Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614005725/fg3317sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614005725/fg33171sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614005725/fg33172sup3.hkl |
CCDC references: 991653; 991654
The crystal engineering of metallo-supramolecular architectures involving metallo-organic frameworks as building blocks has been studied extensively due to their structural versatility, unique properties and applications in different areas of science, such as materials and nanotechnology (Li et al., 2012; Liu et al., 2012; Neogi et al., 2013; Ye et al., 2011). Numerous routes have been investigated for supramolecular architectures, some of which are controlled by the formation of conventional covalent bonds and others by supramolecular contacts, such as hydrogen bonding, π–π stacking and X—H···π (X = O, N, C) interactions etc. (Ji et al., 2010; Wang et al., 2008; Zheng et al., 2010). A variety of molecular architectures, such as multiple helicates, cages, grids, two-dimensional sheets, diamondoid networks and porous frameworks, have been prepared by different interactions. Counter-anions sometimes also take a secondary role in directing supramolecular assembly via weak metal–anion interactions and the geometric effects of templating anions, such as NO3-, ClO4-, CF3SO3-, BF4-, PF6- and SbF6-, and this can result in significant structural variation (Kundu et al., 2010; Audhya et al., 2010; Ni et al., 2010; Raehm et al., 2003). Weak metal–anion interactions usually take place between `soft' metals (AgI and AuI) and `hard' coordination atoms (O and F), which could tune the linking modes of metal–organic building blocks and endow different properties on the resulting supramolecular architectures.
We report here the dinuclear macrocycle cation complex [Ag2(DPP)2]2+ constructed from N-[(diphenylphosphanyl)methyl]pyridin-4-amine (DPP) and the Ag+ cation, which performs as a building block to construct two supramolecular assemblies with counter-anions of NO3- and ClO4- (see scheme). Weak metal–oxygen interactions and the shape of the anions play a key role in determining the supramolecular structures. [Ag2(DPP)2](ClO4)2.CH3CN, (1), forms a one-dimensional chain but [Ag2(DPP)2](NO3)2, (2), is a two-dimensional sheet.
For the synthesis of complex (1), AgClO4 (0.0207 g, 0.1 mmol) was added to a mixture of CH3CN (2 ml) and CH3COCH3 (2 ml) containing DPP (0.0292 g, 0.10 mmol). The resulting solution was diffused with diethyl ether after stirring for 1 h at room temperature. After 2d, colourless block-shaped crystals of (1) were obtained. Analysis, calculated for C38H37Ag2Cl2N5O8P2: C 43.85, H 3.58, N 6.73%; found: C 43.69, H 3.82, N 6.94%. IR ([Medium?, ν, cm-1): 1611, 1579, 1528, 1435, 1225, 1089, 824, 751, 696, 623.
For the synthesis of complex (2), AgNO3 (0.0168 g, 0.1 mmol) was added to a mixture of CH3CN–C6H5CH3–DMF (DMF is dimethylformamide; 5 ml, with a volume ratio of 2:2:1) containing DPP (0.0292 g, 0.10 mmol). The resulting solution was diffused with diethyl ether after stirring for 1 h at room temperature. After a week, colourless block-shaped crystals of (2) suitable for X-ray analysis were obtained. Analysis, calculated for C36H34Ag2N6O6P2: C 46.75, H 3.68, N 9.09%; found: C 47.34, H 3.87, N 8.76%. IR ([Medium?, ν, cm-1): 1607, 1569, 1524, 1430, 1219, 1060, 820, 758, 692, 623.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were generated geometrically, with C—H = 0.93–0.99 Å, and refined with a riding model, with Uiso(H) = 1.2–1.5Ueq(C). [Please check added text]
X-ray diffraction analysis for complex (1) establishes that the asymmetric unit contains one DPP ligand, one Ag+ cation, one ClO4- counter-ion and one half-occupancy acetonitrile molecule, lying with its methyl C atom on a twofold axis (Fig. 1). The [Ag2(DPP)2]2+ dimer lies about an inversion centre. The unique Ag+ cation is coordinated by one P atom and one pyridine N atom from two different DPP ligands, exhibiting a nearly linear geometry. There is also a long contact to the acetonitrile N atom; see Table 2 for geometric details, which are comparable with those of the reported structures of similar complexes (Wang et al., 2008).
In the solid-state structure of (1), two adjacent [Ag2(DPP)2]2+ cations are doubly bridged by two ClO4- anions to form a one-dimensional supramolecular chain through weak Ag···O and N—H···O interactions (Fig. 2 and Table 3). Each ClO4- anion affords two O atoms to contact with two adjacent cations, one O atom (O3) hydrogen-bonding with atom N2 from a cation, while another O atom (O2) interacts weakly with an adjacent Ag1i cation [O2···Ag1i = 3.171 (5) Å; symmetry code: (i) x, -y + 1, z - 1/2]. Each [Ag2(DPP)2]2+ cation bridges four adjacent ClO4- anions via two Ag···O and two N—H···O weak interactions (Fig. 2). Thus, the weak Ag—O and N—H···O interactions are the primary tools in assembling the [Ag2(DPP)2]2+ cations and ClO4- anions into a chain extending in the c direction. Adjacent cations in the chain are located at 62.2 (3)° to each other (defined by their P···P lines). The acetonitrile molecule, lying about a twofold axis, helps to link the centrosymmetric dimers, in addition to the linkage provided by the perchlorate group. A weak C4—H4A···O2ii contact [symmetry code: x, -y + 1, z + 1/2] (see Table 3) is also present in the chain of dimers extending in the c direction. There are only simple van der Waals contacts between these chains.
To study further the influence of the anion as a template for supramolecular self-assembly, complex (2) was prepared using AgNO3 instead of AgClO4. X-ray diffraction analysis shows there are two crystallographically independent but structurally very similar [Ag2(DPP)2](NO3)2 units (Fig. 3), each lying about independent inversion centres. Two Ag+ cations are bridged by two DPP ligands in a head-to-tail fashion, constructing a dinuclear [Ag2(DPP)2]2+ cation similar to that in complex (1), but the coordination environment around the Ag atom is quite different from that in (1). The bond distances (Table 4) are similar to those in (1), but the N—Ag—P angles are much smaller than those in (1), while the Ag···Ag separations [6.497 (2) and 6.262 (2) Å] in the two independent dimers are also much longer than the corresponding value in (1). Furthermore, the Ag···O distances (see Table 4) are much less than the sum of the van der Waals radii of Ag and O atoms (3.27 Å; Winter, 1993). The NO3- anions could be considered as being in a chelating mode to coordinate weakly to Ag+, and thus the coordination environment of Ag+ in (2) could be described as a distorted tetrahedral geometry constructed by one P atom from one DPP, one N atom from another DPP and two chelating O atoms from one NO3- anion.
Such a geometric conformation results in longer Ag···Ag separations and smaller N—Ag—P angles in (2), compared with the corresponding values in (1) where the coordination environment of Ag+ is nearly linear. The pyridine ring-centred distances in the cations of (2) are 4.336 (2) and 4.622 (5) Å, similar to that in (1) [4.417 (1) Å].
