catena-Poly[[silver(I)-μ-[N-(4-pyridyl­meth­yl)pyridine-4-carboxamide-κ²N:N′]] nitrate monohydrate]

The title coordination polymer, {[Ag(C₁₂H₁₁N₃O)]NO₃·H₂O}_n, has a polycationic chain motif in which the Ag atom is bridged by the heterocyclic ligand; the Ag atom shows linear coordination. If the two long Ag...O_nitrate inter­actions [2.794 (6) and 2.867 (5) Å] are regarded as bonds, the compound adopts a three-dimensional network structure. The water mol­ecule consolidates the network structure by forming hydrogen bonds, one to the polycationic chain and one to the nitrate anion.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.053
• wR factor = 0.141
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1         (9)       0.85
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The 4-C₅H₄N–CH₂–NH–C(O)–4-C₅H₄N ligand is a spacer heterocycle that should function like 4,4'-bipyridine, which forms numerous coordination polymers, but should be flexible. There is, however, only one crystal structure report of an adduct, a hydrated disilver oxalate adduct (Tong et al., 2002). The title silver nitrate adduct has the metal in a linear enviroment, but the N–Ag–N skeleton that gives rise to a chain structure is distorted by the presence of two Ag···O_nitrate interactions. If these are regarded as formal bonds, the compound adopts a three-dimensional network structure.

Related literature

For the structure of the hydrated disilver oxalate adduct of the heterocyclic ligand, see Tong et al. (2002).

S2. Experimental

An aqueous solution (5 ml) of silver nitrate (1.0 mmol) was layed over a methanol (5 ml) solution of N-(4-pyridylmethyl)-4-pyridinecarboxamide (1.0 mmol) in a thin tube. The tube was placed vertically and kept away from light. Colorless crystals were obtained after two weeks. These were washed with methanol and collected in 50% yield. CH&N elemental analysis. Found: C 35.88, H 3.53, N 13.76%; calc. for C₁₂H₁₃AgN₄O₅: C 35.93, H 3.27, N 13.96%.

S3. Refinement

Carbon-bound H-atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.97 Å and U(H) set to 1.2U_eq(C). The amino and water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N—H = O—H = 0.85 (1) Å.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. A portion of the chain structure. Ellipsoids are drawn at the 50% probability level, and H atoms of spheres of arbitry radius. The red dashed lines denote the long Ag···O bonds and the dashed cyan line denotes the hydrogen bond. Symmetry codes (i) = 1/2 - x, 1 - y, z - 1/2; (ii) x - 1/2, 3/2 - y, -z.

catena-Poly[[silver(I)-µ-[N-(4-pyridylmethyl)pyridine-4- carboxamide-κ²N:N']] nitrate monohydrate]

Crystal data

[Ag(C12H11N3O)]NO3·H2O	F(000) = 1600
Mr = 401.13	Dx = 1.879 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5655 reflections
a = 12.912 (7) Å	θ = 3.2–27.5°
b = 9.021 (5) Å	µ = 1.45 mm^−1
c = 24.52 (1) Å	T = 295 K
V = 2856 (3) Å^3	Column, colourless
Z = 8	0.6 × 0.4 × 0.2 mm

Data collection

Rigaku Mercury diffractometer	3249 independent reflections
Radiation source: medium-focus sealed tube	2433 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (Jacobson, 1998)	h = −16→16
Tmin = 0.50, Tmax = 0.75	k = −11→11
25888 measured reflections	l = −30→31

