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In the organometallic silver(I) supra­molecular complex poly[[silver(I)-[mu]3-3-[4-(2-thien­yl)-2H-cyclo­penta­[d]pyridazin-1-yl]benzonitrile] perchlorate methanol solvate], {[Ag(C18H11N3S)](ClO4)·CH3OH}n, there is only one type of AgI center, which lies in an {AgN2S[pi]} coordination environment. Two unsymmetric multidentate 3-[4-(2-thien­yl)-2H-cyclo­penta­[d]pyridazin-1-yl]benzonitrile (L) ligands link two AgI atoms through [pi]-AgI inter­actions into an organometallic box-like unit, from which two 3-cyano­benzoyl arms stretch out in opposite directions and bind two AgI atoms from neighboring box-like building blocks. This results in a novel two-dimensional network extending in the crystallographic bc plane. These two-dimensional sheets stack together along the crystallographic a axis to generate parallelogram-like channels. The methanol solvent mol­ecules and the perchlorate counter-ions are located in the channels, where they are fixed by inter­molecular hydrogen-bonding inter­actions. This architecture may provide opportunities for host-guest chemistry, such as guest mol­ecule loss and absorption or ion exchange. The new fulvene-type multidentate ligand L is a good candidate for the preparation of Cp-AgI-containing (Cp is cyclo­penta­dien­yl) organometallic coordination polymers or supra­molecular complexes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108043643/sq3178sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108043643/sq3178Isup2.hkl
Contains datablock I

CCDC reference: 724173

Comment top

The design and synthesis of supramolecular complexes exhibiting novel structures and properties have provided exciting new prospects for the chemists (Fujita et al., 1995; Hagrman et al., 1999; Dong et al., 2000; Kitagawa et al., 2004). It is well known that fulvene is one of the most important classes of ligands in organometallic chemistry and it is widely used in the construction of organometallic complexes (Little, 1961; Knox & Pauson, 1961; Stone & Little, 1984). In principle, the abundant coordination chemistry of fulvene could afford us an excellent opportunity to construct organic–inorganic hybrid materials that might be different in topology and physical and chemical properties from those based on common organic spacers. A continuing project in our laboratory has been the development of organometallic coordination frameworks generated from conjugated symmetric and unsymmetric fulvene ligands, which can adopt either cis- or trans-conformations to bind the soft acid AgI ion through not only the terminal –CN and furan or thiophene functional groups but also the fulvene C atoms into organometallic coordination polymers or discrete complexes (Dong et al., 2002, 2003; Dong, Jin et al., 2004 and/or??? Dong, Wang et al., 2004; Wang et al., 2005). In this paper, we report a novel two-dimensional network which was formed by the self-assembly reaction of a new fulvene ligand with silver perchlorate. We have recently synthesized the new multidentate thiophene- and benzonitrile-containing unsymmetric fulvene ligand L {3-[4-(2-thienyl)-2H-cyclopenta[d] pyridazin-1-yl]benzonitrile; C18H11N3S} and investigated its self-assembly reaction with AgI salts. Crystallization of L with AgClO4 in a methylene chloride/methanol mixed solvent system at room temperature afforded a new organometallic supramolecular complex, namely [Ag(C18H11N3S)(ClO4)].CH3OH, (I).

There is only one type of AgI center in (I), which lies in an {AgN2Sπ} coordination environment (Fig. 1). Two N atoms [N1 and N3ii; symmetry code: (ii) -x, y - 1/2, -z + 1/2] from the pyridazine ring and –CN donors of different ligands [Ag1—N1= 2.313 (5) Å and Ag1—N3ii = 2.171 (6) Å], one S atom from a thiophene ring, which comes from the same ligand as the pyridazine group [Ag1—S1= 2.935 (2) Å], and one π-donor from a coordinated cyclopentadienyl (Cp) ring of a third neighbouring ligand constitute the AgI coordination environment. The two Ag—C bond lengths [2.624 (7) and 2.650 (7) Å] lie in the range of normal Ag—C distances 2.47–2.86 Å, while the remaining Ag—C contacts are greater than 3.12 Å, which is beyond the limit commonly observed in AgI–aromatic complexes. Thus, the substituted five-membered Cp ring in L coordinates to the AgI ion with an η2 bonding mode, which is normally observed in arene–silver complexes (Munakata et al., 2000). In our previous work, some similar fulvene-type ligands, such as 4-[2-phenyl-4-(2-thienyl)-2H-cyclopenta[d]pyridazin-1-yl]benzonitrile (Dong et al., 2006) and 4-[4-(furan-2-yl)-2H-cyclopenta[d]pyridazin-1-yl]benzonitrile (Dong et al., 2005), displayed different coordination modes with AgI ions. In particular, the S atom from thiophene ring or the O atom from the furan ring of the ligand did not coordinate to the AgI ion.

