Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, caesium silver zinc tetrathiocyanate, crystallizes in two polymorphic forms, in space groups P21/n and C2/c. Both structures form a continuous three-dimensional network. The structure in C2/c contains a delocalized Ag atom in a binuclear-like anion, where two [Ag(NCS)4] units (delocalized Ag as an average) share two common NCS- ligands.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017961/iz1027sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017961/iz1027Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017961/iz1027IIsup3.hkl
Contains datablock II

Comment top

Caesium silver zinc tetrathiocyanate monohydrate has been known for a century (Wells, 1902, 1922), but its anhydrous form, Cs[AgZn(SCN)4], has not been mentioned in the literature till now. Our research indicates that Cs[AgZn(SCN)4] crystallizes in two polymorphic forms, in space groups P21/n, (I), and C2/c, (II). There are a total of four different caesium silver zinc thiocyanates known in the literature, namely Cs[AgZn(SCN)4]·H2O, Cs2[AgZn(SCN)5], Cs[Ag3Zn2(SCN)8] and Cs[Ag4Zn2(SCN)9] (Wells, 1902, 1922; Güneş & Valkonen, 2002a,b). Cs, Ag and Zn all form simple thiocyanates. CsSCN crystallizes in spacegroup Pnma, AgSCN in two polymorphic forms in spacegroups C2/c and Pmnn, and Zn(NCS)2 in spacegroup P1. Also, Zn(NCS)2·2H2O is known in the literature and crystallizes in spacegroup P212121. \sch

Our interest in triple thiocyanates of silver arises from the fact that some of them, such as Cs3Sr[Ag2(SCN)7] and Cs3Ba[Ag2(SCN)7], have been found to have a noncentrosymmetric crystal structure (Bohaty & Fröhlich, 1992). A noncentrosymmetric crystal structure can possess some very interesting optical, electro-optic and electrostrictive properties, which could be utilized in, for example, telecommunications, optical computing, optical information processing, optical-disk data storage, laser remote sensing, laser-driven fusion, colour displays, medical diagnostics, and so on. The idea is based on the capability of these materials to convert IR laser radiation efficiently to visible and UV wavelengths, and especially their highly efficient second harmonic generation of blue-violet light (Wang et al., 2001).

The structure of Cs[AgZn(SCN)4] is very interesting, as it seems to crystallize in two different polymorphic forms. In (I), the structure forms a simple three-dimensional network. The Ag is bonded to four S atoms of four thiocyanate groups, which are then bonded from the other end to Zn atoms (Fig. 1). This simple bonding mode continues throughout the structure, where the Cs atoms further connect the thiocyanate groups through S and N atoms.

The Ag and Zn atoms of (I) are both tetrahedrally coordinated, the Ag surrounded by four S atoms and the Zn by four N atoms. The tetrahedron around Ag is quite strongly distorted, but the tetrahedron around Zn is nearly ideal. The Cs atom is ten-coordinated, being surrounded by five S, three C and two N atoms. The C atoms do not actually participate in bonding but Cs can, by back coordination, form a dihapto (η2) π bond to the triple CN bond of a thiocyanate group.

The structure of (II) is slightly more complicated, as it includes an Ag atom disordered over three sites, Ag1, Ag2, Ag3 with occupancies 0.36 (2), 0.26 (2), 0.38 (2) respectively. Only one (Ag3) of the three possible positions of the disordered Ag atom actually has clear four-coordination, which is common for an Ag atom, and the other two possible positions are clearly only three- (Ag1) and two- (Ag2) coordinated. The separations between the three disordered Ag atoms are Ag1—Ag2 0.843 (12), Ag2—Ag3 0.766 (11), Ag3—Ag1 0.775 (9) Å. However, on average, the Ag is in a four-coordinate-like environment and the structure includes a binuclear-like anion (Fig. 2), which can be compared with the binuclear [Ag2(SCN)6]4- anions in K4[Ag2(SCN)6] (Krautscheid & Gerber, 2001), where there are two [Ag(SCN)4] units sharing two common SCN- ligands.

The structure of (II) forms also a three-dimensional network, where the thiocyanate groups of the binuclear-like anion bonded from S to the delocalized Ag atom are bonded from the other end to the four-coordinated Zn atom. One of the thiocyanate groups is not bonded to Ag at all, but from N to the Zn atom and from S only to the Cs atom. The tetrahedron around Zn is very slightly distorted. The Cs atom, which connects the network in all dimensions, is a total of 13-coordinated.

