catena-Poly­[[silver(I)-μ-hexane-1,6-di­amine-κ²N:N′] cinnamate dihydrate]

The title compound, {[Ag(C₆H₁₆N₂)](C₉H₇O₂)·2H₂O}_n, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Ag atom is coordinated in a linear configuration by two N atoms from two hexane-1,6-­diamine ligands, giving a zigzag polymeric chain with an [–Ag—N—C—C—C—C—C—C—N–]_n backbone running parallel to the c axis. In the crystal packing, adjacent chains interact with the anions via the lattice water mol­ecules, thus forming layers parallel to the bc plane.

S1. Comment

A lot of silver(I) complexes with carboxylate anions as counter-ions or ligands have been structurally characterized over the past 30 years because of the wide usage of these compounds in many fields (Graham et al., 1996; Pingrong et al., 1998; Nomiya et al., 2000; Kristiansson, 2001). Recently, we have reported a few dozen silver(I)–carboxylate complexes with various amines and imines, all of which have been structurally characterized (Usman et al., 2003; You et al., 2004; Zhu et al., 1999, 2000; Zhu, Usman et al., 2003; Zhu, Zhang et al., 2003; Zheng, Tong, Zhu & Chen, 2001; Zheng, Tong, Zhu, Fang & Chen, 2001). As an extension of our work on the structural characterization of these silver(I) carboxylates, the title complex, (I), is reported here.

Complex (I) is a polymeric 1,6-diaminohexanesilver(I) complex. Each of the smallest repeat units in the complex contains a 1,6-diaminohexanesilver(I) cation, a cinnamate anion and two lattice water molecules, as shown in Fig. 1. In the cation, the Ag atom is in a linear coordination environment and is coordinated by two N atoms from two 1,6-diaminohexane ligands. The Ag1—N1 and Ag1—N2 bond lengths [2.133 (4) and 2.155 (4) Å, respectively] are slightly longer than the average Ag—N bond lengths [2.126 (4) Å] reported for a similar silver complex with 1,6-diaminohexane (Zhu, Wang et al., 2003). The N1—Ag1—N2 –angle [174.47 (15) °], indicating a slightly distorted linear geometry for atom Ag1, is comparable to the value observed in another similar silver complex [172.37 (8)°; Zhu, Liu et al., 2003]. In the anion, the dihedral angle between the plane of the benzene ring and the plane of the carboxy group (O1/C7/O2) is 25.1 (4) °. The O2—C7—C8—C9 and C7—C8—C9—C10 torsion angles are −168.9 (4) and 176.8 (4) °, respectively. Atom C9 lies in the plane of the phenyl ring. The aminohexane chain is almost planar, the largest displacement from the least-squares plane being only 0.17 Å. This plane makes a dihedral angle of 4.2 (2)° with teh plane of the phenyl ring.

In the crystal, the cinnamate anions are located among the chains. The Ag—N bonds link the amine molecules and the Ag atoms into a zigzag chain along the c axis. Adjacent chains interact with the anions via the lattice water molecules, thus forming layers along the bc direction. (Fig. 2). These layers are linked together by the hydrogen bonds listed in Table 1, thus forming a three-dimensional structure.

S2. Experimental

All reagents and solvents were used as obtained without further purification. Silver cinnamate (1 mmol, 255 mg) and 1,6-diaminohexane (1 mmol, 116 mg) were dissolved in an ammonia solution (10 ml, 30% and the mixture was stirred for about 20 min at room temperature. The resulting clear colorless solution was kept in air and, after slow evaporation of the solvent for a week, large colorless crystals of (I) formed at the bottom of the vessel. The crystals were isolated, washed three times with water and dried in a vacuum desiccator using anhydrous CaCl₂ (yield 78.7%). Analysis found: C 44.19, H 6.72, N 6.82%; calculated for C₁₅H₂₇AgN₂O₄: C 44.24, H 6.68, N 6.88%.

S3. Refinement

All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with N—H distances of 0.90 Å, C—H distances of 0.96 Å and O—H distances of 0.94–1.0 Å, and with U_iso(H) values fixed at 0.08 Ų. The coordinates of the water H atoms were localized by applying the HYDROGEN program (Nardelli, 1999).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I), viewed along the a axis.

