Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113002916/sf3192sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002916/sf3192Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113002916/sf3192Isup3.mol |
CCDC reference: 934550
A mixture of AgNO3 (8.4 mg, 0.05 mmol), KI (50 mg, 0.3 mmol), bmimp (4.1 mg, 0.02 mmol) and dimethylformamide–CH3CN (1.5 ml) mixed solvent was sealed in a glass tube and heated to 393 K over a period of 10 h, kept at 393 K for 50 h and then cooled slowly to 303 K over a period of 13 h. Colourless needle-shaped crystals of (I) were collected and washed with ethanol and finally dried in the air (yield 80%). [Any recrystallization?]
All H atoms were generated geometrically and allowed to ride on their parent atoms in a riding-model approximation, with aromatic C—H = 0.93 Å and methyl C—H = 0.96 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker ,2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
[Ag4I4(C11H16N4)] | F(000) = 1020 |
Mr = 1143.36 | Dx = 3.506 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 1399 reflections |
a = 12.809 (6) Å | θ = 3.5–26.3° |
b = 4.541 (2) Å | µ = 9.27 mm−1 |
c = 18.788 (9) Å | T = 298 K |
β = 97.621 (7)° | Needle, colourless |
V = 1083.1 (9) Å3 | 0.15 × 0.10 × 0.10 mm |
Z = 2 |
Bruker SMART APEXII CCD area-detector diffractometer | 1870 independent reflections |
Radiation source: fine-focus sealed tube | 1350 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −15→8 |
Tmin = 0.337, Tmax = 0.458 | k = −5→4 |
4420 measured reflections | l = −22→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0789P)2 + 4.0792P] where P = (Fo2 + 2Fc2)/3 |
1870 reflections | (Δ/σ)max = 0.001 |
106 parameters | Δρmax = 1.50 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
[Ag4I4(C11H16N4)] | V = 1083.1 (9) Å3 |
Mr = 1143.36 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 12.809 (6) Å | µ = 9.27 mm−1 |
b = 4.541 (2) Å | T = 298 K |
c = 18.788 (9) Å | 0.15 × 0.10 × 0.10 mm |
β = 97.621 (7)° |
Bruker SMART APEXII CCD area-detector diffractometer | 1870 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1350 reflections with I > 2σ(I) |
Tmin = 0.337, Tmax = 0.458 | Rint = 0.037 |
4420 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.50 e Å−3 |
1870 reflections | Δρmin = −1.06 e Å−3 |
106 parameters |
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. |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.75421 (8) | 0.9855 (2) | 0.60049 (5) | 0.0574 (3) | |
Ag2 | 0.85289 (9) | 1.4548 (2) | 0.70705 (6) | 0.0664 (3) | |
I1 | 0.63534 (6) | 1.47674 (16) | 0.64143 (4) | 0.0464 (3) | |
I2 | 0.96478 (6) | 0.95382 (17) | 0.66561 (4) | 0.0499 (3) | |
C1 | 0.8601 (10) | 0.586 (3) | 0.4589 (6) | 0.064 (3) | |
H1A | 0.8950 | 0.6544 | 0.5043 | 0.097* | |
H1B | 0.9058 | 0.6107 | 0.4228 | 0.097* | |
H1C | 0.8427 | 0.3814 | 0.4626 | 0.097* | |
C2 | 0.7609 (8) | 0.761 (3) | 0.4386 (5) | 0.050 (3) | |
C3 | 0.6278 (9) | 1.050 (3) | 0.4420 (6) | 0.053 (3) | |
H3 | 0.5815 | 1.1834 | 0.4588 | 0.064* | |
C4 | 0.6185 (10) | 0.943 (3) | 0.3761 (6) | 0.059 (3) | |
H4 | 0.5652 | 0.9847 | 0.3389 | 0.071* | |
C5 | 0.7218 (13) | 0.581 (3) | 0.3114 (6) | 0.075 (4) | |
H5A | 0.6590 | 0.4682 | 0.2949 | 0.090* | |
H5B | 0.7788 | 0.4433 | 0.3254 | 0.090* | |
C6 | 0.7500 | 0.775 (3) | 0.2500 | 0.042 (3) | |