Experimental top

All reagents used were analytical grade. Caesium thiocyanate was synthesized as follows: NH4SCN (13.96 g) was dissolved in deionized water (40.0 g), and in a separate beaker Cs2CO3 (30.0 g; Aldrich Chemical Company Inc.) was also dissolved in deionized water (110.0 g). The solutions were mixed and the mixture was heated with stirring until the smell of ammonia was no longer sensed. The residue was evaporated close to dryness in a water bath with continuous stirring. The CsSCN was dried and stored in a desiccator. Compound (I) was synthesized at room temperature by dissolving NH4SCN (2.05 g; Aldrich Chemical Company Inc.) in deionized water (20.0 g) and then dissolving AgSCN (0.28 g; City Chemical LLC) in the resulting solution. Next, Zn(NCS)2 (1.33 g; City Chemical LLC) and CsSCN (1.75 g) were added. Not all of the Zn(NCS)2 and CsSCN dissolved. The solution was heated with hot tap water for a while, stirred with a glass rod and then filtered. Within 1 d, colourless crystals of (I) formed. Compound (II) was synthesized at room temperature by dissolving Zn(NCS)2 (4.30 g; City Chemical LLC) in deionized water (5.00 g). The solution was filtered to remove turbidity. Another solution was made by dissolving CsSCN (1.10 g) in deionized water (5.00 g) and adding AgSCN (0.13 g; City Chemical LLC) to the resulting solution. Not all of the AgSCN dissolved, and the second solution was filtered to remove the excess AgSCN. These two solutions were mixed and the precipitate which formed immediately was removed by filtration. Within a couple of days, colourless crystals of (II) formed.

Refinement top

The s.u.s of the cell constants of (I) indicate the internal consistency of the measurements themselves, i.e. the precision of the measurement, not their accuracy.

Structure description top

Caesium silver zinc tetrathiocyanate monohydrate has been known for a century (Wells, 1902, 1922), but its anhydrous form, Cs[AgZn(SCN)4], has not been mentioned in the literature till now. Our research indicates that Cs[AgZn(SCN)4] crystallizes in two polymorphic forms, in space groups P21/n, (I), and C2/c, (II). There are a total of four different caesium silver zinc thiocyanates known in the literature, namely Cs[AgZn(SCN)4]·H2O, Cs2[AgZn(SCN)5], Cs[Ag3Zn2(SCN)8] and Cs[Ag4Zn2(SCN)9] (Wells, 1902, 1922; Güneş & Valkonen, 2002a,b). Cs, Ag and Zn all form simple thiocyanates. CsSCN crystallizes in spacegroup Pnma, AgSCN in two polymorphic forms in spacegroups C2/c and Pmnn, and Zn(NCS)2 in spacegroup P1. Also, Zn(NCS)2·2H2O is known in the literature and crystallizes in spacegroup P212121. \sch

Our interest in triple thiocyanates of silver arises from the fact that some of them, such as Cs3Sr[Ag2(SCN)7] and Cs3Ba[Ag2(SCN)7], have been found to have a noncentrosymmetric crystal structure (Bohaty & Fröhlich, 1992). A noncentrosymmetric crystal structure can possess some very interesting optical, electro-optic and electrostrictive properties, which could be utilized in, for example, telecommunications, optical computing, optical information processing, optical-disk data storage, laser remote sensing, laser-driven fusion, colour displays, medical diagnostics, and so on. The idea is based on the capability of these materials to convert IR laser radiation efficiently to visible and UV wavelengths, and especially their highly efficient second harmonic generation of blue-violet light (Wang et al., 2001).

The structure of Cs[AgZn(SCN)4] is very interesting, as it seems to crystallize in two different polymorphic forms. In (I), the structure forms a simple three-dimensional network. The Ag is bonded to four S atoms of four thiocyanate groups, which are then bonded from the other end to Zn atoms (Fig. 1). This simple bonding mode continues throughout the structure, where the Cs atoms further connect the thiocyanate groups through S and N atoms.

The Ag and Zn atoms of (I) are both tetrahedrally coordinated, the Ag surrounded by four S atoms and the Zn by four N atoms. The tetrahedron around Ag is quite strongly distorted, but the tetrahedron around Zn is nearly ideal. The Cs atom is ten-coordinated, being surrounded by five S, three C and two N atoms. The C atoms do not actually participate in bonding but Cs can, by back coordination, form a dihapto (η2) π bond to the triple CN bond of a thiocyanate group.

The structure of (II) is slightly more complicated, as it includes an Ag atom disordered over three sites, Ag1, Ag2, Ag3 with occupancies 0.36 (2), 0.26 (2), 0.38 (2) respectively. Only one (Ag3) of the three possible positions of the disordered Ag atom actually has clear four-coordination, which is common for an Ag atom, and the other two possible positions are clearly only three- (Ag1) and two- (Ag2) coordinated. The separations between the three disordered Ag atoms are Ag1—Ag2 0.843 (12), Ag2—Ag3 0.766 (11), Ag3—Ag1 0.775 (9) Å. However, on average, the Ag is in a four-coordinate-like environment and the structure includes a binuclear-like anion (Fig. 2), which can be compared with the binuclear [Ag2(SCN)6]4- anions in K4[Ag2(SCN)6] (Krautscheid & Gerber, 2001), where there are two [Ag(SCN)4] units sharing two common SCN- ligands.

The structure of (II) forms also a three-dimensional network, where the thiocyanate groups of the binuclear-like anion bonded from S to the delocalized Ag atom are bonded from the other end to the four-coordinated Zn atom. One of the thiocyanate groups is not bonded to Ag at all, but from N to the Zn atom and from S only to the Cs atom. The tetrahedron around Zn is very slightly distorted. The Cs atom, which connects the network in all dimensions, is a total of 13-coordinated.

