Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029661/ob6588sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029661/ob6588Isup2.hkl |
CCDC reference: 287688
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.009 Å
- R factor = 0.031
- wR factor = 0.081
- Data-to-parameter ratio = 16.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9 PLAT480_ALERT_4_C Long H...A H-Bond Reported H2N .. N3 .. 2.71 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H2N .. CL1 .. 2.87 Ang.
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.189 0.631 Tmin and Tmax expected: 0.145 0.590 RR = 1.212 Please check that your absorption correction is appropriate.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion
Compound (I) was obtained as a by-product in the synthesis of cis-[PtCl4(pzH)2] (Minacheva et al., 2001). A mixture of K2[PtCl6] (0.131 g, 0.27 mmol) and pzH (0.046 g, 0.68 mmol) was heated in water (Volume?) at 343 K for 30 min. The yellow solid which formed was collected by filtration, washed with one 5 ml portion of water and air-dried at room temperature. Under these conditions, a mixture of the target complex cis-[PtCl4(pzH)2] and complex (I) was formed (0.017 g; molar ratio of the products 2:1 by 1H NMR integration). We also found that, when one more equivalent of pzH (0.018 g, 0.27 mmol) was added to the filtrate and the solution was further heated at 343 K for 10 h, a yellow precipitate of the title compound was formed. The solid was collected by filtration, washed with one 5 ml portion of water and air-dried at room temperature (yield 0.082 g, 60%, based on the starting K2[PtCl6]). Suitable crystals of (I) for X-ray study were obtained by slow evaporation of an acetone solution at room temperature. Analysis calculated for C9H11N6Cl3Pt: C 16.65, H 2.20, N 21.42%; found: C 16.55, H 2.22, N 21.50%; 1H NMR (acetone-d6, δ, p.p.m.): 6.56 (pseudo-t, J = 2.4 Hz, 1H, 4CH), 7.92 (d, J = 2.4 Hz, 1H, 5CH), 7.94 (d, J = 2.4 Hz, 1H, 3CH). It should be noted that, in the 1H NMR spectrum, the equivalence of both pyrazole and pyrazolate ligands, on one hand, and the absence of signals from the NH protons, on the other hand, was observed, thus indicating for exchange processes in the solution.
The NH H atom (H2N) was located in a difference Fourier map and refined isotropically. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2005); software used to prepare material for publication: SHELXL97.
[PtCl3(C3H3N2)(C3H4N2)2] | F(000) = 472 |
Mr = 504.68 | Dx = 2.387 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yb | Cell parameters from 4975 reflections |
a = 6.8307 (6) Å | θ = 3.0–27.4° |
b = 13.5005 (7) Å | µ = 10.56 mm−1 |
c = 7.6421 (7) Å | T = 120 K |
β = 94.888 (3)° | Plate, yellow |
V = 702.18 (10) Å3 | 0.24 × 0.16 × 0.05 mm |
Z = 2 |
Nonius KappaCCD area-detector diffractometer | 1645 independent reflections |
