Bis[(4-methyl­phen­yl)di­phenyl­phosphane-κP](nitrato-κ2O,O′)silver(I)

Malan, F.P.; Potgieter, K.; Meijboom, R.

doi:10.1107/S2414314622010458

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 11| November 2022| x221045

https://doi.org/10.1107/S2414314622010458

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Bis[(4-methylphenyl)diphenylphosphane-κP](nitrato-κ²O,O′)silver(I)

Frederick P. Malan,^a Kariska Potgieter ^b and Reinout Meijboom ^b ^*

^aDepartment of Chemistry, University of Pretoria, Lynnwood Road, Hatfield, Pretoria, 0002, South Africa, and ^bDepartment of Chemical Sciences, University of Johannesburg, PO Box 524, Auckland Park, 2006, Johannesburg, South Africa
^*Correspondence e-mail: rmeijboom@uj.ac.za

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 23 September 2022; accepted 31 October 2022; online 8 November 2022)

The molecular structure of the title Ag^I complex, [Ag(NO₃)(C₁₉H₁₇P)₂] or [Ag{(p-CH₃C₆H₄)(C₆H₅)₂P-κP}₂-NO₃-κ²O:O′], is described, where a distorted trigonal–planar coordination environment is exhibited about the central Ag^I atom; in this description, the two O atoms are assumed to occupy one position in the coordination sphere. The compound crystallized with half a molecule in the asymmetric unit having the Ag^I atom lying on a twofold axis.

Keywords: silver(I) complex; diphenyl-p-tolyl phosphine; nitrate; crystal structure.

CCDC reference: 2216475

Structure description

Silver(I) phosphine complexes have been found to exhibit high antimicrobial, antibacterial and anticancer activity (Potgieter et al., 2016 ). The continuously expanding library of active compounds leads to a growing interest into their solid- and solution-state characterization, including by single-crystal X-ray diffraction.

The molecular structure of the title compound is shown in Fig. 1. The complex crystallized in the monoclinic space group C2/c, Z = 4 with the asymmetric unit comprising one half of the silver complex molecule, as the central Ag^I atom, along with the nitrato-N and one nitrato-O atom, lying on a twofold axis. Coordinated to the Ag^I atom are two diphenyl-p-tolylphosphine ligands, and one nitrato ligand, via two O atoms; in this description, the two O atoms are assumed to occupy one position in the coordination environment. The symmetry present in the molecule results in identical Ag—P1 [2.4095 (9) Å] and Ag—O1 [2.522 (3) Å] bond lengths, which fall within the ranges of related compounds (Potgieter et al., 2016). The distorted trigonal–planar coordination displayed by the central Ag^I atom stems from the three coordinating ligands, with corresponding bond angles P1—Ag1—P1ⁱ [152.89 (5)°], P1—Ag1—O1 [109.76 (7)°], and P1—Ag1—O1ⁱ [94.92 (7)°]; symmetry operation: (i) 1 − x, y, $[{3\over 2}]$ − z. The bidentate mode of coordination of the nitrato ligand is confirmed by the O1—Ag1—O1ⁱ bite angle of 50.63 (12)°. The ipso-aryl carbon atoms of each of the phosphine ligands overlap in a near-staggered fashion when viewed down the P1–Ag1–P1ⁱ axis, presumably due to the steric bulk of the phosphine ligands. The corresponding torsion angles are P1ⁱ—Ag1—P1—C1 = −148.40 (15)°, P1ⁱ—Ag1—P1—C8 = −24.78 (17)° and P1ⁱ—Ag1—P1—C14 = 92.91 (14)°. The plane defined by atoms P1, Ag, P1ⁱ and N1 intercepts the plane defined by Ag1, O1, O1ⁱ and O2 at an angle of 72.33 (9)°.

Figure 1
Perspective view of the molecular structure of the title compound showing thermal displacement ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity. Unlabelled atoms are related by a twofold axis of symmetry.

In the crystal, the complex packs in three-dimensions as layers of isolated complexes. Within these layers a metal-containing NO₃ layer is observed, which alternates with dense arene-ring-filled layers. A view of the unit-cell contents is shown in Fig. 2.