Each [Ag2(C18H17N2P)2(NO3)2] dimer molecule of (2) performs as a four-node to bridge four adjacent equivalent molecules through N—H···O interactions, forming a two-dimensional sheet parallel to the bc plane. Adjacent sheets are constructed by dimers with Ag1 and dimers with Ag2, respectively (Fig. 4). The sheets of dimers with Ag1 all lie near a = 1/2, 3/2, 5/2 etc., while the similar sheets with Ag2 dimers all lie near a = 0, 1, 2 etc. There is only one type of contact between these parallel sheets and that is listed as C24—H24A···O3v in Table 5. Thus, the two independent sheets are arranged in an alternating sequence at a = 0, 1/2, 1, 3/2 etc., with C—H···O contacts and simple van der Waals contacts between the sheets.
In summary, two supramolecular structures are constructed with different geometric conformations of the anions as template. The tetrahedrally geometric ClO4- anions link the [Ag2(DPP)2]2+ cations into a one-dimensional chain structure, while trigonal–planar NO3- anions bridge the cations into a two-dimensional supramolecular structure.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).
[Ag2(C18H17N2P)2](ClO4)2·C2H3N | Z = 4 |
Mr = 1040.31 | F(000) = 2088 |
Monoclinic, C2/c | Dx = 1.675 Mg m−3 |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.928 (2) Å | θ = 2.5–28.0° |
b = 18.192 (3) Å | µ = 1.21 mm−1 |
c = 19.026 (3) Å | T = 293 K |
β = 91.988 (3)° | Block, colourless |
V = 4126.0 (12) Å3 | 0.46 × 0.34 × 0.25 mm |
Bruker SMART CCD area-detector diffractometer | 4447 independent reflections |
Radiation source: fine-focus sealed tube | 2995 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 27.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→15 |
Tmin = 0.605, Tmax = 0.751 | k = −23→21 |
10757 measured reflections | l = −21→24 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0727P)2 + 4.9016P] where P = (Fo2 + 2Fc2)/3 |
4447 reflections | (Δ/σ)max = 0.002 |
267 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
[Ag2(C18H17N2P)2](ClO4)2·C2H3N | V = 4126.0 (12) Å3 |
Mr = 1040.31 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.928 (2) Å | µ = 1.21 mm−1 |
b = 18.192 (3) Å | T = 293 K |
c = 19.026 (3) Å | 0.46 × 0.34 × 0.25 mm |
β = 91.988 (3)° |
Bruker SMART CCD area-detector diffractometer | 4447 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2995 reflections with I > 2σ(I) |
Tmin = 0.605, Tmax = 0.751 | Rint = 0.026 |
10757 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.83 e Å−3 |
4447 reflections | Δρmin = −0.98 e Å−3 |
267 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.65542 (3) | 0.38326 (2) | 1.00024 (2) | 0.07792 (19) | |
P1 | 0.81927 (8) | 0.36619 (5) | 0.93652 (5) | 0.0436 (2) | |
N1 | 0.4939 (3) | 0.58932 (18) | 0.94507 (18) | 0.0519 (8) | |
N2 | 0.7689 (2) | 0.48847 (17) | 0.85624 (16) | 0.0474 (7) | |
H2B | 0.7698 | 0.4865 | 0.8111 | 0.057* | |
C1 | 0.4963 (3) | 0.5728 (2) | 0.8764 (2) | 0.0566 (10) | |
H1A | 0.4333 | 0.5839 | 0.8483 | 0.068* | |
C2 | 0.5848 (3) | 0.5409 (2) | 0.8454 (2) | 0.0505 (9) | |
H2A | 0.5814 | 0.5309 | 0.7975 | 0.061* | |
C3 | 0.6811 (3) | 0.52304 (19) | 0.88594 (18) | 0.0417 (8) | |
C4 | 0.6814 (3) | 0.5428 (2) | 0.95672 (19) | 0.0471 (8) | |
H4A | 0.7444 | 0.5342 | 0.9857 | 0.057* | |
C5 | 0.5877 (3) | 0.5750 (2) | 0.9832 (2) | 0.0538 (10) | |
H5A | 0.5895 | 0.5876 | 1.0306 | 0.065* | |
C6 | 0.8610 (3) | 0.4551 (2) | 0.8964 (2) | 0.0483 (9) | |
H6A | 0.8864 | 0.4886 | 0.9333 | 0.058* | |
H6B | 0.9231 | 0.4467 | 0.8658 | 0.058* | |
C7 | 0.8056 (3) | 0.3006 (2) | 0.86509 (19) | 0.0457 (8) | |
C8 | 0.7345 (4) | 0.2411 (2) | 0.8741 (2) | 0.0604 (10) | |
H8A | 0.6939 | 0.2375 | 0.9148 | 0.072* | |
C9 | 0.7234 (4) | 0.1870 (3) | 0.8229 (3) | 0.0715 (13) | |
H9A | 0.6776 | 0.1466 | 0.8301 | 0.086* | |
C10 | 0.7799 (4) | 0.1933 (3) | 0.7619 (3) | 0.0737 (13) | |
H10A | 0.7719 | 0.1576 | 0.7272 | 0.088* | |
C11 | 0.8486 (5) | 0.2527 (3) | 0.7522 (3) | 0.0792 (14) | |
H11A | 0.8866 | 0.2571 | 0.7105 | 0.095* | |
C12 | 0.8622 (4) | 0.3064 (3) | 0.8038 (2) | 0.0661 (12) | |
H12A | 0.9096 | 0.3461 | 0.7967 | 0.079* | |
C13 | 0.9436 (3) | 0.3394 (2) | 0.9874 (2) | 0.0453 (8) | |
C14 | 1.0117 (3) | 0.2812 (2) | 0.9685 (2) | 0.0570 (10) | |
H14A | 0.9967 | 0.2556 | 0.9269 | 0.068* | |