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 5.5451P] where P = (Fo^2 + 2Fc^2)/3
3249 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.91 e Å^−3
3 restraints	Δρmin = −0.75 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.16581 (3)	0.61149 (5)	0.002207 (15)	0.05996 (18)
O1	0.1859 (3)	0.1438 (4)	0.23653 (13)	0.0598 (9)
O2	0.3756 (4)	0.6914 (6)	0.00374 (16)	0.0905 (14)
O3	0.5035 (4)	0.7095 (7)	−0.0481 (2)	0.1077 (17)
O4	0.3682 (5)	0.8329 (7)	−0.0644 (2)	0.118 (2)
O1W	0.5539 (3)	0.2042 (5)	0.17401 (17)	0.0660 (10)
H1W1	0.608 (3)	0.189 (8)	0.193 (2)	0.10 (2)*
H1W2	0.562 (8)	0.176 (10)	0.1412 (13)	0.15 (4)*
N1	0.1990 (3)	0.4795 (4)	0.07408 (14)	0.0448 (8)
N2	0.3572 (3)	0.1578 (4)	0.22161 (14)	0.0458 (9)
H2N	0.408 (3)	0.198 (5)	0.2048 (19)	0.061 (16)*
N3	0.3656 (3)	0.2837 (4)	0.42466 (15)	0.0470 (9)
N4	0.4163 (3)	0.7500 (4)	−0.03557 (16)	0.0469 (9)
C1	0.1231 (4)	0.4240 (6)	0.1046 (2)	0.0567 (12)
H1	0.0551	0.4506	0.0967	0.068*
C2	0.1412 (4)	0.3281 (6)	0.14763 (19)	0.0528 (12)
H2	0.0859	0.2895	0.1674	0.063*
C3	0.2413 (3)	0.2900 (4)	0.16112 (14)	0.0377 (9)
C4	0.3201 (4)	0.3498 (6)	0.1298 (2)	0.0524 (12)
H4	0.3890	0.3279	0.1376	0.063*
C5	0.2952 (4)	0.4425 (6)	0.08692 (19)	0.0513 (11)
H5	0.3489	0.4809	0.0659	0.062*
C6	0.2592 (4)	0.1894 (5)	0.20953 (15)	0.0417 (9)
C7	0.3844 (4)	0.0665 (5)	0.26853 (17)	0.0487 (11)
H7A	0.4547	0.0307	0.2639	0.058*
H7B	0.3390	−0.0191	0.2694	0.058*
C8	0.3770 (3)	0.1465 (4)	0.32274 (16)	0.0379 (9)
C9	0.3479 (4)	0.2929 (5)	0.32757 (19)	0.0474 (11)
H9A	0.3325	0.3486	0.2967	0.057*
C10	0.3418 (4)	0.3559 (5)	0.3786 (2)	0.0515 (12)
H10	0.3201	0.4540	0.3812	0.062*
C11	0.3960 (4)	0.1419 (5)	0.41994 (18)	0.0514 (11)
