(N-Phenyl­thio­urea-κS)bis­(tri­phenylphosphane-κP)silver(I) nitrate

Sofia Mekarat; Chaveng Pakawatchai; Saowanit Saithong

doi:10.1107/S1600536814014147

. 2014 Jun 25;70(Pt 7):m281–m282. doi: 10.1107/S1600536814014147

(N-Phenylthiourea-κS)bis(triphenylphosphane-κP)silver(I) nitrate

Sofia Mekarat ^a, Chaveng Pakawatchai ^b,^*, Saowanit Saithong ^b

PMCID: PMC4120613 PMID: 25161537

Abstract

In the title salt, [Ag(C₇H₈N₂S)(C₁₈H₁₅P)₂]NO₃, the coordination geometry about the Ag^I atom is shallow trigonal pyramidal, with the metal atom displaced by 0.372 (1) Å from the plane of the P and S atoms. In the crystal, the cations are linked to the anions by N—H⋯O hydrogen bonds, generating tetramers (two cations and two anions), which feature R ₂ ²(8) and R ₄ ⁴(8) loops. The cations are linked by weak C—H⋯π interactions, generating a three-dimensional network.

Keywords: N-phenylthiourea, triphenylphosphane, silver(I)nitrate, crystal structure

Related literature

For properties of mixed-ligand d ¹⁰ metal(I) complexes, see: Oshio et al. (1996 ▶); Zheng et al. (2001 ▶); Sewead et al. (2003 ▶); Isab et al. (2010 ▶). For structural studies of mixed-ligand complexes of triphenylphosphane and thione ligands, see: Skoulika et al. (1991 ▶); Aslanidis et al. (1997 ▶); Ghassemzadeh et al.(2004 ▶); Nimthong et al. (2008 ▶); Isab et al. (2010 ▶). graphic file with name e-70-0m281-scheme1.jpg

Experimental

Crystal data

[Ag(C₇H₈N₂S)(C₁₈H₁₅P)₂]NO₃
M _r = 846.63
Monoclinic,
a = 13.6113 (5) Å
b = 10.6431 (4) Å
c = 26.4365 (10) Å
β = 96.068 (1)°
V = 3808.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 173 K
0.27 × 0.14 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.863, T _max = 1.000
44417 measured reflections
9196 independent reflections
8261 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.064
S = 1.05
9196 reflections
478 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010) ▶.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814014147/hb7242sup1.cif

e-70-0m281-sup1.cif^{(1.3MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014147/hb7242Isup2.hkl

e-70-0m281-Isup2.hkl^{(440.7KB, hkl)}

CCDC reference: 1008627

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.86	2.02	2.877 (2)	180
N1—H1B⋯O3ⁱⁱ	0.86	2.17	2.921 (2)	145
N2—H2⋯O1ⁱ	0.86	1.97	2.823 (2)	171
C35—H35⋯Cg2ⁱⁱⁱ	0.93	2.97	3.746 (2)	142
C54—H54⋯Cg2^iv	0.93	2.82	3.531 (2)	134

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

Financial support from the Center of Excellent for Innovation in Chemistry (PERCH–CIC), Office of the Higher Education Commission, Ministry of Education and Graduate School, Prince of Songkla University, are gratefully acknowledged.

supplementary crystallographic information

S1. Chemical context

Mixed-ligand complexes of group 11 metals dispaly many properties such as magnetism (Oshio et al., 1996); microporousity (Zheng et al., 2001); luminescence (Sewead et al., 2003) and antimicrobial activities (Isab et al.,2010). In our earlier work, we synthesized and characterized the neutral monomeric copper(I) complex containing mixed ligands of triphenylphosphane (PPh₃: C₁₈H₁₅P) and N-phynylthiourea (ptu : C₇H₈N₂S), [CuI(ptu)(PPh₃)₂] (Nimthong et al., 2008). As part of our continuing studies in this area, we now describe the synthesis and structure of the title compound, [Ag(ptu)(PPh₃)₂]NO₃ (Scheme I).