Computing details top

Data collection: COLLECT (Nonius, 1997-2000) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997) for (I); CAD-4 Software for (II). Data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK for (I); CAD-4 Software for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of the bonding of the Ag and Zn atoms in (I), with 50% probability displacement ellipsoids. Shading convention: from the heaviest atom (Ag) to the lightest (C), the grey shading gets lighter.
[Figure 2] Fig. 2. A view of the bonding of the Ag and Zn atoms in (II), shown with 50% probability displacement ellipsoids. Shading convention: the grey shading gets lighter in the sequence Ag > Zn > S > N > C. [Symmetry codes: (i) -1/2 + x, 1/2 + y, z; (ii) 1/2 - x, 1/2 - y, -z; (iii) 1/2 - x, 1/2 + y, 1/2 - z; (iv) -1/2 + x, 1/2 - y, -1/2 + z; (v) -x, 1 - y, -z.]
(I) caesium silver zinc tetrathioyanate top
Crystal data top
Cs[AgZn(SCN)4]F(000) = 992
Mr = 538.47Dx = 2.636 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 13915 reflections
a = 9.0398 (2) Åθ = 1.0–24.7°
b = 16.6679 (4) ŵ = 6.44 mm1
c = 9.0973 (2) ÅT = 293 K
β = 98.190 (1)°Botryoidal, colourless
V = 1356.75 (5) Å30.15 × 0.15 × 0.15 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
1852 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.072
Horizonally mounted graphite crystal monochromatorθmax = 24.7°, θmin = 2.4°
Detector resolution: 9 pixels mm-1h = 1010
φ scansk = 1919
12064 measured reflectionsl = 1010
2298 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0287P)2 + 7.9708P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max < 0.001
S = 1.04Δρmax = 1.86 e Å3
2298 reflectionsΔρmin = 1.76 e Å3
137 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0017 (3)
Crystal data top
Cs[AgZn(SCN)4]V = 1356.75 (5) Å3
Mr = 538.47Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.0398 (2) ŵ = 6.44 mm1
b = 16.6679 (4) ÅT = 293 K
c = 9.0973 (2) Å0.15 × 0.15 × 0.15 mm
β = 98.190 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1852 reflections with I > 2σ(I)
12064 measured reflectionsRint = 0.072
2298 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041137 parameters
wR(F2) = 0.1010 restraints
S = 1.04Δρmax = 1.86 e Å3
2298 reflectionsΔρmin = 1.76 e Å3
Special details top

Experimental. Multiscan absorption correction [Blessing, R. H. (1995). Acta Cryst. A51, 33–38] was performed but not applied. The absorption correction was found to have no significant effect on the refinement results. Original values _exptl_absorpt_correction_T_min 0.4601 _exptl_absorpt_correction_T_max 0.5443

