Buy article online - an online subscription or single-article purchase is required to access this article.
The title compound, [Pd2(C8H4N6)2(C3H9P)4], was prepared by treating Pd(PMe3)2(N3)2 with 1,4-phenylene diisocyanide [C6H4(NC)2]. This compound, a cyclic dimer, was formed by concomitant N—C coupling and [2 + 3]-cycloaddition. Around the square-planar Pd atom, the carbodiimide moiety and the tetrazolate ring are mutually trans. The N atom of the carbodiimide moiety is bonded to the Pd center, and the five-membered tetrazolate ring is coordinated to the Pd atoms through the C atom. The molecule is located on a center of symmetry.
Supporting information
CCDC reference: 258659
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.035
- wR factor = 0.094
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT242_ALERT_2_A Check Low U(eq) as Compared to Neighbors for P2
| Author Response: One trimethylphospine ligand is slightly disordered.
Anisotropic refinements applying several possible site occupation
fators were unstable, and that is why the thermal parameters of the
carbon atoms (C12--C14) in that phosphine ligand are relatively
large compared with those in the other phosphine ligand.
|
Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg.
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.12 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pd1 - C1 .. 5.02 su
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors for C4
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for P1
| Author Response: One trimethylphospine ligand is slightly disordered.
Anisotropic refinements applying several possible site occupation
fators were unstable, and that is why the thermal parameters of the
carbon atoms (C12--C14) in that phosphine ligand are relatively
large compared with those in the other phosphine ligand.
|
1 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
bis{µ-1-[4-(carbodiimido)phenyl]tetrazolato-
κ2N:
C5}
bis[bis(trimethylphosphine-
κP)palladium(II)]
top
Crystal data top
[Pd2(C8H4N6)2(C3H9P)4] | Z = 1 |
Mr = 885.43 | F(000) = 448 |
Triclinic, P1 | Dx = 1.518 Mg m−3 |
a = 8.842 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.519 (3) Å | Cell parameters from 26 reflections |
c = 11.996 (3) Å | θ = 5.1–12.5° |
α = 99.095 (19)° | µ = 1.13 mm−1 |
β = 103.42 (2)° | T = 293 K |
γ = 90.85 (2)° | Block, orange |
V = 968.5 (5) Å3 | 0.50 × 0.42 × 0.20 mm |
Data collection top
Siemens P4 diffractometer | 3039 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
ω scans | h = 0→10 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −11→11 |
