Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105004580/sk1813sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105004580/sk1813Isup2.hkl |
CCDC reference: 269011
A mixture of Cu(CH3COO)2·H2O (0.040 g, 0.20 mmol), 5-sulfosalicylic acid dihydrate (0.026 g, 0.10 mmol), 2,2'-dipyridylamine (0.035 g, 0.20 mmol), NaOH (0.019 g, 0.5 mmol) and water (10 ml) was heated at 413 K for 72 h in a 20 ml Teflon-lined stainless steel autoclave. After cooling, green block-shaped crystals of (I) were obtained by filtration.
The aromatic H atoms were generated geometrically, and were included in the refinements in the riding model approximation (C—H 0.93 Å, U 1.2UeqC). The water and amine H atoms were located from a difference Fourier map and were refined with distance restraints of O—H 0.85 (1) and N—H 0.82 (1) and with fixed isotropic displacement parameters of Uiso(H)=0.08 and 0.05 Å2, respectively. The crystals were dried and stored in air. Data collection was directly done using such a crystal without a protective oil at room temperature. PLATON analysis (Spek, 2003) suggests that the structure contains a solvent accessible void which is capable to accommodate an additional water molecule in the region around (1/2, 0, 0), while under present treated procedure, the additional water molecule is not located. Although the crystal was measured to a 2θ limit of 56.7 °, only the intensities below 50.1 ° were used in the refinement; the use of all reflections gave a much lower data completeness (90.5%). In present refinement, there are 55 reflections missing from the dataset.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cu2(C7H3O6S)2(C10H9N3)2][Cu(C10H9N3)2]2·2H2O | Z = 1 |
Mr = 1747.71 | F(000) = 894 |
Triclinic, P1 | Dx = 1.549 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.258 (2) Å | Cell parameters from 4694 reflections |
b = 14.422 (4) Å | θ = 2.5–26.2° |
c = 18.312 (5) Å | µ = 1.25 mm−1 |
α = 82.428 (4)° | T = 295 K |
β = 80.697 (4)° | Block, green |
γ = 86.409 (4)° | 0.28 × 0.19 × 0.14 mm |
V = 1873.5 (9) Å3 |
Bruker SMART APEX area-detector diffractometer | 6582 independent reflections |
Radiation source: fine-focus sealed tube | 6078 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→8 |
Tmin = 0.759, Tmax = 0.844 | k = −17→16 |
13648 measured reflections | l = −21→21 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0469P)2 + 3.6691P] where P = (Fo2 + 2Fc2)/3 |
6582 reflections | (Δ/σ)max < 0.001 |
514 parameters | Δρmax = 0.65 e Å−3 |
5 restraints | Δρmin = −0.41 e Å−3 |
[Cu2(C7H3O6S)2(C10H9N3)2][Cu(C10H9N3)2]2·2H2O | γ = 86.409 (4)° |
Mr = 1747.71 | V = 1873.5 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.258 (2) Å | Mo Kα radiation |
b = 14.422 (4) Å | µ = 1.25 mm−1 |
c = 18.312 (5) Å | T = 295 K |
α = 82.428 (4)° | 0.28 × 0.19 × 0.14 mm |
β = 80.697 (4)° |