In the solid state, two L ligands link two AgI atoms through π–AgI and heteroatom–AgI interactions into an organometallic box-like unit (Fig. 1), from which two 3-cyanobenzoyl arms stretch out in opposite directions and bind two AgI atoms in neighboring box-like building blocks. This results in a novel two-dimensional network extending in the crystallographic bc plane (Fig. 2). The Ag···Ag distance within an individual cage is 6.796 (2) Å. Similar organometallic cages with related fulvene ligands have been observed previously, linked into one-dimensional chains (Dong et al., 2005). By contrast, here we obtained a novel two-dimensional network by linking these box-like units.

This two-dimensional network contains a parallelogram-like macrocycle with approximate (crystallographic) dimensions of 16.2 × 7.7 Å (Fig. 2). The sheets stack along the crystallographic a axis, thus propagating the parallelogram-like channels in this direction. The methanol solvent molecules and perchlorate anions are located in the channels, where they are held in place by hydrogen bonds. The first hydrogen bond (O···H—N) consists of the O atom of the methanol solvent molecule and the NH group in the pyridazine ring of the ligand L. The second hydrogen bond (O—H···O) involves the OH group of the methanol molecule and an O atom of the ClO4- ion. The guest methanol molecules and ClO4- counter-ions are thus fixed in place by intermolecular hydrogen-bonding interactions. Self-assembled coordination polymers containing cavities or channels play an important role in materials science because of their potential applications in adsorption and desorption and host–guest chemistry. The intriguing architecture and topology in (I) may provide opportunities for this type of behavior.

To date, a number of AgI-containing coordination polymers have been successfully generated from inorganic silver salts and various types of rigid and flexible organic spacers based on Ag–heteroatom (Hagrman et al., 1999; Blake et al., 1999; Dong et al., 2002) or Ag–π interactions (Batten & Robson, 1998; Li et al., 2000). In contrast, the chemistry of supramolecular architectures based on fulvene molecules has received considerably less attention. In our previous work (Dong et al., 2005), we synthesized some fulvene-type ligands and obtained a series of coordination polymers by self-assembly of fulvene ligands with various silver salts. In general, these ligands linked Ag atoms through cyclopentadienyl π–Ag and pyridazine N—Ag interactions into one-dimensional zigzag chains. However, in (I), the ligands bind Ag atoms through cyclopentadienyl π–Ag and cyano group N—Ag interactions to form one-dimensional wavy chains. These wavy chains are then linked by the pyridazine N—Ag interactions into a two-dimensional network. Thus, the fulvene organic spacer reported here appears to be a good candidate for preparation of Cp–AgI-containing organometallic coordination supramolecular complexes. This encourages us to undertake further studies on fulvene ligands of this type and explore their interesting coordination chemistry.

Related literature top

For related literature, see: Batten & Robson (1998); Blake et al. (1999); Dong et al. (2000, 2002, 2003, 2006); Dong et al. (2005); Dong, Jin, Zhao, Huang, Smith, Stitzer & zur Loye (2004); Dong, Wang, Huang & Smith (2004); Fujita et al. (1995); Hagrman et al. (1999); Kitagawa et al. (2004); Knox & Pauson (1961); Li et al. (2000); Little (1961); Munakata et al. (2000); Stone & Little (1984); Wang et al. (2005).