C15 | 1.1023 (4) | 0.2616 (3) | 1.0123 (3) | 0.0736 (13) | |
H15A | 1.1488 | 0.2232 | 0.9993 | 0.088* | |
C16 | 1.1240 (4) | 0.2972 (3) | 1.0735 (3) | 0.0756 (14) | |
H16A | 1.1840 | 0.2823 | 1.1026 | 0.091* | |
C17 | 1.0581 (4) | 0.3558 (3) | 1.0933 (3) | 0.0695 (12) | |
H17A | 1.0739 | 0.3805 | 1.1352 | 0.083* | |
C18 | 0.9684 (4) | 0.3770 (2) | 1.0499 (2) | 0.0586 (10) | |
H18A | 0.9243 | 0.4167 | 1.0625 | 0.070* | |
N3 | 0.5292 (8) | 0.3627 (6) | 0.8715 (5) | 0.083 (2) | 0.50 |
C19 | 0.5133 (7) | 0.3485 (6) | 0.8148 (7) | 0.068 (2) | 0.50 |
C20 | 0.5000 | 0.3286 (7) | 0.7500 | 0.126 (4) | |
H20A | 0.4356 | 0.3522 | 0.7285 | 0.189* | 0.50 |
H20B | 0.5656 | 0.3415 | 0.7249 | 0.189* | 0.50 |
H20C | 0.4898 | 0.2763 | 0.7486 | 0.189* | 0.50 |
Cl1 | 0.79174 (11) | 0.45084 (8) | 0.65833 (6) | 0.0758 (4) | |
O1 | 0.7781 (10) | 0.3831 (4) | 0.6219 (3) | 0.223 (5) | |
O2 | 0.7745 (4) | 0.5080 (3) | 0.6096 (2) | 0.1155 (16) | |
O3 | 0.7095 (4) | 0.4532 (3) | 0.7074 (2) | 0.1212 (17) | |
O4 | 0.8910 (4) | 0.4521 (6) | 0.6947 (3) | 0.233 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0604 (2) | 0.0745 (3) | 0.1018 (3) | 0.01911 (17) | 0.0444 (2) | 0.0175 (2) |
P1 | 0.0351 (5) | 0.0460 (5) | 0.0503 (5) | 0.0053 (4) | 0.0116 (4) | 0.0046 (4) |
N1 | 0.0451 (18) | 0.0481 (18) | 0.063 (2) | 0.0104 (14) | 0.0149 (15) | 0.0058 (15) |
N2 | 0.0455 (16) | 0.0538 (19) | 0.0433 (17) | 0.0104 (14) | 0.0074 (13) | 0.0037 (14) |
C1 | 0.044 (2) | 0.065 (3) | 0.062 (3) | 0.0078 (18) | 0.0047 (18) | 0.011 (2) |
C2 | 0.050 (2) | 0.057 (2) | 0.045 (2) | 0.0070 (17) | 0.0053 (17) | 0.0057 (18) |
C3 | 0.0417 (18) | 0.0377 (18) | 0.0461 (19) | 0.0025 (14) | 0.0085 (15) | 0.0059 (15) |
C4 | 0.046 (2) | 0.051 (2) | 0.045 (2) | 0.0056 (16) | 0.0054 (16) | 0.0034 (16) |
C5 | 0.060 (2) | 0.054 (2) | 0.048 (2) | 0.0042 (18) | 0.0113 (18) | 0.0023 (18) |
C6 | 0.0372 (18) | 0.049 (2) | 0.059 (2) | 0.0056 (15) | 0.0123 (16) | 0.0068 (17) |
C7 | 0.0392 (18) | 0.048 (2) | 0.050 (2) | 0.0039 (15) | 0.0048 (15) | 0.0059 (16) |
C8 | 0.062 (3) | 0.062 (3) | 0.057 (2) | −0.004 (2) | 0.0051 (19) | 0.006 (2) |
C9 | 0.075 (3) | 0.060 (3) | 0.080 (3) | −0.009 (2) | 0.000 (3) | 0.005 (2) |
C10 | 0.080 (3) | 0.067 (3) | 0.074 (3) | 0.010 (3) | −0.009 (3) | −0.013 (2) |
C11 | 0.083 (4) | 0.093 (4) | 0.062 (3) | −0.001 (3) | 0.020 (2) | −0.010 (3) |
C12 | 0.062 (3) | 0.073 (3) | 0.064 (3) | −0.012 (2) | 0.022 (2) | −0.007 (2) |
C13 | 0.0403 (18) | 0.043 (2) | 0.053 (2) | −0.0003 (15) | 0.0099 (16) | 0.0077 (16) |
C14 | 0.045 (2) | 0.053 (2) | 0.073 (3) | 0.0095 (17) | 0.0005 (19) | −0.007 (2) |
C15 | 0.050 (3) | 0.058 (3) | 0.112 (4) | 0.007 (2) | −0.010 (2) | −0.002 (3) |
C16 | 0.057 (3) | 0.072 (3) | 0.096 (4) | −0.004 (2) | −0.021 (3) | 0.012 (3) |
C17 | 0.073 (3) | 0.070 (3) | 0.064 (3) | −0.014 (2) | −0.011 (2) | 0.004 (2) |
C18 | 0.056 (2) | 0.056 (3) | 0.065 (3) | −0.0001 (18) | 0.006 (2) | −0.004 (2) |
N3 | 0.069 (6) | 0.102 (7) | 0.077 (6) | 0.013 (5) | −0.004 (5) | −0.006 (5) |
C19 | 0.047 (5) | 0.066 (6) | 0.090 (8) | 0.000 (4) | 0.000 (5) | −0.010 (5) |
C20 | 0.103 (8) | 0.149 (10) | 0.127 (9) | 0.000 | 0.000 (7) | 0.000 |
Cl1 | 0.0710 (7) | 0.1063 (10) | 0.0511 (6) | 0.0160 (6) | 0.0155 (5) | 0.0151 (6) |
O1 | 0.422 (15) | 0.126 (5) | 0.123 (5) | 0.102 (7) | 0.026 (7) | −0.017 (4) |
O2 | 0.161 (4) | 0.110 (3) | 0.074 (2) | −0.030 (3) | −0.016 (3) | 0.026 (2) |
O3 | 0.096 (3) | 0.194 (5) | 0.075 (2) | 0.001 (3) | 0.027 (2) | 0.004 (3) |
O4 | 0.065 (3) | 0.489 (15) | 0.145 (5) | −0.020 (5) | −0.012 (3) | 0.125 (7) |
Ag1—N1i | 2.152 (3) | C9—H9A | 0.9300 |
Ag1—P1 | 2.3560 (10) | C10—C11 | 1.373 (7) |
Ag1—N3 | 2.855 (10) | C10—H10A | 0.9300 |
Ag1—O2ii | 3.171 (5) | C11—C12 | 1.389 (7) |
P1—C13 | 1.809 (4) | C11—H11A | 0.9300 |
P1—C7 | 1.811 (4) | C12—H12A | 0.9300 |
P1—C6 | 1.863 (4) | C13—C14 | 1.390 (5) |
N1—C5 | 1.338 (5) | C13—C18 | 1.395 (6) |
N1—C1 | 1.342 (5) | C14—C15 | 1.388 (6) |
N1—Ag1i | 2.152 (3) | C14—H14A | 0.9300 |
N2—C3 | 1.361 (4) | C15—C16 | 1.349 (7) |
N2—C6 | 1.450 (5) | C15—H15A | 0.9300 |
N2—H2B | 0.8600 | C16—C17 | 1.384 (7) |
C1—C2 | 1.357 (6) | C16—H16A | 0.9300 |
C1—H1A | 0.9300 | C17—C18 | 1.383 (6) |
C2—C3 | 1.399 (5) | C17—H17A | 0.9300 |
C2—H2A | 0.9300 | C18—H18A | 0.9300 |