Bruker SMART APEX area-detector diffractometer | 6582 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 6078 reflections with I > 2σ(I) |
Tmin = 0.759, Tmax = 0.844 | Rint = 0.026 |
13648 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 5 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.65 e Å−3 |
6582 reflections | Δρmin = −0.41 e Å−3 |
514 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 | ||
Cu1 | 0.68516 (8) | 0.45186 (4) | 0.95670 (3) | 0.02985 (17) | |
Cu2 | 0.18868 (10) | 0.75470 (5) | 0.41661 (4) | 0.0536 (2) | |
S1 | 0.71032 (18) | 0.92243 (8) | 0.76677 (6) | 0.0375 (3) | |
O1 | 0.6209 (5) | 0.4850 (2) | 0.85829 (16) | 0.0366 (8) | |
O2 | 0.5829 (5) | 0.5723 (2) | 0.75380 (18) | 0.0427 (8) | |
O3 | 0.6158 (4) | 0.5776 (2) | 0.97907 (16) | 0.0329 (7) | |
O4 | 0.8609 (6) | 0.9702 (3) | 0.7852 (2) | 0.0618 (11) | |
O5 | 0.7470 (7) | 0.8950 (3) | 0.6930 (2) | 0.0634 (12) | |
O6 | 0.5349 (6) | 0.9744 (3) | 0.7804 (3) | 0.0740 (14) | |
O7 | 0.1860 (6) | 0.9049 (3) | 0.8444 (3) | 0.0935 (17) | |
N1 | 0.8028 (5) | 0.4254 (3) | 1.0503 (2) | 0.0313 (8) | |
N2 | 0.7951 (6) | 0.2611 (3) | 1.0568 (2) | 0.0411 (10) | |
N3 | 0.7608 (6) | 0.3196 (3) | 0.9333 (2) | 0.0365 (9) | |
N4 | −0.0029 (6) | 0.8607 (3) | 0.4300 (2) | 0.0418 (10) | |
N5 | −0.0302 (6) | 0.8319 (3) | 0.5614 (2) | 0.0426 (10) | |
N6 | 0.2612 (6) | 0.7623 (3) | 0.5182 (2) | 0.0432 (10) | |
N7 | 0.0631 (6) | 0.6361 (3) | 0.4063 (3) | 0.0523 (12) | |
N8 | 0.3240 (6) | 0.5820 (3) | 0.3260 (2) | 0.0454 (11) | |
N9 | 0.3973 (6) | 0.7387 (3) | 0.3337 (2) | 0.0429 (10) | |
C1 | 0.8459 (7) | 0.4984 (4) | 1.0828 (3) | 0.0394 (11) | |
H1 | 0.8345 | 0.5584 | 1.0576 | 0.047* | |
C2 | 0.9053 (7) | 0.4890 (4) | 1.1509 (3) | 0.0462 (13) | |
H2 | 0.9367 | 0.5410 | 1.1706 | 0.055* | |
C3 | 0.9173 (7) | 0.4009 (4) | 1.1892 (3) | 0.0499 (14) | |
H3 | 0.9521 | 0.3926 | 1.2365 | 0.060* | |
C4 | 0.8782 (7) | 0.3264 (4) | 1.1578 (3) | 0.0453 (13) | |
H4 | 0.8866 | 0.2664 | 1.1831 | 0.054* | |
C5 | 0.8248 (6) | 0.3398 (3) | 1.0868 (3) | 0.0347 (10) | |
C6 | 0.7879 (7) | 0.2477 (3) | 0.9849 (3) | 0.0377 (11) | |
C7 | 0.8082 (10) | 0.1558 (4) | 0.9676 (3) | 0.0615 (17) | |
H7 | 0.8210 | 0.1065 | 1.0049 | 0.074* | |
C8 | 0.8093 (11) | 0.1382 (4) | 0.8970 (4) | 0.078 (2) | |
H8 | 0.8236 | 0.0771 | 0.8853 | 0.094* | |
C9 | 0.7891 (10) | 0.2118 (4) | 0.8425 (4) | 0.0675 (18) | |
H9 | 0.7920 | 0.2016 | 0.7932 | 0.081* | |
C10 | 0.7646 (8) | 0.3001 (4) | 0.8627 (3) | 0.0522 (14) | |
H10 | 0.7497 | 0.3497 | 0.8258 | 0.063* | |
C11 | 0.6120 (6) | 0.5651 (3) | 0.8197 (2) | 0.0287 (9) | |
C12 | 0.6384 (6) | 0.6514 (3) | 0.8522 (2) | 0.0278 (9) | |
C13 | 0.6421 (6) | 0.6523 (3) | 0.9290 (2) | 0.0282 (9) | |
C14 | 0.6713 (7) | 0.7381 (3) | 0.9532 (3) | 0.0358 (11) | |
H14 | 0.6758 | 0.7398 | 1.0035 | 0.043* | |
C15 | 0.6933 (7) | 0.8191 (3) | 0.9051 (3) | 0.0389 (11) | |
H15 | 0.7113 | 0.8749 | 0.9227 | 0.047* | |
C16 | 0.6884 (6) | 0.8175 (3) | 0.8292 (2) | 0.0318 (10) | |
