Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000041X/qb0161sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010000041X/qb0161Isup2.hkl |
CCDC reference: 142928
Hdmbarb (0.313 g, 2.00 mmol) dissolved in water (50 ml) was added to a 20 ml solution of [Pd(en)(OH)2], prepared by passing an aqueous solution of [Pd(en)(ONO2)2] (0.291 g, 1.00 mmol) through a column packed with anion-exchange resin. The solution is evaporated to ca 40 ml keeping at ca 303 K. After standing for 4 d in the dark at 278 K, yellow needles crystallized (0.151 g, 26% yield). Analysis found: C 29.19, H 5.52, N 14.58%; calculated for C14H33N6O11.5Pd: C 29.20, H 5.78, N, 14.59%.
All H atoms other than those on H2O were included as riding models and the positions of the H atoms on H2O were refined with O—H constrained at 0.82 (3) Å; Uiso(H) = 1.2Ueq(parent atom).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN PROCESS (Molecular Structure Corporation, 1993b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Pd(C6H7N2O3)2(C2H8N2)]·5.5H2O | F(000) = 2376 |
Mr = 575.86 | Dx = 1.632 Mg m−3 Dm = 1.67 Mg m−3 Dm measured by flotation in CCl4/CHBr3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 24.225 (3) Å | Cell parameters from 25 reflections |
b = 8.307 (3) Å | θ = 16.8–17.5° |
c = 25.396 (2) Å | µ = 0.86 mm−1 |
β = 113.505 (5)° | T = 296 K |
V = 4686.4 (15) Å3 | Needle, yellow |
Z = 8 | 0.25 × 0.12 × 0.06 mm |
Rigaku AFC-7R diffractometer | Rint = 0.018 |
Radiation source: rotating Mo anticathode | θmax = 30.0°, θmin = 2.6° |
Graphite monochromator | h = 0→34 |
ω/2θ scans | k = 0→11 |
6982 measured reflections | l = −35→32 |
6837 independent reflections | 3 standard reflections every 150 reflections |
4810 reflections with I > 2σ(I) | intensity decay: 0.9% |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0291P)2 + 1.914P] where P = (Fo2 + 2Fc2)/3 |
6837 reflections | (Δ/σ)max = 0.003 |
327 parameters | Δρmax = 0.46 e Å−3 |
11 restraints | Δρmin = −0.49 e Å−3 |
[Pd(C6H7N2O3)2(C2H8N2)]·5.5H2O | V = 4686.4 (15) Å3 |
Mr = 575.86 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.225 (3) Å | µ = 0.86 mm−1 |
b = 8.307 (3) Å | T = 296 K |
c = 25.396 (2) Å | 0.25 × 0.12 × 0.06 mm |
β = 113.505 (5)° |
Rigaku AFC-7R diffractometer | Rint = 0.018 |
6982 measured reflections | 3 standard reflections every 150 reflections |
6837 independent reflections | intensity decay: 0.9% |
4810 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.032 | 11 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.46 e Å−3 |
6837 reflections | Δρmin = −0.49 e Å−3 |
327 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 | ||