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.07831 (8)0.73943 (4)0.84108 (9)0.0740 (3)
Cs10.10708 (7)0.62465 (5)0.35534 (8)0.0854 (3)
Zn10.59170 (9)0.55282 (5)0.78725 (9)0.0446 (3)
S10.7147 (2)0.62710 (11)0.3231 (2)0.0476 (5)
S20.0707 (2)0.59366 (12)0.7472 (3)0.0606 (6)
S30.8999 (3)0.74826 (13)1.0501 (2)0.0588 (5)
S40.6481 (3)0.28110 (12)0.9130 (2)0.0605 (6)
C10.6834 (7)0.5895 (4)0.4815 (8)0.0427 (16)
C20.2513 (8)0.5819 (4)0.7568 (8)0.0424 (16)
C30.7876 (8)0.6795 (4)0.9696 (8)0.0459 (17)
C40.6380 (8)0.3765 (5)0.8828 (7)0.0440 (16)
N10.6612 (8)0.5620 (4)0.5918 (8)0.0640 (18)
N20.3773 (8)0.5739 (4)0.7614 (7)0.0530 (15)
N30.7052 (8)0.6324 (4)0.9124 (8)0.0611 (17)
N40.6376 (7)0.4441 (4)0.8593 (7)0.0574 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0744 (5)0.0433 (4)0.1114 (6)0.0092 (3)0.0374 (4)0.0145 (3)
Cs10.0593 (4)0.1161 (6)0.0834 (5)0.0081 (3)0.0182 (3)0.0110 (4)
Zn10.0468 (5)0.0385 (5)0.0491 (5)0.0015 (4)0.0093 (4)0.0030 (4)
S10.0530 (11)0.0465 (10)0.0451 (10)0.0044 (8)0.0130 (8)0.0038 (8)
S20.0457 (11)0.0469 (11)0.0872 (16)0.0025 (9)0.0030 (10)0.0149 (10)
S30.0654 (13)0.0599 (13)0.0518 (12)0.0159 (10)0.0109 (9)0.0133 (9)
S40.0680 (13)0.0399 (11)0.0689 (14)0.0022 (9)0.0060 (10)0.0112 (9)
C10.036 (4)0.039 (4)0.053 (4)0.002 (3)0.006 (3)0.004 (3)
C20.050 (4)0.032 (4)0.045 (4)0.003 (3)0.005 (3)0.002 (3)
C30.050 (4)0.047 (4)0.044 (4)0.004 (4)0.016 (3)0.000 (3)
C40.045 (4)0.048 (5)0.037 (4)0.002 (3)0.001 (3)0.004 (3)
N10.068 (5)0.073 (5)0.053 (4)0.005 (4)0.017 (3)0.005 (4)
N20.055 (4)0.044 (4)0.061 (4)0.002 (3)0.011 (3)0.001 (3)
N30.067 (4)0.062 (4)0.056 (4)0.013 (4)0.013 (3)0.008 (3)
N40.060 (4)0.043 (4)0.064 (4)0.000 (3)0.006 (3)0.009 (3)
Geometric parameters (Å, º) top
Ag1—S1i2.5600 (19)Zn1—N21.951 (7)
Ag1—S22.573 (2)Zn1—N11.975 (7)
Ag1—S3ii2.667 (2)S1—C11.633 (8)
Ag1—S4iii2.944 (2)S1—Ag1viii2.5600 (19)
Cs1—C4iv3.380 (7)S1—Cs1ix3.517 (2)
Cs1—N4iv3.426 (7)S2—C21.634 (8)
Cs1—S1ii3.517 (2)S3—C31.634 (8)
Cs1—S3v3.647 (2)S3—Ag1ix2.667 (2)
Cs1—S23.663 (3)S3—Cs1x3.647 (2)
Cs1—C3v3.730 (7)S4—C41.614 (8)
Cs1—S3vi3.739 (2)S4—Ag1xi2.944 (2)
Cs1—N1iv3.743 (8)C1—N11.146 (9)
Cs1—C23.767 (7)C2—N21.141 (9)
Cs1—S4iv3.855 (2)C3—N31.153 (10)
Cs1—S2vii4.033 (2)C3—Cs1x3.730 (7)
Zn1—N31.943 (7)C4—N41.148 (9)
Zn1—N41.951 (7)
S1i—Ag1—S2142.15 (7)S3v—Cs1—S2vii150.95 (5)
S1i—Ag1—S3ii110.08 (6)S2—Cs1—S2vii90.56 (5)
S2—Ag1—S3ii107.38 (7)C3v—Cs1—S2vii176.39 (13)
S1i—Ag1—S4iii91.83 (6)S3vi—Cs1—S2vii100.63 (5)
S2—Ag1—S4iii88.83 (7)C2—Cs1—S2vii97.19 (11)
S3ii—Ag1—S4iii97.09 (7)S4iv—Cs1—S2vii117.84 (5)
C4iv—Cs1—S1ii135.90 (12)N3—Zn1—N4111.6 (3)
N4iv—Cs1—S1ii135.19 (11)N3—Zn1—N2112.3 (3)
C4iv—Cs1—S3v78.50 (13)N4—Zn1—N2111.6 (3)
N4iv—Cs1—S3v88.28 (12)N3—Zn1—N1105.4 (3)
S1ii—Cs1—S3v133.42 (5)N4—Zn1—N1107.1 (3)
C4iv—Cs1—S2141.88 (12)N2—Zn1—N1108.4 (3)
N4iv—Cs1—S2131.96 (11)C1—S1—Ag1viii97.5 (2)
S1ii—Cs1—S281.59 (4)C1—S1—Cs1ix102.8 (2)
S3v—Cs1—S276.62 (5)Ag1viii—S1—Cs1ix119.60 (7)
C4iv—Cs1—C3v82.66 (17)C2—S2—Ag196.7 (2)
N4iv—Cs1—C3v98.52 (15)C2—S2—Cs180.9 (3)
S1ii—Cs1—C3v114.14 (12)Ag1—S2—Cs1100.84 (7)
S2—Cs1—C3v87.06 (11)C2—S2—Cs1vii105.5 (2)
C4iv—Cs1—S3vi80.93 (12)Ag1—S2—Cs1vii156.86 (8)