C17 | 0.6620 (6) | 0.7344 (3) | 0.8044 (2) | 0.0291 (10) | |
H17 | 0.6599 | 0.7336 | 0.7538 | 0.035* | |
C18 | −0.0624 (9) | 0.9107 (4) | 0.3696 (3) | 0.0542 (14) | |
H18 | −0.0038 | 0.8987 | 0.3226 | 0.065* | |
C19 | −0.2019 (8) | 0.9769 (4) | 0.3740 (3) | 0.0533 (14) | |
H19 | −0.2403 | 1.0086 | 0.3311 | 0.064* | |
C20 | −0.2859 (7) | 0.9963 (4) | 0.4432 (3) | 0.0473 (13) | |
H20 | −0.3829 | 1.0415 | 0.4476 | 0.057* | |
C21 | −0.2272 (7) | 0.9493 (3) | 0.5056 (3) | 0.0405 (12) | |
H21 | −0.2809 | 0.9629 | 0.5528 | 0.049* | |
C22 | −0.0846 (6) | 0.8803 (3) | 0.4968 (3) | 0.0341 (10) | |
C23 | 0.1413 (7) | 0.7916 (3) | 0.5739 (3) | 0.0379 (11) | |
C24 | 0.1803 (8) | 0.7821 (4) | 0.6462 (3) | 0.0522 (14) | |
H24 | 0.0921 | 0.8013 | 0.6846 | 0.063* | |
C25 | 0.3492 (9) | 0.7444 (5) | 0.6602 (4) | 0.0673 (18) | |
H25 | 0.3776 | 0.7371 | 0.7084 | 0.081* | |
C26 | 0.4779 (9) | 0.7170 (5) | 0.6024 (4) | 0.072 (2) | |
H26 | 0.5952 | 0.6919 | 0.6104 | 0.086* | |
C27 | 0.4288 (8) | 0.7277 (4) | 0.5335 (4) | 0.0615 (16) | |
H27 | 0.5165 | 0.7101 | 0.4943 | 0.074* | |
C28 | −0.1097 (9) | 0.6207 (5) | 0.4427 (4) | 0.077 (2) | |
H28 | −0.1667 | 0.6651 | 0.4725 | 0.093* | |
C29 | −0.2065 (10) | 0.5451 (5) | 0.4391 (5) | 0.091 (3) | |
H29 | −0.3278 | 0.5387 | 0.4643 | 0.109* | |
C30 | −0.1202 (10) | 0.4775 (5) | 0.3970 (4) | 0.081 (2) | |
H30 | −0.1824 | 0.4241 | 0.3938 | 0.097* | |
C31 | 0.0560 (9) | 0.4897 (4) | 0.3604 (3) | 0.0589 (16) | |
H31 | 0.1169 | 0.4442 | 0.3325 | 0.071* | |
C32 | 0.1454 (7) | 0.5717 (3) | 0.3649 (3) | 0.0413 (12) | |
C33 | 0.4361 (7) | 0.6581 (3) | 0.3048 (3) | 0.0402 (11) | |
C34 | 0.5887 (8) | 0.6470 (4) | 0.2497 (4) | 0.0630 (17) | |
H34 | 0.6144 | 0.5901 | 0.2307 | 0.076* | |
C35 | 0.7005 (10) | 0.7209 (5) | 0.2239 (4) | 0.083 (2) | |
H35 | 0.8031 | 0.7148 | 0.1869 | 0.100* | |
C36 | 0.6600 (10) | 0.8044 (5) | 0.2531 (4) | 0.081 (2) | |
H36 | 0.7343 | 0.8555 | 0.2363 | 0.098* | |
C37 | 0.5102 (9) | 0.8102 (4) | 0.3065 (4) | 0.0633 (17) | |
H37 | 0.4830 | 0.8669 | 0.3258 | 0.076* | |
H8A | 0.360 (7) | 0.540 (3) | 0.300 (3) | 0.050* | |
H5A | −0.096 (6) | 0.850 (4) | 0.5980 (19) | 0.050* | |
H2A | 0.794 (8) | 0.213 (2) | 1.086 (2) | 0.050* | |
H7A | 0.0918 | 0.9366 | 0.8294 | 0.080* | |
H7B | 0.2740 | 0.9337 | 0.8175 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0385 (3) | 0.0239 (3) | 0.0268 (3) | 0.0013 (2) | −0.0048 (2) | −0.0034 (2) |
Cu2 | 0.0559 (4) | 0.0516 (4) | 0.0563 (4) | 0.0036 (3) | −0.0011 (3) | −0.0308 (3) |
S1 | 0.0503 (7) | 0.0265 (6) | 0.0321 (6) | −0.0030 (5) | 0.0019 (5) | 0.0003 (5) |
O1 | 0.057 (2) | 0.0263 (17) | 0.0291 (17) | −0.0025 (15) | −0.0139 (15) | −0.0049 (13) |
O2 | 0.069 (2) | 0.0292 (17) | 0.0321 (18) | 0.0016 (16) | −0.0134 (16) | −0.0077 (14) |
O3 | 0.0478 (19) | 0.0224 (15) | 0.0261 (16) | 0.0017 (13) | 0.0008 (14) | −0.0034 (13) |
O4 | 0.085 (3) | 0.043 (2) | 0.056 (2) | −0.027 (2) | −0.015 (2) | 0.0112 (18) |