S2. Structural commentary

Unlike the previous complex mentioned above (Nimthong et al., 2008), this complex is an ionic complex and it crystallizes in monoclinic system space group P2₁/c. The structure consists of the discrete mononuclear [Ag(ptu)(PPh₃)₂]⁺cation and the NO₃^- anion which is similar to those [Ag(PPh₃)₂(pymtH)]NO₃ (Aslanidis et al., 1997). A perspective view of the molecular structure of [Ag(ptu)(PPh₃)₂]NO₃ with atomic labeling is given in Figure 1. The cation part contains silver(I) atom trigonally coordinated by two phosphorus atoms from two triphenylphosphane molecules and one sulfur atom from N–phenylthiourea molecule similar to found in those silver oxyanion complexes containing mixed PPh₃/heterocyclic thione ligands (Aslanidis et al., 1997; Ghassemzadeh et al., 2004). The Ag–P bond lengths of 2.4645 (5) and 2.4693 (4)Å are similar to the values of 2.455 (1) and 2.447 (1) Å observed in [Ag(PPh₃)₂(pymtH)]NO₃ (Aslanidis et al., 1997), however, these values are slightly different from the values of 2.458 (2) and 2.507 (2) Å compared to [Ag(TAMTTO)(PPh₃)₂]NO₃.1.5THF (Ghassemzadeh et al., 2004) because of the massive and steric effect of TAMTTO heterocyclic ligand. The Ag–S bond length [2.5307 (7) Å] is shorter than in those complexes [Ag(PPh₃)₂(pymtH)]NO₃ [2.573 (1)Å] and [Ag(TAMTTO)(PPh₃)₂]NO₃.1.5 THF [2.592 (2) Å] (Aslanidis et al., 1997; Ghassemzadeh et al., 2004 ). The P(1)–Ag–P(2), P(1)–Ag–S(1) and P(2)–Ag–S(1) bond angles are 127.55 (1)° ,113.02 (1)° and 112.69 (1)°, respectively. Due to the steric crowding of six phenyl rings from two bulky triphenyl phosphane ligands and the π(CH)···Ag interaction [3.314 Å] between the centriod of phenyl ring (C2—C7) of the N–phenylthiourea and metal atom, the silver centre atom deviates from idealized trigonal planar with this atom lying ca 0.372 (1) Å out of the P₂S plane. For the anion, although the oxygen atoms of the nitrate have no influence on coordination, they have great influence on the crystal packing of the complex. It is nearly planar with the bond angles around the nitrogen atom ranging from 119.01 (1)-120.53 (1)° and N(3)–O bond distances are 1.231 (2) – 1.264 (2) Å.

S3. Supramolecular features

For the crystal packing, each [Ag(ptu)(PPh₃)₂]⁺ cation is connected to another adjacent cationic part via hydrogen bonding interactions, N–H···O, which are observed between amino and amide groups and nitrate oxygen atoms generate a cyclic hydrogen bond interactions, two R₂²(8) graph sets for cationic-anionic interactions and one R₄⁴(8) graph set for anionic-anionic interaction, [ N(1)–H(1A)···O(3)ⁱ : 2.877 (2)Å, N(1)–H(1B)···O(3)ⁱⁱ : 2.921 (2)Å, N(2)–H(2)···O(1) : 2.823 (2) Å and symmetry code : (i) x-1,y,z, (ii) -x+1,-y+1,-z+2] as depicted in Figure 2 and 3. In addition, the cationic parts are linked together by the CH···π interactions between the phenyl rings with the distance of 3.746 (2) Å for C35–H35···Cg2 and 3.531 (2) Å for C54–H54···Cg2 [Cg2 : C11–C16] generating the three dimensional supramolecular network. All interactions are depicted in Figure 4.

S4. Synthesis and crystallization

The mixture silver(I) nitrate and triphenylphosphane in ethanol was refluxed at the temperature ca 60-70 ^°C for 2 h. After that, N-phenylthiourea ligand was added to the clear mixture solution and then continued to reflux futher for 3 h. The clear filtration was kept and left to evaporate slowly at ambient temperature. After several days, colorless blocks were obtained. The melting point of the complex is 192-194 ^°C . Elemental analysis,calculated for [Ag(PPh₃)₂(ptu)]NO₃ : C, 60.99;H, 4.52; N, 4.96; S, 3.78%, found: C, 65.16; H, 4.96; N, 5.16; S, 4.04%.

S5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The structures were solved by direct methods and refined by a full-matrix least-squares procedure based on F². All hydrogen atoms were placed in geometrically idealised positions and refined isotropically with a riding model for both of amine N [N—H = 0.86 Å and with U_i_so(H) =1.2U_eq(N)] and phenyl ring C-sp²[C—H = 0.93 Å and with U_i_so(H) = 1.2U_eq(C)]. ;