In the title supramolecular complex, [Ag2Cl2(C4H5N3)(C18H15P)2]n, a one-dimensional chain is formed by dimeric {Ag2Cl2(PPh3)2} units bridged by 2-aminopyrimidine moieties. The Ag atoms are four-coordinate, with an AgCl2NP core. A crystallographic inversion centre is located in the centre of the Ag2Cl2 chelate ring, while the crystallographic twofold axis bisects the 2-aminopyrimidine ligand.
Supporting information
CCDC reference: 182980
The synthesis of (I) was carried out by the reaction of AgCl (0.143 g, 1 mmol),
PPh3 (0.26 g, 1 mmol) and 2-aminopyrimidine (0.10 g, 1 mmol) in CH2Cl2
(20 ml) solution at room temperature for 6 h. The solution was then filtered.
It is of interest that white crystals of (I) were obtained from slow
evaporation of a pale-red solution.
The coordinates and equivalent isotropic displacement parameters for H atoms
were refined by difference Fourier synthesis. The final difference Fourier
maps showed highest and lowest electron densities of 0.439 and -0.355 e Å-3, respectively.
Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1994) or XSCANS?; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
catena-Poly[[di-µ-chloro-bis[(triphenylphosphine)silver(I)]]-µ-
2-aminopyrimidine-
κ2N1:
N3]
top
Crystal data top
[Ag2Cl2(C18H15P)2(C4H5N3)] | F(000) = 1816 |
Mr = 906.29 | Dx = 1.587 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.055 (2) Å | Cell parameters from 26 reflections |
b = 16.642 (4) Å | θ = 2.9–15.8° |
c = 15.302 (2) Å | µ = 1.29 mm−1 |
β = 119.13 (1)° | T = 295 K |
V = 3793.9 (11) Å3 | Prism, white |
Z = 4 | 0.46 × 0.46 × 0.40 mm |
Data collection top
Siemens P-4 diffractometer | 2779 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 25.3°, θmin = 1.8° |
ω scans | h = 0→20 |
Absorption correction: empirical (using intensity measurements) Please provide reference | k = 0→19 |
Tmin = 0.518, Tmax = 0.637 | l = −18→16 |
3810 measured reflections | 3 standard reflections every 97 reflections |
3429 independent reflections | intensity decay: 1.4% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0295P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3429 reflections | Δρmax = 0.36 e Å−3 |
294 parameters | Δρmin = −0.35 e Å−3 |
18 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00347 (11) |
Crystal data top
[Ag2Cl2(C18H15P)2(C4H5N3)] | V = 3793.9 (11) Å3 |
Mr = 906.29 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.055 (2) Å | µ = 1.29 mm−1 |
b = 16.642 (4) Å | T = 295 K |
c = 15.302 (2) Å | 0.46 × 0.46 × 0.40 mm |
β = 119.13 (1)° | |
Data collection top