Pd | 0.528342 (8) | 0.63116 (2) | 0.647353 (8) | 0.02633 (5) | |
O12 | 0.32679 (10) | 0.5978 (3) | 0.47730 (8) | 0.0533 (6) | |
O14 | 0.49194 (10) | 0.2878 (3) | 0.56484 (9) | 0.0497 (5) | |
O16 | 0.39987 (10) | 0.5533 (3) | 0.67019 (8) | 0.0499 (6) | |
O22 | 0.32746 (9) | 1.1185 (3) | 0.48312 (8) | 0.0462 (5) | |
O24 | 0.47979 (8) | 0.7749 (2) | 0.57938 (8) | 0.0355 (4) | |
O26 | 0.38871 (10) | 1.0881 (3) | 0.67730 (9) | 0.0522 (6) | |
N1 | 0.59892 (10) | 0.7951 (3) | 0.67728 (10) | 0.0378 (5) | |
H1 | 0.6177 | 0.7998 | 0.6531 | 0.045* | |
H2 | 0.5849 | 0.8939 | 0.6798 | 0.045* | |
N2 | 0.58289 (9) | 0.4947 (3) | 0.71319 (9) | 0.0327 (5) | |
H7 | 0.5701 | 0.4963 | 0.7420 | 0.039* | |
H8 | 0.5823 | 0.3921 | 0.7016 | 0.039* | |
O1 | 0.69871 (12) | 0.8507 (4) | 0.63392 (10) | 0.0581 (7) | |
H11 | 0.6942 (17) | 0.854 (5) | 0.6015 (11) | 0.070* | |
H12 | 0.7296 (13) | 0.811 (5) | 0.6514 (16) | 0.070* | |
O2 | 0.79057 (12) | 0.6500 (4) | 0.70120 (11) | 0.0610 (7) | |
H21 | 0.8246 (12) | 0.639 (5) | 0.7028 (17) | 0.073* | |
H22 | 0.7925 (18) | 0.650 (5) | 0.7348 (11) | 0.073* | |
O3 | 0.7274 (2) | 0.3862 (5) | 0.64117 (12) | 0.1102 (14) | |
H31 | 0.747 (2) | 0.472 (5) | 0.660 (2) | 0.132* | |
H32 | 0.709 (2) | 0.402 (7) | 0.6067 (12) | 0.132* | |
O4 | 0.69753 (14) | 0.1352 (4) | 0.68708 (12) | 0.0633 (7) | |
H41 | 0.7067 (18) | 0.221 (4) | 0.6743 (17) | 0.076* | |
H42 | 0.7028 (19) | 0.052 (4) | 0.6743 (17) | 0.076* | |
O5 | 0.57637 (12) | 0.1548 (4) | 0.66691 (13) | 0.0656 (7) | |
H51 | 0.6097 (13) | 0.163 (5) | 0.6641 (18) | 0.079* | |
H52 | 0.5542 (17) | 0.185 (5) | 0.6352 (12) | 0.079* | |
O6 | 0.5000 | 1.2469 (5) | 0.7500 | 0.0641 (10) | |
H61 | 0.4747 (14) | 1.170 (4) | 0.7416 (19) | 0.077* | |
N11 | 0.36436 (10) | 0.5813 (3) | 0.57406 (9) | 0.0360 (5) | |
N13 | 0.41392 (10) | 0.4577 (3) | 0.52089 (9) | 0.0370 (5) | |
N21 | 0.35743 (10) | 1.1024 (3) | 0.58005 (9) | 0.0336 (5) | |
N23 | 0.40697 (10) | 0.9556 (3) | 0.53268 (9) | 0.0326 (5) | |
C1 | 0.64139 (13) | 0.7391 (4) | 0.73498 (13) | 0.0438 (7) | |
H3 | 0.6271 | 0.7722 | 0.7640 | 0.053* | |
H4 | 0.6809 | 0.7858 | 0.7444 | 0.053* | |
C2 | 0.64509 (12) | 0.5596 (4) | 0.73363 (12) | 0.0415 (7) | |
H5 | 0.6638 | 0.5268 | 0.7079 | 0.050* | |
H6 | 0.6692 | 0.5187 | 0.7717 | 0.050* | |
C11 | 0.31086 (13) | 0.6644 (4) | 0.57382 (14) | 0.0488 (8) | |
H111 | 0.2757 | 0.6011 | 0.5531 | 0.059* | |
H112 | 0.3072 | 0.7675 | 0.5556 | 0.059* | |
H113 | 0.3146 | 0.6790 | 0.6126 | 0.059* | |
C12 | 0.36629 (12) | 0.5485 (4) | 0.52138 (11) | 0.0363 (6) | |
C13 | 0.41512 (15) | 0.4232 (4) | 0.46450 (12) | 0.0508 (8) | |
