catena-Poly[[(4-amino­benzoato)aqua­silver(I)]-μ-hexa­methyl­enetetramine]

In the title coordination polymer, [Ag(C₇H₆NO₂)(C₆H₁₂N₄)(H₂O)]_n, the Ag^I ion is five-coordinated by two carboxyl­ate O atoms from one 4-amino­benzoate anion (L), two N atoms from two different hexa­methyl­enetetramine (hmt) ligands, and one water O atom in a distorted square-pyramidal geometry. The metal atom lies on a mirror plane and the L anion, hmt ligand and water mol­ecule all lie across crystallographic mirror planes. Each hmt ligand bridges two neighboring Ag^I ions, resulting in the formation of a chain structure along the b axis. The chains are linked into a three-dimensional framework by N—H...O and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.019
• wR factor = 0.048
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ag1    --  O1      ..      11.82 su

Alert level C
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          3

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.14 Ratio

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   1 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   4 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
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


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PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

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   1 ALERT level G = General alerts. Data that may be required is missing

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Related literature

For the applications and structures of silver(I) coordination polymers, see: Yang et al. (2007, 2008).

S1. Experimental

An aqueous solution (10 ml) of HL (0.104 g, 0.5 mmol) was added to solid Ag₂CO₃ (0.25 mmol) and stirred for several minutes until no further CO₂ was given off. A solution of hmt (0.5 mmol) in acetonitrile (10 ml) was then added and a white precipitate formed. The precipitate was dissolved by dropwise addition of an aqueous solution of NH₃ (14 M). Colourless blocks of the title compound were obtained by evaporation of the solution for several days at room temperature (33% yield).

S2. Refinement

Amino and water H-atoms were located in a difference Fourier map, and refined freely. The remaining H atoms were positioned geometrically (C-H = 0.93 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C).

Structure description

For the applications and structures of silver(I) coordination polymers, see: Yang et al. (2007, 2008).

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Ag^I centre in the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) x, 3/2 - y, z; (ii) x, 1/2 - y, z.
	Fig. 2. Part of the polymeric chain in the title compound.

catena-Poly[[(4-aminobenzoato)aquasilver(I)]-µ-hexamethylenetetramine]

Crystal data

[Ag(C7H6NO2)(C6H12N4)(H2O)]	F(000) = 816
Mr = 402.21	Dx = 1.835 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1557 reflections
a = 19.8107 (11) Å	θ = 3.0–26.0°
b = 6.4877 (3) Å	µ = 1.41 mm^−1
c = 11.3257 (6) Å	T = 293 K
V = 1455.65 (13) Å^3	Block, colourless
Z = 4	0.31 × 0.27 × 0.22 mm

Data collection

Bruker APEX CCD area-detector diffractometer	1557 independent reflections
Radiation source: fine-focus sealed tube	1373 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→23
Tmin = 0.66, Tmax = 0.87	k = −7→7
7757 measured reflections	l = −13→9