Tmin = 0.574, Tmax = 0.798 | l = −14→13 |
3615 measured reflections | 3 standard reflections every 97 reflections |
3374 independent reflections | intensity decay: none |
Refinement top
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.2618P] where P = (Fo2 + 2Fc2)/3 |
3374 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
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 | |
Pd1 | 0.69364 (3) | 0.89012 (2) | 0.684937 (19) | 0.03877 (12) | |
P1 | 0.86814 (11) | 0.71478 (10) | 0.65981 (8) | 0.0497 (2) | |
P2 | 0.52022 (11) | 1.06752 (10) | 0.71136 (8) | 0.0493 (2) | |
N1 | 0.4193 (4) | 0.6818 (3) | 0.6233 (3) | 0.0593 (8) | |
N2 | 0.3520 (4) | 0.5830 (4) | 0.6699 (3) | 0.0675 (9) | |
N3 | 0.4299 (4) | 0.5816 (4) | 0.7766 (3) | 0.0672 (9) | |
N4 | 0.5512 (3) | 0.6819 (3) | 0.7991 (3) | 0.0494 (7) | |
N5 | 0.8589 (4) | 1.0376 (3) | 0.6725 (3) | 0.0571 (7) | |
N6 | 1.0090 (5) | 1.2573 (4) | 0.7705 (3) | 0.0735 (10) | |
C1 | 0.5439 (4) | 0.7435 (3) | 0.7030 (3) | 0.0464 (7) | |
C2 | 0.6636 (4) | 0.7005 (3) | 0.9077 (3) | 0.0474 (8) | |
C3 | 0.6839 (5) | 0.5913 (4) | 0.9737 (4) | 0.0711 (12) | |
H3 | 0.6237 | 0.5065 | 0.9467 | 0.085* | |
C4 | 0.7915 (6) | 0.6077 (4) | 1.0776 (4) | 0.0794 (14) | |
H4 | 0.8032 | 0.5329 | 1.1198 | 0.095* | |
C5 | 0.8845 (5) | 0.7330 (4) | 1.1226 (3) | 0.0553 (9) | |
C6 | 0.8630 (5) | 0.8417 (4) | 1.0558 (3) | 0.0535 (9) | |
H6 | 0.9240 | 0.9261 | 1.0817 | 0.064* | |
C7 | 0.7528 (5) | 0.8257 (4) | 0.9522 (3) | 0.0553 (9) | |
H7 | 0.7380 | 0.9014 | 0.9111 | 0.066* | |
C8 | 0.9326 (4) | 1.1400 (4) | 0.7241 (3) | 0.0525 (8) | |
C9 | 0.8030 (6) | 0.5303 (4) | 0.6480 (5) | 0.0768 (13) | |
H9A | 0.7609 | 0.5195 | 0.7133 | 0.092* | |
H9B | 0.8895 | 0.4707 | 0.6471 | 0.092* | |
H9C | 0.7242 | 0.5030 | 0.5774 | 0.092* | |
C10 | 1.0392 (5) | 0.7415 (6) | 0.7802 (4) | 0.0756 (12) | |
H10A | 1.0084 | 0.7388 | 0.8515 | 0.091* | |
H10B | 1.0904 | 0.8323 | 0.7839 | 0.091* | |
H10C | 1.1093 | 0.6674 | 0.7688 | 0.091* | |
C11 | 0.9429 (6) | 0.7205 (5) | 0.5329 (4) | 0.0775 (13) | |
H11A | 0.9806 | 0.8159 | 0.5339 | 0.093* | |
H11B | 0.8614 | 0.6912 | 0.4643 | 0.093* | |
H11C | 1.0266 | 0.6574 | 0.5330 | 0.093* | |
C12 | 0.5553 (9) | 1.1560 (9) | 0.8590 (5) | 0.145 (3) | |
H12A | 0.5424 | 1.0883 | 0.9079 | 0.174* | |
H12B | 0.4827 | 1.2292 | 0.8649 | 0.174* | |
H12C | 0.6596 | 1.1979 | 0.8832 | 0.174* | |
C13 | 0.3158 (6) | 1.0171 (6) | 0.6672 (7) | 0.111 (2) | |
H13A | 0.2898 | 0.9729 | 0.5870 | 0.133* | |
H13B | 0.2570 | 1.1003 | 0.6768 | 0.133* | |
H13C | 0.2914 | 0.9511 | 0.7141 | 0.133* | |
