0.072 (2)	0.071 (3)	0.071 (3)	−0.008 (2)	−0.001 (2)	−0.021 (2)

Geometric parameters (Å, º)

Ag1—N1	2.179 (2)	C5—H5	0.93
Ag1—N3	2.193 (2)	C6—H6	0.93
Ag1—O1	2.647 (2)	C8—C9	1.415 (4)
Cl1—C1	1.748 (3)	C9—C10	1.348 (5)
O1—C7	1.263 (4)	C9—H9	0.93
O2—C7	1.240 (4)	C10—C11	1.404 (5)
N1—C8	1.342 (4)	C10—H10	0.93
N1—C12	1.356 (4)	C11—C12	1.362 (4)
N2—C8	1.340 (4)	C11—C13	1.501 (5)
N2—H2B	0.888 (10)	C12—H12	0.93
N2—H2A	0.88 (3)	C13—H13A	0.96
N3—C14	1.339 (4)	C13—H13B	0.96
N3—C18	1.351 (4)	C13—H13C	0.96
N4—C14	1.347 (4)	C14—C15	1.401 (4)
N4—H4B	0.883 (10)	C15—C16	1.344 (5)
N4—H4A	0.88 (3)	C15—H15	0.93
C1—C2	1.366 (5)	C16—C17	1.405 (5)
C1—C6	1.369 (5)	C16—H16	0.93
C2—C3	1.379 (4)	C17—C18	1.363 (5)
C2—H2	0.93	C17—C19	1.513 (5)
C3—C4	1.384 (4)	C18—H18	0.93
C3—H3	0.93	C19—H19A	0.96
C4—C5	1.375 (4)	C19—H19B	0.96
C4—C7	1.510 (4)	C19—H19C	0.96
C5—C6	1.373 (5)
N1—Ag1—N3	151.99 (9)	C10—C9—C8	120.0 (3)
N1—Ag1—O1	103.05 (9)	C10—C9—H9	120.0
N3—Ag1—O1	104.89 (9)	C8—C9—H9	120.0
C8—N1—C12	118.0 (3)	C9—C10—C11	120.5 (3)
C8—N1—Ag1	124.1 (2)	C9—C10—H10	119.7
C12—N1—Ag1	117.89 (19)	C11—C10—H10	119.7
C8—N2—H2B	125 (2)	C12—C11—C10	116.2 (3)
C8—N2—H2A	125 (2)	C12—C11—C13	121.3 (3)
H2B—N2—H2A	110 (2)	C10—C11—C13	122.4 (3)
C14—N3—C18	118.3 (3)	N1—C12—C11	125.1 (3)
C14—N3—Ag1	122.7 (2)	N1—C12—H12	117.5
C18—N3—Ag1	118.44 (19)	C11—C12—H12	117.5
C14—N4—H4B	123 (2)	C11—C13—H13A	109.5
C14—N4—H4A	125 (2)	C11—C13—H13B	109.5
H4B—N4—H4A	111 (2)	H13A—C13—H13B	109.5
C2—C1—C6	121.4 (3)	C11—C13—H13C	109.5
C2—C1—Cl1	119.4 (3)	H13A—C13—H13C	109.5
C6—C1—Cl1	119.2 (3)	H13B—C13—H13C	109.5
C1—C2—C3	119.1 (3)	N3—C14—N4	118.2 (3)
C1—C2—H2	120.4	N3—C14—C15	120.1 (3)
C3—C2—H2	120.4	N4—C14—C15	121.6 (3)
C2—C3—C4	120.7 (3)	C16—C15—C14	120.5 (3)
C2—C3—H3	119.6	C16—C15—H15	119.8
C4—C3—H3	119.6	C14—C15—H15	119.8
C5—C4—C3	118.4 (3)	C15—C16—C17	120.4 (3)
C5—C4—C7	120.3 (3)	C15—C16—H16	119.8
C3—C4—C7	121.2 (3)	C17—C16—H16	119.8
C6—C5—C4	121.4 (3)	C18—C17—C16	115.9 (3)
C6—C5—H5	119.3	C18—C17—C19	122.3 (3)
C4—C5—H5	119.3	C16—C17—C19	121.8 (3)
C1—C6—C5	118.9 (3)	N3—C18—C17	124.8 (3)
C1—C6—H6	120.6	N3—C18—H18	117.6
C5—C6—H6	120.6	C17—C18—H18	117.6
O2—C7—O1	125.0 (3)	C17—C19—H19A	109.5
O2—C7—C4	117.2 (3)	C17—C19—H19B	109.5
O1—C7—C4	117.7 (3)	H19A—C19—H19B	109.5
N2—C8—N1	118.3 (3)	C17—C19—H19C	109.5
N2—C8—C9	121.4 (3)	H19A—C19—H19C	109.5
N1—C8—C9	120.2 (3)	H19B—C19—H19C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.88 (3)	2.11 (3)	2.977 (4)	169 (4)
N2—H2B···O2^i	0.89 (1)	1.94 (1)	2.822 (4)	174 (3)
N4—H4A···O1	0.88 (3)	2.09 (3)	2.966 (4)	167 (4)
N4—H4B···O1^ii	0.88 (1)	2.09 (3)	2.955 (3)	167 (3)

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