O5 | 0.106 (3) | 0.047 (2) | 0.032 (2) | −0.010 (2) | 0.004 (2) | −0.0013 (17) |
O6 | 0.070 (3) | 0.050 (2) | 0.083 (3) | 0.016 (2) | 0.014 (2) | 0.023 (2) |
O7 | 0.072 (3) | 0.086 (3) | 0.107 (4) | −0.006 (3) | −0.016 (3) | 0.052 (3) |
N1 | 0.033 (2) | 0.030 (2) | 0.030 (2) | 0.0009 (16) | −0.0052 (16) | −0.0027 (16) |
N2 | 0.052 (3) | 0.033 (2) | 0.036 (2) | 0.002 (2) | −0.008 (2) | 0.0023 (18) |
N3 | 0.044 (2) | 0.031 (2) | 0.035 (2) | 0.0050 (17) | −0.0033 (18) | −0.0118 (17) |
N4 | 0.050 (3) | 0.038 (2) | 0.037 (2) | 0.0027 (19) | −0.0029 (19) | −0.0115 (19) |
N5 | 0.045 (3) | 0.053 (3) | 0.030 (2) | 0.010 (2) | −0.0047 (18) | −0.0100 (19) |
N6 | 0.039 (2) | 0.042 (2) | 0.049 (3) | 0.0040 (19) | −0.006 (2) | −0.012 (2) |
N7 | 0.042 (3) | 0.053 (3) | 0.065 (3) | −0.006 (2) | 0.000 (2) | −0.027 (2) |
N8 | 0.051 (3) | 0.039 (2) | 0.047 (3) | −0.003 (2) | 0.004 (2) | −0.021 (2) |
N9 | 0.046 (3) | 0.038 (2) | 0.046 (2) | −0.0016 (19) | −0.002 (2) | −0.0166 (19) |
C1 | 0.035 (3) | 0.042 (3) | 0.042 (3) | −0.001 (2) | −0.006 (2) | −0.011 (2) |
C2 | 0.034 (3) | 0.063 (4) | 0.046 (3) | 0.001 (2) | −0.007 (2) | −0.025 (3) |
C3 | 0.040 (3) | 0.072 (4) | 0.041 (3) | 0.006 (3) | −0.012 (2) | −0.015 (3) |
C4 | 0.042 (3) | 0.055 (3) | 0.036 (3) | 0.009 (2) | −0.009 (2) | 0.002 (2) |
C5 | 0.027 (2) | 0.039 (3) | 0.036 (3) | 0.002 (2) | −0.0004 (19) | −0.007 (2) |
C6 | 0.040 (3) | 0.031 (2) | 0.041 (3) | 0.005 (2) | −0.006 (2) | −0.002 (2) |
C7 | 0.095 (5) | 0.032 (3) | 0.059 (4) | 0.010 (3) | −0.019 (3) | −0.005 (3) |
C8 | 0.131 (7) | 0.035 (3) | 0.075 (5) | 0.018 (4) | −0.035 (4) | −0.023 (3) |
C9 | 0.106 (5) | 0.050 (4) | 0.054 (4) | 0.020 (3) | −0.025 (4) | −0.028 (3) |
C10 | 0.075 (4) | 0.042 (3) | 0.042 (3) | 0.012 (3) | −0.015 (3) | −0.014 (2) |
C11 | 0.027 (2) | 0.031 (2) | 0.027 (2) | 0.0016 (18) | −0.0021 (18) | −0.0038 (19) |
C12 | 0.025 (2) | 0.028 (2) | 0.030 (2) | 0.0030 (17) | 0.0001 (18) | −0.0070 (18) |
C13 | 0.028 (2) | 0.026 (2) | 0.029 (2) | 0.0043 (18) | 0.0008 (18) | −0.0070 (18) |
C14 | 0.047 (3) | 0.036 (3) | 0.025 (2) | −0.005 (2) | −0.002 (2) | −0.0073 (19) |
C15 | 0.054 (3) | 0.025 (2) | 0.038 (3) | −0.008 (2) | −0.002 (2) | −0.007 (2) |
C16 | 0.039 (3) | 0.024 (2) | 0.030 (2) | −0.0028 (19) | −0.0013 (19) | 0.0013 (18) |
C17 | 0.033 (2) | 0.030 (2) | 0.024 (2) | 0.0014 (19) | −0.0029 (18) | −0.0054 (18) |
C18 | 0.072 (4) | 0.057 (4) | 0.033 (3) | −0.002 (3) | −0.003 (3) | −0.007 (3) |
C19 | 0.058 (4) | 0.056 (4) | 0.043 (3) | −0.001 (3) | −0.010 (3) | 0.007 (3) |
C20 | 0.038 (3) | 0.045 (3) | 0.054 (3) | 0.000 (2) | −0.003 (2) | 0.004 (3) |
C21 | 0.036 (3) | 0.046 (3) | 0.038 (3) | 0.002 (2) | −0.001 (2) | −0.009 (2) |
C22 | 0.031 (2) | 0.036 (3) | 0.036 (3) | −0.006 (2) | −0.001 (2) | −0.006 (2) |
C23 | 0.042 (3) | 0.031 (2) | 0.041 (3) | −0.003 (2) | −0.006 (2) | −0.002 (2) |