C3—C4 | 1.393 (5) | N3—C19 | 1.120 (13) |
C4—C5 | 1.373 (5) | C19—C20 | 1.289 (13) |
C4—H4A | 0.9300 | C20—C19iii | 1.289 (13) |
C5—H5A | 0.9300 | C20—H20A | 0.9600 |
C6—H6A | 0.9700 | C20—H20B | 0.9600 |
C6—H6B | 0.9700 | C20—H20C | 0.9599 |
C7—C12 | 1.372 (6) | Cl1—O4 | 1.351 (5) |
C7—C8 | 1.389 (6) | Cl1—O3 | 1.377 (4) |
C8—C9 | 1.387 (6) | Cl1—O2 | 1.404 (4) |
C8—H8A | 0.9300 | Cl1—O1 | 1.421 (7) |
C9—C10 | 1.367 (7) | ||
N1i—Ag1—P1 | 174.00 (9) | C9—C10—H10A | 120.2 |
C13—P1—C7 | 105.95 (17) | C11—C10—H10A | 120.2 |
C13—P1—C6 | 103.12 (17) | C10—C11—C12 | 120.9 (5) |
C7—P1—C6 | 106.42 (18) | C10—C11—H11A | 119.5 |
C13—P1—Ag1 | 116.05 (12) | C12—C11—H11A | 119.5 |
C7—P1—Ag1 | 114.73 (12) | C7—C12—C11 | 119.9 (4) |
C6—P1—Ag1 | 109.56 (12) | C7—C12—H12A | 120.1 |
C5—N1—C1 | 116.0 (3) | C11—C12—H12A | 120.1 |
C5—N1—Ag1i | 118.3 (3) | C14—C13—C18 | 119.0 (4) |
C1—N1—Ag1i | 124.7 (3) | C14—C13—P1 | 122.9 (3) |
C3—N2—C6 | 123.7 (3) | C18—C13—P1 | 118.1 (3) |
C3—N2—H2B | 118.1 | C15—C14—C13 | 119.4 (4) |
C6—N2—H2B | 118.3 | C15—C14—H14A | 120.3 |
N1—C1—C2 | 124.2 (4) | C13—C14—H14A | 120.3 |
N1—C1—H1A | 117.9 | C16—C15—C14 | 121.1 (4) |
C2—C1—H1A | 117.9 | C16—C15—H15A | 119.5 |
C1—C2—C3 | 119.7 (4) | C14—C15—H15A | 119.5 |
C1—C2—H2A | 120.1 | C15—C16—C17 | 120.7 (4) |
C3—C2—H2A | 120.1 | C15—C16—H16A | 119.6 |
N2—C3—C4 | 123.0 (3) | C17—C16—H16A | 119.6 |
N2—C3—C2 | 120.5 (3) | C18—C17—C16 | 119.2 (5) |
C4—C3—C2 | 116.6 (3) | C18—C17—H17A | 120.4 |
C5—C4—C3 | 119.3 (3) | C16—C17—H17A | 120.4 |
C5—C4—H4A | 120.3 | C17—C18—C13 | 120.6 (4) |
C3—C4—H4A | 120.3 | C17—C18—H18A | 119.7 |
N1—C5—C4 | 124.1 (4) | C13—C18—H18A | 119.7 |
N1—C5—H5A | 118.0 | N3—C19—C20 | 176.1 (11) |
C4—C5—H5A | 118.0 | C19iii—C20—C19 | 147.4 (15) |
N2—C6—P1 | 111.8 (3) | C19iii—C20—H20A | 52.8 |
N2—C6—H6A | 109.3 | C19—C20—H20A | 110.6 |
P1—C6—H6A | 109.3 | C19iii—C20—H20B | 62.1 |
N2—C6—H6B | 109.3 | C19—C20—H20B | 109.3 |
P1—C6—H6B | 109.3 | H20A—C20—H20B | 109.5 |
H6A—C6—H6B | 107.9 | C19iii—C20—H20C | 103.9 |
C12—C7—C8 | 119.0 (4) | C19—C20—H20C | 108.5 |
C12—C7—P1 | 123.6 (3) | H20A—C20—H20C | 109.5 |
C8—C7—P1 | 117.4 (3) | H20B—C20—H20C | 109.5 |
C9—C8—C7 | 120.7 (4) | O4—Cl1—O3 | 106.5 (3) |
C9—C8—H8A | 119.7 | O4—Cl1—O2 | 115.6 (4) |
C7—C8—H8A | 119.7 | O3—Cl1—O2 | 109.4 (3) |
C10—C9—C8 | 119.9 (5) | O4—Cl1—O1 | 110.3 (6) |
C10—C9—H9A | 120.0 | O3—Cl1—O1 | 106.6 (5) |
C8—C9—H9A | 120.0 | O2—Cl1—O1 | 108.0 (3) |
C9—C10—C11 | 119.6 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1, z+1/2; (iii) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O3 | 0.86 | 2.16 | 2.966 (5) | 155 |
C4—H4A···O2ii | 0.93 | 2.49 | 3.213 (5) | 134 |
Symmetry code: (ii) x, −y+1, z+1/2. |
[Ag2(C18H17N2P)2(NO3)2] | Z = 4 |
Mr = 924.37 | F(000) = 1856 |
Monoclinic, P21/c | Dx = 1.644 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.448 (5) Å | θ = 2.6–28.1° |
b = 17.498 (6) Å | µ = 1.19 mm−1 |
c = 16.006 (5) Å | T = 296 K |
β = 97.475 (4)° | Block, colourless |
V = 3734 (2) Å3 | 0.20 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 8472 independent reflections |
Radiation source: fine-focus sealed tube | 6592 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 27.6°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→17 |
Tmin = 0.797, Tmax = 0.891 | k = −22→22 |
24006 measured reflections | l = −20→20 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0434P)2] where P = (Fo2 + 2Fc2)/3 |
8472 reflections | (Δ/σ)max = 0.004 |
469 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.89 e Å−3 |
[Ag2(C18H17N2P)2(NO3)2] | V = 3734 (2) Å3 |
Mr = 924.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.448 (5) Å | µ = 1.19 mm−1 |
b = 17.498 (6) Å | T = 296 K |
c = 16.006 (5) Å | 0.20 × 0.10 × 0.10 mm |
β = 97.475 (4)° |
Bruker SMART CCD area-detector diffractometer | 8472 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 6592 reflections with I > 2σ(I) |
Tmin = 0.797, Tmax = 0.891 | Rint = 0.029 |
24006 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.38 e Å−3 |
8472 reflections | Δρmin = −0.89 e Å−3 |
469 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.530647 (15) | 0.509563 (10) | 0.204426 (12) | 0.04690 (7) | |
P1 | 0.51910 (4) | 0.39222 (3) | 0.27560 (3) | 0.03469 (13) | |