Figure 2
Packing diagram viewed along the a-axis.

Synthesis and crystallization

Diphenyl-p-tolylphosphine (2 mmol) and silver nitrate (1 mmol) were dissolved separately in acetonitrile (10 ml). The solutions were carefully mixed together and heated to 353 K for approximately 2 h. The solution was left to crystallize, and small clear crystals were obtained.

Refinement

For full experimental details including crystal data, data collection and structure refinement details, refer to Table 1. The maximum and minimum residual electron density peaks of 0.60 and 1.14 e Å⁻³ are located 1.29 and 0.83 Å, respectively, from the Ag1 atom, features ascribed to the presence of the strong absorber.

Table 1
Experimental details

Crystal data
Chemical formula	[Ag(NO₃){C₁₉H₁₇P)₂]
M_r	722.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	18.1290 (6), 11.0936 (5), 17.9971 (7)
β (°)	104.849 (4)
V (Å³)	3498.6 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.77
Crystal size (mm)	0.21 × 0.18 × 0.10

Data collection
Diffractometer	XtaLAB Synergy R, DW system, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.344, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20162, 3668, 3383
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.637

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.109, 1.06
No. of reflections	3668
No. of parameters	206
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −1.14
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2216475

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622010458/tk4086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622010458/tk4086Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622010458/tk4086Isup3.cdx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Bis[(4-methylphenyl)diphenylphosphane-κP](nitrato-κ²O,O')silver(I) top

Crystal data top

[Ag(NO₃){C₁₉H₁₇P)₂]	F(000) = 1480
M_r = 722.47	D_x = 1.372 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 18.1290 (6) Å	Cell parameters from 14857 reflections
b = 11.0936 (5) Å	θ = 4.7–78.5°
c = 17.9971 (7) Å	µ = 5.77 mm⁻¹
β = 104.849 (4)°	T = 150 K
V = 3498.6 (2) Å³	Blade, colourless
Z = 4	0.21 × 0.18 × 0.10 mm