Experimental top

The fulvene ligand L1 was prepared according to the literature method (Dong et al., 2005). A solution of L1 (0.4 g) in anhydrous EtOH (20 ml) and a large excess of hydrazine hydrate was heated to reflux for about 7 h. After the mixture was cooled to room temperature, the solvent was removed under reduced pressure to give a red–orange solid. The product was recrystallized from EtOH to give orange crystals of L. A solution of AgClO4 (20.7 mg, 0.10 mmol) in MeOH (10 ml) was layered onto a solution of L (29.1 mg, 0.10 mmol) in methylene chloride (10 ml). The solutions were left for about one week at room temperature, and yellow single crystals of (I) suitable for single-crystal X-ray diffraction were obtained.

Refinement top

All non-H atoms were refined anisotropically and independently. H atoms attached to non-H atoms were placed in geometrically idealized positions and included as riding atoms, with C—H distances of 0.93 (CHaromatic; sp2), 0.98 (CHaromatic with C coordinated to Ag; sp3) and 0.96 Å (CH3), an N—H distance of 0.86 Å, and an O—H distance of 0.93Å, with Uiso(H) set at 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C,N,O) otherwise.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : A view of (I), with displacement ellipsoids drawn at the 30% probability level. For the sake of clarity, only the major component of the anion is shown. H atoms have been omitted. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x, y - 1/2, -z + 1/2.]
[Figure 2] Fig. 2. : The crystal packing of (I), viewed along the a axis. Methanol solvent molecules and ClO4- counter-ions are are located in channels, where they are fixed by intermolecular hydrogen-bonding interactions (dashed lines).
catena-poly[[silver(I)-µ3-3-[4-(2-thienyl)-2H- cyclopenta[d]pyridazin-1-yl]benzonitrile] perchlorate methanol solvate], top
Crystal data top
[Ag(C18H11N3S)]ClO4·CH4OF(000) = 1080
Mr = 540.72Dx = 1.831 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3183 reflections
a = 7.2729 (17) Åθ = 2.9–26.0°
b = 20.340 (5) ŵ = 1.31 mm1
c = 13.608 (3) ÅT = 298 K
β = 103.022 (3)°Plan, yellow
V = 1961.3 (8) Å30.34 × 0.24 × 0.07 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3443 independent reflections
Radiation source: fine-focus sealed tube2713 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
phi and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.665, Tmax = 0.914k = 1824
8044 measured reflectionsl = 1416
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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0823P)2 + 5.5262P]
where P = (Fo2 + 2Fc2)/3
3443 reflections(Δ/σ)max = 0.002
272 parametersΔρmax = 1.74 e Å3
3 restraintsΔρmin = 1.06 e Å3
Crystal data top
[Ag(C18H11N3S)]ClO4·CH4OV = 1961.3 (8) Å3
Mr = 540.72Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2729 (17) ŵ = 1.31 mm1
b = 20.340 (5) ÅT = 298 K
c = 13.608 (3) Å0.34 × 0.24 × 0.07 mm
β = 103.022 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3443 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2713 reflections with I > 2σ(I)
Tmin = 0.665, Tmax = 0.914Rint = 0.054
8044 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0653 restraints
wR(F2) = 0.181H-atom parameters constrained
S = 1.05Δρmax = 1.74 e Å3
3443 reflectionsΔρmin = 1.06 e Å3
272 parameters
Special details top