H131 | 0.3776 | 0.3753 | 0.4399 | 0.061* | |
H132 | 0.4475 | 0.3503 | 0.4692 | 0.061* | |
H133 | 0.4210 | 0.5216 | 0.4476 | 0.061* | |
C14 | 0.45795 (12) | 0.3908 (3) | 0.56993 (11) | 0.0341 (6) | |
C15 | 0.46112 (11) | 0.4512 (3) | 0.62491 (11) | 0.0319 (6) | |
H15 | 0.4740 | 0.3646 | 0.6535 | 0.038* | |
C16 | 0.40789 (12) | 0.5303 (4) | 0.62637 (11) | 0.0334 (6) | |
C21 | 0.30710 (13) | 1.2055 (4) | 0.57626 (14) | 0.0453 (7) | |
H211 | 0.3170 | 1.2615 | 0.6119 | 0.054* | |
H212 | 0.2719 | 1.1406 | 0.5685 | 0.054* | |
H213 | 0.2993 | 1.2821 | 0.5458 | 0.054* | |
C22 | 0.36213 (12) | 1.0621 (3) | 0.52921 (12) | 0.0342 (6) | |
C23 | 0.41402 (14) | 0.9190 (4) | 0.47898 (12) | 0.0458 (7) | |
H231 | 0.4461 | 0.8428 | 0.4866 | 0.055* | |
H232 | 0.4234 | 1.0161 | 0.4637 | 0.055* | |
H233 | 0.3772 | 0.8743 | 0.4516 | 0.055* | |
C24 | 0.44432 (11) | 0.8821 (3) | 0.58403 (11) | 0.0312 (5) | |
C25 | 0.43921 (12) | 0.9299 (4) | 0.63368 (11) | 0.0352 (6) | |
H25 | 0.4655 | 0.8867 | 0.6685 | 0.042* | |
C26 | 0.39580 (12) | 1.0412 (4) | 0.63383 (12) | 0.0369 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.02640 (9) | 0.02812 (9) | 0.02290 (8) | 0.00418 (9) | 0.00817 (6) | 0.00083 (9) |
O12 | 0.0474 (12) | 0.0711 (17) | 0.0288 (10) | 0.0100 (12) | 0.0020 (9) | 0.0051 (11) |
O14 | 0.0514 (13) | 0.0461 (13) | 0.0539 (13) | 0.0077 (11) | 0.0232 (11) | −0.0082 (11) |
O16 | 0.0490 (12) | 0.0729 (16) | 0.0316 (10) | 0.0088 (12) | 0.0201 (9) | 0.0024 (11) |
O22 | 0.0427 (11) | 0.0581 (14) | 0.0342 (10) | 0.0199 (11) | 0.0116 (9) | 0.0137 (10) |
O24 | 0.0390 (10) | 0.0373 (11) | 0.0290 (9) | 0.0128 (9) | 0.0123 (8) | 0.0065 (8) |
O26 | 0.0477 (12) | 0.0730 (16) | 0.0328 (10) | 0.0162 (12) | 0.0128 (9) | −0.0088 (11) |
N1 | 0.0357 (12) | 0.0352 (13) | 0.0403 (13) | −0.0003 (10) | 0.0129 (10) | 0.0012 (11) |
N2 | 0.0342 (11) | 0.0353 (12) | 0.0267 (10) | 0.0048 (10) | 0.0099 (9) | 0.0004 (9) |
O1 | 0.0585 (15) | 0.0781 (19) | 0.0402 (12) | 0.0180 (14) | 0.0221 (12) | 0.0053 (13) |
O2 | 0.0534 (14) | 0.086 (2) | 0.0445 (13) | 0.0177 (15) | 0.0209 (12) | 0.0060 (14) |
O3 | 0.171 (4) | 0.092 (3) | 0.0387 (15) | −0.043 (3) | 0.011 (2) | 0.0046 (17) |
O4 | 0.0702 (17) | 0.0676 (19) | 0.0568 (15) | −0.0052 (17) | 0.0303 (13) | −0.0072 (15) |
O5 | 0.0562 (16) | 0.0595 (17) | 0.0702 (18) | 0.0154 (14) | 0.0139 (14) | −0.0001 (14) |
O6 | 0.059 (2) | 0.068 (3) | 0.056 (2) | 0.000 | 0.0130 (19) | 0.000 |
N11 | 0.0267 (11) | 0.0493 (14) | 0.0287 (11) | 0.0024 (10) | 0.0078 (9) | −0.0007 (10) |
N13 | 0.0375 (12) | 0.0453 (14) | 0.0271 (11) | −0.0063 (11) | 0.0117 (9) | −0.0072 (10) |