H11	0.4134	0.0895	0.4513	0.062*
C12	0.4021 (4)	0.0715 (5)	0.37027 (17)	0.0482 (11)
H12	0.4233	−0.0270	0.3686	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0659 (3)	0.0671 (3)	0.0469 (3)	0.00106 (19)	−0.01097 (16)	0.01944 (19)
O1	0.065 (2)	0.074 (2)	0.0410 (18)	−0.0126 (18)	0.0093 (16)	0.0097 (17)
O2	0.111 (4)	0.103 (4)	0.058 (3)	−0.013 (3)	0.013 (2)	0.026 (2)
O3	0.076 (3)	0.171 (5)	0.076 (3)	0.009 (3)	0.003 (2)	−0.016 (3)
O4	0.130 (4)	0.135 (5)	0.089 (4)	0.049 (4)	0.001 (3)	0.050 (3)
O1W	0.056 (2)	0.087 (3)	0.055 (2)	0.005 (2)	−0.0059 (19)	0.011 (2)
N1	0.052 (2)	0.048 (2)	0.0343 (18)	0.0005 (18)	−0.0060 (16)	0.0031 (16)
N2	0.058 (2)	0.047 (2)	0.0318 (18)	0.0024 (19)	0.0050 (17)	0.0092 (16)
N3	0.053 (2)	0.049 (2)	0.0394 (19)	−0.0026 (18)	−0.0003 (17)	−0.0094 (17)
N4	0.053 (2)	0.048 (2)	0.041 (2)	−0.0017 (19)	0.0040 (18)	0.0014 (17)
C1	0.047 (3)	0.071 (3)	0.052 (3)	0.001 (2)	−0.008 (2)	0.014 (2)
C2	0.046 (2)	0.071 (3)	0.041 (2)	−0.011 (2)	−0.0001 (19)	0.006 (2)
C3	0.049 (2)	0.037 (2)	0.0265 (17)	−0.0034 (19)	0.0008 (17)	−0.0015 (15)
C4	0.043 (2)	0.063 (3)	0.051 (3)	0.007 (2)	0.005 (2)	0.018 (2)
C5	0.045 (2)	0.059 (3)	0.049 (3)	0.005 (2)	0.007 (2)	0.022 (2)
C6	0.056 (3)	0.043 (2)	0.0255 (18)	−0.004 (2)	0.0057 (18)	−0.0009 (16)
C7	0.071 (3)	0.043 (2)	0.032 (2)	0.008 (2)	−0.001 (2)	0.0033 (18)
C8	0.043 (2)	0.037 (2)	0.0333 (19)	−0.0026 (18)	−0.0003 (17)	−0.0010 (16)
C9	0.057 (3)	0.041 (2)	0.044 (2)	0.005 (2)	−0.009 (2)	−0.0001 (19)
C10	0.057 (3)	0.043 (2)	0.054 (3)	0.006 (2)	−0.006 (2)	−0.009 (2)
C11	0.073 (3)	0.046 (3)	0.035 (2)	0.001 (2)	−0.005 (2)	−0.0004 (19)
C12	0.069 (3)	0.037 (2)	0.039 (2)	0.004 (2)	0.002 (2)	0.0023 (18)