Siemens P-4 diffractometer | 2779 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) Please provide reference | Rint = 0.019 |
Tmin = 0.518, Tmax = 0.637 | 3 standard reflections every 97 reflections |
3810 measured reflections | intensity decay: 1.4% |
3429 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 18 restraints |
wR(F2) = 0.058 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.36 e Å−3 |
3429 reflections | Δρmin = −0.35 e Å−3 |
294 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ag | 0.408369 (13) | 0.478158 (14) | 0.398313 (15) | 0.04607 (10) | |
Cl | 0.48746 (5) | 0.38441 (4) | 0.54771 (5) | 0.04695 (18) | |
P | 0.25461 (4) | 0.52073 (4) | 0.31224 (5) | 0.03521 (16) | |
N1 | 0.48195 (14) | 0.41581 (13) | 0.31609 (16) | 0.0422 (5) | |
N2 | 0.5000 | 0.5333 (2) | 0.2500 | 0.0541 (9) | |
C2 | 0.5000 | 0.4534 (2) | 0.2500 | 0.0357 (8) | |
C5 | 0.5000 | 0.2927 (3) | 0.2500 | 0.0600 (12) | |
C6 | 0.4852 (2) | 0.33603 (18) | 0.3164 (2) | 0.0538 (8) | |
C7 | 0.22927 (15) | 0.58938 (15) | 0.20913 (18) | 0.0347 (6) | |
C8 | 0.26633 (19) | 0.57086 (19) | 0.1484 (2) | 0.0487 (7) | |
C9 | 0.2476 (2) | 0.6169 (2) | 0.0656 (2) | 0.0587 (8) | |
C10 | 0.1912 (2) | 0.68168 (19) | 0.0415 (2) | 0.0534 (8) | |
C11 | 0.1547 (2) | 0.70060 (19) | 0.1008 (2) | 0.0539 (8) | |
C12 | 0.17401 (19) | 0.65535 (18) | 0.1844 (2) | 0.0480 (7) | |
C13 | 0.17024 (16) | 0.44192 (15) | 0.25202 (18) | 0.0359 (6) | |
C14 | 0.19122 (19) | 0.36443 (17) | 0.2882 (2) | 0.0466 (7) | |
C15 | 0.1290 (2) | 0.30336 (18) | 0.2451 (2) | 0.0571 (8) | |
C16 | 0.0457 (2) | 0.31956 (19) | 0.1656 (2) | 0.0551 (8) | |
C17 | 0.02441 (19) | 0.39624 (19) | 0.1289 (2) | 0.0546 (8) | |
C18 | 0.08687 (18) | 0.45719 (17) | 0.1714 (2) | 0.0476 (7) | |
C19 | 0.22025 (16) | 0.57232 (16) | 0.39315 (18) | 0.0371 (6) | |
C20 | 0.2851 (2) | 0.6129 (2) | 0.4746 (2) | 0.0633 (9) | |
C21 | 0.2641 (3) | 0.6517 (3) | 0.5405 (3) | 0.0810 (11) | |
C22 | 0.1788 (2) | 0.6503 (2) | 0.5258 (3) | 0.0680 (9) | |
C23 | 0.1138 (2) | 0.6107 (2) | 0.4457 (3) | 0.0673 (9) | |
C24 | 0.13348 (19) | 0.5707 (2) | 0.3794 (2) | 0.0573 (8) | |
H2N | 0.496 (2) | 0.5620 (15) | 0.2935 (17) | 0.056 (9)* | |
H5 | 0.5000 | 0.2369 (7) | 0.2500 | 0.064 (13)* | |
H6 | 0.4768 (16) | 0.3119 (13) | 0.3661 (14) | 0.041 (7)* | |
H8 | 0.3045 (16) | 0.5264 (11) | 0.169 (2) | 0.059 (9)* | |
H9 | 0.272 (2) | 0.6049 (19) | 0.025 (2) | 0.080 (11)* | |
H10 | 0.1724 (18) | 0.7110 (15) | −0.0170 (13) | 0.063 (9)* | |
H11 | 0.1176 (17) | 0.7445 (13) | 0.086 (2) | 0.075 (10)* | |
H12 | 0.1479 (16) | 0.6681 (16) | 0.2231 (17) | 0.054 (8)* | |