N21 | 0.0303 (11) | 0.0367 (13) | 0.0323 (11) | 0.0059 (10) | 0.0112 (9) | 0.0015 (10) |
N23 | 0.0359 (12) | 0.0362 (12) | 0.0248 (10) | 0.0066 (10) | 0.0111 (9) | 0.0038 (9) |
C1 | 0.0371 (16) | 0.0501 (19) | 0.0372 (16) | −0.0077 (14) | 0.0074 (13) | −0.0028 (13) |
C2 | 0.0307 (14) | 0.0523 (18) | 0.0356 (15) | 0.0080 (13) | 0.0069 (12) | 0.0068 (13) |
C11 | 0.0350 (15) | 0.059 (2) | 0.0498 (17) | 0.0096 (14) | 0.0142 (13) | −0.0009 (15) |
C12 | 0.0335 (13) | 0.0420 (16) | 0.0292 (13) | −0.0044 (12) | 0.0081 (11) | −0.0020 (12) |
C13 | 0.061 (2) | 0.061 (2) | 0.0327 (15) | −0.0073 (17) | 0.0216 (14) | −0.0122 (15) |
C14 | 0.0353 (13) | 0.0312 (14) | 0.0352 (13) | −0.0005 (12) | 0.0134 (11) | −0.0015 (11) |
C15 | 0.0305 (13) | 0.0359 (14) | 0.0261 (12) | 0.0015 (11) | 0.0078 (10) | 0.0021 (11) |
C16 | 0.0329 (13) | 0.0419 (15) | 0.0242 (12) | −0.0029 (12) | 0.0102 (10) | −0.0012 (11) |
C21 | 0.0392 (16) | 0.0480 (18) | 0.0492 (17) | 0.0140 (14) | 0.0181 (14) | 0.0023 (15) |
C22 | 0.0320 (13) | 0.0332 (14) | 0.0362 (14) | 0.0014 (11) | 0.0123 (11) | 0.0041 (12) |
C23 | 0.0507 (18) | 0.0530 (19) | 0.0356 (15) | 0.0152 (15) | 0.0192 (13) | 0.0101 (14) |
C24 | 0.0285 (12) | 0.0307 (13) | 0.0300 (12) | 0.0015 (11) | 0.0069 (10) | 0.0041 (11) |
C25 | 0.0324 (13) | 0.0417 (15) | 0.0260 (12) | 0.0093 (12) | 0.0057 (10) | 0.0022 (11) |
C26 | 0.0342 (14) | 0.0417 (16) | 0.0321 (13) | 0.0000 (12) | 0.0104 (11) | −0.0046 (12) |
Pd—N1 | 2.078 (2) | C1—H3 | 0.97 |
Pd—N2 | 2.016 (2) | C1—H4 | 0.97 |
Pd—C15 | 2.115 (3) | C2—H5 | 0.97 |
Pd—O24 | 2.042 (2) | C2—H6 | 0.97 |
N1—C1 | 1.490 (4) | N2—H7 | 0.90 |
N2—C2 | 1.486 (3) | N2—H8 | 0.90 |
C1—C2 | 1.495 (5) | O1—H11 | 0.79 (2) |
N11—C11 | 1.466 (4) | O1—H12 | 0.78 (2) |
N11—C12 | 1.384 (3) | O2—H21 | 0.81 (2) |
N11—C16 | 1.393 (3) | O2—H22 | 0.84 (2) |
N13—C12 | 1.383 (4) | O3—H31 | 0.88 (3) |
N13—C13 | 1.472 (3) | O3—H32 | 0.82 (3) |
N13—C14 | 1.392 (3) | O4—H41 | 0.85 (2) |
C14—C15 | 1.457 (4) | O4—H42 | 0.80 (2) |
C15—C16 | 1.461 (4) | O5—H51 | 0.84 (2) |
O12—C12 | 1.218 (3) | O5—H52 | 0.81 (2) |
O14—C14 | 1.229 (3) | O6—H61 | 0.85 (2) |
O16—C16 | 1.219 (3) | C11—H111 | 0.96 |
N21—C22 | 1.382 (3) | C11—H112 | 0.96 |
N21—C26 | 1.405 (3) | C11—H113 | 0.96 |
N21—C21 | 1.461 (3) | C13—H131 | 0.96 |
N23—C22 | 1.376 (3) | C13—H132 | 0.96 |
N23—C24 | 1.397 (3) | C13—H133 | 0.96 |
N23—C23 | 1.472 (3) | C15—H15 | 0.98 |
C24—C25 | 1.374 (4) | C21—H211 | 0.96 |
C25—C26 | 1.402 (4) | C21—H212 | 0.96 |
O22—C22 | 1.229 (3) | C21—H213 | 0.96 |
O24—C24 | 1.275 (3) | C23—H231 | 0.96 |
O26—C26 | 1.246 (3) | C23—H232 | 0.96 |
N1—H1 | 0.90 | C23—H233 | 0.96 |
N1—H2 | 0.90 | C25—H25 | 0.93 |