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 0.5726P] where P = (Fo^2 + 2Fc^2)/3
1557 reflections	(Δ/σ)max = 0.001
123 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Ag1	0.425226 (10)	0.2500	0.638361 (18)	0.02218 (9)
O1W	0.54862 (12)	0.2500	0.6362 (2)	0.0324 (5)
H1W1	0.5643 (11)	0.352 (4)	0.606 (2)	0.036 (7)*
O1	0.38093 (7)	0.4203 (2)	0.45173 (12)	0.0306 (4)
N1	0.42059 (7)	0.5604 (3)	0.75114 (14)	0.0198 (4)
N2	0.23019 (13)	0.2500	−0.0371 (2)	0.0261 (6)
H2A	0.2075 (11)	0.358 (3)	−0.0497 (19)	0.033 (7)*
N3	0.47738 (11)	0.7500	0.9101 (2)	0.0186 (5)
N4	0.35383 (11)	0.7500	0.8979 (2)	0.0228 (5)
C1	0.26785 (13)	0.2500	0.0657 (2)	0.0182 (6)
C2	0.28812 (9)	0.4347 (3)	0.11800 (16)	0.0206 (4)
H2	0.2781	0.5594	0.0814	0.025*
C3	0.32294 (9)	0.4339 (3)	0.22365 (16)	0.0196 (4)
H3	0.3357	0.5585	0.2576	0.024*
C4	0.33924 (13)	0.2500	0.2803 (2)	0.0178 (6)
C5	0.36952 (13)	0.2500	0.4018 (2)	0.0222 (6)
C6	0.35759 (9)	0.5670 (3)	0.82288 (17)	0.0235 (5)
H6A	0.3189	0.5649	0.7704	0.028*
H6B	0.3554	0.4448	0.8721	0.028*
C7	0.47854 (9)	0.5664 (3)	0.83436 (16)	0.0214 (4)
H7A	0.4776	0.4440	0.8836	0.026*
H7B	0.5203	0.5647	0.7897	0.026*
C8	0.41317 (12)	0.7500	0.9761 (2)	0.0223 (6)
H8A	0.4115	0.6292	1.0264	0.027*	0.50
H8B	0.4115	0.8708	1.0264	0.027*	0.50
C9	0.42303 (13)	0.7500	0.6783 (2)	0.0200 (6)
H9A	0.4642	0.7500	0.6321	0.024*
H9B	0.3852	0.7500	0.6240	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.02328 (13)	0.02679 (14)	0.01649 (13)	0.000	−0.00302 (9)	0.000
O1W	0.0240 (12)	0.0378 (15)	0.0352 (14)	0.000	0.0073 (10)	0.000
O1	0.0353 (8)	0.0378 (9)	0.0187 (7)	−0.0053 (8)	−0.0049 (6)	−0.0054 (7)
N1	0.0170 (8)	0.0292 (10)	0.0130 (8)	−0.0014 (7)	−0.0024 (6)	0.0004 (7)
N2	0.0244 (14)	0.0349 (17)	0.0189 (13)	0.000	−0.0072 (11)	0.000
N3	0.0137 (11)	0.0288 (14)	0.0134 (11)	0.000	0.0003 (9)	0.000
N4	0.0140 (11)	0.0378 (15)	0.0165 (12)	0.000	−0.0014 (9)	0.000
C1	0.0126 (12)	0.0283 (15)	0.0137 (14)	0.000	0.0039 (11)	0.000
C2	0.0208 (10)	0.0229 (11)	0.0179 (10)	0.0016 (8)	0.0010 (8)	0.0035 (8)
C3	0.0200 (10)	0.0210 (11)	0.0179 (10)	−0.0011 (8)	0.0041 (8)	−0.0020 (8)
C4	0.0112 (12)	0.0279 (16)	0.0143 (13)	0.000	0.0024 (10)	0.000
C5	0.0145 (13)	0.0355 (18)	0.0168 (14)	0.000	0.0022 (11)	0.000
C6	0.0159 (9)	0.0355 (13)	0.0192 (10)	−0.0040 (9)	−0.0024 (8)	0.0019 (9)
C7	0.0167 (10)	0.0308 (12)	0.0167 (10)	0.0015 (9)	−0.0025 (8)	0.0019 (8)
C8	0.0152 (14)	0.0377 (18)	0.0139 (14)	0.000	−0.0018 (11)	0.000
C9	0.0168 (13)	0.0301 (17)	0.0132 (13)	0.000	−0.0041 (11)	0.000

Geometric parameters (Å, º)