H14 | 0.2482 (9) | 0.3545 (16) | 0.3421 (13) | 0.053 (8)* | |
H15 | 0.1430 (19) | 0.2513 (9) | 0.269 (2) | 0.072 (10)* | |
H16 | 0.0063 (15) | 0.2766 (12) | 0.140 (2) | 0.061 (9)* | |
H17 | −0.0317 (10) | 0.4088 (17) | 0.0758 (14) | 0.059 (9)* | |
H18 | 0.0696 (17) | 0.5085 (9) | 0.1425 (19) | 0.049 (8)* | |
H20 | 0.3431 (10) | 0.6157 (19) | 0.485 (2) | 0.072 (10)* | |
H21 | 0.3077 (16) | 0.6807 (18) | 0.5939 (17) | 0.085 (11)* | |
H22 | 0.1644 (18) | 0.6741 (15) | 0.5706 (17) | 0.058 (9)* | |
H23 | 0.0548 (10) | 0.616 (2) | 0.434 (2) | 0.086 (11)* | |
H24 | 0.0887 (15) | 0.5448 (17) | 0.3231 (15) | 0.068 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag | 0.03322 (13) | 0.05696 (16) | 0.04458 (14) | 0.00706 (10) | 0.01622 (10) | 0.00312 (11) |
Cl | 0.0634 (4) | 0.0366 (4) | 0.0382 (3) | −0.0044 (3) | 0.0227 (3) | 0.0021 (3) |
P | 0.0293 (3) | 0.0367 (4) | 0.0365 (3) | 0.0013 (3) | 0.0135 (3) | 0.0006 (3) |
N1 | 0.0476 (13) | 0.0450 (14) | 0.0427 (12) | 0.0000 (11) | 0.0287 (11) | 0.0021 (11) |
N2 | 0.079 (3) | 0.045 (2) | 0.057 (2) | 0.000 | 0.048 (2) | 0.000 |
C2 | 0.0315 (18) | 0.043 (2) | 0.0341 (19) | 0.000 | 0.0169 (16) | 0.000 |
C5 | 0.085 (3) | 0.038 (2) | 0.077 (3) | 0.000 | 0.055 (3) | 0.000 |
C6 | 0.070 (2) | 0.0492 (19) | 0.0591 (19) | −0.0045 (16) | 0.0447 (17) | 0.0037 (16) |
C7 | 0.0298 (12) | 0.0358 (14) | 0.0366 (13) | −0.0044 (11) | 0.0146 (11) | −0.0008 (11) |
C8 | 0.0511 (17) | 0.0501 (18) | 0.0480 (16) | 0.0091 (15) | 0.0266 (14) | 0.0038 (15) |
C9 | 0.064 (2) | 0.072 (2) | 0.0501 (18) | −0.0040 (18) | 0.0350 (17) | 0.0013 (17) |
C10 | 0.0511 (18) | 0.0537 (19) | 0.0475 (18) | −0.0113 (15) | 0.0178 (15) | 0.0094 (15) |
C11 | 0.0512 (18) | 0.0448 (18) | 0.064 (2) | 0.0091 (15) | 0.0270 (16) | 0.0151 (15) |
C12 | 0.0490 (16) | 0.0478 (17) | 0.0559 (18) | 0.0051 (14) | 0.0323 (15) | 0.0059 (14) |
C13 | 0.0348 (13) | 0.0371 (14) | 0.0374 (13) | −0.0002 (11) | 0.0190 (11) | −0.0014 (12) |
C14 | 0.0479 (17) | 0.0427 (17) | 0.0440 (16) | 0.0003 (14) | 0.0182 (14) | 0.0039 (13) |
C15 | 0.074 (2) | 0.0373 (17) | 0.063 (2) | −0.0046 (16) | 0.0359 (18) | 0.0035 (16) |
C16 | 0.0544 (19) | 0.052 (2) | 0.061 (2) | −0.0200 (16) | 0.0301 (17) | −0.0158 (16) |
C17 | 0.0371 (16) | 0.0508 (19) | 0.062 (2) | −0.0055 (14) | 0.0133 (15) | −0.0104 (16) |
C18 | 0.0379 (15) | 0.0385 (17) | 0.0563 (18) | 0.0017 (12) | 0.0151 (13) | −0.0008 (14) |
C19 | 0.0359 (13) | 0.0401 (15) | 0.0360 (13) | −0.0011 (12) | 0.0182 (11) | 0.0023 (12) |
C20 | 0.0412 (17) | 0.086 (2) | 0.063 (2) | −0.0106 (17) | 0.0249 (16) | −0.0277 (18) |
