Poly[(μ₃-N,N-dibenzyl­dithio­carbamato-κ⁴S,S′:S:S′)silver(I)]

The title Ag^I coordination polymer, [Ag(C₁₅H₁₄NS₂)]_n, was synthesized by a solvothermal reaction of AgNO₃ with sodium N,N-dibenzyl­dithio­carbamate in a methanol solution. The compound displays a helical structure and each Ag^I ion is four-coordinated by four S atoms from two dithiocarbamate ligands and can be described as a distorted tetrahedral configuration. While the Ag^I ions are bridged by both S atoms of the dithocarbamate group to form the polymeric structure, the Ag...Ag distance of 3.0633 (11) Å suggests weaker metal bonding between Ag^I ions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.045
• wR factor = 0.080
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Ag1
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         14

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.20
           From the CIF: _reflns_number_total               2500
           Count of symmetry unique reflns         1263
           Completeness (_total/calc)            197.94%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1237
           Fraction of Friedel pairs measured     0.979
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1         (1)       1.02
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

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S1. Comment

Synthesis and crystal structure of the Ag(I) complexes with dialkyldithiocarbamates have been widely studied owing to variable coordination configurations since the first description by Akerström (1959). Monomeric, dimeric, hexameric and polymeric structure etc in the Ag(I) complexes have been reported in the past decade years, which was indicated that differently substituted alkyl groups and reaction conditions may play crucial roles in the formation of a variety of complexes with unprecedented structures (Zhang et al., 2002; Liu et al., 2006; Song et al., 2006). We have maintained an interest in silver(I)-dithiocarbamate complexes and report herein the structure of the title compound, [(AgC₁₅H₁₄NS₂)₃]_n.

In the solid state, the title complex has a one-dimensional chain-like polymeric structure and the each repeated Ag(I) units consists of three silver(I) cations and three ligand anions (Fig. 1). Each Ag(I) cation is coordinated with four sulfur atoms from three N,N-dibenzyldithiocarbamate (DBTC) ligands and shown as an distorted tetrahedral coordination environment. There are two types of sulfur atoms: S1 and the symmetry equivalents are acting as bridges between each two silver atoms with Ag—S distances of 2.446 (1) and 2.478 (2) Å (Table 1). On the other hand, the distances between the Ag(I) atoms and the S2 atoms (2.860 and 3.010 Å) are appreciably different, and both are much longer than the Ag—S(dithiocarbamate) distances [2.5–2.6 Å] (Song et al., 2006; Yin et al., 2007), but smaller Ag1—C1—S1 angles of 94.92° suggests the weaker Ag1—S2 bonding in the compound, as pointed out by Li et al. (2005). This grees with the related compounds reported previously [Anacker-Eickhoff et al., 1982; Song et al., 2006]. Thus the DBTC displays both roles of chelating ligand and asym-bridging ligand.

The Ag—Ag distances between adjacent Ag^I ions are 3.0633 (11) Å, which are longer than 2.886 Å found in metallic Ag (Greenwood et al., 1989) but shorter than the sum of the van der Waals radii of Ag atoms. This may suggest the existence of the weaker metal bonding between Ag^I ions (Tang et al., 2004). So multi-dentate bridging coordination modes of the chelating ligands and the agentophilic Ag—Ag interactions linked in the [(AgC₁₅H₁₄NS₂)₃] units leads to formation of the one-dimensional chain-like coordination polymer (Fig. 2).

Related literature

For general background, see Akerström (1959); Zhang et al. (2002); Liu et al. (2006); Song et al. (2006). For related structures, see: Yin et al. (2007); Anacker-Eickhoff et al. (1982); Li et al. (2005); Greenwood & Earnshaw (1989). For synthesis, see: Fan et al. (2004).

For related literature, see: Tang et al. (2004).

S2. Experimental

The title compound was prepared by the reaction of AgNO₃ (0.170 g, 1.0 mmol), sodium N, N-dibenzyldithiocardbanmate (NaDBTC) (0.296 g, 2.0 mmol) (Fan et al., 2004) and anhydrous methanol (7 ml) in an 15 ml Teflon liner sealed in a Parr autoclave. The autoclave was placed in a programmable furnace and heated to 353 K for 2 days. Yellow crystals were obtained after cooling to room temperature at 5 K.h^-1 (yield 50%). The compound is hardly soluble in general organic solvent.

S3. Refinement

All H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene) and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, YEAR?); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. The packing diagram of the title compound viewed down the b axis (H atoms have been omitted for clarity).

