The layered polyphosphide Ag3.73(4)Zn2.27(4)P16.

The silver zinc hexa-deca-phosphide Ag3.73(4)Zn2.27(4)P16 is the first polyphosphide in the ternary system Ag/Zn/P. It was synthesized from stoichiometric mixtures of Ag, Zn and P in the molar ratio 4:2:16, using AgI as a mineralizing agent in a gas-phase-assisted reaction. Ag3.73(4)Zn2.27(4)P16 crystallizes in the Cu5InP16 structure type. The asymmetric unit contains two Ag/Zn sites with mixed occupancies and four P sites. One of the Ag/Zn sites is located on a twofold rotation axis. The polyanionic [P16]-substructure consists of corrugated six-membered rings that are connected into a layer via the 1-, 2-, 4- and 5-positions of the rings by a bridging P atom in each case. The layers extend parallel to the bc plane and are stacked along the a axis. Both Ag/Zn sites are tetra-hedrally coordinated by P atoms.

Related literature

For background to and structures of related polyphosphides, see: Bawohl & Nilges (2009 ▶); Dommann et al. (1989 ▶); Edmunds & Qurashi (1951 ▶); Lange et al. (2008 ▶); Möller & Jeitschko (1981 ▶); Olofsson (1965 ▶); Zanin et al. (2003 ▶). For background to the extinction correction, see: Becker & Coppens (1974 ▶).

Experimental

Crystal data

Ag3.73Zn2.27P16

M = 1046.3

Monoclinic,

a = 11.492 (1) Å

b = 9.9604 (8) Å

c = 7.7106 (9) Å

β = 109.585 (9)°

V = 831.5 (2) Å3

Z = 2

Mo Kα radiation

μ = 9.05 mm−1

T = 293 K

0.02 × 0.02 × 0.02 mm

Data collection

IPDS Stoe 2T diffractometer

Absorption correction: numerical (X-AREA; Stoe & Cie, 2011 ▶) T min = 0.730, T max = 0.771

4398 measured reflections

1265 independent reflections

1135 reflections with I > 3σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.042

S = 1.39

1265 reflections

54 parameters

Δρmax = 0.56 e Å−3

Δρmin = −0.66 e Å−3

Data collection: X-AREA (Stoe & Cie, 2011 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: JANA2006 (Petřiček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812045667/wm2694sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045667/wm2694Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Ag3.73Zn2.27P16	F(000) = 966
Mr = 1046.3	Dx = 4.17 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4528 reflections
a = 11.492 (1) Å	θ = 2.8–30.5°
b = 9.9604 (8) Å	µ = 9.05 mm−1
c = 7.7106 (9) Å	T = 293 K
β = 109.585 (9)°	Isomorphic, black
V = 831.5 (2) Å3	0.02 × 0.02 × 0.02 mm
Z = 2

IPDS Stoe 2T diffractometer	1265 independent reflections
Radiation source: X-ray tube	1135 reflections with I > 3σ(I)
Plane graphite monochromator	Rint = 0.015
Detector resolution: 6.67 pixels mm-1	θmax = 30.5°, θmin = 2.8°
rotation method scans	h = −16→16
Absorption correction: numerical (X-AREA; Stoe & Cie, 2011)	k = −13→14
Tmin = 0.730, Tmax = 0.771	l = −10→10
4398 measured reflections

Refinement on F2	14 constraints
R[F2 > 2σ(F2)] = 0.018	Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.042	(Δ/σ)max = 0.038
S = 1.39	Δρmax = 0.56 e Å−3
1265 reflections	Δρmin = −0.66 e Å−3
54 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 0.084 (5)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0	0.41699 (3)	0.25	0.01075 (10)	0.422 (6)
Zn1	0	0.41699 (3)	0.25	0.01075 (10)	0.578 (6)
Ag2	−0.089927 (17)	0.13768 (2)	−0.08750 (3)	0.01608 (7)	0.721 (7)
Zn2	−0.089927 (17)	0.13768 (2)	−0.08750 (3)	0.01608 (7)	0.279 (7)
P1	−0.16624 (5)	0.56752 (5)	0.05996 (7)	0.00731 (15)
P2	−0.24029 (5)	0.32264 (5)	−0.24701 (7)	0.00785 (15)
P3	0.09157 (4)	0.27552 (6)	0.07194 (7)	0.00827 (15)
P4	−0.33325 (5)	0.48032 (5)	−0.14361 (8)	0.00915 (15)