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. Three restraints were used for the "Hirshfeld Test" problem regarding the Ag atom (delu).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.00311 (9)0.33335 (3)0.48318 (5)0.0662 (3)
C10.3563 (9)0.4174 (3)0.3797 (5)0.0469 (15)
H10.39080.42130.30990.056*
C20.3629 (10)0.3601 (3)0.4359 (5)0.0529 (16)
H20.45560.32560.41090.063*
C30.3035 (9)0.3720 (3)0.5377 (5)0.0487 (14)
H30.35510.34810.58800.058*
C40.2555 (8)0.5602 (3)0.4515 (4)0.0361 (12)
C50.1990 (8)0.5187 (3)0.3694 (4)0.0350 (12)
C60.1849 (8)0.5358 (3)0.2615 (4)0.0353 (12)
C70.1287 (8)0.5986 (3)0.2262 (4)0.0410 (14)
H70.09580.62970.26930.049*
C80.1222 (9)0.6144 (3)0.1263 (4)0.0431 (14)
C90.0664 (10)0.6795 (3)0.0911 (5)0.0495 (16)
C100.1678 (10)0.5684 (3)0.0616 (4)0.0492 (16)
H100.16140.57910.00560.059*
C110.2228 (11)0.5066 (3)0.0967 (5)0.0506 (16)
H110.25520.47560.05320.061*
C120.2306 (9)0.4898 (3)0.1956 (4)0.0438 (15)
H120.26660.44750.21820.053*
C130.2881 (8)0.5322 (3)0.5516 (4)0.0371 (13)
C140.2455 (8)0.4652 (3)0.5615 (4)0.0341 (12)
C150.2786 (8)0.4306 (3)0.6580 (4)0.0390 (13)
C160.2976 (9)0.4560 (4)0.7550 (4)0.0495 (16)
H160.28310.50010.76970.059*
C170.3424 (10)0.4049 (4)0.8283 (5)0.0579 (19)
H170.36220.41240.89730.069*
C180.3532 (11)0.3455 (4)0.7890 (5)0.0584 (18)
H180.37860.30730.82740.070*
C190.084 (2)0.3103 (7)0.2297 (11)0.140 (5)
H19A0.12260.32780.17200.210*
H19C0.00070.27370.20930.210*
H19B0.19320.29580.27860.210*
Cl10.4630 (3)0.32418 (10)0.10863 (14)0.0721 (6)
N10.1766 (7)0.4284 (2)0.4806 (3)0.0361 (11)
N20.1585 (7)0.4564 (2)0.3887 (3)0.0377 (11)
H2A0.11650.43170.33740.045*
N30.0212 (9)0.7310 (3)0.0632 (5)0.0638 (17)
O10.0031 (12)0.3557 (3)0.2692 (5)0.100 (2)
H1A0.13410.35330.25450.121*
O20.4328 (18)0.2892 (4)0.1931 (6)0.173 (5)
O30.433 (2)0.2930 (5)0.0296 (6)0.201 (6)
O40.6582 (18)0.3414 (8)0.0763 (14)0.237 (7)
O50.3800 (15)0.3857 (4)0.1254 (6)0.133 (3)
S10.3154 (3)0.34700 (9)0.66097 (13)0.0556 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0906 (5)0.0299 (3)0.0750 (4)0.0074 (3)0.0121 (3)0.0075 (2)
C10.054 (4)0.036 (3)0.048 (4)0.006 (3)0.006 (3)0.004 (3)
C20.064 (3)0.036 (3)0.058 (4)0.015 (3)0.012 (3)0.008 (3)
C30.062 (4)0.030 (3)0.054 (4)0.012 (3)0.014 (3)0.003 (3)
C40.037 (3)0.031 (3)0.042 (3)0.002 (2)0.013 (2)0.004 (2)
C50.036 (3)0.028 (3)0.041 (3)0.005 (2)0.012 (2)0.005 (2)