Poly[(µ₃-N,N-dibenzyldithiocarbamato-κ⁴S,S':S:S')silver(I)]

Crystal data

[Ag(C15H14NS2)]	Dx = 1.782 Mg m^−3
Mr = 380.26	Melting point = 491–492 K
Trigonal, P31	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 31	Cell parameters from 2450 reflections
a = 15.6505 (19) Å	θ = 2.4–25.0°
c = 5.0120 (14) Å	µ = 1.70 mm^−1
V = 1063.2 (3) Å^3	T = 293 K
Z = 3	Block, yellow
F(000) = 570	0.15 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	1519 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
φ and ω scans	θmax = 25.2°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −18→18
Tmin = 0.785, Tmax = 0.848	k = −18→18
7409 measured reflections	l = −6→6

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2500 reflections	Δρmax = 0.46 e Å^−3
172 parameters	Δρmin = −0.41 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1227 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (5)

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
C1	1.0066 (5)	0.2099 (6)	0.5559 (15)	0.0355 (19)
C2	1.0318 (6)	0.3398 (6)	0.8847 (15)	0.043 (2)
H2A	0.9870	0.3301	1.0303	0.051*
H2B	1.0825	0.3273	0.9528	0.051*
C3	1.0786 (5)	0.4436 (6)	0.7943 (16)	0.039 (2)
C4	1.0607 (7)	0.5107 (7)	0.9319 (19)	0.053 (2)
H4	1.0165	0.4894	1.0739	0.064*
C5	1.1086 (8)	0.6088 (7)	0.857 (2)	0.067 (3)
H5	1.0963	0.6529	0.9504	0.081*
C6	1.1742 (7)	0.6428 (7)	0.646 (2)	0.069 (3)
H6	1.2070	0.7092	0.6005	0.083*
C7	1.1905 (7)	0.5768 (8)	0.506 (2)	0.064 (3)
H7	1.2335	0.5980	0.3613	0.077*
C8	1.1424 (7)	0.4788 (6)	0.5810 (17)	0.051 (2)
H8	1.1537	0.4347	0.4835	0.062*
C9	0.8849 (6)	0.2674 (6)	0.5893 (16)	0.041 (2)
H9A	0.8627	0.2342	0.4187	0.049*
H9B	0.8997	0.3350	0.5667	0.049*
C10	0.8041 (6)	0.2174 (6)	0.7892 (17)	0.040 (2)
C11	0.7728 (6)	0.2713 (7)	0.9324 (17)	0.050 (2)
H11	0.8028	0.3389	0.9036	0.059*
C12	0.6973 (6)	0.2274 (7)	1.1197 (18)	0.054 (3)
H12	0.6766	0.2649	1.2147	0.065*
C13	0.6544 (7)	0.1282 (8)	1.161 (2)	0.060 (3)
H13	0.6040	0.0976	1.2853	0.072*
C14	0.6844 (6)	0.0740 (7)	1.0219 (19)	0.052 (3)
H14	0.6539	0.0063	1.0515	0.063*
C15	0.7590 (7)	0.1168 (6)	0.8386 (18)	0.052 (2)
H15	0.7794	0.0785	0.7471	0.062*
N1	0.9764 (4)	0.2672 (4)	0.6704 (13)	0.0360 (16)
S1	0.93514 (15)	0.12847 (14)	0.3071 (5)	0.0439 (5)
S2	1.11785 (16)	0.21987 (18)	0.6397 (5)	0.0543 (7)
Ag1	1.07051 (5)	0.10767 (5)	0.12225 (17)	0.0688 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.023 (4)	0.036 (5)	0.045 (5)	0.012 (4)	0.005 (4)	0.006 (4)
C2	0.050 (6)	0.040 (5)	0.032 (5)	0.018 (5)	0.000 (4)	−0.012 (4)
C3	0.036 (5)	0.038 (5)	0.038 (5)	0.016 (4)	−0.006 (4)	0.006 (4)
C4	0.051 (5)	0.039 (6)	0.060 (6)	0.016 (5)	0.002 (5)	0.004 (5)
C5	0.081 (8)	0.054 (7)	0.073 (8)	0.038 (6)	−0.014 (7)	−0.012 (6)
C6	0.056 (7)	0.047 (7)	0.085 (9)	0.010 (6)	−0.007 (6)	0.022 (6)
C7	0.050 (6)	0.067 (7)	0.056 (7)	0.015 (6)	0.001 (5)	0.016 (6)
C8	0.063 (6)	0.034 (5)	0.047 (6)	0.016 (5)	−0.005 (5)	0.008 (5)
C9	0.046 (5)	0.035 (5)	0.048 (6)	0.024 (4)	0.004 (5)	0.008 (4)
C10	0.038 (5)	0.053 (6)	0.040 (5)	0.032 (5)	−0.003 (4)	0.010 (5)
C11	0.044 (5)	0.057 (6)	0.057 (6)	0.033 (5)	0.009 (5)	0.009 (5)
C12	0.057 (6)	0.067 (7)	0.061 (7)	0.048 (6)	0.018 (5)	0.006 (5)
C13	0.056 (6)	0.071 (7)	0.058 (7)	0.037 (6)	0.020 (5)	0.017 (6)
C14	0.041 (6)	0.040 (5)	0.071 (7)	0.016 (5)	0.001 (5)	0.008 (5)
C15	0.063 (6)	0.050 (6)	0.048 (6)	0.033 (5)	0.008 (5)	0.006 (5)
N1	0.034 (4)	0.033 (4)	0.045 (4)	0.019 (3)	0.003 (4)	0.004 (3)
S1	0.0467 (14)	0.0406 (13)	0.0462 (13)	0.0232 (12)	0.0014 (11)	0.0026 (12)
S2	0.0424 (14)	0.0696 (18)	0.0624 (17)	0.0367 (14)	0.0043 (12)	0.0062 (14)
Ag1	0.0639 (5)	0.0686 (6)	0.0880 (5)	0.0438 (5)	0.0161 (5)	−0.0017 (5)