	U11	U22	U33	U12	U13	U23
Ag1	0.01067 (15)	0.01146 (16)	0.01117 (17)	0	0.00506 (10)	0
Zn1	0.01067 (15)	0.01146 (16)	0.01117 (17)	0	0.00506 (10)	0
Ag2	0.01637 (11)	0.01572 (12)	0.01331 (12)	−0.00637 (6)	0.00121 (7)	−0.00034 (6)
Zn2	0.01637 (11)	0.01572 (12)	0.01331 (12)	−0.00637 (6)	0.00121 (7)	−0.00034 (6)
P1	0.0079 (2)	0.0074 (2)	0.0071 (2)	0.00021 (16)	0.00310 (17)	0.00069 (17)
P2	0.0090 (2)	0.0076 (2)	0.0072 (2)	−0.00064 (16)	0.00309 (17)	−0.00022 (18)
P3	0.0077 (2)	0.0082 (2)	0.0093 (3)	0.00004 (16)	0.00342 (18)	0.00121 (17)
P4	0.0096 (2)	0.0104 (2)	0.0080 (2)	−0.00069 (17)	0.00363 (17)	−0.00171 (18)

Ag1—P1	2.4836 (7)	Ag2—P4iii	2.5280 (7)
Ag1—P1i	2.4836 (7)	P1—P2iv	2.2328 (9)
Ag1—P3	2.4385 (7)	P1—P3v	2.1909 (9)
Ag1—P3i	2.4385 (7)	P1—P4	2.2095 (9)
Ag2—P2	2.5432 (7)	P2—P3vi	2.1976 (8)
Ag2—P3	2.4551 (7)	P2—P4	2.1941 (9)
Ag2—P4ii	2.5115 (7)
P1—Ag1—P1i	105.73 (2)	Ag2—P2—P4	132.64 (3)
P1—Ag1—P3	114.11 (2)	P1vii—P2—P3vi	104.18 (3)
P1—Ag1—P3i	106.81 (2)	P1vii—P2—P4	103.43 (3)
P1i—Ag1—P3	106.81 (2)	P3vi—P2—P4	96.77 (3)
P1i—Ag1—P3i	114.11 (2)	Ag1—P3—Ag2	98.66 (2)
P3—Ag1—P3i	109.40 (2)	Ag1—P3—Zn2	98.66 (2)
P2—Ag2—P3	99.36 (2)	Ag1—P3—P1v	99.15 (3)
P2—Ag2—P4ii	93.38 (2)	Ag1—P3—P2viii	110.66 (3)
P2—Ag2—P4iii	109.66 (2)	Ag2—P3—P1v	124.46 (3)
P3—Ag2—P4ii	140.08 (2)	Ag2—P3—P2viii	119.19 (3)
P3—Ag2—P4iii	110.23 (2)	P1v—P3—P2viii	102.39 (3)
P4ii—Ag2—P4iii	100.52 (2)	Ag2ix—P4—Ag2iii	139.72 (3)
Ag1—P1—P2iv	106.99 (3)	Ag2ix—P4—Zn2iii	139.72 (3)
Ag1—P1—P3v	111.18 (3)	Ag2ix—P4—P1	108.81 (3)
Ag1—P1—P4	119.67 (3)	Ag2ix—P4—P2	103.06 (3)
P2iv—P1—P3v	104.82 (3)	Ag2iii—P4—Zn2ix	139.72 (3)
P2iv—P1—P4	103.40 (3)	Ag2iii—P4—P1	96.17 (3)
P3v—P1—P4	109.44 (3)	Ag2iii—P4—P2	104.53 (3)
Ag2—P2—P1vii	109.17 (3)	P1—P4—P2	97.28 (3)
Ag2—P2—P3vi	107.16 (3)