C21 | 0.067 (2) | 0.105 (3) | 0.070 (2) | −0.021 (2) | 0.034 (2) | −0.046 (2) |
C22 | 0.079 (2) | 0.080 (3) | 0.066 (2) | −0.001 (2) | 0.052 (2) | −0.0138 (19) |
C23 | 0.055 (2) | 0.088 (3) | 0.074 (2) | −0.0105 (19) | 0.0441 (19) | −0.019 (2) |
C24 | 0.0429 (16) | 0.075 (2) | 0.0568 (19) | −0.0137 (16) | 0.0266 (15) | −0.0164 (17) |
Geometric parameters (Å, º) top
Ag—P | 2.3981 (7) | C11—C12 | 1.379 (4) |
Ag—N1 | 2.402 (2) | C11—H11 | 0.92 (3) |
Ag—Cl | 2.5451 (8) | C12—H12 | 0.92 (3) |
Ag—Cli | 2.7643 (8) | C13—C18 | 1.379 (4) |
Ag—Agi | 3.2424 (7) | C13—C14 | 1.380 (4) |
Cl—Agi | 2.7643 (8) | C14—C15 | 1.384 (4) |
P—C7 | 1.821 (2) | C14—H14 | 0.933 (10) |
P—C19 | 1.822 (3) | C15—C16 | 1.374 (4) |
P—C13 | 1.830 (3) | C15—H15 | 0.923 (10) |
N1—C6 | 1.329 (4) | C16—C17 | 1.370 (4) |
N1—C2 | 1.346 (3) | C16—H16 | 0.926 (10) |
N2—C2 | 1.329 (5) | C17—C18 | 1.383 (4) |
N2—H2N | 0.85 (3) | C17—H17 | 0.929 (10) |
C2—N1ii | 1.346 (3) | C18—H18 | 0.940 (10) |
C5—C6 | 1.367 (4) | C19—C20 | 1.375 (4) |
C5—C6ii | 1.367 (4) | C19—C24 | 1.390 (4) |
C5—H5 | 0.929 (10) | C20—C21 | 1.382 (4) |
C6—H6 | 0.930 (10) | C20—H20 | 0.926 (10) |
C7—C12 | 1.375 (4) | C21—C22 | 1.361 (5) |
C7—C8 | 1.389 (4) | C21—H21 | 0.93 (3) |
C8—C9 | 1.378 (4) | C22—C23 | 1.357 (5) |
C8—H8 | 0.933 (10) | C22—H22 | 0.92 (3) |
C9—C10 | 1.372 (5) | C23—C24 | 1.386 (4) |
C9—H9 | 0.92 (3) | C23—H23 | 0.935 (10) |
C10—C11 | 1.362 (4) | C24—H24 | 0.932 (10) |
C10—H10 | 0.929 (10) | | |
| | | |
P—Ag—N1 | 123.39 (6) | C10—C11—C12 | 120.8 (3) |
P—Ag—Cl | 129.36 (3) | C10—C11—H11 | 120 (2) |
N1—Ag—Cl | 91.26 (6) | C12—C11—H11 | 119 (2) |
P—Ag—Cli | 106.96 (3) | C7—C12—C11 | 120.9 (3) |
N1—Ag—Cli | 95.18 (6) | C7—C12—H12 | 119.2 (18) |
Cl—Ag—Cli | 104.85 (2) | C11—C12—H12 | 119.9 (18) |
P—Ag—Agi | 138.28 (2) | C18—C13—C14 | 119.0 (2) |
N1—Ag—Agi | 95.41 (5) | C18—C13—P | 122.3 (2) |
Cl—Ag—Agi | 55.50 (2) | C14—C13—P | 118.74 (19) |
Cli—Ag—Agi | 49.354 (16) | C13—C14—C15 | 120.4 (3) |
Ag—Cl—Agi | 75.15 (2) | C13—C14—H14 | 118.3 (17) |
C7—P—C19 | 105.90 (11) | C15—C14—H14 | 121.3 (17) |
C7—P—C13 | 102.50 (11) | C16—C15—C14 | 120.1 (3) |
C19—P—C13 | 104.23 (11) | C16—C15—H15 | 119.3 (19) |
C7—P—Ag | 113.33 (8) | C14—C15—H15 | 121 (2) |
C19—P—Ag | 113.17 (8) | C17—C16—C15 | 120.0 (3) |
C13—P—Ag | 116.51 (8) | C17—C16—H16 | 123.7 (18) |
C6—N1—C2 | 116.3 (2) | C15—C16—H16 | 116.3 (18) |
C6—N1—Ag | 117.44 (17) | C16—C17—C18 | 120.0 (3) |
C2—N1—Ag | 124.15 (19) | C16—C17—H17 | 121.6 (18) |
C2—N2—H2N | 124 (2) | C18—C17—H17 | 118.4 (18) |