C60.035 (3)0.034 (3)0.038 (3)0.002 (2)0.010 (2)0.006 (2)
C70.041 (3)0.037 (3)0.046 (3)0.003 (3)0.013 (3)0.005 (3)
C80.043 (3)0.040 (3)0.044 (3)0.003 (3)0.008 (3)0.012 (3)
C90.063 (4)0.040 (4)0.045 (3)0.008 (3)0.012 (3)0.004 (3)
C100.062 (4)0.053 (4)0.033 (3)0.004 (3)0.011 (3)0.007 (3)
C110.064 (4)0.049 (4)0.040 (3)0.001 (3)0.014 (3)0.007 (3)
C120.046 (4)0.038 (3)0.047 (4)0.002 (3)0.009 (3)0.003 (3)
C130.037 (3)0.032 (3)0.043 (3)0.000 (2)0.009 (2)0.001 (2)
C140.032 (3)0.033 (3)0.038 (3)0.002 (2)0.009 (2)0.002 (2)
C150.038 (3)0.038 (3)0.042 (3)0.001 (3)0.010 (2)0.004 (2)
C160.054 (4)0.054 (4)0.039 (3)0.009 (3)0.007 (3)0.001 (3)
C170.059 (4)0.075 (5)0.038 (3)0.013 (4)0.006 (3)0.007 (3)
C180.060 (4)0.058 (4)0.055 (4)0.001 (4)0.009 (3)0.022 (3)
C190.185 (14)0.124 (11)0.139 (11)0.037 (10)0.097 (11)0.003 (9)
Cl10.1013 (16)0.0631 (12)0.0524 (11)0.0175 (11)0.0181 (10)0.0105 (9)
N10.046 (3)0.025 (2)0.038 (2)0.002 (2)0.011 (2)0.0033 (19)
N20.048 (3)0.031 (3)0.032 (2)0.000 (2)0.006 (2)0.0008 (19)
N30.088 (5)0.033 (3)0.068 (4)0.005 (3)0.013 (3)0.015 (3)
O10.135 (6)0.070 (4)0.091 (4)0.013 (4)0.013 (4)0.032 (4)
O20.309 (14)0.109 (7)0.074 (5)0.079 (8)0.013 (6)0.021 (4)
O30.415 (18)0.105 (7)0.081 (5)0.094 (10)0.052 (8)0.012 (5)
O40.129 (10)0.29 (2)0.286 (19)0.008 (10)0.039 (11)0.001 (14)
O50.230 (10)0.073 (5)0.110 (6)0.042 (6)0.069 (6)0.011 (4)
S10.0734 (11)0.0407 (9)0.0545 (9)0.0093 (8)0.0181 (7)0.0135 (7)
Geometric parameters (Å, º) top
Ag1—N3i2.171 (6)C11—H110.9300
Ag1—N12.313 (5)C12—H120.9300
Ag1—C32.624 (7)C13—C1ii1.400 (8)
Ag1—C22.650 (7)C13—C141.410 (8)
Ag1—S12.935 (2)C14—N11.333 (7)
C1—C13ii1.400 (8)C14—C151.462 (8)
C1—C21.402 (9)C15—C161.394 (9)
C1—H10.9300C15—S11.720 (6)
C2—C31.376 (9)C16—C171.427 (9)
C2—H20.9800C16—H160.9300
C3—C4ii1.423 (8)C17—C181.330 (11)
C3—H30.9800C17—H170.9300
C4—C51.386 (8)C18—S11.702 (7)
C4—C3ii1.423 (8)C18—H180.9300
C4—C131.446 (8)C19—O11.303 (12)
C5—N21.339 (7)C19—H19A0.9600
C5—C61.489 (8)C19—H19C0.9600
C6—C121.388 (8)C19—H19B0.9600
C6—C71.394 (8)Cl1—O31.309 (8)
C7—C81.387 (8)Cl1—O21.327 (8)
C7—H70.9300Cl1—O51.385 (7)
C8—C101.376 (9)Cl1—O41.432 (13)
C8—C91.435 (9)N1—N21.353 (6)
C9—N31.137 (8)N2—H2A0.8600
C10—C111.373 (9)N3—Ag1iii2.171 (6)
C10—H100.9300O1—H1A0.9300
C11—C121.376 (9)
N3i—Ag1—N1143.7 (2)C6—C12—H12120.0