N1 | 0.49043 (16) | 0.41706 (11) | −0.09121 (12) | 0.0444 (5) | |
N2 | 0.49198 (15) | 0.29787 (11) | 0.13468 (11) | 0.0429 (5) | |
H2B | 0.4475 | 0.2625 | 0.1339 | 0.052* | |
C1 | 0.49460 (17) | 0.33701 (11) | 0.06218 (14) | 0.0373 (5) | |
C2 | 0.4189 (2) | 0.32552 (13) | −0.00539 (15) | 0.0472 (6) | |
H2A | 0.3680 | 0.2905 | −0.0006 | 0.057* | |
C3 | 0.4199 (2) | 0.36564 (14) | −0.07810 (15) | 0.0485 (6) | |
H3A | 0.3683 | 0.3569 | −0.1216 | 0.058* | |
C4 | 0.56390 (19) | 0.42666 (13) | −0.02697 (15) | 0.0450 (6) | |
H4A | 0.6147 | 0.4611 | −0.0345 | 0.054* | |
C5 | 0.56990 (17) | 0.38968 (13) | 0.04888 (14) | 0.0398 (5) | |
H5A | 0.6229 | 0.3992 | 0.0909 | 0.048* | |
C6 | 0.55601 (18) | 0.30921 (13) | 0.21275 (14) | 0.0402 (5) | |
H6A | 0.6242 | 0.3169 | 0.2008 | 0.048* | |
H6B | 0.5553 | 0.2632 | 0.2465 | 0.048* | |
C7 | 0.59728 (16) | 0.38149 (13) | 0.37663 (14) | 0.0374 (5) | |
C8 | 0.60856 (17) | 0.31144 (13) | 0.41723 (14) | 0.0421 (5) | |
H8A | 0.5804 | 0.2680 | 0.3902 | 0.051* | |
C9 | 0.66056 (19) | 0.30513 (16) | 0.49659 (15) | 0.0510 (6) | |
H9A | 0.6685 | 0.2576 | 0.5225 | 0.061* | |
C10 | 0.7008 (2) | 0.36917 (19) | 0.53764 (17) | 0.0634 (8) | |
H10A | 0.7351 | 0.3651 | 0.5918 | 0.076* | |
C11 | 0.6905 (3) | 0.4384 (2) | 0.4991 (2) | 0.0771 (9) | |
H11A | 0.7180 | 0.4816 | 0.5270 | 0.092* | |
C12 | 0.6391 (2) | 0.44519 (16) | 0.41825 (18) | 0.0631 (8) | |
H12A | 0.6329 | 0.4928 | 0.3922 | 0.076* | |
C13 | 0.39427 (16) | 0.36832 (11) | 0.30128 (14) | 0.0355 (5) | |
C14 | 0.37305 (18) | 0.36469 (14) | 0.38424 (15) | 0.0472 (6) | |
H14A | 0.4245 | 0.3719 | 0.4283 | 0.057* | |
C15 | 0.2770 (2) | 0.35061 (15) | 0.40192 (17) | 0.0540 (7) | |
H15A | 0.2643 | 0.3482 | 0.4576 | 0.065* | |
C16 | 0.1998 (2) | 0.34013 (14) | 0.33739 (18) | 0.0527 (7) | |
H16A | 0.1351 | 0.3308 | 0.3494 | 0.063* | |
C17 | 0.2187 (2) | 0.34360 (15) | 0.25528 (18) | 0.0576 (7) | |
H17A | 0.1669 | 0.3362 | 0.2116 | 0.069* | |
C18 | 0.31548 (18) | 0.35813 (15) | 0.23730 (15) | 0.0490 (6) | |
H18A | 0.3274 | 0.3610 | 0.1814 | 0.059* | |
N5 | 0.64176 (16) | 0.63684 (11) | 0.31203 (13) | 0.0457 (5) | |
O1 | 0.68227 (15) | 0.68426 (11) | 0.36233 (14) | 0.0714 (6) | |
O2 | 0.54888 (15) | 0.63702 (12) | 0.29282 (15) | 0.0744 (6) | |
O3 | 0.69176 (14) | 0.58799 (10) | 0.27911 (13) | 0.0599 (5) | |
Ag2 | 0.948112 (16) | 1.031511 (11) | 0.806690 (12) | 0.05028 (7) | |
P2 | 0.96514 (5) | 0.92081 (3) | 0.72632 (3) | 0.03697 (13) | |
N3 | 1.01525 (15) | 0.90435 (10) | 1.07593 (12) | 0.0414 (4) | |
N4 | 0.97578 (15) | 0.80084 (11) | 0.83938 (11) | 0.0435 (5) | |
H4B | 1.0090 | 0.7596 | 0.8339 | 0.052* | |
C19 | 0.98394 (17) | 0.83311 (12) | 0.91674 (13) | 0.0357 (5) | |
C20 | 1.06046 (19) | 0.80921 (13) | 0.97965 (14) | 0.0451 (6) | |
H20A | 1.1018 | 0.7685 | 0.9697 | 0.054* | |
C21 | 1.07377 (19) | 0.84648 (13) | 1.05596 (15) | 0.0453 (6) | |
H21A | 1.1261 | 0.8308 | 1.0960 | 0.054* | |
C22 | 0.93888 (18) | 0.92384 (13) | 1.01702 (14) | 0.0414 (5) | |
H22A | 0.8961 | 0.9626 | 1.0301 | 0.050* | |
C23 | 0.91964 (17) | 0.89065 (13) | 0.93906 (14) | 0.0386 (5) | |
H23A | 0.8647 | 0.9060 | 0.9014 | 0.046* | |
C24 | 0.91577 (18) | 0.83046 (13) | 0.76570 (14) | 0.0428 (5) | |
H24A | 0.8482 | 0.8393 | 0.7787 | 0.051* | |
H24B | 0.9120 | 0.7924 | 0.7213 | 0.051* | |
C25 | 0.90645 (18) | 0.92720 (14) | 0.61701 (14) | 0.0439 (5) | |
C26 | 0.8839 (3) | 0.86482 (18) | 0.56470 (17) | 0.0724 (9) | |
H26A | 0.8946 | 0.8157 | 0.5861 | 0.087* | |
C27 | 0.8462 (3) | 0.8747 (2) | 0.48184 (19) | 0.0935 (12) | |
H27A | 0.8309 | 0.8322 | 0.4477 | 0.112* | |
C28 | 0.8310 (3) | 0.9455 (2) | 0.44909 (19) | 0.0823 (10) | |
H28A | 0.8064 | 0.9515 | 0.3924 | 0.099* | |
C29 | 0.8515 (3) | 1.0079 (2) | 0.4988 (2) | 0.0848 (11) | |
H29A | 0.8398 | 1.0567 | 0.4766 | 0.102* | |
C30 | 0.8900 (3) | 0.99846 (17) | 0.58287 (18) | 0.0667 (8) | |
H30A | 0.9049 | 1.0413 | 0.6166 | 0.080* | |
C31 | 1.09599 (17) | 0.89874 (12) | 0.71842 (14) | 0.0375 (5) | |
C32 | 1.1251 (2) | 0.83544 (15) | 0.6761 (2) | 0.0653 (8) | |
H32A | 1.0767 | 0.8015 | 0.6514 | 0.078* | |
C33 | 1.2243 (2) | 0.82208 (18) | 0.6701 (2) | 0.0790 (10) | |
H33A | 1.2425 | 0.7793 | 0.6411 | 0.095* | |
C34 | 1.2968 (2) | 0.87061 (17) | 0.7062 (2) | 0.0651 (8) | |
H34A | 1.3639 | 0.8613 | 0.7015 | 0.078* | |