1,6-Diaminohexanesilver(I) cinnamate dihydrate

Crystal data

[Ag(C6H16N2)](C9H7O2)·2H2O	F(000) = 840
Mr = 407.26	Dx = 1.567 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7511 reflections
a = 7.272 (1) Å	θ = 2.8–25.5°
b = 23.070 (5) Å	µ = 1.19 mm^−1
c = 10.753 (2) Å	T = 293 K
β = 106.82 (3)°	Block, colorless
V = 1726.8 (5) Å^3	0.45 × 0.32 × 0.19 mm
Z = 4

Data collection

Bruker CCD area-detector diffractometer	3381 independent reflections
Radiation source: fine-focus sealed tube	2800 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
Tmin = 0.641, Tmax = 0.798	k = −28→26
7641 measured reflections	l = −13→13

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0361P)^2] where P = (Fo^2 + 2Fc^2)/3
3381 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

Experimental. The CHN elemental analyses were performed on a Perkin-Elmer elemental analyzer.

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	0.04626 (5)	0.062053 (14)	0.86671 (3)	0.03132 (13)
N1	0.1666 (5)	0.07435 (13)	1.0708 (3)	0.0268 (9)
H1A	0.2259	0.0414	1.1054	0.080*
H1B	0.0699	0.0806	1.1059	0.080*
N2	0.4503 (5)	0.44706 (14)	1.1584 (3)	0.0299 (9)
H2A	0.3900	0.4814	1.1392	0.080*
H2B	0.5544	0.4481	1.1292	0.080*
C1	0.3066 (6)	0.12324 (17)	1.1101 (4)	0.0283 (10)
H1C	0.4138	0.1161	1.0771	0.080*
H1D	0.3539	0.1250	1.2031	0.080*
C2	0.2151 (6)	0.18121 (16)	1.0582 (4)	0.0250 (10)
H2C	0.1004	0.1866	1.0840	0.080*
H2D	0.1794	0.1807	0.9650	0.080*
C3	0.3512 (6)	0.23214 (17)	1.1083 (4)	0.0263 (10)
H3A	0.4604	0.2283	1.0758	0.080*
H3B	0.3965	0.2301	1.2014	0.080*
C4	0.2585 (6)	0.29155 (16)	1.0687 (4)	0.0268 (10)
H4A	0.1451	0.2948	1.0968	0.080*
H4B	0.2207	0.2949	0.9758	0.080*
C5	0.3958 (6)	0.34066 (17)	1.1280 (4)	0.0278 (10)
H5A	0.5130	0.3351	1.1053	0.080*
H5B	0.4263	0.3384	1.2209	0.080*
C6	0.3190 (6)	0.40092 (17)	1.0852 (4)	0.0273 (10)
H6A	0.3032	0.4052	0.9939	0.080*
H6B	0.1952	0.4054	1.0991	0.080*
O1W	0.1748 (5)	0.54549 (12)	1.0900 (3)	0.0413 (9)
H1WA	0.1471	0.5416	1.0090	0.080*
H1WB	0.0914	0.5275	1.1168	0.080*
O1	−0.1245 (5)	0.53418 (13)	0.6273 (3)	0.0427 (9)
O2	0.1022 (5)	0.52311 (12)	0.8169 (3)	0.0346 (8)
C7	0.0018 (7)	0.55364 (17)	0.7232 (4)	0.0291 (10)
C8	0.0388 (6)	0.61797 (17)	0.7326 (4)	0.0263 (10)
H8A	0.1494	0.6319	0.7985	0.080*