N4iv—Cs1—S3vi93.90 (11)Cs1—S2—Cs1vii89.44 (5)
S1ii—Cs1—S3vi62.56 (5)C3—S3—Ag1ix92.4 (2)
S3v—Cs1—S3vi107.03 (2)C3—S3—Cs1x80.1 (3)
S2—Cs1—S3vi134.07 (5)Ag1ix—S3—Cs1x98.99 (7)
C3v—Cs1—S3vi82.97 (12)C3—S3—Cs1xii99.2 (3)
C4iv—Cs1—N1iv69.98 (16)Ag1ix—S3—Cs1xii102.08 (7)
S1ii—Cs1—N1iv124.02 (12)Cs1x—S3—Cs1xii158.92 (7)
S3v—Cs1—N1iv93.80 (12)C4—S4—Ag1xi94.7 (3)
S2—Cs1—N1iv83.33 (11)C4—S4—Cs1iv61.0 (3)
C3v—Cs1—N1iv118.49 (17)Ag1xi—S4—Cs1iv89.81 (6)
S3vi—Cs1—N1iv139.94 (11)N1—C1—S1179.0 (7)
C4iv—Cs1—C2116.55 (16)N2—C2—S2179.0 (7)
N4iv—Cs1—C2108.73 (15)N2—C2—Cs1105.3 (5)
S1ii—Cs1—C2106.78 (12)S2—C2—Cs173.8 (3)
S3v—Cs1—C260.77 (11)N3—C3—S3178.1 (7)
C3v—Cs1—C279.52 (15)N3—C3—Cs1x103.9 (6)
S3vi—Cs1—C2153.09 (11)S3—C3—Cs1x74.4 (3)
N1iv—Cs1—C266.94 (15)N4—C4—S4176.7 (7)
N4iv—Cs1—S4iv44.06 (11)N4—C4—Cs1iv82.6 (5)
S1ii—Cs1—S4iv127.26 (5)S4—C4—Cs1iv94.4 (3)
S3v—Cs1—S4iv68.20 (5)C1—N1—Zn1159.5 (7)
S2—Cs1—S4iv144.37 (5)C1—N1—Cs1iv106.3 (5)
C3v—Cs1—S4iv63.39 (11)Zn1—N1—Cs1iv93.7 (3)
S3vi—Cs1—S4iv65.00 (5)C2—N2—Zn1174.0 (6)
N1iv—Cs1—S4iv93.37 (11)C3—N3—Zn1169.0 (6)
C2—Cs1—S4iv122.71 (12)C4—N4—Zn1165.9 (6)
C4iv—Cs1—S2vii97.61 (13)C4—N4—Cs1iv78.0 (5)
N4iv—Cs1—S2vii81.08 (12)Zn1—N4—Cs1iv104.3 (3)
S1ii—Cs1—S2vii68.12 (4)
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x1, y, z; (iii) x+1/2, y+1/2, z+3/2; (iv) x+1, y+1, z+1; (v) x1/2, y+3/2, z1/2; (vi) x1, y, z1; (vii) x, y+1, z+1; (viii) x+1/2, y+3/2, z1/2; (ix) x+1, y, z; (x) x+1/2, y+3/2, z+1/2; (xi) x+1/2, y1/2, z+3/2; (xii) x+1, y, z+1.
(II) caesium silver zinc tetrathioyanate top
Crystal data top
Cs[AgZn(SCN)4]F(000) = 1984
Mr = 538.47Dx = 2.806 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 13.964 (2) Åθ = 4.4–12.5°
b = 14.851 (2) ŵ = 6.86 mm1
c = 13.389 (2) ÅT = 293 K
β = 113.35 (1)°Rod, colourless
V = 2549.2 (7) Å30.20 × 0.05 × 0.05 mm
Z = 8
Data collection top
Nonius MACH3
diffractometer
1447 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.084
Graphite monochromatorθmax = 30.0°, θmin = 3.0°
ω/2θ scansh = 1919
Absorption correction: ψ scan
(North et al., 1968)
k = 2020
Tmin = 0.579, Tmax = 0.710l = 1818
7410 measured reflections3 standard reflections every 60 min
3705 independent reflections intensity decay: 0.8%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060 w = 1/[σ2(Fo2) + (0.0374P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119(Δ/σ)max < 0.001
S = 0.94Δρmax = 0.67 e Å3
3705 reflectionsΔρmin = 0.78 e Å3
155 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00018 (4)
Crystal data top
Cs[AgZn(SCN)4]V = 2549.2 (7) Å3
Mr = 538.47Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.964 (2) ŵ = 6.86 mm1
b = 14.851 (2) ÅT = 293 K
c = 13.389 (2) Å0.20 × 0.05 × 0.05 mm
β = 113.35 (1)°
Data collection top
Nonius MACH3
diffractometer
1447 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.084
Tmin = 0.579, Tmax = 0.7103 standard reflections every 60 min
7410 measured reflections intensity decay: 0.8%
3705 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060155 parameters
wR(F2) = 0.1190 restraints
S = 0.94Δρmax = 0.67 e Å3
3705 reflectionsΔρmin = 0.78 e Å3
Special details top