C35 | 1.2700 (2) | 0.93291 (17) | 0.74934 (19) | 0.0627 (8) | |
H35A | 1.3192 | 0.9658 | 0.7749 | 0.075* | |
C36 | 1.1702 (2) | 0.94759 (14) | 0.75541 (16) | 0.0510 (6) | |
H36A | 1.1527 | 0.9905 | 0.7845 | 0.061* | |
O4 | 0.79309 (14) | 1.11428 (11) | 0.74249 (13) | 0.0657 (5) | |
O5 | 0.80158 (17) | 1.20439 (13) | 0.65210 (14) | 0.0805 (7) | |
O6 | 0.93558 (15) | 1.16341 (10) | 0.72664 (13) | 0.0633 (5) | |
N6 | 0.84259 (17) | 1.16112 (11) | 0.70640 (13) | 0.0491 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.05831 (14) | 0.03519 (10) | 0.04811 (12) | −0.00184 (8) | 0.01032 (9) | 0.00993 (7) |
P1 | 0.0373 (3) | 0.0311 (3) | 0.0351 (3) | −0.0013 (2) | 0.0027 (2) | 0.0041 (2) |
N1 | 0.0577 (13) | 0.0366 (10) | 0.0397 (11) | −0.0034 (9) | 0.0091 (10) | 0.0045 (8) |
N2 | 0.0566 (12) | 0.0355 (10) | 0.0369 (10) | −0.0108 (9) | 0.0071 (9) | 0.0011 (8) |
C1 | 0.0471 (14) | 0.0276 (10) | 0.0387 (12) | 0.0007 (9) | 0.0114 (10) | −0.0014 (9) |
C2 | 0.0543 (15) | 0.0431 (13) | 0.0442 (13) | −0.0147 (11) | 0.0061 (12) | 0.0017 (10) |
C3 | 0.0578 (16) | 0.0465 (14) | 0.0392 (13) | −0.0078 (12) | −0.0010 (12) | 0.0005 (10) |
C4 | 0.0482 (15) | 0.0386 (12) | 0.0501 (14) | −0.0045 (11) | 0.0134 (12) | 0.0030 (10) |
C5 | 0.0403 (13) | 0.0385 (12) | 0.0409 (12) | −0.0020 (10) | 0.0066 (10) | −0.0008 (9) |
C6 | 0.0482 (14) | 0.0338 (12) | 0.0389 (12) | 0.0031 (10) | 0.0062 (10) | 0.0037 (9) |
C7 | 0.0356 (12) | 0.0386 (12) | 0.0370 (11) | −0.0026 (10) | 0.0015 (10) | 0.0032 (9) |
C8 | 0.0396 (13) | 0.0428 (13) | 0.0430 (13) | −0.0021 (11) | 0.0018 (10) | 0.0030 (10) |
C9 | 0.0505 (15) | 0.0582 (16) | 0.0432 (14) | 0.0058 (13) | 0.0017 (12) | 0.0107 (12) |
C10 | 0.0639 (19) | 0.077 (2) | 0.0447 (15) | 0.0014 (16) | −0.0083 (14) | 0.0008 (14) |
C11 | 0.087 (2) | 0.068 (2) | 0.069 (2) | −0.0174 (18) | −0.0184 (18) | −0.0148 (17) |
C12 | 0.076 (2) | 0.0456 (15) | 0.0625 (18) | −0.0130 (14) | −0.0107 (15) | 0.0013 (13) |
C13 | 0.0378 (12) | 0.0271 (10) | 0.0414 (12) | 0.0011 (9) | 0.0047 (10) | 0.0028 (9) |
C14 | 0.0436 (14) | 0.0559 (15) | 0.0420 (13) | 0.0070 (12) | 0.0053 (11) | 0.0023 (11) |
C15 | 0.0569 (17) | 0.0577 (16) | 0.0513 (15) | 0.0070 (13) | 0.0216 (13) | 0.0025 (12) |
C16 | 0.0458 (15) | 0.0426 (14) | 0.0736 (18) | −0.0047 (11) | 0.0220 (14) | −0.0042 (12) |
C17 | 0.0432 (15) | 0.0631 (17) | 0.0648 (18) | −0.0096 (13) | 0.0006 (13) | −0.0091 (14) |
C18 | 0.0435 (14) | 0.0618 (16) | 0.0414 (13) | −0.0065 (12) | 0.0042 (11) | −0.0008 (11) |
N5 | 0.0490 (13) | 0.0349 (10) | 0.0524 (12) | −0.0002 (9) | 0.0035 (10) | 0.0004 (9) |
O1 | 0.0670 (13) | 0.0566 (12) | 0.0860 (15) | −0.0006 (10) | −0.0077 (11) | −0.0247 (11) |
O2 | 0.0462 (12) | 0.0701 (13) | 0.1033 (17) | 0.0098 (10) | −0.0036 (11) | −0.0253 (12) |
O3 | 0.0554 (11) | 0.0468 (10) | 0.0789 (13) | 0.0029 (9) | 0.0145 (10) | −0.0116 (9) |
Ag2 | 0.06975 (15) | 0.03882 (11) | 0.04263 (11) | 0.00932 (9) | 0.00868 (10) | −0.00563 (7) |
P2 | 0.0415 (3) | 0.0350 (3) | 0.0331 (3) | 0.0060 (2) | 0.0000 (2) | −0.0023 (2) |
N3 | 0.0518 (12) | 0.0370 (10) | 0.0359 (10) | 0.0055 (9) | 0.0080 (9) | −0.0002 (8) |
N4 | 0.0549 (12) | 0.0373 (10) | 0.0375 (10) | 0.0090 (9) | 0.0035 (9) | −0.0009 (8) |
C19 | 0.0414 (13) | 0.0319 (11) | 0.0351 (11) | −0.0040 (9) | 0.0094 (10) | 0.0015 (8) |
C20 | 0.0528 (15) | 0.0391 (12) | 0.0435 (13) | 0.0118 (11) | 0.0069 (11) | −0.0017 (10) |
C21 | 0.0531 (15) | 0.0416 (13) | 0.0399 (13) | 0.0102 (11) | 0.0011 (11) | 0.0028 (10) |
C22 | 0.0446 (14) | 0.0408 (12) | 0.0413 (12) | 0.0059 (10) | 0.0153 (11) | 0.0006 (10) |
C23 | 0.0339 (12) | 0.0446 (13) | 0.0382 (12) | 0.0041 (10) | 0.0080 (10) | 0.0057 (9) |
C24 | 0.0429 (14) | 0.0450 (13) | 0.0404 (12) | −0.0036 (11) | 0.0050 (11) | −0.0047 (10) |
C25 | 0.0397 (13) | 0.0559 (15) | 0.0355 (12) | 0.0068 (11) | 0.0029 (10) | 0.0023 (10) |
C26 | 0.106 (3) | 0.0630 (18) | 0.0417 (15) | −0.0123 (18) | −0.0143 (16) | 0.0013 (13) |
C27 | 0.131 (3) | 0.095 (3) | 0.0457 (18) | −0.024 (2) | −0.022 (2) | −0.0008 (18) |
C28 | 0.086 (2) | 0.116 (3) | 0.0387 (16) | −0.011 (2) | −0.0148 (16) | 0.0131 (18) |
C29 | 0.109 (3) | 0.084 (2) | 0.059 (2) | 0.021 (2) | −0.003 (2) | 0.0264 (18) |
C30 | 0.088 (2) | 0.0589 (18) | 0.0502 (16) | 0.0185 (16) | −0.0011 (16) | 0.0041 (13) |