C24 | 0.048 (3) | 0.063 (4) | 0.041 (3) | 0.000 (3) | −0.008 (2) | 0.007 (3) |
C25 | 0.056 (4) | 0.092 (5) | 0.050 (4) | −0.004 (3) | −0.017 (3) | 0.018 (3) |
C26 | 0.038 (3) | 0.088 (5) | 0.083 (5) | 0.007 (3) | −0.017 (3) | 0.016 (4) |
C27 | 0.046 (3) | 0.069 (4) | 0.066 (4) | 0.008 (3) | −0.002 (3) | −0.007 (3) |
C28 | 0.047 (4) | 0.072 (4) | 0.112 (6) | −0.014 (3) | 0.019 (4) | −0.043 (4) |
C29 | 0.057 (4) | 0.083 (5) | 0.125 (7) | −0.023 (4) | 0.032 (4) | −0.034 (5) |
C30 | 0.075 (5) | 0.067 (4) | 0.099 (6) | −0.030 (4) | 0.012 (4) | −0.022 (4) |
C31 | 0.068 (4) | 0.047 (3) | 0.062 (4) | −0.015 (3) | 0.005 (3) | −0.019 (3) |
C32 | 0.048 (3) | 0.039 (3) | 0.039 (3) | −0.004 (2) | −0.008 (2) | −0.012 (2) |
C33 | 0.041 (3) | 0.040 (3) | 0.042 (3) | 0.000 (2) | −0.003 (2) | −0.017 (2) |
C34 | 0.055 (4) | 0.052 (4) | 0.083 (5) | −0.008 (3) | 0.007 (3) | −0.033 (3) |
C35 | 0.060 (4) | 0.075 (5) | 0.110 (6) | −0.020 (4) | 0.031 (4) | −0.043 (4) |
C36 | 0.074 (5) | 0.062 (4) | 0.105 (6) | −0.031 (4) | 0.020 (4) | −0.028 (4) |
C37 | 0.065 (4) | 0.046 (3) | 0.081 (5) | −0.010 (3) | 0.000 (3) | −0.028 (3) |
Cu1—O1 | 1.926 (3) | C7—C8 | 1.349 (8) |
Cu1—O3 | 1.930 (3) | C7—H7 | 0.9300 |
Cu1—N1 | 2.019 (4) | C8—C9 | 1.375 (9) |
Cu1—N3 | 2.033 (4) | C8—H8 | 0.9300 |
Cu1—O3i | 2.343 (3) | C9—C10 | 1.366 (7) |
Cu2—N9 | 1.989 (4) | C9—H9 | 0.9300 |
Cu2—N4 | 2.013 (4) | C10—H10 | 0.9300 |
Cu2—N6 | 2.031 (4) | C11—C12 | 1.484 (6) |
Cu2—N7 | 2.032 (4) | C12—C17 | 1.389 (6) |
S1—O4 | 1.435 (4) | C12—C13 | 1.411 (6) |
S1—O5 | 1.436 (4) | C13—C14 | 1.408 (6) |
S1—O6 | 1.440 (4) | C14—C15 | 1.369 (6) |
S1—C16 | 1.772 (4) | C14—H14 | 0.9300 |
O1—C11 | 1.276 (5) | C15—C16 | 1.398 (6) |
O2—C11 | 1.249 (5) | C15—H15 | 0.9300 |
O3—C13 | 1.321 (5) | C16—C17 | 1.371 (6) |
O3—Cu1i | 2.343 (3) | C17—H17 | 0.9300 |
O7—H7A | 0.86 | C18—C19 | 1.348 (8) |
O7—H7B | 0.84 | C18—H18 | 0.9300 |
N1—C5 | 1.338 (6) | C19—C20 | 1.369 (8) |
N1—C1 | 1.352 (6) | C19—H19 | 0.9300 |
N2—C6 | 1.365 (6) | C20—C21 | 1.366 (7) |
N2—C5 | 1.367 (6) | C20—H20 | 0.9300 |
N2—H2A | 0.82 (3) | C21—C22 | 1.394 (7) |
N3—C6 | 1.336 (6) | C21—H21 | 0.9300 |
N3—C10 | 1.354 (6) | C23—C24 | 1.386 (7) |
N4—C22 | 1.328 (6) | C24—C25 | 1.359 (8) |
N4—C18 | 1.354 (7) | C24—H24 | 0.9300 |
N5—C23 | 1.381 (6) | C25—C26 | 1.376 (9) |
N5—C22 | 1.394 (6) | C25—H25 | 0.9300 |
N5—H5A | 0.82 (4) | C26—C27 | 1.352 (9) |
N6—C23 | 1.326 (6) | C26—H26 | 0.9300 |
N6—C27 | 1.343 (7) | C27—H27 | 0.9300 |
N7—C32 | 1.327 (6) | C28—C29 | 1.347 (9) |
N7—C28 | 1.339 (7) | C28—H28 | 0.9300 |
N8—C32 | 1.382 (7) | C29—C30 | 1.379 (10) |
N8—C33 | 1.383 (6) | C29—H29 | 0.9300 |
N8—H8A | 0.82 (5) | C30—C31 | 1.355 (9) |
N9—C33 | 1.336 (6) | C30—H30 | 0.9300 |
N9—C37 | 1.350 (7) | C31—C32 | 1.402 (7) |
C1—C2 | 1.371 (7) | C31—H31 | 0.9300 |
C1—H1 | 0.9300 | C33—C34 | 1.389 (7) |
C2—C3 | 1.374 (8) | C34—C35 | 1.367 (9) |
C2—H2 | 0.9300 | C34—H34 | 0.9300 |