N1—Pd—N2 | 83.91 (9) | N1—C1—H3 | 110.0 |
N1—Pd—C15 | 174.09 (10) | C2—C1—H3 | 110.0 |
N1—Pd—O24 | 92.20 (9) | N1—C1—H4 | 110.0 |
N2—Pd—C15 | 90.31 (10) | C2—C1—H4 | 110.0 |
N2—Pd—O24 | 174.85 (8) | H3—C1—H4 | 108.4 |
C15—Pd—O24 | 93.65 (9) | N2—C2—H5 | 110.1 |
Pd—C15—C14 | 104.0 (2) | C1—C2—H5 | 110.1 |
Pd—C15—C16 | 105.6 (2) | N2—C2—H6 | 110.1 |
Pd—O24—C24 | 120.8 (2) | C1—C2—H6 | 110.1 |
Pd—N1—C1 | 107.4 (2) | H5—C2—H6 | 108.4 |
Pd—N2—C2 | 108.9 (2) | C2—N2—H7 | 109.9 |
N1—C1—C2 | 108.2 (2) | Pd—N2—H7 | 109.9 |
N2—C2—C1 | 108.0 (2) | C2—N2—H8 | 109.9 |
C12—N11—C16 | 123.9 (2) | Pd—N2—H8 | 109.9 |
C12—N11—C11 | 117.4 (2) | H7—N2—H8 | 108.3 |
C16—N11—C11 | 118.6 (2) | H11—O1—H12 | 108 (4) |
C12—N13—C14 | 123.6 (2) | H21—O2—H22 | 108 (4) |
C12—N13—C13 | 117.1 (2) | H31—O3—H32 | 114 (5) |
C14—N13—C13 | 119.2 (2) | H41—O4—H42 | 118 (4) |
O12—C12—N13 | 121.9 (3) | H51—O5—H52 | 100 (4) |
O12—C12—N11 | 120.3 (3) | N11—C11—H111 | 109.5 |
N13—C12—N11 | 117.8 (2) | N11—C11—H112 | 109.5 |
O14—C14—N13 | 119.3 (3) | H111—C11—H112 | 109.5 |
O14—C14—C15 | 124.0 (3) | N11—C11—H113 | 109.5 |
N13—C14—C15 | 116.7 (2) | H111—C11—H113 | 109.5 |
C14—C15—C16 | 118.0 (2) | H112—C11—H113 | 109.5 |
O16—C16—N11 | 119.2 (3) | N13—C13—H131 | 109.5 |
O16—C16—C15 | 123.9 (2) | N13—C13—H132 | 109.5 |
N11—C16—C15 | 116.9 (2) | H131—C13—H132 | 109.5 |
C22—N21—C26 | 123.5 (2) | N13—C13—H133 | 109.5 |
C22—N21—C21 | 117.3 (2) | H131—C13—H133 | 109.5 |
C26—N21—C21 | 119.1 (2) | H132—C13—H133 | 109.5 |
C22—N23—C24 | 122.8 (2) | C14—C15—H15 | 109.6 |
C22—N23—C23 | 117.0 (2) | C16—C15—H15 | 109.6 |
C24—N23—C23 | 120.2 (2) | Pd—C15—H15 | 109.6 |
O22—C22—N23 | 121.9 (3) | N21—C21—H211 | 109.5 |
O22—C22—N21 | 121.2 (3) | N21—C21—H212 | 109.5 |
N23—C22—N21 | 116.9 (2) | H211—C21—H212 | 109.5 |
O24—C24—N23 | 115.4 (2) | N21—C21—H213 | 109.5 |
O24—C24—C25 | 126.7 (2) | H211—C21—H213 | 109.5 |
N23—C24—C25 | 118.0 (2) | H212—C21—H213 | 109.5 |
C24—C25—C26 | 122.4 (2) | N23—C23—H231 | 109.5 |
O26—C26—N21 | 118.5 (3) | N23—C23—H232 | 109.5 |
O26—C26—C25 | 125.3 (3) | H231—C23—H232 | 109.5 |
N21—C26—C25 | 116.2 (2) | N23—C23—H233 | 109.5 |
C1—N1—H1 | 110.2 | H231—C23—H233 | 109.5 |
Pd—N1—H1 | 110.2 | H232—C23—H233 | 109.5 |
C1—N1—H2 | 110.2 | C24—C25—H25 | 118.8 |
Pd—N1—H2 | 110.2 | C26—C25—H25 | 118.8 |
H1—N1—H2 | 108.5 | ||
N2—Pd—O24—C24 | −129.1 (9) | O24—Pd—C15—C16 | −60.38 (17) |
N1—Pd—O24—C24 | −88.4 (2) | N1—Pd—C15—C16 | 110.8 (10) |
C15—Pd—O24—C24 | 90.7 (2) | C12—N11—C16—O16 | −173.9 (3) |
N2—Pd—N1—C1 | −12.38 (19) | C11—N11—C16—O16 | 1.3 (4) |
O24—Pd—N1—C1 | 170.99 (19) | C12—N11—C16—C15 | 6.1 (4) |