Experimental. For the absorption correction: Number of ψ-scan sets used was 3. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ag10.0768 (6)0.4945 (3)0.1098 (4)0.0850 (14)0.36 (2)
Ag20.1285 (6)0.4878 (5)0.0490 (10)0.102 (2)0.26 (2)
Ag30.0721 (4)0.4932 (3)0.0545 (6)0.0694 (12)0.38 (3)
Cs10.13009 (5)0.16177 (5)0.15826 (6)0.0775 (3)
Zn10.38575 (7)0.33058 (6)0.31512 (7)0.0445 (3)
S10.3410 (2)0.14476 (16)0.01544 (19)0.0755 (8)
S20.4008 (2)0.16715 (16)0.6190 (2)0.0711 (7)
S30.11573 (19)0.54139 (16)0.1738 (2)0.0743 (8)
S40.63549 (19)0.55862 (16)0.4191 (2)0.0700 (7)
C10.3674 (5)0.2051 (5)0.1246 (7)0.0366 (18)
C20.3882 (6)0.2164 (5)0.5048 (7)0.042 (2)
C30.1967 (6)0.4576 (6)0.2197 (6)0.044 (2)
C40.5574 (6)0.4734 (6)0.3920 (6)0.045 (2)
N10.3802 (5)0.2493 (4)0.1978 (5)0.0463 (18)
N20.3810 (7)0.2527 (4)0.4299 (7)0.072 (3)
N30.2572 (6)0.4016 (5)0.2523 (5)0.0579 (19)
N40.5027 (6)0.4127 (5)0.3762 (6)0.060 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.092 (4)0.0418 (14)0.137 (4)0.0003 (18)0.062 (4)0.003 (3)
Ag20.158 (7)0.034 (2)0.112 (7)0.007 (4)0.052 (6)0.009 (3)
Ag30.076 (3)0.0406 (14)0.076 (3)0.0116 (17)0.015 (2)0.0047 (17)
Cs10.0517 (4)0.0887 (5)0.0905 (5)0.0022 (3)0.0265 (3)0.0262 (4)
Zn10.0572 (6)0.0309 (5)0.0429 (5)0.0003 (5)0.0173 (5)0.0008 (4)
S10.105 (2)0.0550 (14)0.0451 (14)0.0266 (14)0.0074 (14)0.0104 (12)
S20.120 (2)0.0471 (13)0.0518 (14)0.0037 (14)0.0400 (15)0.0054 (12)
S30.0591 (16)0.0415 (13)0.108 (2)0.0117 (12)0.0176 (15)0.0055 (14)
S40.0658 (16)0.0474 (13)0.099 (2)0.0106 (12)0.0355 (15)0.0165 (14)
C10.033 (4)0.027 (4)0.047 (5)0.002 (3)0.013 (4)0.000 (4)
C20.049 (5)0.023 (4)0.055 (6)0.001 (4)0.023 (5)0.003 (4)
C30.044 (5)0.058 (5)0.036 (5)0.002 (4)0.022 (4)0.003 (4)
C40.048 (5)0.053 (5)0.031 (5)0.007 (4)0.014 (4)0.015 (4)
N10.055 (4)0.035 (4)0.046 (5)0.003 (3)0.017 (4)0.007 (4)
N20.126 (8)0.033 (4)0.067 (6)0.013 (4)0.050 (6)0.009 (4)
N30.068 (5)0.069 (5)0.040 (4)0.024 (4)0.025 (4)0.015 (4)
N40.064 (5)0.057 (5)0.060 (5)0.015 (4)0.024 (4)0.016 (4)
Geometric parameters (Å, º) top
Ag1—Ag20.853 (9)Cs1—S3iv3.811 (3)
Ag2—Ag30.766 (10)Cs1—S1vi3.817 (3)
Ag1—Ag30.770 (5)Cs1—C3iv3.819 (8)
Ag1—S2i2.430 (5)Cs1—N2i3.825 (8)
Ag1—S32.573 (8)Cs1—C4i3.861 (8)
Ag1—S1ii2.598 (6)Zn1—N41.940 (7)
Ag2—S1ii2.381 (8)Zn1—N21.945 (8)
Ag2—S2i2.457 (8)Zn1—N11.958 (7)
Ag3—S1ii2.512 (5)Zn1—N31.961 (7)
Ag3—S32.573 (7)S1—C11.627 (9)
Ag3—S2i2.612 (6)S2—C21.640 (9)
Ag3—S3iii2.916 (8)S2—Cs1vii3.955 (3)
Cs1—N13.564 (7)S3—C31.628 (9)
Cs1—C13.575 (7)S4—C41.615 (9)
Cs1—N4i3.651 (8)C1—N11.133 (9)
Cs1—C2i3.662 (8)C2—N21.108 (9)
Cs1—C4iv3.706 (8)C3—N31.142 (9)
Cs1—S4iv3.759 (3)C4—N41.146 (9)
Cs1—S4v3.787 (3)
S2i—Ag1—S3112.9 (3)C3iv—Cs1—C4i82.67 (18)
S2i—Ag1—S1ii146.3 (3)N2i—Cs1—C4i67.13 (17)
S3—Ag1—S1ii97.6 (2)N4—Zn1—N2109.1 (3)
S1ii—Ag2—S2i168.4 (7)N4—Zn1—N1119.0 (3)
S1ii—Ag3—S399.8 (2)N2—Zn1—N1105.3 (3)
S1ii—Ag3—S2i139.8 (2)N4—Zn1—N3108.5 (3)
S3—Ag3—S2i107.1 (2)N2—Zn1—N3110.3 (3)
S1ii—Ag3—S3iii93.3 (2)N1—Zn1—N3104.5 (3)
S3—Ag3—S3iii116.00 (19)C1—S1—Ag2viii114.2 (4)
S2i—Ag3—S3iii100.9 (2)C1—S1—Ag3viii112.8 (3)
N1—Cs1—N4i108.13 (16)C1—S1—Ag1viii97.9 (3)
C1—Cs1—N4i91.15 (18)C1—S1—Cs1vi95.3 (3)
N1—Cs1—C2i122.35 (15)Ag2viii—S1—Cs1vi142.9 (4)
C1—Cs1—C2i122.37 (16)Ag3viii—S1—Cs1vi129.92 (17)
N4i—Cs1—C2i66.82 (18)Ag1viii—S1—Cs1vi144.1 (2)
N1—Cs1—C4iv151.92 (18)C1—S1—Cs159.8 (3)
C1—Cs1—C4iv137.41 (18)Ag2viii—S1—Cs194.6 (4)
N4i—Cs1—C4iv64.15 (16)Ag3viii—S1—Cs1109.59 (16)