C9	−0.0739 (6)	0.65637 (18)	0.6542 (4)	0.0269 (10)
H9A	−0.1791	0.6410	0.5863	0.080*
C10	−0.0546 (6)	0.71985 (18)	0.6600 (4)	0.0240 (10)
C11	−0.2105 (7)	0.75411 (18)	0.5925 (4)	0.0303 (11)
H11A	−0.3268	0.7358	0.5422	0.080*
C15	0.1117 (6)	0.74837 (17)	0.7318 (4)	0.0273 (10)
H15A	0.2208	0.7259	0.7789	0.080*
C12	−0.2001 (7)	0.81427 (19)	0.5976 (4)	0.0310 (10)
H12A	−0.3083	0.8370	0.5500	0.080*
C13	−0.0350 (7)	0.84164 (19)	0.6698 (4)	0.0301 (11)
H13A	−0.0287	0.8832	0.6740	0.080*
C14	0.1223 (7)	0.80829 (18)	0.7368 (4)	0.0311 (11)
H14A	0.2383	0.8269	0.7865	0.080*
O2W	0.2742 (5)	0.44786 (12)	0.6404 (3)	0.0412 (8)
H2WA	0.2141	0.4672	0.6845	0.080*
H2WB	0.2195	0.4535	0.5614	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0352 (2)	0.02271 (19)	0.0318 (2)	0.00008 (17)	0.00294 (15)	0.00089 (15)
N1	0.033 (2)	0.0165 (18)	0.0300 (19)	−0.0005 (16)	0.0069 (17)	0.0008 (14)
N2	0.035 (2)	0.0159 (19)	0.039 (2)	0.0011 (16)	0.0095 (19)	0.0037 (15)
C1	0.028 (3)	0.027 (2)	0.030 (2)	0.004 (2)	0.007 (2)	−0.0002 (18)
C2	0.025 (2)	0.019 (2)	0.028 (2)	−0.0037 (19)	0.0034 (19)	0.0009 (17)
C3	0.026 (3)	0.027 (2)	0.024 (2)	−0.001 (2)	0.0049 (19)	−0.0022 (18)
C4	0.028 (3)	0.025 (2)	0.026 (2)	0.000 (2)	0.006 (2)	−0.0011 (18)
C5	0.030 (3)	0.024 (2)	0.028 (2)	0.001 (2)	0.006 (2)	−0.0007 (18)
C6	0.029 (3)	0.024 (2)	0.028 (2)	−0.001 (2)	0.007 (2)	0.0017 (19)
O1W	0.042 (2)	0.0292 (17)	0.0457 (19)	−0.0035 (15)	0.0010 (17)	−0.0001 (14)
O1	0.057 (2)	0.0271 (17)	0.0360 (18)	−0.0122 (17)	0.0004 (18)	−0.0027 (14)
O2	0.039 (2)	0.0270 (16)	0.0368 (18)	0.0036 (15)	0.0089 (16)	0.0058 (14)
C7	0.032 (3)	0.023 (2)	0.036 (2)	0.000 (2)	0.016 (2)	0.001 (2)
C8	0.025 (3)	0.025 (2)	0.028 (2)	−0.005 (2)	0.007 (2)	−0.0023 (18)
C9	0.028 (3)	0.025 (2)	0.028 (2)	−0.005 (2)	0.007 (2)	−0.0039 (18)
C10	0.027 (3)	0.029 (2)	0.019 (2)	−0.003 (2)	0.011 (2)	−0.0022 (17)
C11	0.032 (3)	0.033 (3)	0.025 (2)	−0.003 (2)	0.007 (2)	−0.001 (2)
C15	0.025 (3)	0.028 (2)	0.028 (2)	0.002 (2)	0.007 (2)	0.0006 (18)
C12	0.034 (3)	0.032 (2)	0.029 (2)	0.002 (2)	0.011 (2)	0.001 (2)
C13	0.043 (3)	0.022 (2)	0.030 (2)	0.005 (2)	0.018 (2)	0.0012 (18)
C14	0.034 (3)	0.026 (2)	0.034 (2)	−0.002 (2)	0.011 (2)	−0.003 (2)
O2W	0.041 (2)	0.0346 (18)	0.047 (2)	0.0061 (16)	0.0112 (17)	0.0024 (15)