N3i—Ag1—C3110.5 (2)C1ii—C13—C14134.0 (5)
N1—Ag1—C3104.78 (18)C1ii—C13—C4107.4 (5)
N3i—Ag1—C296.6 (2)C14—C13—C4118.5 (5)
N1—Ag1—C2110.25 (19)N1—C14—C13120.9 (5)
C3—Ag1—C230.2 (2)N1—C14—C15115.2 (5)
N3i—Ag1—S1109.11 (18)C13—C14—C15123.8 (5)
N1—Ag1—S167.05 (12)C16—C15—C14129.2 (6)
C3—Ag1—S1106.72 (15)C16—C15—S1111.3 (5)
C2—Ag1—S1136.81 (15)C14—C15—S1119.4 (4)
C13ii—C1—C2107.1 (5)C15—C16—C17110.5 (6)
C13ii—C1—H1126.4C15—C16—H16124.8
C2—C1—H1126.4C17—C16—H16124.8
C3—C2—C1111.2 (6)C18—C17—C16113.9 (6)
C3—C2—Ag173.8 (4)C18—C17—H17123.0
C1—C2—Ag198.5 (4)C16—C17—H17123.0
C3—C2—H2120.8C17—C18—S1112.6 (5)
C1—C2—H2120.8C17—C18—H18123.7
Ag1—C2—H2120.8S1—C18—H18123.7
C2—C3—C4ii106.8 (5)O1—C19—H19A109.5
C2—C3—Ag175.9 (4)O1—C19—H19C109.5
C4ii—C3—Ag196.6 (4)H19A—C19—H19C109.5
C2—C3—H3122.2O1—C19—H19B109.5
C4ii—C3—H3122.2H19A—C19—H19B109.5
Ag1—C3—H3122.2H19C—C19—H19B109.5
C5—C4—C3ii134.0 (5)O3—Cl1—O2115.3 (7)
C5—C4—C13118.4 (5)O3—Cl1—O5115.2 (7)
C3ii—C4—C13107.4 (5)O2—Cl1—O5111.1 (5)
N2—C5—C4117.1 (5)O3—Cl1—O4101.8 (10)
N2—C5—C6116.5 (5)O2—Cl1—O4110.8 (9)
C4—C5—C6126.4 (5)O5—Cl1—O4101.2 (8)
C12—C6—C7119.3 (5)C14—N1—N2117.8 (5)
C12—C6—C5120.4 (5)C14—N1—Ag1124.2 (4)
C7—C6—C5120.3 (5)N2—N1—Ag1115.3 (3)
C8—C7—C6119.6 (6)C5—N2—N1126.9 (5)
C8—C7—H7120.2C5—N2—O1132.9 (4)
C6—C7—H7120.2N1—N2—O1100.0 (3)
C10—C8—C7120.6 (6)C5—N2—H2A116.5
C10—C8—C9120.3 (6)N1—N2—H2A116.5
C7—C8—C9119.0 (6)O1—N2—H2A17.1
N3—C9—C8179.6 (8)C9—N3—Ag1iii168.2 (6)
C11—C10—C8119.6 (6)C19—O1—N2126.7 (9)
C11—C10—H10120.2C19—O1—H1A116.4
C8—C10—H10120.2N2—O1—H1A117.0
C10—C11—C12120.9 (6)Cl1—O5—H1A95.9
C10—C11—H11119.6C18—S1—C1591.7 (3)
C12—C11—H11119.6C18—S1—Ag1139.3 (3)
C11—C12—C6120.1 (6)C15—S1—Ag189.2 (2)
C11—C12—H12120.0
C13ii—C1—C2—C30.6 (8)C13—C14—C15—C1622.1 (10)
C13ii—C1—C2—Ag175.3 (5)N1—C14—C15—S124.4 (7)
N3i—Ag1—C2—C3120.2 (4)C13—C14—C15—S1153.4 (5)
N1—Ag1—C2—C384.7 (4)C14—C15—C16—C17175.8 (6)
S1—Ag1—C2—C37.0 (5)S1—C15—C16—C170.1 (7)
N3i—Ag1—C2—C1130.1 (4)C15—C16—C17—C180.9 (9)
N1—Ag1—C2—C125.0 (4)C16—C17—C18—S11.4 (9)
C3—Ag1—C2—C1109.7 (6)C13—C14—N1—N23.4 (8)
S1—Ag1—C2—C1102.7 (4)C15—C14—N1—N2174.4 (5)
C1—C2—C3—C4ii0.2 (8)C13—C14—N1—Ag1156.8 (4)
Ag1—C2—C3—C4ii92.8 (5)C15—C14—N1—Ag125.3 (7)
C1—C2—C3—Ag193.0 (6)N3i—Ag1—N1—C14130.3 (5)
N3i—Ag1—C3—C266.5 (4)C3—Ag1—N1—C1463.2 (5)
N1—Ag1—C3—C2105.0 (4)C2—Ag1—N1—C1494.5 (5)