H6A | 0.6907 | 0.9001 | 0.2327 | 0.050* | |
N1 | 0.7162 (7) | 0.936 (2) | 0.4819 (4) | 0.050 (2) | |
N2 | 0.7037 (7) | 0.754 (2) | 0.3730 (4) | 0.051 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0645 (6) | 0.0700 (6) | 0.0364 (5) | 0.0015 (5) | 0.0013 (4) | −0.0080 (4) |
Ag2 | 0.0675 (7) | 0.0709 (7) | 0.0610 (6) | −0.0054 (5) | 0.0089 (5) | −0.0070 (5) |
I1 | 0.0477 (5) | 0.0462 (4) | 0.0458 (4) | −0.0001 (3) | 0.0083 (3) | 0.0001 (3) |
I2 | 0.0431 (4) | 0.0543 (5) | 0.0516 (5) | −0.0032 (4) | 0.0040 (3) | −0.0034 (3) |
C1 | 0.075 (8) | 0.077 (8) | 0.046 (7) | 0.010 (8) | 0.027 (6) | 0.000 (6) |
C2 | 0.066 (7) | 0.057 (7) | 0.026 (5) | −0.010 (7) | 0.006 (5) | 0.008 (5) |
C3 | 0.050 (6) | 0.072 (8) | 0.038 (6) | 0.001 (6) | 0.007 (5) | 0.004 (5) |
C4 | 0.057 (7) | 0.074 (8) | 0.042 (7) | −0.022 (7) | −0.009 (5) | 0.005 (6) |
C5 | 0.141 (13) | 0.050 (7) | 0.037 (6) | −0.008 (8) | 0.015 (7) | −0.003 (5) |
C6 | 0.048 (8) | 0.047 (8) | 0.033 (7) | 0.000 | 0.013 (6) | 0.000 |
N1 | 0.050 (5) | 0.073 (6) | 0.029 (4) | −0.017 (5) | 0.015 (4) | −0.011 (4) |
N2 | 0.078 (6) | 0.046 (5) | 0.030 (4) | −0.014 (6) | 0.008 (4) | −0.003 (4) |
Ag1—N1 | 2.228 (8) | C1—H1A | 0.9600 |
Ag1—I2 | 2.8139 (16) | C1—H1B | 0.9600 |
Ag1—I1 | 2.8628 (15) | C1—H1C | 0.9600 |
Ag1—I1i | 2.9255 (15) | C2—N1 | 1.323 (14) |
Ag1—Ag2 | 3.0780 (17) | C2—N2 | 1.348 (12) |
Ag1—Ag2i | 3.2777 (18) | C3—C4 | 1.321 (16) |
Ag2—I1ii | 2.832 (2) | C3—N1 | 1.375 (14) |
Ag2—I2iii | 2.8447 (16) | C3—H3 | 0.9300 |
Ag2—I2 | 2.8514 (16) | C4—N2 | 1.395 (15) |
Ag2—I1 | 2.8956 (17) | C4—H4 | 0.9300 |
Ag2—Ag2ii | 3.268 (3) | C5—N2 | 1.443 (14) |
Ag2—Ag1iii | 3.2777 (18) | C5—C6 | 1.532 (15) |
I1—Ag2ii | 2.832 (2) | C5—H5A | 0.9700 |
I1—Ag1iii | 2.9255 (15) | C5—H5B | 0.9700 |
I2—Ag2i | 2.8447 (16) | C6—C5iv | 1.532 (15) |
C1—C2 | 1.502 (16) | C6—H6A | 0.9700 |
N1—Ag1—I2 | 120.0 (2) | Ag1—I1—Ag2 | 64.62 (4) |
N1—Ag1—I1 | 107.1 (3) | Ag2ii—I1—Ag1iii | 109.38 (4) |
I2—Ag1—I1 | 115.87 (4) | Ag1—I1—Ag1iii | 103.34 (5) |
N1—Ag1—I1i | 97.6 (2) | Ag2—I1—Ag1iii | 68.54 (4) |
I2—Ag1—I1i | 110.34 (4) | Ag1—I2—Ag2i | 70.79 (4) |
I1—Ag1—I1i | 103.34 (5) | Ag1—I2—Ag2 | 65.81 (4) |
N1—Ag1—Ag2 | 137.4 (2) | Ag2i—I2—Ag2 | 105.72 (5) |
I2—Ag1—Ag2 | 57.68 (3) | C2—C1—H1A | 109.5 |
I1—Ag1—Ag2 | 58.21 (4) | C2—C1—H1B | 109.5 |
I1i—Ag1—Ag2 | 123.97 (5) | H1A—C1—H1B | 109.5 |
N1—Ag1—Ag2i | 123.5 (3) | C2—C1—H1C | 109.5 |
I2—Ag1—Ag2i | 55.04 (3) | H1A—C1—H1C | 109.5 |
I1—Ag1—Ag2i | 125.77 (5) | H1B—C1—H1C | 109.5 |
I1i—Ag1—Ag2i | 55.30 (4) | N1—C2—N2 | 110.3 (10) |
Ag2—Ag1—Ag2i | 91.14 (5) | N1—C2—C1 | 125.6 (9) |
I1ii—Ag2—I2iii | 106.58 (4) | N2—C2—C1 | 124.1 (11) |
I1ii—Ag2—I2 | 109.93 (4) | C4—C3—N1 | 109.7 (11) |
I2iii—Ag2—I2 | 105.72 (5) | C4—C3—H3 | 125.1 |
I1ii—Ag2—I1 | 110.28 (4) | N1—C3—H3 | 125.1 |
I2iii—Ag2—I1 | 110.33 (4) | C3—C4—N2 | 107.0 (10) |
I2—Ag2—I1 | 113.67 (4) | C3—C4—H4 | 126.5 |
I1ii—Ag2—Ag1 | 129.84 (5) | N2—C4—H4 | 126.5 |
I2iii—Ag2—Ag1 | 123.49 (5) | N2—C5—C6 | 111.7 (10) |
I2—Ag2—Ag1 | 56.51 (4) | N2—C5—H5A | 109.3 |
I1—Ag2—Ag1 | 57.17 (3) | C6—C5—H5A | 109.3 |
I1ii—Ag2—Ag2ii | 56.13 (4) | N2—C5—H5B | 109.3 |
I2iii—Ag2—Ag2ii | 127.14 (3) | C6—C5—H5B | 109.3 |
I2—Ag2—Ag2ii | 127.04 (3) | H5A—C5—H5B | 107.9 |
I1—Ag2—Ag2ii | 54.30 (5) | C5iv—C6—C5 | 109.9 (13) |
Ag1—Ag2—Ag2ii | 91.87 (5) | C5iv—C6—H6A | 109.7 |