Ag1—N1	2.3862 (17)	C1—C2	1.396 (2)
Ag1—N1^i	2.3862 (17)	C1—C2^i	1.396 (2)
Ag1—O1W	2.445 (2)	C2—C3	1.381 (3)
Ag1—O1	2.5413 (14)	C2—H2	0.93
Ag1—O1^i	2.5413 (14)	C3—C4	1.393 (2)
O1W—H1W1	0.81 (2)	C3—H3	0.93
O1—C5	1.2615 (19)	C4—C3^i	1.393 (2)
N1—C9	1.482 (2)	C4—C5	1.500 (4)
N1—C7	1.486 (2)	C5—O1^i	1.2615 (19)
N1—C6	1.490 (2)	C6—H6A	0.97
N2—C1	1.383 (4)	C6—H6B	0.97
N2—H2A	0.84 (2)	C7—H7A	0.97
N3—C7	1.468 (2)	C7—H7B	0.97
N3—C7^ii	1.468 (2)	C8—H8A	0.97
N3—C8	1.475 (3)	C8—H8B	0.97
N4—C6	1.462 (2)	C9—N1^ii	1.482 (2)
N4—C6^ii	1.462 (2)	C9—H9A	0.97
N4—C8	1.472 (3)	C9—H9B	0.97
N1—Ag1—N1^i	115.09 (8)	C2—C3—H3	119.4
N1—Ag1—O1W	92.52 (5)	C4—C3—H3	119.4
N1^i—Ag1—O1W	92.52 (5)	C3^i—C4—C3	117.9 (2)
N1—Ag1—O1	93.74 (5)	C3^i—C4—C5	121.01 (12)
N1^i—Ag1—O1	143.00 (5)	C3—C4—C5	121.01 (12)
O1W—Ag1—O1	109.69 (6)	O1^i—C5—O1	122.2 (3)
N1—Ag1—O1^i	143.00 (5)	O1^i—C5—C4	118.87 (13)
N1^i—Ag1—O1^i	93.74 (5)	O1—C5—C4	118.87 (13)
O1W—Ag1—O1^i	109.69 (6)	N4—C6—N1	112.52 (17)
O1—Ag1—O1^i	51.53 (7)	N4—C6—H6A	109.1
Ag1—O1W—H1W1	112.9 (17)	N1—C6—H6A	109.1
C5—O1—Ag1	93.12 (14)	N4—C6—H6B	109.1
C9—N1—C7	107.80 (16)	N1—C6—H6B	109.1
C9—N1—C6	107.87 (17)	H6A—C6—H6B	107.8
C7—N1—C6	107.49 (15)	N3—C7—N1	112.34 (17)
C9—N1—Ag1	113.67 (12)	N3—C7—H7A	109.1
C7—N1—Ag1	109.39 (12)	N1—C7—H7A	109.1
C6—N1—Ag1	110.39 (12)	N3—C7—H7B	109.1
C1—N2—H2A	115.4 (16)	N1—C7—H7B	109.1
C7—N3—C7^ii	108.4 (2)	H7A—C7—H7B	107.9
C7—N3—C8	108.02 (14)	N4—C8—N3	112.6 (2)
C7^ii—N3—C8	108.02 (14)	N4—C8—H8A	109.1
C6—N4—C6^ii	108.6 (2)	N3—C8—H8A	109.1
C6—N4—C8	107.99 (14)	N4—C8—H8B	109.1
C6^ii—N4—C8	107.99 (14)	N3—C8—H8B	109.1
N2—C1—C2	120.83 (12)	H8A—C8—H8B	107.8
N2—C1—C2^i	120.83 (12)	N1^ii—C9—N1	112.3 (2)
C2—C1—C2^i	118.3 (2)	N1^ii—C9—H9A	109.2
C3—C2—C1	120.53 (19)	N1—C9—H9A	109.2
C3—C2—H2	119.7	N1^ii—C9—H9B	109.2
C1—C2—H2	119.7	N1—C9—H9B	109.2
C2—C3—C4	121.23 (19)	H9A—C9—H9B	107.9
N1—Ag1—O1—C5	−166.41 (14)	Ag1—O1—C5—C4	178.7 (2)
N1^i—Ag1—O1—C5	−23.97 (18)	C3^i—C4—C5—O1^i	0.9 (4)
O1W—Ag1—O1—C5	99.57 (14)	C3—C4—C5—O1^i	177.1 (2)
O1^i—Ag1—O1—C5	−0.38 (15)	C3^i—C4—C5—O1	−177.1 (2)
N1^i—Ag1—N1—C9	−179.54 (11)	C3—C4—C5—O1	−0.9 (4)
O1W—Ag1—N1—C9	86.50 (15)	C6^ii—N4—C6—N1	58.4 (3)
O1—Ag1—N1—C9	−23.43 (14)	C8—N4—C6—N1	−58.5 (2)
O1^i—Ag1—N1—C9	−41.73 (17)	C9—N1—C6—N4	−57.9 (2)
N1^i—Ag1—N1—C7	59.91 (14)	C7—N1—C6—N4	58.1 (2)
O1W—Ag1—N1—C7	−34.05 (13)	Ag1—N1—C6—N4	177.33 (13)
O1—Ag1—N1—C7	−143.98 (12)	C7^ii—N3—C7—N1	−58.6 (2)
O1^i—Ag1—N1—C7	−162.28 (10)	C8—N3—C7—N1	58.2 (2)
N1^i—Ag1—N1—C6	−58.17 (14)	C9—N1—C7—N3	58.2 (2)
O1W—Ag1—N1—C6	−152.14 (12)	C6—N1—C7—N3	−57.8 (2)
O1—Ag1—N1—C6	97.94 (12)	Ag1—N1—C7—N3	−177.73 (13)
O1^i—Ag1—N1—C6	79.64 (15)	C6—N4—C8—N3	58.64 (14)
N2—C1—C2—C3	176.9 (2)	C6^ii—N4—C8—N3	−58.64 (14)
C2^i—C1—C2—C3	−4.8 (4)	C7—N3—C8—N4	−58.54 (13)
C1—C2—C3—C4	0.5 (3)	C7^ii—N3—C8—N4	58.54 (13)
C2—C3—C4—C3^i	3.8 (4)	C7—N1—C9—N1^ii	−58.1 (2)
C2—C3—C4—C5	−172.5 (2)	C6—N1—C9—N1^ii	57.7 (2)
Ag1—O1—C5—O1^i	0.7 (3)	Ag1—N1—C9—N1^ii	−179.56 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1^iii	0.81 (2)	1.95 (2)	2.742 (2)	168 (2)
N2—H2A···O1^iv	0.84 (2)	2.27 (2)	3.072 (2)	159 (2)

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