N2—C2—N1 | 117.71 (17) | C13—C18—C17 | 120.6 (3) |
N2—C2—N1ii | 117.71 (17) | C13—C18—H18 | 122.6 (17) |
N1—C2—N1ii | 124.6 (3) | C17—C18—H18 | 116.8 (17) |
C6—C5—C6ii | 116.3 (4) | C20—C19—C24 | 118.3 (3) |
C6—C5—H5 | 121.9 (2) | C20—C19—P | 117.7 (2) |
C6ii—C5—H5 | 121.9 (2) | C24—C19—P | 123.9 (2) |
N1—C6—C5 | 123.2 (3) | C19—C20—C21 | 120.8 (3) |
N1—C6—H6 | 114.3 (16) | C19—C20—H20 | 120 (2) |
C5—C6—H6 | 122.5 (16) | C21—C20—H20 | 119 (2) |
C12—C7—C8 | 117.9 (2) | C22—C21—C20 | 120.4 (3) |
C12—C7—P | 125.5 (2) | C22—C21—H21 | 119 (2) |
C8—C7—P | 116.6 (2) | C20—C21—H21 | 120 (2) |
C9—C8—C7 | 121.0 (3) | C23—C22—C21 | 119.7 (3) |
C9—C8—H8 | 124.1 (19) | C23—C22—H22 | 118.9 (18) |
C7—C8—H8 | 114.9 (19) | C21—C22—H22 | 121.3 (18) |
C10—C9—C8 | 120.1 (3) | C22—C23—C24 | 120.8 (3) |
C10—C9—H9 | 118 (2) | C22—C23—H23 | 117 (2) |
C8—C9—H9 | 122 (2) | C24—C23—H23 | 121 (2) |
C11—C10—C9 | 119.4 (3) | C23—C24—C19 | 120.0 (3) |
C11—C10—H10 | 117.8 (18) | C23—C24—H24 | 121.1 (19) |
C9—C10—H10 | 122.6 (19) | C19—C24—H24 | 118.9 (19) |
| | | |
P—Ag—Cl—Agi | −127.42 (3) | P—C7—C8—C9 | 176.8 (2) |
N1—Ag—Cl—Agi | 95.70 (5) | C7—C8—C9—C10 | −0.5 (5) |
N1—Ag—P—C7 | −55.30 (11) | C8—C9—C10—C11 | 0.8 (5) |
Cl—Ag—P—C7 | 179.62 (9) | C9—C10—C11—C12 | 0.0 (5) |
Cli—Ag—P—C7 | 53.00 (9) | C8—C7—C12—C11 | 1.3 (4) |
Agi—Ag—P—C7 | 100.05 (9) | P—C7—C12—C11 | −175.8 (2) |
N1—Ag—P—C19 | −175.89 (11) | C10—C11—C12—C7 | −1.0 (5) |
Cl—Ag—P—C19 | 59.03 (10) | C7—P—C13—C18 | −30.3 (2) |
Cli—Ag—P—C19 | −67.59 (9) | C19—P—C13—C18 | 80.0 (2) |
Agi—Ag—P—C19 | −20.54 (10) | Ag—P—C13—C18 | −154.6 (2) |
N1—Ag—P—C13 | 63.29 (11) | C7—P—C13—C14 | 149.2 (2) |
Cl—Ag—P—C13 | −61.78 (9) | C19—P—C13—C14 | −100.5 (2) |
Cli—Ag—P—C13 | 171.59 (9) | Ag—P—C13—C14 | 24.9 (2) |
Agi—Ag—P—C13 | −141.36 (9) | C18—C13—C14—C15 | −0.9 (4) |
P—Ag—N1—C6 | −95.9 (2) | P—C13—C14—C15 | 179.6 (2) |
Cl—Ag—N1—C6 | 44.8 (2) | C13—C14—C15—C16 | 0.1 (5) |
Cli—Ag—N1—C6 | 149.9 (2) | C14—C15—C16—C17 | 0.2 (5) |
Agi—Ag—N1—C6 | 100.3 (2) | C15—C16—C17—C18 | 0.3 (5) |
P—Ag—N1—C2 | 66.99 (17) | C14—C13—C18—C17 | 1.5 (4) |
Cl—Ag—N1—C2 | −152.27 (16) | P—C13—C18—C17 | −179.0 (2) |
Cli—Ag—N1—C2 | −47.24 (16) | C16—C17—C18—C13 | −1.2 (5) |
Agi—Ag—N1—C2 | −96.82 (16) | C7—P—C19—C20 | −96.5 (3) |
C6—N1—C2—N2 | −177.97 (19) | C13—P—C19—C20 | 155.7 (2) |
Ag—N1—C2—N2 | 18.97 (17) | Ag—P—C19—C20 | 28.2 (3) |
C6—N1—C2—N1ii | 2.03 (19) | C7—P—C19—C24 | 85.8 (3) |
Ag—N1—C2—N1ii | −161.03 (17) | C13—P—C19—C24 | −21.9 (3) |
C2—N1—C6—C5 | −4.2 (4) | Ag—P—C19—C24 | −149.5 (2) |
Ag—N1—C6—C5 | 160.02 (19) | C24—C19—C20—C21 | −0.7 (5) |