I1ii—Ag2—Ag1iii | 123.56 (5) | C5—C6—H6A | 109.7 |
I2iii—Ag2—Ag1iii | 54.16 (4) | C2—N1—C3 | 106.5 (9) |
I2—Ag2—Ag1iii | 125.94 (5) | C2—N1—Ag1 | 128.4 (7) |
I1—Ag2—Ag1iii | 56.16 (3) | C3—N1—Ag1 | 124.3 (7) |
Ag1—Ag2—Ag1iii | 91.14 (5) | C2—N2—C4 | 106.4 (9) |
Ag2ii—Ag2—Ag1iii | 91.76 (5) | C2—N2—C5 | 128.2 (11) |
Ag2ii—I1—Ag1 | 106.45 (4) | C4—N2—C5 | 125.3 (10) |
Ag2ii—I1—Ag2 | 69.57 (4) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) x, y+1, z; (iv) −x+3/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag4I4(C11H16N4)] |
Mr | 1143.36 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 298 |
a, b, c (Å) | 12.809 (6), 4.541 (2), 18.788 (9) |
β (°) | 97.621 (7) |
V (Å3) | 1083.1 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 9.27 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.337, 0.458 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4420, 1870, 1350 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.141, 1.01 |
No. of reflections | 1870 |
No. of parameters | 106 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.50, −1.06 |
Computer programs: APEX2 (Bruker ,2005), APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), publCIF (Westrip, 2010).
Ag1—N1 | 2.228 (8) | Ag2—I1ii | 2.832 (2) |
Ag1—I2 | 2.8139 (16) | Ag2—I2iii | 2.8447 (16) |
Ag1—I1 | 2.8628 (15) | Ag2—I2 | 2.8514 (16) |
Ag1—I1i | 2.9255 (15) | Ag2—I1 | 2.8956 (17) |
Ag1—Ag2 | 3.0780 (17) | Ag2—Ag2ii | 3.268 (3) |
Ag1—Ag2i | 3.2777 (18) | ||
N1—Ag1—I2 | 120.0 (2) | I1ii—Ag2—I2iii | 106.58 (4) |
N1—Ag1—I1 | 107.1 (3) | I1ii—Ag2—I2 | 109.93 (4) |
I2—Ag1—I1 | 115.87 (4) | I2iii—Ag2—I2 | 105.72 (5) |
N1—Ag1—I1i | 97.6 (2) | I1ii—Ag2—I1 | 110.28 (4) |
I2—Ag1—I1i | 110.34 (4) | I2iii—Ag2—I1 | 110.33 (4) |
I1—Ag1—I1i | 103.34 (5) | I2—Ag2—I1 | 113.67 (4) |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y, −z+3/2; (iii) x, y+1, z. |
The construction of AgI coordination compounds has become a fruitful field because of their fascinating and diverse structures, including discrete clusters (Anson et al., 2008; Jia & Wang, 2009; Wu et al., 2010; Sun et al., 2011) and infinite coordination polymers (Sun et al., 2010; Mak et al., 2007; Khlobystov et al., 2001; Young & Hanton 2008). Among the AgI coordination architectures, subgroups incorporating AgI halides as inorganic functional modules have attracted particular attention because of their rich structural motifs and outstanding photophysical properties (Cheng et al., 2004). Various AgI–iodide aggregates, including discrete Ag2I2, Ag3I3 and Ag4I4 clusters (Di Nicola et al., 2005; Bowen et al., 1994; Effendy et al., 1991) and infinite looped-chain motifs (Peters et al., 1984), a staircase double chain (Healy et al., 1983), and wave-like quadruple-chain chains (Chen et al., 2012) have been documented. Of the reported silver(I)–iodide aggregates, those constructed by one-dimensional silver(I)–iodide motifs are quite limited and the architectures are mostly based on rigid ligands. Flexible N-heterocyclic bidentate ligands, on the other hand, have variable configurations according to the torsion angles of the flexible carbon chain (Moss, 1996). Hence, we chose a flexible N-heterocyclic ligand, 1,3-bis(2-methyl-1H-imidazol-1-yl)propane (bmimp), and carried out reactions under solvothermal conditions which gave rise to a two-dimensional AgI–iodide network containing a unique [Ag6I6] hexagonal prism-based one-dimensional column motif, the title compound, (I).