Data collection top

XtaLAB Synergy R, DW system, HyPix diffractometer	3668 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	3383 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.082
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.2°, θ_min = 4.7°
ω scans	h = −22→23
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −13→12
T_min = 0.344, T_max = 1.000	l = −22→22
20162 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.029P)² + 20.5034P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3668 reflections	Δρ_max = 0.60 e Å⁻³
206 parameters	Δρ_min = −1.13 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.5000	0.42530 (4)	0.7500	0.03274 (12)
P1	0.39526 (5)	0.37440 (9)	0.64210 (5)	0.0295 (2)
O1	0.55106 (15)	0.6308 (3)	0.72975 (18)	0.0428 (7)
O2	0.5000	0.7999 (4)	0.7500	0.0573 (12)
N1	0.5000	0.6886 (4)	0.7500	0.0361 (10)
C8	0.4038 (2)	0.2263 (4)	0.6014 (2)	0.0332 (8)
C14	0.3048 (2)	0.3676 (3)	0.6690 (2)	0.0317 (8)
C1	0.3777 (2)	0.4809 (4)	0.5629 (2)	0.0329 (8)
C13	0.3896 (2)	0.2044 (4)	0.5231 (2)	0.0378 (9)
H13	0.3746	0.2688	0.4877	0.045*
C18	0.1918 (2)	0.2650 (4)	0.6813 (2)	0.0405 (9)
H18	0.1604	0.1952	0.6736	0.049*
C19	0.2580 (2)	0.2661 (4)	0.6569 (2)	0.0349 (8)
H19	0.2717	0.1975	0.6318	0.042*
C15	0.2837 (2)	0.4685 (4)	0.7050 (2)	0.0407 (9)
H15	0.3152	0.5381	0.7136	0.049*
C17	0.1711 (2)	0.3650 (4)	0.7169 (2)	0.0448 (10)
H17	0.1254	0.3639	0.7336	0.054*
C2	0.3067 (2)	0.4939 (4)	0.5108 (2)	0.0426 (9)
H2	0.2650	0.4456	0.5159	0.051*
C6	0.4374 (2)	0.5548 (4)	0.5552 (3)	0.0449 (10)
H6	0.4863	0.5470	0.5902	0.054*
C3	0.2965 (3)	0.5765 (5)	0.4519 (3)	0.0538 (12)
H3	0.2481	0.5826	0.4159	0.065*
C9	0.4264 (3)	0.1314 (4)	0.6525 (3)	0.0466 (10)
H9	0.4370	0.1457	0.7062	0.056*
C12	0.3973 (3)	0.0894 (4)	0.4965 (3)	0.0496 (11)
H12	0.3874	0.0754	0.4428	0.060*
C16	0.2163 (2)	0.4664 (4)	0.7282 (3)	0.0456 (10)
H16	0.2014	0.5353	0.7521	0.055*
C4	0.3559 (3)	0.6513 (5)	0.4439 (3)	0.0533 (11)
C11	0.4192 (3)	−0.0056 (4)	0.5472 (3)	0.0552 (12)
H11	0.4242	−0.0845	0.5285	0.066*
C5	0.4258 (3)	0.6397 (5)	0.4970 (3)	0.0555 (12)
H5	0.4667	0.6909	0.4934	0.067*
C10	0.4338 (3)	0.0157 (4)	0.6257 (3)	0.0540 (11)
H10	0.4488	−0.0489	0.6610	0.065*
C7	0.3448 (4)	0.7468 (6)	0.3819 (3)	0.0817 (19)
H7A	0.3270	0.7088	0.3313	0.123*
H7B	0.3934	0.7878	0.3852	0.123*
H7C	0.3069	0.8055	0.3891	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.02296 (18)	0.0399 (2)	0.0335 (2)	0.000	0.00388 (14)	0.000
P1	0.0214 (4)	0.0375 (5)	0.0295 (4)	−0.0018 (3)	0.0064 (3)	0.0016 (4)
O1	0.0279 (13)	0.0427 (16)	0.0639 (18)	−0.0022 (12)	0.0233 (13)	−0.0038 (14)
O2	0.045 (3)	0.033 (2)	0.095 (4)	0.000	0.020 (2)	0.000
N1	0.026 (2)	0.035 (2)	0.045 (3)	0.000	0.0062 (19)	0.000
C8	0.0216 (16)	0.041 (2)	0.0380 (19)	−0.0008 (14)	0.0088 (14)	0.0016 (16)
C14	0.0285 (17)	0.040 (2)	0.0271 (16)	−0.0037 (15)	0.0079 (14)	0.0028 (15)
C1	0.0276 (17)	0.0384 (19)	0.0331 (18)	−0.0005 (15)	0.0084 (14)	0.0022 (15)
C13	0.0292 (18)	0.045 (2)	0.038 (2)	0.0015 (16)	0.0074 (16)	−0.0025 (17)
C18	0.0287 (19)	0.052 (2)	0.042 (2)	−0.0087 (17)	0.0118 (16)	0.0056 (18)
C19	0.0301 (18)	0.042 (2)	0.0329 (18)	−0.0043 (16)	0.0082 (15)	0.0011 (16)
C15	0.0294 (19)	0.048 (2)	0.047 (2)	−0.0053 (17)	0.0130 (17)	−0.0059 (19)
C17	0.031 (2)	0.062 (3)	0.046 (2)	−0.0012 (19)	0.0179 (18)	0.004 (2)
C2	0.033 (2)	0.050 (2)	0.041 (2)	−0.0052 (18)	0.0032 (17)	0.0079 (18)
C6	0.0280 (19)	0.056 (3)	0.051 (2)	0.0009 (18)	0.0112 (17)	0.013 (2)
C3	0.046 (3)	0.064 (3)	0.045 (2)	0.002 (2)	0.000 (2)	0.013 (2)
C9	0.042 (2)	0.049 (2)	0.047 (2)	0.0025 (19)	0.0088 (19)	0.0061 (19)
C12	0.043 (2)	0.053 (3)	0.051 (2)	0.004 (2)	0.009 (2)	−0.009 (2)
C16	0.036 (2)	0.054 (3)	0.051 (2)	−0.0006 (19)	0.0193 (19)	−0.005 (2)
C4	0.056 (3)	0.062 (3)	0.043 (2)	0.002 (2)	0.014 (2)	0.015 (2)
C11	0.045 (3)	0.047 (3)	0.072 (3)	0.003 (2)	0.013 (2)	−0.009 (2)
C5	0.046 (3)	0.065 (3)	0.058 (3)	−0.006 (2)	0.018 (2)	0.018 (2)
C10	0.050 (3)	0.046 (3)	0.065 (3)	0.007 (2)	0.013 (2)	0.012 (2)
C7	0.096 (5)	0.083 (4)	0.058 (3)	−0.010 (4)	0.003 (3)	0.025 (3)