C6ii—C5—C6—N1 | 2.2 (2) | P—C19—C20—C21 | −178.4 (3) |
C19—P—C7—C12 | −15.9 (3) | C19—C20—C21—C22 | 0.2 (6) |
C13—P—C7—C12 | 93.1 (2) | C20—C21—C22—C23 | −0.3 (7) |
Ag—P—C7—C12 | −140.5 (2) | C21—C22—C23—C24 | 0.9 (6) |
C19—P—C7—C8 | 167.0 (2) | C22—C23—C24—C19 | −1.4 (6) |
C13—P—C7—C8 | −84.1 (2) | C20—C19—C24—C23 | 1.3 (5) |
Ag—P—C7—C8 | 42.3 (2) | P—C19—C24—C23 | 178.9 (3) |
C12—C7—C8—C9 | −0.5 (4) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cli | 0.85 (1) | 2.47 (1) | 3.2954 (17) | 164 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ag2Cl2(C18H15P)2(C4H5N3)] |
Mr | 906.29 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 17.055 (2), 16.642 (4), 15.302 (2) |
β (°) | 119.13 (1) |
V (Å3) | 3793.9 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.29 |
Crystal size (mm) | 0.46 × 0.46 × 0.40 |
|
Data collection |
Diffractometer | Siemens P-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) Please provide reference |
Tmin, Tmax | 0.518, 0.637 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3810, 3429, 2779 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.600 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.058, 1.03 |
No. of reflections | 3429 |
No. of parameters | 294 |
No. of restraints | 18 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.36, −0.35 |
Selected geometric parameters (Å, º) topAg—P | 2.3981 (7) | Ag—Agi | 3.2424 (7) |
Ag—N1 | 2.402 (2) | Cl—Agi | 2.7643 (8) |
Ag—Cl | 2.5451 (8) | N2—C2 | 1.329 (5) |
Ag—Cli | 2.7643 (8) | N2—H2N | 0.85 (3) |
| | | |
P—Ag—N1 | 123.39 (6) | Cl—Ag—Cli | 104.85 (2) |
P—Ag—Cl | 129.36 (3) | P—Ag—Agi | 138.28 (2) |
N1—Ag—Cl | 91.26 (6) | N1—Ag—Agi | 95.41 (5) |
P—Ag—Cli | 106.96 (3) | Cl—Ag—Agi | 55.50 (2) |
N1—Ag—Cli | 95.18 (6) | Cli—Ag—Agi | 49.354 (16) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cli | 0.849 (10) | 2.472 (13) | 3.2954 (17) | 164 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Recently, we have obtained a series of d10 metal CuI and AgI complexes containing triphenylphosphine and nitrogenous heterocyclic ligands (Jin, Long et al., 1998; Jin, Xin et al., 1998; Jin, Wang & Xin, 1999; Jin, Xin, Deng & Yu, 1999; Jin, Xin, Zhu & Li, 1999). Here, we report the crystal and molecular structure of [Ag2Cl2(PPh3)2(C4H5N3)]n, (I), which is the first AgI complex containing the bridging ligand 2-aminopyrimidine (AMP). This work complements and extends our structural characterization of this series of compounds. We have also recently reported a similar infinite-chain CuI complex, [Cu2I2(PPh3)2(C4H5N3)]n, (II) (Jin et al., 2000). \sch