C2i—Cs1—C4iv80.97 (18)Ag1viii—S1—Cs194.99 (19)
N1—Cs1—S4iv172.44 (12)Cs1vi—S1—Cs1120.41 (6)
C1—Cs1—S4iv154.30 (14)C2—S2—Ag1vii111.2 (3)
N4i—Cs1—S4iv64.42 (13)C2—S2—Ag2vii97.0 (4)
C2i—Cs1—S4iv57.09 (12)C2—S2—Ag3vii94.2 (3)
N1—Cs1—S4v110.51 (11)C2—S2—Cs1vii67.7 (3)
C1—Cs1—S4v120.56 (13)Ag1vii—S2—Cs1vii121.8 (2)
N4i—Cs1—S4v130.92 (12)Ag2vii—S2—Cs1vii131.0 (3)
C2i—Cs1—S4v113.21 (14)Ag3vii—S2—Cs1vii114.45 (13)
C4iv—Cs1—S4v67.45 (12)C2—S2—Cs1ix113.7 (3)
S4iv—Cs1—S4v75.30 (7)Ag1vii—S2—Cs1ix135.02 (16)
N1—Cs1—S3iv56.95 (10)Ag2vii—S2—Cs1ix144.5 (4)
C1—Cs1—S3iv57.70 (12)Ag3vii—S2—Cs1ix152.06 (18)
N4i—Cs1—S3iv115.23 (12)Cs1vii—S2—Cs1ix79.46 (5)
C2i—Cs1—S3iv177.91 (15)C3—S3—Ag1113.3 (3)
C4iv—Cs1—S3iv100.29 (14)C3—S3—Ag3113.9 (3)
S4iv—Cs1—S3iv123.91 (6)C3—S3—Ag3iii94.9 (3)
S4v—Cs1—S3iv65.97 (6)Ag1—S3—Ag3iii81.15 (17)
N1—Cs1—S1vi58.80 (11)Ag3—S3—Ag3iii64.00 (19)
C1—Cs1—S1vi57.35 (12)C3—S3—Cs1x78.0 (3)
N4i—Cs1—S1vi73.96 (12)Ag1—S3—Cs1x158.35 (16)
C2i—Cs1—S1vi65.36 (13)Ag3—S3—Cs1x168.09 (13)
C4iv—Cs1—S1vi134.05 (13)Ag3iii—S3—Cs1x117.39 (13)
S4iv—Cs1—S1vi118.03 (6)C4—S4—Cs1x75.7 (3)
S4v—Cs1—S1vi153.91 (6)C4—S4—Cs1xi110.1 (3)
S3iv—Cs1—S1vi114.44 (6)Cs1x—S4—Cs1xi85.64 (6)
N1—Cs1—C3iv78.96 (16)N1—C1—S1176.0 (7)
C1—Cs1—C3iv74.64 (17)N1—C1—Cs180.3 (5)
N4i—Cs1—C3iv99.70 (17)S1—C1—Cs197.0 (3)
C2i—Cs1—C3iv156.88 (18)N2—C2—S2177.2 (8)
C4iv—Cs1—C3iv76.14 (19)N2—C2—Cs1vii89.9 (6)
S4iv—Cs1—C3iv100.54 (14)S2—C2—Cs1vii87.8 (3)
S4v—Cs1—C3iv60.43 (12)N3—C3—S3176.7 (8)
S1vi—Cs1—C3iv131.01 (13)N3—C3—Cs1x99.6 (6)
N1—Cs1—N2i121.66 (15)S3—C3—Cs1x77.4 (3)
C1—Cs1—N2i115.73 (17)N4—C4—S4177.8 (8)
N4i—Cs1—N2i50.03 (16)N4—C4—Cs1x100.9 (6)
C4iv—Cs1—N2i75.66 (16)S4—C4—Cs1x79.4 (3)
S4iv—Cs1—N2i55.23 (11)N4—C4—Cs1vii70.9 (6)
S4v—Cs1—N2i123.44 (13)S4—C4—Cs1vii107.0 (3)
S3iv—Cs1—N2i165.14 (13)Cs1x—C4—Cs1vii117.9 (2)
S1vi—Cs1—N2i62.96 (12)C1—N1—Zn1173.3 (7)
C3iv—Cs1—N2i145.78 (17)C1—N1—Cs181.4 (5)
N1—Cs1—C4i102.14 (16)Zn1—N1—Cs193.9 (2)
C1—Cs1—C4i83.96 (18)C2—N2—Zn1170.3 (8)
N4i—Cs1—C4i17.26 (14)C2—N2—Cs1vii73.2 (6)
C2i—Cs1—C4i83.83 (19)Zn1—N2—Cs1vii97.4 (3)
C4iv—Cs1—C4i62.1 (2)C3—N3—Zn1165.6 (7)
S4iv—Cs1—C4i70.35 (12)C4—N4—Zn1163.9 (8)
S4v—Cs1—C4i122.90 (12)C4—N4—Cs1vii91.8 (6)
S3iv—Cs1—C4i98.24 (14)Zn1—N4—Cs1vii103.2 (3)
S1vi—Cs1—C4i83.19 (12)
Symmetry codes: (i) x1/2, y+1/2, z1/2; (ii) x1/2, y+1/2, z; (iii) x, y+1, z; (iv) x+1/2, y1/2, z+1/2; (v) x1/2, y1/2, z; (vi) x+1/2, y+1/2, z; (vii) x+1/2, y+1/2, z+1/2; (viii) x+1/2, y1/2, z; (ix) x+1/2, y+1/2, z+1; (x) x+1/2, y+1/2, z+1/2; (xi) x+1/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaCs[AgZn(SCN)4]Cs[AgZn(SCN)4]
Mr538.47538.47
Crystal system, space groupMonoclinic, P21/nMonoclinic, C2/c
Temperature (K)293293
a, b, c (Å)9.0398 (2), 16.6679 (4), 9.0973 (2)13.964 (2), 14.851 (2), 13.389 (2)
β (°) 98.190 (1) 113.35 (1)
V3)1356.75 (5)2549.2 (7)
Z48
Radiation typeMo KαMo Kα
µ (mm1)6.446.86
Crystal size (mm)0.15 × 0.15 × 0.150.20 × 0.05 × 0.05
Data collection
DiffractometerNonius KappaCCD area-detectorNonius MACH3
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.579, 0.710
No. of measured, independent and
observed [I > 2σ(I)] reflections
12064, 2298, 1852 7410, 3705, 1447
Rint0.0720.084
(sin θ/λ)max1)0.5870.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.101, 1.04 0.060, 0.119, 0.94
No. of reflections22983705
No. of parameters137155
Δρmax, Δρmin (e Å3)1.86, 1.760.67, 0.78