C15—Pd—N1—C1 | −0.2 (11) | C11—N11—C16—C15 | −178.7 (3) |
O24—Pd—N2—C2 | 24.7 (10) | C14—C15—C16—O16 | 163.0 (3) |
N1—Pd—N2—C2 | −16.27 (18) | Pd—C15—C16—O16 | −81.3 (3) |
C15—Pd—N2—C2 | 164.97 (18) | C14—C15—C16—N11 | −17.0 (4) |
Pd—N1—C1—C2 | 38.6 (3) | Pd—C15—C16—N11 | 98.7 (2) |
Pd—N2—C2—C1 | 42.2 (3) | C24—N23—C22—O22 | −175.8 (3) |
N1—C1—C2—N2 | −53.8 (3) | C23—N23—C22—O22 | 3.5 (4) |
C14—N13—C12—O12 | −175.9 (3) | C24—N23—C22—N21 | 3.8 (4) |
C13—N13—C12—O12 | 0.2 (4) | C23—N23—C22—N21 | −176.9 (3) |
C14—N13—C12—N11 | 3.6 (4) | C26—N21—C22—O22 | 179.9 (3) |
C13—N13—C12—N11 | 179.7 (3) | C21—N21—C22—O22 | 4.2 (4) |
C16—N11—C12—O12 | −179.6 (3) | C26—N21—C22—N23 | 0.3 (4) |
C11—N11—C12—O12 | 5.1 (4) | C21—N21—C22—N23 | −175.4 (3) |
C16—N11—C12—N13 | 0.9 (4) | Pd—O24—C24—C25 | 8.8 (4) |
C11—N11—C12—N13 | −174.3 (3) | Pd—O24—C24—N23 | −170.63 (17) |
C12—N13—C14—O14 | 166.4 (3) | C22—N23—C24—O24 | 173.5 (2) |
C13—N13—C14—O14 | −9.7 (4) | C23—N23—C24—O24 | −5.7 (4) |
C12—N13—C14—C15 | −14.6 (4) | C22—N23—C24—C25 | −5.9 (4) |
C13—N13—C14—C15 | 169.4 (3) | C23—N23—C24—C25 | 174.9 (3) |
O14—C14—C15—C16 | −160.0 (3) | O24—C24—C25—C26 | −175.5 (3) |
N13—C14—C15—C16 | 21.0 (4) | N23—C24—C25—C26 | 3.9 (4) |
O14—C14—C15—Pd | 83.5 (3) | C24—C25—C26—O26 | 179.4 (3) |
N13—C14—C15—Pd | −95.5 (2) | C24—C25—C26—N21 | −0.1 (4) |
N2—Pd—C15—C14 | −112.19 (18) | C22—N21—C26—O26 | 178.3 (3) |
O24—Pd—C15—C14 | 64.51 (18) | C21—N21—C26—O26 | −6.1 (4) |
N1—Pd—C15—C14 | −124.3 (9) | C22—N21—C26—C25 | −2.1 (4) |
N2—Pd—C15—C16 | 122.92 (17) | C21—N21—C26—C25 | 173.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O22i | 0.79 (2) | 2.01 (2) | 2.793 (3) | 172 (4) |
O1—H12···O2 | 0.78 (2) | 2.02 (3) | 2.760 (4) | 160 (4) |
O2—H21···O26ii | 0.81 (2) | 1.95 (3) | 2.727 (3) | 159 (4) |
O2—H22···O4iii | 0.84 (2) | 1.91 (2) | 2.738 (4) | 175 (4) |
O3—H31···O2 | 0.88 (3) | 1.88 (3) | 2.758 (5) | 177 (6) |
O3—H32···O12iv | 0.82 (3) | 1.96 (3) | 2.765 (3) | 169 (6) |
O4—H41···O3 | 0.85 (2) | 1.78 (3) | 2.628 (5) | 173 (4) |
O4—H42···O1v | 0.80 (2) | 1.94 (3) | 2.727 (4) | 169 (4) |
O5—H51···O4 | 0.84 (2) | 1.98 (3) | 2.776 (4) | 157 (4) |
O5—H52···O14 | 0.81 (2) | 2.01 (3) | 2.810 (4) | 169 (4) |
O6—H61···O26 | 0.85 (2) | 2.18 (3) | 2.907 (3) | 143 (4) |
N1—H1···O1 | 0.90 | 2.24 | 3.065 (4) | 152 |
N1—H2···O5vi | 0.90 | 2.19 | 3.030 (4) | 155 |
N2—H7···O16vii | 0.90 | 2.11 | 2.863 (3) | 141 |
N2—H8···O5 | 0.90 | 2.14 | 3.038 (4) | 175 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z; (vi) x, y+1, z; (vii) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C6H7N2O3)2(C2H8N2)]·5.5H2O |