Our research objective is to synthesize supramolecular complexes using ligands which have the potential to bridge metal atoms. Until now, supramolecular complexes reported in the literature have used a variety of bridging ligands. Both inorganic anion ligands, such as S2- (Huang et al., 1997) and SO42- (Lumme et al., 1996), and neutral organic ligands, such as 4,4'-bipyridine (Lu et al., 1997), pyrazine (Tong et al., 1998) and AMP (Smith et al., 1985; Jin et al., 2000), have been used to synthesize supramolecular complexes.
The structure of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1. The compound has a one-dimensional chain structure, formed by two N atoms from the pyrimidine ring of the 2-aminopyrimidine bridging two dimeric {Ag2Cl2(PPh3)2} units. The pyrimidine ring N atoms are related by a crystallographic twofold axis which bisects the pyrimidine ring.
In the [Ag2Cl2(PPh3)2(C4H5N3)] unit of (I), the Ag atom is in the centre of a distorted coordination tetrahedron. Each Ag atom is coordinated to one P atom from PPh3, two Cl atoms and one N atom from the pyrimidine ring in AMP. As a result of the coordination of the N atom to Ag, the electric charge of AMP is transferred and the AMP molecules are isomerized to the carbamamidine structure, as indicated by the C2—N2 bond length of 1.329 (5) Å; this is similar to what is observed in (II). The Ag2Cl2 ring of (I), just like the Cu2I2 ring of (II), is strictly planar.
The Ag—P distance is slightly shorter in (I) than in [AgCl(PPh3)2]2, (III) (2.469 Å; Cassel, 1979) or [AgXP(C6H11)3]2 (X is Cl, Br or I; Bowmaker et al., 1996). The Ag—Cl distances in (I) agree with those in (III) (2.669 Å). The Ag—N distance is slightly shorter in (I) than in [AgCl(C9H7N)]n (2.27 Å; Mills & White, 1984), or [AgI(3-MeC5H4N)], [2.324 (7) Å], [AgI(C9H7N)]2 [2.32 (2) Å] and [AgI(2-MeC5H4N)]2 [2.352 (9) Å; Healy et al., 1983]. Does this reference apply to all of these last three compounds?
The Ag···Ag distance in (I) is significantly shorter than that in (III) [3.840 (2) Å], while the Cl.·Cl distance of 4.210(?)Å Please provide s.u. in (I) is significantly longer than that in (III) [3.710 (2) Å]. This is because PPh3 is much bigger than AMP, so the effect of the additional steric hindrance of having two PPh3 coordinated to Ag in (III), compared with one PPh3 and one AMP in (I), results in the two Cl atoms being forced closer together, resulting in the longer Ag···Ag and shorter Cl···Cl distances, and larger Ag—Cl—Ag and smaller Cl—Ag—Cl angles, in (III) than in (I).