S1—Ag1—C3—C2175.0 (3)S1—Ag1—N1—C1439.0 (4)
N3i—Ag1—C3—C4ii172.2 (4)N3i—Ag1—N1—N268.9 (5)
N1—Ag1—C3—C4ii0.7 (4)C3—Ag1—N1—N297.5 (4)
C2—Ag1—C3—C4ii105.7 (5)C2—Ag1—N1—N266.3 (4)
S1—Ag1—C3—C4ii69.3 (4)S1—Ag1—N1—N2160.3 (4)
C3ii—C4—C5—N2177.6 (6)C4—C5—N2—N13.9 (8)
C13—C4—C5—N27.1 (8)C6—C5—N2—N1174.1 (5)
C3ii—C4—C5—C64.6 (11)C4—C5—N2—O1170.0 (5)
C13—C4—C5—C6170.7 (5)C6—C5—N2—O112.0 (8)
N2—C5—C6—C1233.9 (8)C14—N1—N2—C51.5 (8)
C4—C5—C6—C12143.8 (6)Ag1—N1—N2—C5160.5 (4)
N2—C5—C6—C7147.1 (5)C14—N1—N2—O1177.0 (4)
C4—C5—C6—C735.1 (9)Ag1—N1—N2—O115.0 (4)
C12—C6—C7—C81.0 (9)C5—N2—O1—C1993.2 (11)
C5—C6—C7—C8177.9 (5)N1—N2—O1—C1991.7 (10)
C6—C7—C8—C101.0 (9)O3—Cl1—O5—H1A102.8
C6—C7—C8—C9179.2 (6)O2—Cl1—O5—H1A30.6
C7—C8—C10—C110.9 (10)O4—Cl1—O5—H1A148.3
C9—C8—C10—C11179.3 (6)C17—C18—S1—C151.1 (6)
C8—C10—C11—C120.8 (11)C17—C18—S1—Ag192.0 (7)
C10—C11—C12—C60.8 (10)C16—C15—S1—C180.6 (5)
C7—C6—C12—C110.9 (9)C14—C15—S1—C18176.9 (5)
C5—C6—C12—C11178.0 (6)C16—C15—S1—Ag1139.9 (4)
C5—C4—C13—C1ii175.8 (5)C14—C15—S1—Ag143.8 (5)
C3ii—C4—C13—C1ii0.7 (7)N3i—Ag1—S1—C1891.4 (5)
C5—C4—C13—C145.4 (8)N1—Ag1—S1—C18127.3 (5)
C3ii—C4—C13—C14178.2 (5)C3—Ag1—S1—C1828.0 (5)
C1ii—C13—C14—N1178.4 (6)C2—Ag1—S1—C1831.7 (5)
C4—C13—C14—N10.0 (8)N3i—Ag1—S1—C15176.8 (3)
C1ii—C13—C14—C153.9 (10)N1—Ag1—S1—C1535.6 (2)
C4—C13—C14—C15177.6 (5)C3—Ag1—S1—C1563.8 (2)
N1—C14—C15—C16160.1 (6)C2—Ag1—S1—C1560.1 (3)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1, z+1; (iii) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.912.714 (7)155
O1—H1A···O50.932.303.049 (13)137

Experimental details

Crystal data
Chemical formula[Ag(C18H11N3S)]ClO4·CH4O
Mr540.72
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.2729 (17), 20.340 (5), 13.608 (3)
β (°) 103.022 (3)
V3)1961.3 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.31
Crystal size (mm)0.34 × 0.24 × 0.07
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.665, 0.914
No. of measured, independent and
observed [I > 2σ(I)] reflections
8044, 3443, 2713
Rint0.054
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.181, 1.05
No. of reflections3443
No. of parameters272
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.74, 1.06

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.912.714 (7)155.3
O1—H1A···O50.932.303.049 (13)136.9
 

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