Mr | 575.86 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 24.225 (3), 8.307 (3), 25.396 (2) |
β (°) | 113.505 (5) |
V (Å3) | 4686.4 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.25 × 0.12 × 0.06 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6982, 6837, 4810 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.080, 1.02 |
No. of reflections | 6837 |
No. of parameters | 327 |
No. of restraints | 11 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.49 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a), MSC/AFC Diffractometer Control Software, TEXSAN PROCESS (Molecular Structure Corporation, 1993b), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Pd—N1 | 2.078 (2) | O14—C14 | 1.229 (3) |
Pd—N2 | 2.016 (2) | O16—C16 | 1.219 (3) |
Pd—C15 | 2.115 (3) | C24—C25 | 1.374 (4) |
Pd—O24 | 2.042 (2) | C25—C26 | 1.402 (4) |
C14—C15 | 1.457 (4) | O22—C22 | 1.229 (3) |
C15—C16 | 1.461 (4) | O24—C24 | 1.275 (3) |
O12—C12 | 1.218 (3) | O26—C26 | 1.246 (3) |
N1—Pd—N2 | 83.91 (9) | Pd—O24—C24 | 120.8 (2) |
N1—Pd—C15 | 174.09 (10) | O14—C14—C15 | 124.0 (3) |
N1—Pd—O24 | 92.20 (9) | C14—C15—C16 | 118.0 (2) |
N2—Pd—C15 | 90.31 (10) | O16—C16—C15 | 123.9 (2) |
N2—Pd—O24 | 174.85 (8) | O24—C24—C25 | 126.7 (2) |
C15—Pd—O24 | 93.65 (9) | C24—C25—C26 | 122.4 (2) |
Pd—C15—C14 | 104.0 (2) | O26—C26—C25 | 125.3 (3) |
Pd—C15—C16 | 105.6 (2) | ||
Pd—O24—C24—C25 | 8.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O22i | 0.79 (2) | 2.01 (2) | 2.793 (3) | 172 (4) |
O1—H12···O2 | 0.78 (2) | 2.02 (3) | 2.760 (4) | 160 (4) |
O2—H21···O26ii | 0.81 (2) | 1.95 (3) | 2.727 (3) | 159 (4) |
O2—H22···O4iii | 0.84 (2) | 1.91 (2) | 2.738 (4) | 175 (4) |
O3—H31···O2 | 0.88 (3) | 1.88 (3) | 2.758 (5) | 177 (6) |
O3—H32···O12iv | 0.82 (3) | 1.96 (3) | 2.765 (3) | 169 (6) |
O4—H41···O3 | 0.85 (2) | 1.78 (3) | 2.628 (5) | 173 (4) |
O4—H42···O1v | 0.80 (2) | 1.94 (3) | 2.727 (4) | 169 (4) |
O5—H51···O4 | 0.84 (2) | 1.98 (3) | 2.776 (4) | 157 (4) |
O5—H52···O14 | 0.81 (2) | 2.01 (3) | 2.810 (4) | 169 (4) |
O6—H61···O26 | 0.85 (2) | 2.18 (3) | 2.907 (3) | 143 (4) |
N1—H1···O1 | 0.90 | 2.24 | 3.065 (4) | 152 |
N1—H2···O5vi | 0.90 | 2.19 | 3.030 (4) | 155 |
N2—H7···O16vii | 0.90 | 2.11 | 2.863 (3) | 141 |
N2—H8···O5 | 0.90 | 2.14 | 3.038 (4) | 175 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z; (vi) x, y+1, z; (vii) −x+1, y, −z+3/2. |