Radiation source: fine-focus sealed tube | 1522 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.044 |
Detector resolution: 9 pixels mm-1 | θmax = 27.4°, θmin = 3.0° |
ϕ scans, and ω scans with κ offset | h = −8→7 |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | k = −17→14 |
Tmin = 0.189, Tmax = 0.631 | l = −8→9 |
4975 measured reflections |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0542P)2 + 1.4982P] where P = (Fo2 + 2Fc2)/3 |
1645 reflections | (Δ/σ)max = 0.002 |
101 parameters | Δρmax = 1.82 e Å−3 |
0 restraints | Δρmin = −2.94 e Å−3 |
[PtCl3(C3H3N2)(C3H4N2)2] | V = 702.18 (10) Å3 |
Mr = 504.68 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 6.8307 (6) Å | µ = 10.56 mm−1 |
b = 13.5005 (7) Å | T = 120 K |
c = 7.6421 (7) Å | 0.24 × 0.16 × 0.05 mm |
β = 94.888 (3)° |
Nonius KappaCCD area-detector diffractometer | 1645 independent reflections |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | 1522 reflections with I > 2σ(I) |
Tmin = 0.189, Tmax = 0.631 | Rint = 0.044 |
4975 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.82 e Å−3 |
1645 reflections | Δρmin = −2.94 e Å−3 |
101 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 | ||
Pt1 | 0.31554 (3) | 0.2500 | 1.01373 (3) | 0.01119 (12) | |
Cl1 | 0.49671 (18) | 0.12879 (9) | 0.89008 (18) | 0.0156 (3) | |
Cl2 | 0.5399 (3) | 0.2500 | 1.2607 (3) | 0.0188 (4) | |
N1 | 0.1595 (6) | 0.1404 (3) | 1.1278 (6) | 0.0123 (8) | |
N2 | −0.0356 (6) | 0.1266 (3) | 1.0947 (6) | 0.0150 (9) | |
H2N | −0.099 (10) | 0.155 (5) | 1.014 (9) | 0.016 (16)* | |
N3 | 0.1260 (8) | 0.2500 | 0.7924 (8) | 0.0113 (12) | |
N4 | −0.0686 (8) | 0.2500 | 0.8079 (8) | 0.0127 (12) | |
C1 | −0.0928 (8) | 0.0486 (4) | 1.1857 (7) | 0.0178 (11) | |
H1 | −0.2229 | 0.0235 | 1.1843 | 0.021* | |
C2 | 0.0693 (8) | 0.0115 (4) | 1.2809 (8) | 0.0191 (11) | |
H2 | 0.0742 | −0.0439 | 1.3577 | 0.023* | |
C3 | 0.2252 (8) | 0.0713 (4) | 1.2424 (7) | 0.0178 (11) | |
H3 | 0.3574 | 0.0642 | 1.2902 | 0.021* | |
C4 | −0.1519 (10) | 0.2500 | 0.6438 (10) | 0.0147 (14) | |
H4 | −0.2897 | 0.2500 | 0.6134 | 0.018* | |
C5 | −0.0083 (11) | 0.2500 | 0.5202 (10) | 0.0165 (15) | |
H5 | −0.0271 | 0.2500 | 0.3956 | 0.020* | |
C6 | 0.1685 (11) | 0.2500 | 0.6281 (10) | 0.0165 (15) | |
H6 | 0.2968 | 0.2500 | 0.5890 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.00831 (17) | 0.01220 (18) | 0.01306 (18) | 0.000 | 0.00093 (11) | 0.000 |
Cl1 | 0.0118 (5) | 0.0129 (6) | 0.0224 (7) | 0.0027 (4) | 0.0035 (5) | −0.0013 (5) |
Cl2 | 0.0134 (8) | 0.0232 (9) | 0.0187 (10) | 0.000 | −0.0040 (7) | 0.000 |
N1 | 0.0101 (19) | 0.012 (2) | 0.015 (2) | 0.0000 (15) | 0.0015 (16) | 0.0014 (17) |
N2 | 0.014 (2) | 0.017 (2) | 0.014 (2) | −0.0010 (17) | 0.0010 (18) | 0.0014 (18) |
N3 | 0.011 (3) | 0.009 (3) | 0.013 (3) | 0.000 | −0.004 (2) | 0.000 |
N4 | 0.013 (3) | 0.017 (3) | 0.009 (3) | 0.000 | 0.004 (2) | 0.000 |