C3—C4 | 1.350 (8) | C35—C36 | 1.377 (9) |
C3—H3 | 0.9300 | C35—H35 | 0.9300 |
C4—C5 | 1.401 (7) | C36—C37 | 1.346 (9) |
C4—H4 | 0.9300 | C36—H36 | 0.9300 |
C6—C7 | 1.396 (7) | C37—H37 | 0.9300 |
O1—Cu1—O3 | 89.89 (13) | C9—C10—H10 | 118.2 |
O1—Cu1—N1 | 168.73 (15) | O2—C11—O1 | 120.7 (4) |
O3—Cu1—N1 | 90.05 (14) | O2—C11—C12 | 118.8 (4) |
O1—Cu1—N3 | 90.36 (14) | O1—C11—C12 | 120.5 (4) |
O3—Cu1—N3 | 179.45 (16) | C17—C12—C13 | 119.1 (4) |
N1—Cu1—N3 | 89.61 (15) | C17—C12—C11 | 118.0 (4) |
O1—Cu1—O3i | 98.07 (13) | C13—C12—C11 | 122.9 (4) |
O3—Cu1—O3i | 82.45 (12) | O3—C13—C14 | 118.6 (4) |
N1—Cu1—O3i | 93.09 (13) | O3—C13—C12 | 123.6 (4) |
N3—Cu1—O3i | 97.99 (14) | C14—C13—C12 | 117.8 (4) |
N9—Cu2—N4 | 130.02 (18) | C15—C14—C13 | 122.0 (4) |
N9—Cu2—N6 | 116.50 (18) | C15—C14—H14 | 119.0 |
N4—Cu2—N6 | 91.23 (16) | C13—C14—H14 | 119.0 |
N9—Cu2—N7 | 94.58 (17) | C14—C15—C16 | 119.6 (4) |
N4—Cu2—N7 | 110.31 (18) | C14—C15—H15 | 120.2 |
N6—Cu2—N7 | 115.75 (19) | C16—C15—H15 | 120.2 |
O4—S1—O5 | 113.4 (3) | C17—C16—C15 | 119.3 (4) |
O4—S1—O6 | 111.7 (3) | C17—C16—S1 | 120.7 (3) |
O5—S1—O6 | 112.4 (3) | C15—C16—S1 | 120.1 (3) |
O4—S1—C16 | 106.3 (2) | C16—C17—C12 | 122.1 (4) |
O5—S1—C16 | 106.3 (2) | C16—C17—H17 | 118.9 |
O6—S1—C16 | 106.2 (2) | C12—C17—H17 | 118.9 |
C11—O1—Cu1 | 129.8 (3) | C19—C18—N4 | 123.5 (5) |
C13—O3—Cu1 | 123.1 (3) | C19—C18—H18 | 118.2 |
C13—O3—Cu1i | 119.6 (3) | N4—C18—H18 | 118.2 |
Cu1—O3—Cu1i | 97.55 (12) | C18—C19—C20 | 118.5 (5) |
H7A—O7—H7B | 100.00 | C18—C19—H19 | 120.7 |
C5—N1—C1 | 117.1 (4) | C20—C19—H19 | 120.7 |
C5—N1—Cu1 | 123.9 (3) | C21—C20—C19 | 119.9 (5) |
C1—N1—Cu1 | 118.7 (3) | C21—C20—H20 | 120.0 |
C6—N2—C5 | 130.9 (4) | C19—C20—H20 | 120.0 |
C6—N2—H2A | 115 (4) | C20—C21—C22 | 118.4 (5) |
C5—N2—H2A | 113 (4) | C20—C21—H21 | 120.8 |
C6—N3—C10 | 117.2 (4) | C22—C21—H21 | 120.8 |
C6—N3—Cu1 | 123.8 (3) | N4—C22—N5 | 120.7 (4) |
C10—N3—Cu1 | 118.5 (3) | N4—C22—C21 | 122.1 (4) |
C22—N4—C18 | 117.5 (4) | N5—C22—C21 | 117.2 (4) |
C22—N4—Cu2 | 122.4 (3) | N6—C23—N5 | 120.3 (4) |
C18—N4—Cu2 | 119.9 (3) | N6—C23—C24 | 122.1 (5) |
C23—N5—C22 | 130.1 (4) | N5—C23—C24 | 117.6 (5) |
C23—N5—H5A | 115 (4) | C25—C24—C23 | 119.1 (6) |
C22—N5—H5A | 110 (4) | C25—C24—H24 | 120.5 |
C23—N6—C27 | 117.2 (5) | C23—C24—H24 | 120.5 |
C23—N6—Cu2 | 122.3 (3) | C24—C25—C26 | 119.4 (6) |
C27—N6—Cu2 | 120.2 (4) | C24—C25—H25 | 120.3 |
C32—N7—C28 | 117.6 (5) | C26—C25—H25 | 120.3 |
C32—N7—Cu2 | 122.9 (4) | C27—C26—C25 | 118.0 (6) |
C28—N7—Cu2 | 119.5 (4) | C27—C26—H26 | 121.0 |
C32—N8—C33 | 133.1 (4) | C25—C26—H26 | 121.0 |
C32—N8—H8A | 114 (4) | N6—C27—C26 | 124.1 (6) |
C33—N8—H8A | 110 (4) | N6—C27—H27 | 118.0 |
C33—N9—C37 | 117.6 (5) | C26—C27—H27 | 118.0 |
C33—N9—Cu2 | 122.6 (3) | N7—C28—C29 | 124.4 (6) |
C37—N9—Cu2 | 119.7 (4) | N7—C28—H28 | 117.8 |
N1—C1—C2 | 123.6 (5) | C29—C28—H28 | 117.8 |
N1—C1—H1 | 118.2 | C28—C29—C30 | 118.0 (6) |
C2—C1—H1 | 118.2 | C28—C29—H29 | 121.0 |