C31 | 0.0379 (12) | 0.0339 (11) | 0.0391 (12) | 0.0012 (9) | −0.0007 (10) | 0.0031 (9) |
C32 | 0.0450 (16) | 0.0501 (16) | 0.101 (2) | −0.0025 (12) | 0.0124 (15) | −0.0291 (15) |
C33 | 0.0511 (18) | 0.0581 (18) | 0.131 (3) | 0.0046 (15) | 0.0245 (19) | −0.0241 (19) |
C34 | 0.0396 (15) | 0.0589 (18) | 0.098 (2) | 0.0030 (13) | 0.0137 (15) | 0.0223 (17) |
C35 | 0.0469 (16) | 0.0601 (17) | 0.077 (2) | −0.0155 (14) | −0.0066 (14) | 0.0088 (15) |
C36 | 0.0521 (16) | 0.0412 (13) | 0.0574 (15) | −0.0056 (12) | −0.0013 (12) | −0.0035 (11) |
O4 | 0.0570 (12) | 0.0579 (11) | 0.0846 (14) | 0.0015 (9) | 0.0180 (10) | 0.0247 (10) |
O5 | 0.0800 (15) | 0.0818 (15) | 0.0767 (14) | 0.0109 (12) | −0.0008 (11) | 0.0417 (12) |
O6 | 0.0508 (12) | 0.0524 (11) | 0.0853 (14) | −0.0042 (9) | 0.0028 (10) | 0.0144 (10) |
N6 | 0.0558 (14) | 0.0401 (11) | 0.0516 (12) | 0.0052 (10) | 0.0084 (11) | 0.0075 (9) |
Ag1—N1i | 2.2089 (19) | Ag2—N3ii | 2.1889 (19) |
Ag1—P1 | 2.3630 (8) | Ag2—P2 | 2.3528 (8) |
Ag1—O2 | 2.636 (2) | Ag2—O4 | 2.635 (2) |
Ag1—O3 | 2.708 (2) | Ag2—O6 | 2.634 (2) |
P1—C7 | 1.820 (2) | P2—C31 | 1.822 (2) |
P1—C13 | 1.828 (2) | P2—C25 | 1.827 (2) |
P1—C6 | 1.870 (2) | P2—C24 | 1.856 (2) |
N1—C4 | 1.341 (3) | N3—C22 | 1.345 (3) |
N1—C3 | 1.343 (3) | N3—C21 | 1.346 (3) |
N1—Ag1i | 2.2089 (19) | N3—Ag2ii | 2.1889 (19) |
N2—C1 | 1.352 (3) | N4—C19 | 1.352 (3) |
N2—C6 | 1.436 (3) | N4—C24 | 1.436 (3) |
N2—H2B | 0.8601 | N4—H4B | 0.8591 |
C1—C2 | 1.400 (3) | C19—C23 | 1.403 (3) |
C1—C5 | 1.406 (3) | C19—C20 | 1.406 (3) |
C2—C3 | 1.361 (3) | C20—C21 | 1.376 (3) |
C2—H2A | 0.9300 | C20—H20A | 0.9300 |
C3—H3A | 0.9300 | C21—H21A | 0.9300 |
C4—C5 | 1.369 (3) | C22—C23 | 1.370 (3) |
C4—H4A | 0.9300 | C22—H22A | 0.9300 |
C5—H5A | 0.9300 | C23—H23A | 0.9300 |
C6—H6A | 0.9700 | C24—H24A | 0.9700 |
C6—H6B | 0.9700 | C24—H24B | 0.9700 |
C7—C12 | 1.380 (3) | C25—C30 | 1.368 (4) |
C7—C8 | 1.386 (3) | C25—C26 | 1.385 (4) |
C8—C9 | 1.372 (3) | C26—C27 | 1.368 (4) |
C8—H8A | 0.9300 | C26—H26A | 0.9300 |
C9—C10 | 1.374 (4) | C27—C28 | 1.350 (5) |
C9—H9A | 0.9300 | C27—H27A | 0.9300 |
C10—C11 | 1.358 (4) | C28—C29 | 1.359 (5) |
C10—H10A | 0.9300 | C28—H28A | 0.9300 |
C11—C12 | 1.391 (4) | C29—C30 | 1.388 (4) |
C11—H11A | 0.9300 | C29—H29A | 0.9300 |
C12—H12A | 0.9300 | C30—H30A | 0.9300 |
C13—C18 | 1.386 (3) | C31—C32 | 1.381 (3) |
C13—C14 | 1.395 (3) | C31—C36 | 1.387 (3) |
C14—C15 | 1.380 (3) | C32—C33 | 1.371 (4) |
C14—H14A | 0.9300 | C32—H32A | 0.9300 |
C15—C16 | 1.378 (4) | C33—C34 | 1.363 (4) |
C15—H15A | 0.9300 | C33—H33A | 0.9300 |
C16—C17 | 1.372 (4) | C34—C35 | 1.364 (4) |
C16—H16A | 0.9300 | C34—H34A | 0.9300 |
C17—C18 | 1.392 (4) | C35—C36 | 1.381 (4) |
C17—H17A | 0.9300 | C35—H35A | 0.9300 |
C18—H18A | 0.9300 | C36—H36A | 0.9300 |
N5—O1 | 1.233 (3) | O4—N6 | 1.244 (3) |
N5—O3 | 1.246 (2) | O5—N6 | 1.228 (3) |
N5—O2 | 1.247 (3) | O6—N6 | 1.251 (3) |
N1i—Ag1—P1 | 153.01 (5) | N3ii—Ag2—P2 | 149.81 (5) |
C7—P1—C13 | 102.59 (10) | C31—P2—C25 | 104.32 (10) |
C7—P1—C6 | 103.57 (10) | C31—P2—C24 | 103.55 (10) |
C13—P1—C6 | 105.01 (10) | C25—P2—C24 | 104.37 (11) |
C7—P1—Ag1 | 116.83 (7) | C31—P2—Ag2 | 112.09 (7) |
C13—P1—Ag1 | 115.28 (7) | C25—P2—Ag2 | 114.37 (8) |
C6—P1—Ag1 | 112.13 (8) | C24—P2—Ag2 | 116.81 (8) |
C4—N1—C3 | 115.4 (2) | C22—N3—C21 | 116.2 (2) |
C4—N1—Ag1i | 124.02 (16) | C22—N3—Ag2ii | 122.55 (15) |
C3—N1—Ag1i | 119.98 (17) | C21—N3—Ag2ii | 121.07 (16) |
C1—N2—C6 | 126.68 (19) | C19—N4—C24 | 124.83 (19) |
C1—N2—H2B | 116.7 | C19—N4—H4B | 117.6 |
C6—N2—H2B | 116.7 | C24—N4—H4B | 117.6 |
N2—C1—C2 | 119.5 (2) | N4—C19—C23 | 123.6 (2) |
N2—C1—C5 | 124.2 (2) | N4—C19—C20 | 119.7 (2) |
C2—C1—C5 | 116.3 (2) | C23—C19—C20 | 116.7 (2) |
C3—C2—C1 | 120.0 (2) | C21—C20—C19 | 119.6 (2) |
C3—C2—H2A | 120.0 | C21—C20—H20A | 120.2 |
C1—C2—H2A | 120.0 | C19—C20—H20A | 120.2 |
N1—C3—C2 | 124.4 (2) | N3—C21—C20 | 123.7 (2) |
N1—C3—H3A | 117.8 | N3—C21—H21A | 118.2 |
C2—C3—H3A | 117.8 | C20—C21—H21A | 118.2 |
N1—C4—C5 | 125.0 (2) | N3—C22—C23 | 124.6 (2) |
N1—C4—H4A | 117.5 | N3—C22—H22A | 117.7 |
C5—C4—H4A | 117.5 | C23—C22—H22A | 117.7 |
C4—C5—C1 | 118.9 (2) | C22—C23—C19 | 119.1 (2) |
C4—C5—H5A | 120.5 | C22—C23—H23A | 120.5 |
C1—C5—H5A | 120.5 | C19—C23—H23A | 120.5 |
N2—C6—P1 | 113.85 (16) | N4—C24—P2 | 113.48 (16) |