C1 | 0.022 (3) | 0.015 (3) | 0.018 (3) | −0.007 (2) | 0.010 (2) | −0.001 (2) |
C2 | 0.028 (3) | 0.011 (2) | 0.020 (3) | 0.001 (2) | 0.009 (2) | −0.002 (2) |
C3 | 0.019 (2) | 0.013 (2) | 0.021 (3) | 0.0032 (19) | 0.001 (2) | 0.002 (2) |
C4 | 0.010 (3) | 0.014 (3) | 0.019 (4) | 0.000 | 0.001 (3) | 0.000 |
C5 | 0.021 (4) | 0.018 (4) | 0.011 (4) | 0.000 | 0.004 (3) | 0.000 |
C6 | 0.015 (3) | 0.023 (4) | 0.012 (4) | 0.000 | 0.005 (3) | 0.000 |
Pt1—N3 | 2.041 (6) | N4—C4 | 1.333 (10) |
Pt1—N1 | 2.060 (4) | C1—C2 | 1.367 (8) |
Pt1—N1i | 2.060 (4) | C1—H1 | 0.9500 |
Pt1—Cl1 | 2.3026 (12) | C2—C3 | 1.388 (7) |
Pt1—Cl1i | 2.3026 (12) | C2—H2 | 0.9500 |
Pt1—Cl2 | 2.3274 (19) | C3—H3 | 0.9500 |
N1—C3 | 1.331 (7) | C4—C5 | 1.418 (10) |
N1—N2 | 1.348 (6) | C4—H4 | 0.9500 |
N2—C1 | 1.339 (7) | C5—C6 | 1.403 (11) |
N2—H2N | 0.81 (7) | C5—H5 | 0.9500 |
N3—C6 | 1.312 (10) | C6—H6 | 0.9500 |
N3—N4 | 1.344 (8) | ||
N3—Pt1—N1 | 92.07 (18) | C6—N3—Pt1 | 128.0 (5) |
N3—Pt1—N1i | 92.07 (17) | N4—N3—Pt1 | 119.3 (5) |
N1—Pt1—N1i | 91.8 (2) | C4—N4—N3 | 105.2 (6) |
N3—Pt1—Cl1 | 89.14 (13) | N2—C1—C2 | 107.8 (5) |
N1—Pt1—Cl1 | 88.78 (13) | N2—C1—H1 | 126.1 |
N1i—Pt1—Cl1 | 178.62 (12) | C2—C1—H1 | 126.1 |
N3—Pt1—Cl1i | 89.14 (13) | C1—C2—C3 | 106.0 (5) |
N1—Pt1—Cl1i | 178.62 (12) | C1—C2—H2 | 127.0 |
N1i—Pt1—Cl1i | 88.77 (13) | C3—C2—H2 | 127.0 |
Cl1—Pt1—Cl1i | 90.59 (6) | N1—C3—C2 | 109.0 (5) |
N3—Pt1—Cl2 | 178.21 (17) | N1—C3—H3 | 125.5 |
N1—Pt1—Cl2 | 89.18 (13) | C2—C3—H3 | 125.5 |
N1i—Pt1—Cl2 | 89.18 (13) | N4—C4—C5 | 111.3 (6) |
Cl1—Pt1—Cl2 | 89.60 (5) | N4—C4—H4 | 124.4 |
Cl1i—Pt1—Cl2 | 89.60 (5) | C5—C4—H4 | 124.4 |
C3—N1—N2 | 107.4 (4) | C6—C5—C4 | 102.6 (7) |
C3—N1—Pt1 | 128.6 (4) | C6—C5—H5 | 128.7 |
N2—N1—Pt1 | 124.0 (3) | C4—C5—H5 | 128.7 |
C1—N2—N1 | 109.8 (5) | N3—C6—C5 | 108.2 (6) |
C1—N2—H2N | 127 (5) | N3—C6—H6 | 125.9 |
N1—N2—H2N | 122 (5) | C5—C6—H6 | 125.9 |
C6—N3—N4 | 112.7 (6) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N4 | 0.81 (7) | 2.06 (7) | 2.747 (7) | 142 (6) |
N2—H2N···N3 | 0.81 (7) | 2.71 (7) | 3.125 (7) | 114 (5) |
N2—H2N···Cl1ii | 0.81 (7) | 2.87 (7) | 3.435 (5) | 129 (6) |
Symmetry code: (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [PtCl3(C3H3N2)(C3H4N2)2] |
Mr | 504.68 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 120 |
a, b, c (Å) | 6.8307 (6), 13.5005 (7), 7.6421 (7) |
β (°) | 94.888 (3) |
V (Å3) | 702.18 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 10.56 |
Crystal size (mm) | 0.24 × 0.16 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.189, 0.631 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4975, 1645, 1522 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.081, 1.03 |
No. of reflections | 1645 |
No. of parameters | 101 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.82, −2.94 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2005), SHELXL97.
Pt1—N3 | 2.041 (6) | Pt1—Cl1 | 2.3026 (12) |
Pt1—N1 | 2.060 (4) | Pt1—Cl2 | 2.3274 (19) |
N3—Pt1—N1 | 92.07 (18) | Cl1—Pt1—Cl1i | 90.59 (6) |
N1—Pt1—N1i | 91.8 (2) | N3—Pt1—Cl2 | 178.21 (17) |
N3—Pt1—Cl1 | 89.14 (13) | N1—Pt1—Cl2 | 89.18 (13) |
N1—Pt1—Cl1 | 88.78 (13) | Cl1—Pt1—Cl2 | 89.60 (5) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N4 | 0.81 (7) | 2.06 (7) | 2.747 (7) | 142 (6) |
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Complexes containing various pyrazole ligands currently attract significant attention, due to their intrinsic biological, synthetic, catalytic and magnetic properties (Ardizzoia et al., 1991, 1994; Trofimenko, 1993; Sakai et al., 2000; Bigmore et al., 2005). During our ongoing studies of platinum complexes with N-donor ligands (Kukushkin & Pombeiro, 1999, 2002, 2005; Bokach & Kukushkin, 2005), the title complex, (I), was obtained as a by-product in the synthesis of cis-[PtCl4(pzH)2] by the known method of Minacheva et al. (2001) or as the target compound in the reaction described in the Experimental section. In this work, complex (I) has been characterized by X-ray crystallography, elemental analyses and 1H NMR spectroscopy.
Complex (I) belongs to a class of octahedral platinum(IV) species bearing three Cl− ligands in the fac arrangement (Fig. 1). The remaining coordination sites are occupied by one negatively charged pyrazolate (pz; N3/N4/C4–C6) and two neutral pyrazole ligands (pzH; N1/N2/C1–C3). The bond distances and angles in the heterocyclic rings are comparable with those previously reported for free pyrazole molecules (Berthou et al., 1970; Larsen et al., 1970; la Cour et al., 1973) and coordinated pyrazoles in cis-[PtCl4(pzH)2] (Minacheva et al., 2001; Khripun et al., 2005) and trans-[PtCl4(pzH)2] (Khripun et al., 2005).
An intramolecular N2—H2N···N4···H2Ni—N2i hydrogen-bonding system is formed (Table 2). The N···N distances [2.747 (7) Å] are similar to those observed in fac-[Re(pz)(pzH)2(CO)3] [2.749 (7)–2.883 (6) Å; Ardizzoia et al., 1998]. Structurally characterized complexes with fac-M(pyrazole/ate)3 moieties, resembling protonated or diprotonated tris(pyrazolyl)borates (Trofimenko, 1993), are known and include compounds with a fac-M(pz)2(pzH) or fac-M(pz)(pzH)2 structural unit, namely [Ir(η5-C5Me5)(pz)2(pzH)] (Carmona et al., 1986), [Ru(η6-p-cymene)(pz)2(pzH)] (p-cymene is 1-isopropyl-4-methylbenzene; Carmona et al., 1990), [Ru(η6-mesitylene)(pz)2(pzH)] (Carmona et al., 1996), [Ru(η6-p-cymene)(pz)(pzH)2][BF4] (Carmona et al., 1990) and [Re(pz)(pzH)2(CO)3] (Ardizzoia et al., 1998). Thus, complex (I) represents the first example of a platinum complex of the fac-M(pyrazole/ate)3 type and the second example of a structurally characterized complex with a fac-M(pz)(pzH)2 hydrogen-bonding system. In [Ru(η6-p-cymene)(pz)(pzH)2][BF4] (Carmona et al., 1990), there is an intramolecular hydrogen bond between one of the pzH ligands and a pz anion, while the NH group of the second pzH ligand is involved in an intermolecular hydrogen bond with the counter-ion.