C1—C2—C3 | 118.4 (5) | C30—C29—H29 | 121.0 |
C1—C2—H2 | 120.8 | C31—C30—C29 | 119.4 (6) |
C3—C2—H2 | 120.8 | C31—C30—H30 | 120.3 |
C4—C3—C2 | 119.3 (5) | C29—C30—H30 | 120.3 |
C4—C3—H3 | 120.3 | C30—C31—C32 | 119.2 (6) |
C2—C3—H3 | 120.3 | C30—C31—H31 | 120.4 |
C3—C4—C5 | 119.8 (5) | C32—C31—H31 | 120.4 |
C3—C4—H4 | 120.1 | N7—C32—N8 | 121.3 (4) |
C5—C4—H4 | 120.1 | N7—C32—C31 | 121.3 (5) |
N1—C5—N2 | 121.6 (4) | N8—C32—C31 | 117.4 (5) |
N1—C5—C4 | 121.6 (4) | N9—C33—N8 | 122.3 (4) |
N2—C5—C4 | 116.8 (4) | N9—C33—C34 | 121.6 (5) |
N3—C6—N2 | 121.3 (4) | N8—C33—C34 | 116.1 (4) |
N3—C6—C7 | 121.3 (5) | C35—C34—C33 | 119.1 (5) |
N2—C6—C7 | 117.4 (5) | C35—C34—H34 | 120.5 |
C8—C7—C6 | 120.2 (5) | C33—C34—H34 | 120.5 |
C8—C7—H7 | 119.9 | C34—C35—C36 | 119.4 (6) |
C6—C7—H7 | 119.9 | C34—C35—H35 | 120.3 |
C7—C8—C9 | 119.2 (5) | C36—C35—H35 | 120.3 |
C7—C8—H8 | 120.4 | C37—C36—C35 | 118.4 (6) |
C9—C8—H8 | 120.4 | C37—C36—H36 | 120.8 |
C10—C9—C8 | 118.3 (6) | C35—C36—H36 | 120.8 |
C10—C9—H9 | 120.9 | C36—C37—N9 | 123.9 (5) |
C8—C9—H9 | 120.9 | C36—C37—H37 | 118.1 |
N3—C10—C9 | 123.7 (5) | N9—C37—H37 | 118.1 |
N3—C10—H10 | 118.2 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O7i | 0.82 (3) | 2.00 (3) | 2.814 (6) | 175 (6) |
N5—H5A···O5ii | 0.82 (4) | 2.08 (4) | 2.896 (5) | 178 (5) |
N8—H8A···O2iii | 0.82 (5) | 1.99 (5) | 2.809 (5) | 172 (5) |
O7—H7A···O4ii | 0.86 | 1.98 | 2.813 (6) | 162 |
O7—H7B···O6 | 0.84 | 2.00 | 2.801 (6) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C7H3O6S)2(C10H9N3)2][Cu(C10H9N3)2]2·2H2O |
Mr | 1747.71 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 7.258 (2), 14.422 (4), 18.312 (5) |
α, β, γ (°) | 82.428 (4), 80.697 (4), 86.409 (4) |
V (Å3) | 1873.5 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.28 × 0.19 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.759, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13648, 6582, 6078 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.148, 1.23 |
No. of reflections | 6582 |
No. of parameters | 514 |
No. of restraints | 5 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.41 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu1—O1 | 1.926 (3) | Cu2—N9 | 1.989 (4) |
Cu1—O3 | 1.930 (3) | Cu2—N4 | 2.013 (4) |
Cu1—N1 | 2.019 (4) | Cu2—N6 | 2.031 (4) |
Cu1—N3 | 2.033 (4) | Cu2—N7 | 2.032 (4) |
Cu1—O3i | 2.343 (3) | ||
O1—Cu1—O3 | 89.89 (13) | N1—Cu1—O3i | 93.09 (13) |
O1—Cu1—N1 | 168.73 (15) | N3—Cu1—O3i | 97.99 (14) |
O3—Cu1—N1 | 90.05 (14) | N9—Cu2—N4 | 130.02 (18) |
O1—Cu1—N3 | 90.36 (14) | N9—Cu2—N6 | 116.50 (18) |
O3—Cu1—N3 | 179.45 (16) | N4—Cu2—N6 | 91.23 (16) |
N1—Cu1—N3 | 89.61 (15) | N9—Cu2—N7 | 94.58 (17) |
O1—Cu1—O3i | 98.07 (13) | N4—Cu2—N7 | 110.31 (18) |
O3—Cu1—O3i | 82.45 (12) | N6—Cu2—N7 | 115.75 (19) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O7i | 0.82 (3) | 2.00 (3) | 2.814 (6) | 175 (6) |