Geometric parameters (Å, º)

C1—N1	1.336 (9)	C9—H9B	0.9700
C1—S2	1.720 (8)	C10—C11	1.370 (11)
C1—S1	1.734 (8)	C10—C15	1.387 (10)
C2—C3	1.480 (10)	C11—C12	1.392 (11)
C2—N1	1.487 (9)	C11—H11	0.9300
C2—H2A	0.9700	C12—C13	1.365 (11)
C2—H2B	0.9700	C12—H12	0.9300
C3—C8	1.376 (10)	C13—C14	1.350 (12)
C3—C4	1.398 (12)	C13—H13	0.9300
C4—C5	1.381 (13)	C14—C15	1.369 (11)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.380 (13)	C15—H15	0.9300
C5—H5	0.9300	S1—Ag1^i	2.446 (2)
C6—C7	1.375 (13)	S1—Ag1	2.478 (2)
C6—H6	0.9300	S2—Ag1	3.010 (2)
C7—C8	1.381 (12)	S2—Ag1^ii	2.860 (2)
C7—H7	0.9300	Ag1—S1^iii	2.446 (2)
C8—H8	0.9300	Ag1—S2^iv	2.860 (2)
C9—N1	1.489 (9)	Ag1—Ag1^iii	3.0633 (11)
C9—C10	1.493 (10)	Ag1—Ag1^i	3.0633 (11)
C9—H9A	0.9700
N1—C1—S2	121.1 (6)	C11—C10—C9	119.9 (8)
N1—C1—S1	119.2 (6)	C15—C10—C9	122.1 (8)
S2—C1—S1	119.6 (5)	C10—C11—C12	121.8 (8)
C3—C2—N1	113.4 (6)	C10—C11—H11	119.1
C3—C2—H2A	108.9	C12—C11—H11	119.1
N1—C2—H2A	108.9	C13—C12—C11	118.4 (8)
C3—C2—H2B	108.9	C13—C12—H12	120.8
N1—C2—H2B	108.9	C11—C12—H12	120.8
H2A—C2—H2B	107.7	C14—C13—C12	120.7 (9)
C8—C3—C4	117.5 (8)	C14—C13—H13	119.7
C8—C3—C2	122.6 (8)	C12—C13—H13	119.7
C4—C3—C2	119.9 (8)	C13—C14—C15	121.1 (9)
C5—C4—C3	120.0 (9)	C13—C14—H14	119.4
C5—C4—H4	120.0	C15—C14—H14	119.4
C3—C4—H4	120.0	C14—C15—C10	120.1 (8)
C6—C5—C4	121.5 (10)	C14—C15—H15	120.0
C6—C5—H5	119.3	C10—C15—H15	120.0
C4—C5—H5	119.3	C1—N1—C2	123.8 (6)
C7—C6—C5	119.0 (9)	C1—N1—C9	123.2 (6)
C7—C6—H6	120.5	C2—N1—C9	113.0 (6)
C5—C6—H6	120.5	C1—S1—Ag1^i	107.1 (3)
C6—C7—C8	119.5 (9)	C1—S1—Ag1	94.9 (3)
C6—C7—H7	120.3	Ag1^i—S1—Ag1	76.92 (6)
C8—C7—H7	120.3	C1—S2—Ag1^ii	102.2 (2)
C3—C8—C7	122.6 (9)	S1^iii—Ag1—S1	171.87 (8)
C3—C8—H8	118.7	S1^iii—Ag1—S2^iv	85.02 (8)
C7—C8—H8	118.7	S1—Ag1—S2^iv	102.21 (7)
N1—C9—C10	112.3 (6)	S1^iii—Ag1—Ag1^iii	52.01 (6)
N1—C9—H9A	109.1	S1—Ag1—Ag1^iii	123.76 (6)
C10—C9—H9A	109.1	S2^iv—Ag1—Ag1^iii	88.38 (5)
N1—C9—H9B	109.1	S1^iii—Ag1—Ag1^i	120.83 (6)
C10—C9—H9B	109.1	S1—Ag1—Ag1^i	51.07 (5)
H9A—C9—H9B	107.9	S2^iv—Ag1—Ag1^i	140.89 (5)
C11—C10—C15	118.0 (8)	Ag1^iii—Ag1—Ag1^i	86.91 (2)

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