By using a cyclic β-diketone, cyclohexane-1,3-dione (Hchdo) and 1,3-dimethylbarbituric acid (Hdmbarb), we have recently synthesized new organoplatinum(II) compounds. Among them, two linkage isomers of Pt(en)(dmbarb-C)(dmbarb-O)], (I'), and [Pt(en)(dmbarb-C)2]·2H2O, (II'), (en = 1,2-diaminoethane) have been found (Noguchi et al., 2000); in aqueous solution, the monoalkyl (I') has gradually rearranged to the dialkyl (II'). The palladium(II) compounds in the same group as the platinum(II) generally react much more rapidly. From an aqueous solution containing Hdmbarb and [Pd(en)(OH)2], replacing PtII with PdII, we have obtained only monoalkylpalladium(II) compound [Pt(en)(dmbarb-C)(dmbarb-O)].5.5H2O, (I).
The molecular structure of [Pd(en)(dmbarb-C)(dmbarb-O)] in (I) is similar to that of [Pt(en)(dmbarb-C)(dmbarb-O)] in (I'); the two independent dmbarb− anions as monodentate ligands coordinate to the Pd atom at the tetrahedral C15 atom and the enolate O24 atom. In spite of difference between Pd and Pt, the bond lengths and angles about the coordination centers in (I) and (I') almost correspond with each other within their s.u.'s except for Pd—N1 and Pt—N1. The shorter Pd—N1 bond length of 2.078 (2) Å in (I) may be influenced more weakly by the tetrahedral C15 atom at the trans position, compared with the Pt—N1 of 2.098 (3) Å in (I'). In the palladium(II) barbiturate complex [Pd(en)(µ-barb-C,N)]2.4H2O, (III), where barb is a barbiturate dianion, the Pd—N bond length of 2.070 (3) Å at the trans position of the C atom is quite comparable (Sinn et al., 1978). The Pd—N1 in (I) and the Pt—N1 in (I') are apparently longer than the Pd—N2 and Pt—N2 distances of 2.016 (2) and 2.015 (3) Å, respectively.
Both dmbarb− ligands are approximately planar within 0.027 Å, except the tetrahedral C15 atom with the deviation of 0.213 (4) Å from the least-squares plane of N11, C12, N13, C14 and C16. The moleuclar planes of the two dmbarb− ligands except C15, are almost parallel with the dihedral angle of 7.2 (1)° different from the Pt-analog (I') with 40.7 (2)°, and are perpendicular to the Pd coordination plane with the dihedral angles of 89.44 (8) and 87.00 (7)° for the β-diketonato and the enolato dmbarb−, respectively. The Pt—O24—C24═C25 torsion angle is 8.8 (4)°.
The water molecules included in (I) seem to make a remarkable difference between the structures of (I) and (I'). Water molecules in (I) occupy the intermolecular space to form a close hydrogen-bonded lattice together with the carbonyl O12, O14, O22 and O26 of the dmbarb− ligands and the amino N1 and N2 of the en (Table 2). The hydrogen bonds between the adjacent Pd complexes are found only between N2 and O16 in (I), while a two-dimensional hydrogen-bond network is formed between the adjacent Pt complexes in (I'). The water molecules seem to determine the orientations of the O-bonded enolato dmbarb−.