N2—C6—H6A | 108.8 | N4—C24—H24A | 108.9 |
P1—C6—H6A | 108.8 | P2—C24—H24A | 108.9 |
N2—C6—H6B | 108.8 | N4—C24—H24B | 108.9 |
P1—C6—H6B | 108.8 | P2—C24—H24B | 108.9 |
H6A—C6—H6B | 107.7 | H24A—C24—H24B | 107.7 |
C12—C7—C8 | 118.3 (2) | C30—C25—C26 | 117.8 (2) |
C12—C7—P1 | 119.84 (19) | C30—C25—P2 | 117.8 (2) |
C8—C7—P1 | 121.53 (17) | C26—C25—P2 | 124.3 (2) |
C9—C8—C7 | 121.1 (2) | C27—C26—C25 | 120.7 (3) |
C9—C8—H8A | 119.5 | C27—C26—H26A | 119.6 |
C7—C8—H8A | 119.5 | C25—C26—H26A | 119.6 |
C8—C9—C10 | 119.9 (3) | C28—C27—C26 | 120.7 (3) |
C8—C9—H9A | 120.0 | C28—C27—H27A | 119.6 |
C10—C9—H9A | 120.0 | C26—C27—H27A | 119.6 |
C11—C10—C9 | 120.0 (3) | C27—C28—C29 | 120.1 (3) |
C11—C10—H10A | 120.0 | C27—C28—H28A | 120.0 |
C9—C10—H10A | 120.0 | C29—C28—H28A | 120.0 |
C10—C11—C12 | 120.5 (3) | C28—C29—C30 | 119.6 (3) |
C10—C11—H11A | 119.7 | C28—C29—H29A | 120.2 |
C12—C11—H11A | 119.7 | C30—C29—H29A | 120.2 |
C7—C12—C11 | 120.1 (3) | C25—C30—C29 | 121.1 (3) |
C7—C12—H12A | 119.9 | C25—C30—H30A | 119.4 |
C11—C12—H12A | 119.9 | C29—C30—H30A | 119.4 |
C18—C13—C14 | 117.8 (2) | C32—C31—C36 | 118.0 (2) |
C18—C13—P1 | 119.97 (17) | C32—C31—P2 | 122.79 (19) |
C14—C13—P1 | 122.13 (18) | C36—C31—P2 | 119.20 (18) |
C15—C14—C13 | 121.1 (2) | C33—C32—C31 | 120.8 (3) |
C15—C14—H14A | 119.5 | C33—C32—H32A | 119.6 |
C13—C14—H14A | 119.5 | C31—C32—H32A | 119.6 |
C16—C15—C14 | 120.3 (2) | C34—C33—C32 | 120.9 (3) |
C16—C15—H15A | 119.9 | C34—C33—H33A | 119.6 |
C14—C15—H15A | 119.9 | C32—C33—H33A | 119.6 |
C17—C16—C15 | 119.7 (2) | C33—C34—C35 | 119.4 (3) |
C17—C16—H16A | 120.1 | C33—C34—H34A | 120.3 |
C15—C16—H16A | 120.1 | C35—C34—H34A | 120.3 |
C16—C17—C18 | 120.1 (3) | C34—C35—C36 | 120.5 (3) |
C16—C17—H17A | 120.0 | C34—C35—H35A | 119.8 |
C18—C17—H17A | 120.0 | C36—C35—H35A | 119.8 |
C13—C18—C17 | 121.1 (2) | C35—C36—C31 | 120.5 (2) |
C13—C18—H18A | 119.5 | C35—C36—H36A | 119.8 |
C17—C18—H18A | 119.5 | C31—C36—H36A | 119.8 |
O1—N5—O3 | 121.4 (2) | O5—N6—O4 | 121.1 (2) |
O1—N5—O2 | 120.2 (2) | O5—N6—O6 | 120.4 (2) |
O3—N5—O2 | 118.4 (2) | O4—N6—O6 | 118.6 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1iii | 0.86 | 2.22 | 3.078 (3) | 172 |
N2—H2B···O2iii | 0.86 | 2.49 | 3.120 (3) | 131 |
N4—H4B···O6iv | 0.86 | 2.12 | 2.941 (3) | 158 |
C24—H24A···O3v | 0.97 | 2.46 | 3.365 (3) | 155 |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x, −y+3/2, z+1/2. |
Experimental details
(1) | (2) | |
Crystal data | ||
Chemical formula | [Ag2(C18H17N2P)2](ClO4)2·C2H3N | [Ag2(C18H17N2P)2(NO3)2] |
Mr | 1040.31 | 924.37 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 293 | 296 |
a, b, c (Å) | 11.928 (2), 18.192 (3), 19.026 (3) | 13.448 (5), 17.498 (6), 16.006 (5) |
β (°) | 91.988 (3) | 97.475 (4) |
V (Å3) | 4126.0 (12) | 3734 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.21 | 1.19 |
Crystal size (mm) | 0.46 × 0.34 × 0.25 | 0.20 × 0.10 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.605, 0.751 | 0.797, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10757, 4447, 2995 | 24006, 8472, 6592 |
Rint | 0.026 | 0.029 |
(sin θ/λ)max (Å−1) | 0.642 | 0.651 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.139, 1.04 | 0.030, 0.081, 1.02 |
No. of reflections | 4447 | 8472 |
No. of parameters | 267 | 469 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.98 | 0.38, −0.89 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL97 (Sheldrick, 2008).
Ag1—N1i | 2.152 (3) | Ag1—N3 | 2.855 (10) |
Ag1—P1 | 2.3560 (10) | Ag1—O2ii | 3.171 (5) |
N1i—Ag1—P1 | 174.00 (9) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O3 | 0.86 | 2.16 | 2.966 (5) | 155.2 |
C4—H4A···O2ii | 0.93 | 2.49 | 3.213 (5) | 134.4 |
Symmetry code: (ii) x, −y+1, z+1/2. |
Ag1—N1i | 2.2089 (19) | Ag2—N3ii | 2.1889 (19) |
Ag1—P1 | 2.3630 (8) | Ag2—P2 | 2.3528 (8) |
Ag1—O2 | 2.636 (2) | Ag2—O4 | 2.635 (2) |
Ag1—O3 | 2.708 (2) | Ag2—O6 | 2.634 (2) |
N1i—Ag1—P1 | 153.01 (5) | N3ii—Ag2—P2 | 149.81 (5) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1iii | 0.86 | 2.22 | 3.078 (3) | 171.7 |
N2—H2B···O2iii | 0.86 | 2.49 | 3.120 (3) | 131.1 |
N4—H4B···O6iv | 0.86 | 2.12 | 2.941 (3) | 158.4 |
C24—H24A···O3v | 0.97 | 2.46 | 3.365 (3) | 155.2 |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x, −y+3/2, z+1/2. |