Geometric parameters (Å, º)

Ag1—N1	2.133 (3)	C6—H6A	0.9601
Ag1—N2^i	2.155 (3)	C6—H6B	0.9600
N1—C1	1.496 (5)	O1W—H1WA	0.8401
N1—H1A	0.9001	O1W—H1WB	0.8504
N1—H1B	0.9000	O1—C7	1.249 (5)
N2—C6	1.493 (5)	O2—C7	1.272 (5)
N2—Ag1^ii	2.155 (3)	C7—C8	1.507 (5)
N2—H2A	0.9000	C8—C9	1.330 (5)
N2—H2B	0.9000	C8—H8A	0.9602
C1—C2	1.525 (5)	C9—C10	1.471 (5)
C1—H1C	0.9600	C9—H9A	0.9600
C1—H1D	0.9600	C10—C15	1.397 (6)
C2—C3	1.530 (5)	C10—C11	1.401 (5)
C2—H2C	0.9600	C11—C12	1.390 (6)
C2—H2D	0.9601	C11—H11A	0.9600
C3—C4	1.532 (5)	C15—C14	1.385 (5)
C3—H3A	0.9600	C15—H15A	0.9599
C3—H3B	0.9600	C12—C13	1.379 (6)
C4—C5	1.523 (5)	C12—H12A	0.9600
C4—H4A	0.9601	C13—C14	1.394 (6)
C4—H4B	0.9600	C13—H13A	0.9599
C5—C6	1.519 (5)	C14—H14A	0.9601
C5—H5A	0.9600	O2W—H2WA	0.8569
C5—H5B	0.9601	O2W—H2WB	0.8373
N1—Ag1—N2^i	174.47 (14)	C4—C5—H5A	108.5
C1—N1—Ag1	115.7 (2)	C6—C5—H5B	108.6
C1—N1—H1A	108.4	C4—C5—H5B	108.7
Ag1—N1—H1A	108.5	H5A—C5—H5B	107.6
C1—N1—H1B	108.2	N2—C6—C5	111.7 (3)
Ag1—N1—H1B	108.3	N2—C6—H6A	109.6
H1A—N1—H1B	107.5	C5—C6—H6A	109.2
C6—N2—Ag1^ii	116.4 (2)	N2—C6—H6B	109.1
C6—N2—H2A	108.2	C5—C6—H6B	109.3
Ag1^ii—N2—H2A	108.3	H6A—C6—H6B	107.9
C6—N2—H2B	108.0	H1WA—O1W—H1WB	108.6
Ag1^ii—N2—H2B	108.3	O1—C7—O2	124.9 (4)
H2A—N2—H2B	107.4	O1—C7—C8	118.9 (4)
N1—C1—C2	111.6 (3)	O2—C7—C8	116.2 (4)
N1—C1—H1C	109.0	C9—C8—C7	123.3 (4)
C2—C1—H1C	109.3	C9—C8—H8A	118.4
N1—C1—H1D	109.6	C7—C8—H8A	118.3
C2—C1—H1D	109.3	C8—C9—C10	127.1 (4)
H1C—C1—H1D	107.9	C8—C9—H9A	116.5
C1—C2—C3	112.0 (3)	C10—C9—H9A	116.5
C1—C2—H2C	109.3	C15—C10—C11	117.5 (4)
C3—C2—H2C	109.1	C15—C10—C9	123.3 (4)
C1—C2—H2D	109.2	C11—C10—C9	119.1 (4)
C3—C2—H2D	109.2	C12—C11—C10	121.1 (4)
H2C—C2—H2D	107.9	C12—C11—H11A	119.4
C2—C3—C4	113.7 (3)	C10—C11—H11A	119.5
C2—C3—H3A	108.7	C14—C15—C10	121.4 (4)
C4—C3—H3A	108.9	C14—C15—H15A	119.3
C2—C3—H3B	108.8	C10—C15—H15A	119.3
C4—C3—H3B	108.9	C13—C12—C11	120.5 (4)
H3A—C3—H3B	107.7	C13—C12—H12A	119.7
C5—C4—C3	111.5 (3)	C11—C12—H12A	119.8
C5—C4—H4A	109.2	C12—C13—C14	119.3 (4)
C3—C4—H4A	109.4	C12—C13—H13A	120.3
C5—C4—H4B	109.3	C14—C13—H13A	120.4
C3—C4—H4B	109.4	C15—C14—C13	120.2 (4)
H4A—C4—H4B	108.0	C15—C14—H14A	119.9
C6—C5—C4	114.5 (3)	C13—C14—H14A	119.9
C6—C5—H5A	108.7	H2WA—O2W—H2WB	108.2
N2^i—Ag1—N1—C1	29.9 (14)	C8—C9—C10—C15	15.1 (7)
Ag1—N1—C1—C2	59.5 (4)	C8—C9—C10—C11	−163.8 (4)
N1—C1—C2—C3	174.6 (3)	C15—C10—C11—C12	−0.4 (6)
C1—C2—C3—C4	−174.6 (3)	C9—C10—C11—C12	178.6 (4)
C2—C3—C4—C5	176.5 (3)	C11—C10—C15—C14	0.3 (6)
C3—C4—C5—C6	175.8 (4)	C9—C10—C15—C14	−178.7 (4)
Ag1^ii—N2—C6—C5	−48.8 (4)	C10—C11—C12—C13	−0.1 (6)
C4—C5—C6—N2	173.2 (3)	C11—C12—C13—C14	0.6 (6)
O1—C7—C8—C9	10.1 (7)	C10—C15—C14—C13	0.3 (6)
O2—C7—C8—C9	−168.9 (4)	C12—C13—C14—C15	−0.7 (6)
C7—C8—C9—C10	176.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^ii	0.90	2.03	2.901 (4)	161
N1—H1B···O2W^iii	0.90	2.38	3.194 (5)	150
N2—H2B···O2^iv	0.90	2.48	3.261 (5)	144
O1W—H1WB···O2^v	0.85	2.11	2.955 (5)	175
O2W—H2WB···O1^vi	0.84	1.97	2.798 (4)	172
N2—H2A···O1W	0.90	2.11	2.977 (5)	162
O1W—H1WA···O2	0.84	2.04	2.876 (4)	172
O2W—H2WA···O2	0.86	2.24	3.091 (4)	171

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