Computer programs: COLLECT (Nonius, 1997-2000), CAD-4 Software (Enraf-Nonius, 1989), HKL SCALEPACK (Otwinowski & Minor 1997), CAD-4 Software, HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2000), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) for (I) top
Ag1—S1i2.5600 (19)S1—C11.633 (8)
Ag1—S22.573 (2)S2—C21.634 (8)
Ag1—S3ii2.667 (2)S3—C31.634 (8)
Ag1—S4iii2.944 (2)S4—C41.614 (8)
Zn1—N31.943 (7)C1—N11.146 (9)
Zn1—N41.951 (7)C2—N21.141 (9)
Zn1—N21.951 (7)C3—N31.153 (10)
Zn1—N11.975 (7)C4—N41.148 (9)
S1i—Ag1—S2142.15 (7)N4—Zn1—N2111.6 (3)
S1i—Ag1—S3ii110.08 (6)N3—Zn1—N1105.4 (3)
S2—Ag1—S3ii107.38 (7)N4—Zn1—N1107.1 (3)
S1i—Ag1—S4iii91.83 (6)N2—Zn1—N1108.4 (3)
S2—Ag1—S4iii88.83 (7)N1—C1—S1179.0 (7)
S3ii—Ag1—S4iii97.09 (7)N2—C2—S2179.0 (7)
N3—Zn1—N4111.6 (3)N3—C3—S3178.1 (7)
N3—Zn1—N2112.3 (3)N4—C4—S4176.7 (7)
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x1, y, z; (iii) x+1/2, y+1/2, z+3/2.
Selected geometric parameters (Å, º) for (II) top
Ag1—S2i2.430 (5)Zn1—N11.958 (7)
Ag1—S32.573 (8)Zn1—N31.961 (7)
Ag1—S1ii2.598 (6)S1—C11.627 (9)
Ag2—S1ii2.381 (8)S2—C21.640 (9)
Ag2—S2i2.457 (8)S3—C31.628 (9)
Ag3—S1ii2.512 (5)S4—C41.615 (9)
Ag3—S32.573 (7)C1—N11.133 (9)
Ag3—S2i2.612 (6)C2—N21.108 (9)
Ag3—S3iii2.916 (8)C3—N31.142 (9)
Zn1—N41.940 (7)C4—N41.146 (9)
Zn1—N21.945 (8)
S2i—Ag1—S3112.9 (3)N4—Zn1—N2109.1 (3)
S2i—Ag1—S1ii146.3 (3)N4—Zn1—N1119.0 (3)
S3—Ag1—S1ii97.6 (2)N2—Zn1—N1105.3 (3)
S1ii—Ag2—S2i168.4 (7)N4—Zn1—N3108.5 (3)
S1ii—Ag3—S399.8 (2)N2—Zn1—N3110.3 (3)
S1ii—Ag3—S2i139.8 (2)N1—Zn1—N3104.5 (3)
S3—Ag3—S2i107.1 (2)N1—C1—S1176.0 (7)
S1ii—Ag3—S3iii93.3 (2)N2—C2—S2177.2 (8)
S3—Ag3—S3iii116.00 (19)N3—C3—S3176.7 (8)
S2i—Ag3—S3iii100.9 (2)N4—C4—S4177.8 (8)
Symmetry codes: (i) x1/2, y+1/2, z1/2; (ii) x1/2, y+1/2, z; (iii) x, y+1, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds