metal-organic compounds
The title compound, [PdCl(C14H23N5)]Cl·2H2O, contains a four-coordinate palladium complex, in which the planes of the pyrazole rings are almost perpendicular. This is mainly a consequence of the close steric contacts between the methyl groups which would occur in the case of mirror symmetry, which are avoided by adopting a quasi-twofold rotation symmetry.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806041985/br2016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806041985/br2016Isup2.hkl |
CCDC reference: 627332
Computing details top
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus, Mercury (Version 1.4.1; Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus.
Crystal data top
[PdCl(C14H23N5)]Cl·2H2O | F(000) = 968 |
Mr = 474.71 | Dx = 1.562 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 79 reflections |
a = 8.0061 (10) Å | θ = 4.6–12.5° |
b = 22.6390 (19) Å | µ = 1.20 mm−1 |
c = 11.8202 (8) Å | T = 298 K |
β = 109.607 (7)° | Prism, yellow |
V = 2018.2 (3) Å3 | 0.48 × 0.24 × 0.22 mm |
Z = 4 |
Data collection top
Bruker P4 diffractometer | 3591 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, FN4 | Rint = 0.018 |
Graphite monochromator | θmax = 26.3°, θmin = 2.0° |
2θ/ω scans | h = −9→4 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −1→28 |
Tmin = 0.666, Tmax = 0.768 | l = −14→14 |
6611 measured reflections | 3 standard reflections every 97 reflections |
4070 independent reflections | intensity decay: 1.5% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.039P)2 + 1.5198P] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
4070 reflections | Δρmax = 0.54 e Å−3 |
234 parameters | Δρmin = −0.47 e Å−3 |
4 restraints | Extinction correction: SHELXTL-Plus, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0016 (3) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.29119 (2) | 0.173806 (7) | 0.810261 (15) | 0.03237 (8) | |
Cl1 | 0.48644 (10) | 0.22414 (3) | 0.96993 (6) | 0.05195 (18) | |
Cl2 | 0.24351 (15) | 0.01245 (5) | 0.34113 (8) | 0.0822 (3) | |
N1 | 0.3939 (3) | 0.20946 (9) | 0.69025 (18) | 0.0393 (5) | |
N2 | 0.4188 (3) | 0.17384 (9) | 0.6037 (2) | 0.0411 (5) | |
C3 | 0.4893 (4) | 0.20473 (12) | 0.5328 (2) | 0.0438 (6) | |
C4 | 0.5156 (4) | 0.26090 (13) | 0.5780 (3) | 0.0495 (7) | |
H4A | 0.5674 | 0.2919 | 0.5500 | 0.059* | |
C5 | 0.4509 (4) | 0.26326 (11) | 0.6733 (2) | 0.0441 (6) | |
C6 | 0.5204 (5) | 0.17903 (15) | 0.4256 (3) | 0.0584 (8) | |
H6A | 0.5708 | 0.1403 | 0.4447 | 0.088* | |
H6B | 0.6007 | 0.2038 | 0.4024 | 0.088* | |
H6C | 0.4099 | 0.1764 | 0.3605 | 0.088* | |
C7 | 0.4322 (6) | 0.31662 (13) | 0.7420 (3) | 0.0639 (9) | |
H7A | 0.3362 | 0.3109 | 0.7724 | 0.096* | |
H7B | 0.4081 | 0.3505 | 0.6901 | 0.096* | |
H7C | 0.5402 | 0.3229 | 0.8078 | 0.096* | |
C8 | 0.3455 (4) | 0.11426 (12) | 0.5860 (2) | 0.0455 (6) | |
H8A | 0.4040 | 0.0904 | 0.6564 | 0.055* | |
H8B | 0.3665 | 0.0962 | 0.5176 | 0.055* | |
C9 | 0.1492 (4) | 0.11613 (13) | 0.5646 (2) | 0.0474 (7) | |
H9A | 0.0963 | 0.1485 | 0.5109 | 0.057* | |
H9B | 0.0950 | 0.0797 | 0.5265 | 0.057* | |
N10 | 0.1136 (3) | 0.12394 (9) | 0.67930 (18) | 0.0387 (5) | |
H10A | 0.1235 | 0.0870 | 0.7112 | 0.046* | |
N11 | 0.1762 (3) | 0.13362 (9) | 0.91793 (18) | 0.0365 (4) | |
N12 | −0.0055 (3) | 0.12909 (9) | 0.87468 (19) | 0.0395 (5) | |
C13 | −0.0634 (4) | 0.09367 (12) | 0.9452 (2) | 0.0422 (6) | |
C14 | 0.0846 (4) | 0.07452 (12) | 1.0359 (2) | 0.0450 (6) | |
H14A | 0.0865 | 0.0496 | 1.0988 | 0.054* | |
C15 | 0.2310 (3) | 0.09955 (11) | 1.0158 (2) | 0.0389 (5) | |
C16 | −0.2542 (4) | 0.08136 (15) | 0.9217 (3) | 0.0601 (8) | |
H16A | −0.3164 | 0.1179 | 0.9187 | 0.090* | |
H16B | −0.2670 | 0.0571 | 0.9849 | 0.090* | |
H16C | −0.3027 | 0.0611 | 0.8463 | 0.090* | |
C17 | 0.4214 (4) | 0.08978 (16) | 1.0871 (3) | 0.0594 (8) | |
H17A | 0.4858 | 0.1260 | 1.0917 | 0.089* | |
H17B | 0.4694 | 0.0600 | 1.0489 | 0.089* | |
H17C | 0.4317 | 0.0770 | 1.1666 | 0.089* | |
C18 | −0.1028 (4) | 0.16328 (12) | 0.7692 (3) | 0.0456 (6) | |
H18A | −0.0653 | 0.2042 | 0.7819 | 0.055* | |
H18B | −0.2283 | 0.1618 | 0.7585 | 0.055* | |
C19 | −0.0745 (4) | 0.14071 (13) | 0.6564 (2) | 0.0474 (6) | |
H19A | −0.1497 | 0.1066 | 0.6265 | 0.057* | |
H19B | −0.1085 | 0.1711 | 0.5951 | 0.057* | |
O1 | 0.6531 (4) | 0.03563 (13) | 0.3981 (3) | 0.0792 (7) | |
H11 | 0.692 (7) | 0.025 (2) | 0.4708 (17) | 0.119* | |
H12 | 0.542 (2) | 0.029 (2) | 0.366 (5) | 0.119* | |
O2 | 0.1649 (4) | 0.00023 (11) | 0.7621 (2) | 0.0640 (6) | |
H21 | 0.066 (3) | −0.010 (2) | 0.718 (4) | 0.096* | |
H22 | 0.235 (5) | −0.004 (2) | 0.725 (4) | 0.096* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03664 (12) | 0.02954 (11) | 0.03010 (11) | −0.00247 (7) | 0.01010 (8) | 0.00017 (7) |
Cl1 | 0.0591 (4) | 0.0459 (4) | 0.0416 (3) | −0.0105 (3) | 0.0048 (3) | −0.0068 (3) |
Cl2 | 0.0909 (7) | 0.0954 (7) | 0.0578 (5) | −0.0127 (6) | 0.0216 (5) | −0.0095 (5) |
N1 | 0.0484 (13) | 0.0337 (10) | 0.0369 (10) | −0.0043 (9) | 0.0158 (9) | −0.0007 (8) |
N2 | 0.0532 (14) | 0.0356 (11) | 0.0376 (11) | −0.0024 (9) | 0.0191 (10) | 0.0002 (8) |
C3 | 0.0460 (15) | 0.0474 (15) | 0.0395 (13) | 0.0026 (12) | 0.0162 (11) | 0.0100 (11) |
C4 | 0.0575 (17) | 0.0438 (15) | 0.0502 (15) | −0.0066 (13) | 0.0219 (13) | 0.0104 (12) |
C5 | 0.0513 (15) | 0.0359 (13) | 0.0447 (14) | −0.0078 (12) | 0.0156 (12) | 0.0030 (11) |
C6 | 0.068 (2) | 0.064 (2) | 0.0514 (17) | 0.0080 (16) | 0.0307 (16) | 0.0078 (14) |
C7 | 0.101 (3) | 0.0365 (15) | 0.0589 (19) | −0.0117 (16) | 0.0329 (19) | −0.0035 (13) |
C8 | 0.0631 (18) | 0.0353 (13) | 0.0418 (13) | −0.0036 (12) | 0.0225 (13) | −0.0039 (11) |
C9 | 0.0627 (18) | 0.0450 (14) | 0.0313 (12) | −0.0132 (13) | 0.0116 (12) | −0.0057 (11) |
N10 | 0.0432 (12) | 0.0358 (11) | 0.0351 (10) | −0.0047 (9) | 0.0106 (9) | 0.0009 (8) |
N11 | 0.0359 (11) | 0.0389 (11) | 0.0364 (10) | 0.0012 (9) | 0.0143 (9) | 0.0006 (8) |
N12 | 0.0384 (11) | 0.0387 (11) | 0.0427 (11) | 0.0007 (9) | 0.0155 (9) | −0.0006 (9) |
C13 | 0.0468 (15) | 0.0374 (13) | 0.0516 (14) | 0.0001 (11) | 0.0285 (12) | −0.0044 (11) |
C14 | 0.0567 (17) | 0.0401 (13) | 0.0470 (14) | 0.0035 (12) | 0.0290 (13) | 0.0058 (11) |
C15 | 0.0443 (14) | 0.0403 (13) | 0.0360 (12) | 0.0072 (11) | 0.0188 (11) | 0.0042 (10) |
C16 | 0.0497 (17) | 0.0592 (19) | 0.083 (2) | −0.0020 (15) | 0.0375 (16) | −0.0012 (17) |
C17 | 0.0487 (17) | 0.077 (2) | 0.0523 (16) | 0.0110 (15) | 0.0163 (13) | 0.0257 (16) |
C18 | 0.0371 (14) | 0.0413 (14) | 0.0549 (16) | 0.0060 (11) | 0.0107 (12) | 0.0031 (12) |
C19 | 0.0397 (14) | 0.0525 (16) | 0.0419 (14) | −0.0061 (12) | 0.0031 (11) | 0.0067 (12) |
O1 | 0.0864 (19) | 0.0690 (17) | 0.0886 (19) | 0.0100 (15) | 0.0380 (17) | 0.0141 (15) |
O2 | 0.0799 (17) | 0.0601 (13) | 0.0612 (14) | 0.0288 (13) | 0.0358 (12) | 0.0175 (11) |
Geometric parameters (Å, º) top
Pd1—N11 | 2.021 (2) | N10—H10A | 0.9100 |
Pd1—N1 | 2.030 (2) | N11—C15 | 1.336 (3) |
Pd1—N10 | 2.053 (2) | N11—N12 | 1.374 (3) |
Pd1—Cl1 | 2.3073 (7) | N12—C13 | 1.346 (3) |
N1—C5 | 1.339 (3) | N12—C18 | 1.452 (3) |
N1—N2 | 1.369 (3) | C13—C14 | 1.374 (4) |
N2—C3 | 1.351 (3) | C13—C16 | 1.484 (4) |
N2—C8 | 1.458 (3) | C14—C15 | 1.392 (4) |
C3—C4 | 1.368 (4) | C14—H14A | 0.9300 |
C3—C6 | 1.490 (4) | C15—C17 | 1.490 (4) |
C4—C5 | 1.391 (4) | C16—H16A | 0.9600 |
C4—H4A | 0.9300 | C16—H16B | 0.9600 |
C5—C7 | 1.491 (4) | C16—H16C | 0.9600 |
C6—H6A | 0.9600 | C17—H17A | 0.9600 |
C6—H6B | 0.9600 | C17—H17B | 0.9600 |
C6—H6C | 0.9600 | C17—H17C | 0.9600 |
C7—H7A | 0.9600 | C18—C19 | 1.515 (4) |
C7—H7B | 0.9600 | C18—H18A | 0.9700 |
C7—H7C | 0.9600 | C18—H18B | 0.9700 |
C8—C9 | 1.506 (4) | C19—H19A | 0.9700 |
C8—H8A | 0.9700 | C19—H19B | 0.9700 |
C8—H8B | 0.9700 | O1—H11 | 0.848 (10) |
C9—N10 | 1.486 (3) | O1—H12 | 0.853 (10) |
C9—H9A | 0.9700 | O2—H21 | 0.827 (10) |
C9—H9B | 0.9700 | O2—H22 | 0.823 (10) |
N10—C19 | 1.487 (3) | ||
N11—Pd1—N1 | 174.95 (8) | C9—N10—Pd1 | 117.20 (16) |
N11—Pd1—N10 | 83.15 (8) | C19—N10—Pd1 | 113.55 (17) |
N1—Pd1—N10 | 91.84 (8) | C9—N10—H10A | 104.6 |
N11—Pd1—Cl1 | 91.95 (6) | C19—N10—H10A | 104.6 |
N1—Pd1—Cl1 | 93.05 (6) | Pd1—N10—H10A | 104.6 |
N10—Pd1—Cl1 | 174.85 (6) | C15—N11—N12 | 106.2 (2) |
C5—N1—N2 | 106.3 (2) | C15—N11—Pd1 | 135.94 (18) |
C5—N1—Pd1 | 134.77 (18) | N12—N11—Pd1 | 116.65 (15) |
N2—N1—Pd1 | 118.88 (15) | C13—N12—N11 | 110.8 (2) |
C3—N2—N1 | 110.8 (2) | C13—N12—C18 | 130.7 (2) |
C3—N2—C8 | 128.4 (2) | N11—N12—C18 | 118.4 (2) |
N1—N2—C8 | 119.9 (2) | N12—C13—C14 | 106.6 (2) |
N2—C3—C4 | 106.3 (2) | N12—C13—C16 | 122.9 (3) |
N2—C3—C6 | 123.3 (3) | C14—C13—C16 | 130.6 (3) |
C4—C3—C6 | 130.3 (3) | C13—C14—C15 | 107.1 (2) |
C3—C4—C5 | 107.6 (2) | C13—C14—H14A | 126.5 |
C3—C4—H4A | 126.2 | C15—C14—H14A | 126.5 |
C5—C4—H4A | 126.2 | N11—C15—C14 | 109.4 (2) |
N1—C5—C4 | 108.9 (2) | N11—C15—C17 | 123.5 (2) |
N1—C5—C7 | 123.6 (3) | C14—C15—C17 | 127.1 (2) |
C4—C5—C7 | 127.3 (3) | C13—C16—H16A | 109.5 |
C3—C6—H6A | 109.5 | C13—C16—H16B | 109.5 |
C3—C6—H6B | 109.5 | H16A—C16—H16B | 109.5 |
H6A—C6—H6B | 109.5 | C13—C16—H16C | 109.5 |
C3—C6—H6C | 109.5 | H16A—C16—H16C | 109.5 |
H6A—C6—H6C | 109.5 | H16B—C16—H16C | 109.5 |
H6B—C6—H6C | 109.5 | C15—C17—H17A | 109.5 |
C5—C7—H7A | 109.5 | C15—C17—H17B | 109.5 |
C5—C7—H7B | 109.5 | H17A—C17—H17B | 109.5 |
H7A—C7—H7B | 109.5 | C15—C17—H17C | 109.5 |
C5—C7—H7C | 109.5 | H17A—C17—H17C | 109.5 |
H7A—C7—H7C | 109.5 | H17B—C17—H17C | 109.5 |
H7B—C7—H7C | 109.5 | N12—C18—C19 | 112.4 (2) |
N2—C8—C9 | 110.2 (2) | N12—C18—H18A | 109.1 |
N2—C8—H8A | 109.6 | C19—C18—H18A | 109.1 |
C9—C8—H8A | 109.6 | N12—C18—H18B | 109.1 |
N2—C8—H8B | 109.6 | C19—C18—H18B | 109.1 |
C9—C8—H8B | 109.6 | H18A—C18—H18B | 107.9 |
H8A—C8—H8B | 108.1 | N10—C19—C18 | 111.6 (2) |
N10—C9—C8 | 111.0 (2) | N10—C19—H19A | 109.3 |
N10—C9—H9A | 109.4 | C18—C19—H19A | 109.3 |
C8—C9—H9A | 109.4 | N10—C19—H19B | 109.3 |
N10—C9—H9B | 109.4 | C18—C19—H19B | 109.3 |
C8—C9—H9B | 109.4 | H19A—C19—H19B | 108.0 |
H9A—C9—H9B | 108.0 | H11—O1—H12 | 111 (5) |
C9—N10—C19 | 110.9 (2) | H21—O2—H22 | 108 (5) |
**N11—Pd1—N1—C5 | 147.1 (9) | N11—Pd1—N10—C19 | 65.97 (17) |
N10—Pd1—N1—C5 | 140.7 (3) | N1—Pd1—N10—C19 | −114.59 (17) |
Cl1—Pd1—N1—C5 | −40.9 (3) | **Cl1—Pd1—N10—C19 | 84.1 (8) |
**N11—Pd1—N1—N2 | −34.2 (11) | **N1—Pd1—N11—C15 | 115.5 (9) |
N10—Pd1—N1—N2 | −40.5 (2) | N10—Pd1—N11—C15 | 121.9 (3) |
Cl1—Pd1—N1—N2 | 137.81 (18) | Cl1—Pd1—N11—C15 | −56.5 (2) |
C5—N1—N2—C3 | −0.4 (3) | **N1—Pd1—N11—N12 | −49.6 (10) |
Pd1—N1—N2—C3 | −179.47 (17) | N10—Pd1—N11—N12 | −43.22 (17) |
C5—N1—N2—C8 | −170.8 (2) | Cl1—Pd1—N11—N12 | 138.39 (16) |
Pd1—N1—N2—C8 | 10.2 (3) | C15—N11—N12—C13 | 1.0 (3) |
N1—N2—C3—C4 | 2.1 (3) | Pd1—N11—N12—C13 | 170.25 (16) |
C8—N2—C3—C4 | 171.4 (3) | C15—N11—N12—C18 | 178.2 (2) |
N1—N2—C3—C6 | −175.8 (3) | Pd1—N11—N12—C18 | −12.5 (3) |
C8—N2—C3—C6 | −6.5 (5) | N11—N12—C13—C14 | −0.4 (3) |
N2—C3—C4—C5 | −3.0 (3) | C18—N12—C13—C14 | −177.2 (3) |
C6—C3—C4—C5 | 174.8 (3) | N11—N12—C13—C16 | 179.0 (2) |
N2—N1—C5—C4 | −1.5 (3) | C18—N12—C13—C16 | 2.2 (4) |
Pd1—N1—C5—C4 | 177.4 (2) | N12—C13—C14—C15 | −0.4 (3) |
N2—N1—C5—C7 | 174.3 (3) | C16—C13—C14—C15 | −179.6 (3) |
Pd1—N1—C5—C7 | −6.9 (5) | N12—N11—C15—C14 | −1.2 (3) |
C3—C4—C5—N1 | 2.8 (3) | Pd1—N11—C15—C14 | −167.34 (19) |
C3—C4—C5—C7 | −172.8 (3) | N12—N11—C15—C17 | 177.0 (3) |
C3—N2—C8—C9 | −113.7 (3) | Pd1—N11—C15—C17 | 10.9 (4) |
N1—N2—C8—C9 | 54.7 (3) | C13—C14—C15—N11 | 1.0 (3) |
N2—C8—C9—N10 | −78.6 (3) | C13—C14—C15—C17 | −177.1 (3) |
C8—C9—N10—C19 | 165.8 (2) | C13—N12—C18—C19 | −113.6 (3) |
C8—C9—N10—Pd1 | 33.2 (3) | N11—N12—C18—C19 | 69.8 (3) |
N11—Pd1—N10—C9 | −162.6 (2) | C9—N10—C19—C18 | −166.1 (2) |
N1—Pd1—N10—C9 | 16.8 (2) | Pd1—N10—C19—C18 | −31.6 (3) |
**Cl1—Pd1—N10—C9 | −144.5 (6) | N12—C18—C19—N10 | −40.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···Cl2i | 0.85 (1) | 2.27 (1) | 3.108 (3) | 171 (5) |
O1—H12···Cl2 | 0.85 (1) | 2.34 (2) | 3.162 (3) | 162 (5) |
O2—H21···Cl2ii | 0.83 (1) | 2.34 (2) | 3.096 (3) | 153 (5) |
O2—H22···O1i | 0.82 (1) | 2.08 (2) | 2.867 (4) | 160 (5) |
N10—H10A···O2 | 0.91 | 2.05 | 2.950 (3) | 171 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1. |