C14 | 0.5331 (7) | 1.2117 (6) | 0.6326 (7) | 0.106 (2) | |
H14A | 0.5138 | 1.1749 | 0.5511 | 0.128* | |
H14B | 0.6353 | 1.2578 | 0.6589 | 0.128* | |
H14C | 0.4570 | 1.2792 | 0.6460 | 0.128* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd1 | 0.04284 (17) | 0.03285 (16) | 0.04123 (16) | 0.00057 (10) | 0.01206 (11) | 0.00502 (10) |
P1 | 0.0526 (5) | 0.0447 (5) | 0.0551 (5) | 0.0115 (4) | 0.0182 (4) | 0.0091 (4) |
P2 | 0.0540 (5) | 0.0398 (5) | 0.0564 (5) | 0.0080 (4) | 0.0198 (4) | 0.0043 (4) |
N1 | 0.0543 (18) | 0.0523 (18) | 0.0639 (19) | −0.0095 (14) | 0.0049 (15) | 0.0022 (14) |
N2 | 0.0559 (19) | 0.060 (2) | 0.080 (2) | −0.0145 (16) | 0.0080 (17) | 0.0046 (17) |
N3 | 0.062 (2) | 0.0547 (19) | 0.086 (2) | −0.0179 (16) | 0.0230 (19) | 0.0092 (17) |
N4 | 0.0505 (16) | 0.0377 (14) | 0.0610 (17) | −0.0099 (12) | 0.0195 (13) | 0.0026 (12) |
N5 | 0.0537 (18) | 0.0533 (18) | 0.0681 (19) | −0.0030 (15) | 0.0147 (15) | 0.0213 (15) |
N6 | 0.085 (2) | 0.0473 (18) | 0.080 (2) | −0.0100 (17) | −0.0055 (19) | 0.0271 (16) |
C1 | 0.0496 (19) | 0.0374 (17) | 0.0515 (18) | 0.0020 (14) | 0.0132 (15) | 0.0034 (14) |
C2 | 0.0559 (19) | 0.0378 (17) | 0.0537 (19) | −0.0017 (14) | 0.0226 (16) | 0.0086 (14) |
C3 | 0.081 (3) | 0.0355 (19) | 0.091 (3) | −0.0127 (18) | 0.007 (2) | 0.0181 (19) |
C4 | 0.097 (3) | 0.040 (2) | 0.096 (3) | −0.009 (2) | −0.002 (3) | 0.033 (2) |
C5 | 0.066 (2) | 0.0402 (18) | 0.063 (2) | 0.0005 (16) | 0.0146 (18) | 0.0165 (16) |
C6 | 0.076 (2) | 0.0349 (17) | 0.0507 (19) | −0.0119 (16) | 0.0169 (17) | 0.0079 (14) |
C7 | 0.082 (3) | 0.0371 (17) | 0.0500 (19) | −0.0074 (17) | 0.0200 (18) | 0.0117 (14) |
C8 | 0.051 (2) | 0.053 (2) | 0.061 (2) | 0.0070 (17) | 0.0156 (17) | 0.0279 (17) |
C9 | 0.096 (3) | 0.043 (2) | 0.097 (3) | 0.015 (2) | 0.037 (3) | 0.005 (2) |
C10 | 0.057 (2) | 0.092 (3) | 0.075 (3) | 0.021 (2) | 0.007 (2) | 0.016 (2) |
C11 | 0.085 (3) | 0.087 (3) | 0.076 (3) | 0.028 (3) | 0.044 (3) | 0.021 (2) |
C12 | 0.169 (7) | 0.174 (7) | 0.072 (4) | 0.095 (6) | 0.017 (4) | −0.028 (4) |
C13 | 0.060 (3) | 0.074 (3) | 0.198 (7) | 0.011 (3) | 0.034 (4) | 0.017 (4) |
C14 | 0.102 (4) | 0.069 (3) | 0.174 (6) | 0.032 (3) | 0.059 (4) | 0.057 (4) |
Geometric parameters (Å, º) top
Pd1—C1 | 1.980 (3) | C4—H4 | 0.9300 |
Pd1—N5 | 2.058 (3) | C5—N6i | 1.393 (5) |
Pd1—P1 | 2.3219 (11) | C5—C6 | 1.395 (5) |
Pd1—P2 | 2.3318 (11) | C6—C7 | 1.375 (5) |
P1—C11 | 1.802 (4) | C6—H6 | 0.9300 |
P1—C9 | 1.814 (4) | C7—H7 | 0.9300 |
P1—C10 | 1.816 (4) | C9—H9A | 0.9600 |
P2—C12 | 1.791 (5) | C9—H9B | 0.9600 |
P2—C13 | 1.797 (5) | C9—H9C | 0.9600 |
P2—C14 | 1.801 (5) | C10—H10A | 0.9600 |