Geometric parameters (Å, º)

Ag1—N3^i	2.162 (4)	C2—C3	1.377 (6)
Ag1—N1	2.170 (4)	C2—H2	0.9300
Ag1—O2	2.803 (6)	C3—C4	1.385 (6)
Ag1—O3^ii	2.874 (6)	C3—C6	1.512 (5)
O1—C6	1.226 (5)	C4—C5	1.381 (6)
O2—N4	1.219 (5)	C4—H4	0.9300
O3—N4	1.223 (6)	C5—H5	0.9300
O4—N4	1.202 (6)	C7—C8	1.516 (6)
O1W—H1W1	0.85 (4)	C7—H7A	0.9700
O1W—H1W2	0.85 (4)	C7—H7B	0.9700
N1—C5	1.325 (6)	C8—C9	1.378 (6)
N1—C1	1.331 (6)	C8—C12	1.386 (6)
N2—C6	1.330 (6)	C9—C10	1.377 (6)
N2—C7	1.458 (5)	C9—H9A	0.9300
N2—H2N	0.86 (4)	C10—H10	0.9300
N3—C10	1.340 (6)	C11—C12	1.376 (6)
N3—C11	1.343 (6)	C11—H11	0.9300
C1—C2	1.385 (7)	C12—H12	0.9300
C1—H1	0.9300
N3^i—Ag1—N1	172.52 (14)	C5—C4—H4	120.4
N3^i—Ag1—O2	94.61 (13)	C3—C4—H4	120.4
N1—Ag1—O2	86.53 (14)	N1—C5—C4	123.5 (4)
N3^i—Ag1—O3^ii	87.80 (15)	N1—C5—H5	118.3
N1—Ag1—O3^ii	97.73 (15)	C4—C5—H5	118.3
O2—Ag1—O3^ii	123.69 (16)	O1—C6—N2	122.8 (4)
N4—O2—Ag1	121.2 (4)	O1—C6—C3	120.5 (4)
H1W1—O1W—H1W2	111 (8)	N2—C6—C3	116.7 (4)
C5—N1—C1	117.5 (4)	N2—C7—C8	114.0 (4)
C5—N1—Ag1	121.1 (3)	N2—C7—H7A	108.7
C1—N1—Ag1	121.2 (3)	C8—C7—H7A	108.7
C6—N2—C7	121.8 (4)	N2—C7—H7B	108.7
C6—N2—H2N	122 (4)	C8—C7—H7B	108.7
C7—N2—H2N	116 (4)	H7A—C7—H7B	107.6
C10—N3—C11	117.2 (4)	C9—C8—C12	117.4 (4)
C10—N3—Ag1^iii	119.1 (3)	C9—C8—C7	123.3 (4)
C11—N3—Ag1^iii	123.2 (3)	C12—C8—C7	119.3 (4)
O4—N4—O2	120.8 (5)	C10—C9—C8	119.3 (4)
O4—N4—O3	120.9 (5)	C10—C9—H9A	120.4
O2—N4—O3	117.8 (5)	C8—C9—H9A	120.4
N1—C1—C2	122.6 (5)	N3—C10—C9	123.5 (4)
N1—C1—H1	118.7	N3—C10—H10	118.2
C2—C1—H1	118.7	C9—C10—H10	118.2
C3—C2—C1	119.8 (4)	N3—C11—C12	122.2 (4)
C3—C2—H2	120.1	N3—C11—H11	118.9
C1—C2—H2	120.1	C12—C11—H11	118.9
C2—C3—C4	117.4 (4)	C11—C12—C8	120.3 (4)
C2—C3—C6	118.8 (4)	C11—C12—H12	119.8
C4—C3—C6	123.8 (4)	C8—C12—H12	119.8
C5—C4—C3	119.1 (4)
N3^i—Ag1—O2—N4	−7.1 (5)	C7—N2—C6—O1	−0.4 (7)
N1—Ag1—O2—N4	165.5 (5)	C7—N2—C6—C3	177.7 (4)
O3^ii—Ag1—O2—N4	−97.5 (4)	C2—C3—C6—O1	−0.7 (6)
O2—Ag1—N1—C5	−17.8 (4)	C4—C3—C6—O1	177.8 (4)
O3^ii—Ag1—N1—C5	−141.4 (4)	C2—C3—C6—N2	−178.8 (4)
O2—Ag1—N1—C1	167.1 (4)	C4—C3—C6—N2	−0.3 (6)
O3^ii—Ag1—N1—C1	43.5 (4)	C6—N2—C7—C8	−76.5 (6)
Ag1—O2—N4—O4	33.5 (7)	N2—C7—C8—C9	−0.5 (7)
Ag1—O2—N4—O3	−138.7 (4)	N2—C7—C8—C12	−179.3 (4)
C5—N1—C1—C2	−1.5 (8)	C12—C8—C9—C10	−2.1 (7)
Ag1—N1—C1—C2	173.8 (4)	C7—C8—C9—C10	179.1 (4)
N1—C1—C2—C3	1.7 (8)	C11—N3—C10—C9	−0.6 (7)
C1—C2—C3—C4	−0.7 (7)	Ag1^iii—N3—C10—C9	−172.5 (4)
C1—C2—C3—C6	177.9 (4)	C8—C9—C10—N3	1.9 (7)
C2—C3—C4—C5	−0.5 (7)	C10—N3—C11—C12	−0.5 (7)
C6—C3—C4—C5	−179.0 (4)	Ag1^iii—N3—C11—C12	171.1 (4)
C1—N1—C5—C4	0.2 (8)	N3—C11—C12—C8	0.2 (8)
Ag1—N1—C5—C4	−175.1 (4)	C9—C8—C12—C11	1.1 (7)
C3—C4—C5—N1	0.8 (8)	C7—C8—C12—C11	180.0 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1W	0.86 (4)	2.04 (2)	2.827 (6)	154 (5)
O1W—H1W1···O1^iv	0.85 (4)	2.05 (3)	2.831 (5)	154 (7)
O1W—H1W2···O4^v	0.85 (4)	2.09 (4)	2.888 (7)	157 (9)

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