Geometric parameters (Å, º) top

Ag1—P1ⁱ	2.4095 (9)	C1—C6	1.393 (5)
Ag1—P1	2.4095 (9)	C13—C12	1.383 (6)
Ag1—O1ⁱ	2.522 (3)	C18—C19	1.380 (5)
Ag1—O1	2.522 (3)	C18—C17	1.380 (6)
P1—C8	1.822 (4)	C15—C16	1.388 (5)
P1—C14	1.827 (4)	C17—C16	1.375 (6)
P1—C1	1.815 (4)	C2—C3	1.377 (6)
O1—N1	1.255 (3)	C6—C5	1.384 (6)
O2—N1	1.235 (6)	C3—C4	1.395 (7)
N1—O1ⁱ	1.255 (3)	C9—C10	1.390 (7)
C8—C13	1.386 (5)	C12—C11	1.383 (7)
C8—C9	1.389 (6)	C4—C5	1.385 (7)
C14—C19	1.393 (5)	C4—C7	1.514 (7)
C14—C15	1.395 (6)	C11—C10	1.389 (7)
C1—C2	1.392 (5)

P1ⁱ—Ag1—P1	152.89 (5)	C15—C14—P1	117.5 (3)
P1—Ag1—O1	109.76 (7)	C2—C1—P1	122.9 (3)
P1ⁱ—Ag1—O1ⁱ	109.76 (7)	C2—C1—C6	118.6 (4)
P1ⁱ—Ag1—O1	94.92 (7)	C6—C1—P1	118.5 (3)
P1—Ag1—O1ⁱ	94.92 (7)	C12—C13—C8	120.3 (4)
O1—Ag1—O1ⁱ	50.63 (12)	C19—C18—C17	120.2 (4)
C8—P1—Ag1	113.90 (12)	C18—C19—C14	120.1 (4)
C8—P1—C14	104.11 (17)	C16—C15—C14	119.6 (4)
C14—P1—Ag1	111.84 (12)	C16—C17—C18	120.2 (4)
C1—P1—Ag1	115.07 (12)	C3—C2—C1	120.4 (4)
C1—P1—C8	106.68 (18)	C5—C6—C1	120.4 (4)
C1—P1—C14	104.22 (17)	C2—C3—C4	121.3 (4)
N1—O1—Ag1	95.4 (2)	C8—C9—C10	120.5 (4)
O1—N1—O1ⁱ	118.5 (4)	C13—C12—C11	120.8 (4)
O2—N1—O1	120.8 (2)	C17—C16—C15	120.4 (4)
O2—N1—O1ⁱ	120.8 (2)	C3—C4—C7	122.2 (5)
C13—C8—P1	123.6 (3)	C5—C4—C3	117.9 (4)
C13—C8—C9	119.1 (4)	C5—C4—C7	119.9 (5)
C9—C8—P1	117.3 (3)	C12—C11—C10	119.3 (4)
C19—C14—P1	122.9 (3)	C6—C5—C4	121.3 (4)
C19—C14—C15	119.5 (3)	C11—C10—C9	120.0 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

We would like to acknowledge the National Research Foundation (NRF, SA), the University of Pretoria and the University of Johannesburg for funding provided.

Funding information

Funding for this research was provided by: National Research Foundation (grant No. 138280).

References

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