N1—C1 | 1.336 (5) | C10—H10B | 0.9600 |
N1—N2 | 1.361 (5) | C10—H10C | 0.9600 |
N2—N3 | 1.308 (5) | C11—H11A | 0.9600 |
N3—N4 | 1.375 (4) | C11—H11B | 0.9600 |
N4—C1 | 1.362 (4) | C11—H11C | 0.9600 |
N4—C2 | 1.428 (5) | C12—H12A | 0.9600 |
N5—C8 | 1.166 (5) | C12—H12B | 0.9600 |
N6—C8 | 1.272 (5) | C12—H12C | 0.9600 |
N6—C5i | 1.393 (5) | C13—H13A | 0.9600 |
C2—C7 | 1.380 (5) | C13—H13B | 0.9600 |
C2—C3 | 1.392 (5) | C13—H13C | 0.9600 |
C3—C4 | 1.367 (6) | C14—H14A | 0.9600 |
C3—H3 | 0.9300 | C14—H14B | 0.9600 |
C4—C5 | 1.397 (5) | C14—H14C | 0.9600 |
| | | |
C1—Pd1—N5 | 176.78 (13) | C7—C6—H6 | 119.5 |
C1—Pd1—P1 | 89.50 (10) | C5—C6—H6 | 119.5 |
N5—Pd1—P1 | 88.28 (10) | C6—C7—C2 | 121.8 (3) |
C1—Pd1—P2 | 90.86 (10) | C6—C7—H7 | 119.1 |
N5—Pd1—P2 | 91.35 (10) | C2—C7—H7 | 119.1 |
P1—Pd1—P2 | 179.48 (3) | N5—C8—N6 | 173.9 (4) |
C11—P1—C9 | 105.0 (2) | P1—C9—H9A | 109.5 |
C11—P1—C10 | 104.6 (2) | P1—C9—H9B | 109.5 |
C9—P1—C10 | 104.6 (2) | H9A—C9—H9B | 109.5 |
C11—P1—Pd1 | 112.42 (15) | P1—C9—H9C | 109.5 |
C9—P1—Pd1 | 118.37 (16) | H9A—C9—H9C | 109.5 |
C10—P1—Pd1 | 110.68 (16) | H9B—C9—H9C | 109.5 |
C12—P2—C13 | 106.1 (4) | P1—C10—H10A | 109.5 |
C12—P2—C14 | 103.0 (4) | P1—C10—H10B | 109.5 |
C13—P2—C14 | 101.9 (3) | H10A—C10—H10B | 109.5 |
C12—P2—Pd1 | 112.7 (2) | P1—C10—H10C | 109.5 |
C13—P2—Pd1 | 117.55 (19) | H10A—C10—H10C | 109.5 |
C14—P2—Pd1 | 114.05 (19) | H10B—C10—H10C | 109.5 |
C1—N1—N2 | 108.4 (3) | P1—C11—H11A | 109.5 |
N3—N2—N1 | 109.9 (3) | P1—C11—H11B | 109.5 |
N2—N3—N4 | 106.4 (3) | H11A—C11—H11B | 109.5 |
C1—N4—N3 | 109.1 (3) | P1—C11—H11C | 109.5 |
C1—N4—C2 | 130.9 (3) | H11A—C11—H11C | 109.5 |
N3—N4—C2 | 119.9 (3) | H11B—C11—H11C | 109.5 |
C8—N5—Pd1 | 142.0 (3) | P2—C12—H12A | 109.5 |
C8—N6—C5i | 119.7 (3) | P2—C12—H12B | 109.5 |
N1—C1—N4 | 106.2 (3) | H12A—C12—H12B | 109.5 |
N1—C1—Pd1 | 127.4 (3) | P2—C12—H12C | 109.5 |
N4—C1—Pd1 | 126.3 (3) | H12A—C12—H12C | 109.5 |
C7—C2—C3 | 117.7 (4) | H12B—C12—H12C | 109.5 |
C7—C2—N4 | 122.2 (3) | P2—C13—H13A | 109.5 |
C3—C2—N4 | 120.1 (3) | P2—C13—H13B | 109.5 |
C4—C3—C2 | 120.6 (4) | H13A—C13—H13B | 109.5 |
C4—C3—H3 | 119.7 | P2—C13—H13C | 109.5 |
C2—C3—H3 | 119.7 | H13A—C13—H13C | 109.5 |
C3—C4—C5 | 122.2 (3) | H13B—C13—H13C | 109.5 |
C3—C4—H4 | 118.9 | P2—C14—H14A | 109.5 |
C5—C4—H4 | 118.9 | P2—C14—H14B | 109.5 |
N6i—C5—C6 | 124.2 (3) | H14A—C14—H14B | 109.5 |
N6i—C5—C4 | 119.1 (3) | P2—C14—H14C | 109.5 |
C6—C5—C4 | 116.7 (4) | H14A—C14—H14C | 109.5 |
C7—C6—C5 | 121.0 (3) | H14B—C14—H14C | 109.5 |
Symmetry code: (i) −x+2, −y+2, −z+2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.