As shown in Fig. 1, the asymmetric unit of (I) contains two crystallographically independent AgI cations, two I- anions and half of a bmimp ligand. A crystallographic twofold axis passes through atom C6 of the bmimp ligand. The coordination environments of the two AgI cations can be described as distorted tetrahedra with different ligating atoms. Atom Ag1 is in a distorted tetrahedral environment defined by three I- anions and one N atom from a bmimp ligand, while atom Ag2 displays a tetrahedral AgI4 geometry. The Ag—N and average Ag—I bond lengths are 2.228 (8) and 2.8608 (16) Å, respectively, which are in the normal ranges observed in related AgI–iodide compounds (Ansell, 1976; Powell et al., 1996). The distortion of the tetrahedron can be indicated by the value of the τ4 parameter (Yang et al., 2007) which describes the geometry of a four-coordinate metal system; in (I), τ4 = 0.88 and 0.96 for atoms Ag1 and Ag2, respectively (cf τ4 = 1 for a perfect tetrahedral geometry). The distances between adjacent AgI cations in the AgI–iodide aggregate range from 3.0780 (17) to 3.2777 (18) Å, which are shorter than twice the van der Waals radius of AgI (3.44 Å; Bondi, 1964), indicating appreciable argentophilicity (Tong et al., 1999).
Interestingly, a hexanuclear [Ag6I6] core (Fig. 2a) is observed in (I). The structure of the hexanuclear [Ag6I6] core is similar to that of the double six-membered rings (D6R, hexagonal prisms) found in zeolite (Baerlocher et al., 2001). The [Ag6I6] hexagonal prism can also be described as two face-to-face six-membered Ag3I3 rings with a chair conformation, arranged alternately and connected by six pairs of perpendicular alternating Ag—I bonds. It is noteworthy that this infinite AgI–iodide column has not been reported previously, according to a survey of the 2012 version of the Cambridge Structural Database (CSD; Version 5.33, August 2012 update; Allen, 2002), although a two-dimensional AgI–iodide double sheet built from the fused arrangement of this kind of one-dimensional column has been reported (Niu et al., 2006). The hexanuclear [Ag6I6] cores in (I) are connected to each other by sharing of the rhombic [Ag2I2] four-membered faces to form an infinite one-dimensional column (Fig. 2b). These columns are connected by bmimp ligands to form two-dimensional layers (Fig. 2c), which are packed in an ABAB fashion to form the resultant three-dimensional supramolecular framework by van der Waals interactions.
Diimidazole-based silver(I)–iodide compounds have not been widely studied. A related structure constructed from AgI and the semi-rigid diimidazole ligand 1,4-bis[(imidazol-1-yl)methyl]benzene (bix), viz. [Ag4I4(bix)]n, (II), has been reported (Chen et al., 2012). In (II), the AgI cations and I- anions form an inorganic wave-like chain which is bridged by bidentate bix ligands, giving a two-dimensional network. Compound (II) has a similar two-dimensional network to that in (I) but with different AgI–iodide cores, which indicates that differences in the diimidazole ligand and the reactant ratio play important roles in the formation of the different structural motifs.