N5—H5A···O5ii | 0.82 (4) | 2.08 (4) | 2.896 (5) | 178 (5) |
N8—H8A···O2iii | 0.82 (5) | 1.99 (5) | 2.809 (5) | 172 (5) |
O7—H7A···O4ii | 0.86 | 1.98 | 2.813 (6) | 162 |
O7—H7B···O6 | 0.84 | 2.00 | 2.801 (6) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1. |
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It is well known that CuII ions can be reduced to CuI by N-heterocyclic ligands under hydrothermal conditions, such as 4,4'-bipyridine or pyridine derivatives (Wen et al., 2004). Interesting reactions and novel structures can be achieved when CuII is reduced. Mixed-valence CuI,II complexes are of great importance in structural topology and functional materials (Zhang & Chen, 2003). In general, mixed-valence copper complexes exist as polynuclear species or ion pairs (Pawlowski et al., 2004). Although numerous complexes with CuII cationic and CuI anionic components have been prepared, complexes containing CuI cationic and CuII anionic motifs have been apparently ignored. In our recent report on metal 5-sulfosalicylates, a copper salt was reacted with 5-sulfosalicylic acid (H3ssal) and 2,2'-dipyridylamine (dpa), and [Cu3(dpa)3(ssal)2]·3H2O was obtained (Fan & Zhu, 2005). Without an abstracting reagent, a similar synthesis but addition of NaOH yielded the mixed-valence compound with CuI cationic components, [CuII2(ssal)2(dpa)2]·2[CuI(dpa)2]·2H2O, (I).
The molecular structure consists of [Cu2(dpa)2(ssal)2]2− anions, [Cu(dpa)2]+ cations and uncoordinated water molecules (Figs. 1 and 2, and Table 1). The anionic dimer [Cu2(dpa)2(ssal)2]2− consists of two centrosymmetrically related five-coordinate CuII centers, with a Cu···Cui distance of 3.225 (1) Å [symmetry code: (i) 1 − x, 1 − y, 2 − z]. The basal plane of the square-pyramidal geometry of the CuII center is occupied by two N atoms of a dpa ligand and two O atoms of the fully deprotonated ssal3− ligand, while the apical position is taken by the phenoxo O atom of a second centrosymmetrically imposed ssal3− ligand. A four-membered bridging unit, Cu2O2, is formed between the CuII atoms via phenoxo atoms O3 and O3i. Only one carboxylate O atom from the ssal3− ligand is directly bonded to the CuII atom, and the coordination mode of the carboxylate moiety is obviously anti monodentate. As expected, in the anion, the C11—O1 bond is significantly longer than the C11—O2 distance, indicating a more keto character in the latter. The dihedral angle between the planes of the ring (atoms C2–C7) and its carboxyl group is 11.0 (4)°. The structure of the anion is closely related to that of the ternary dimeric compound [CuII2(dpa)2(salal)2(ClO4)2] (Garland et al., 1987), in which the CuII atom is coordinated by a sixth O atom from a ClO4− anion and the Cu···Cu distance is longer than that in the title compound.
The cation consists of a CuI atom and two dpa ligands (Fig. 2). The CuI center adopts tetrahedral geometry. The CuI—N bond lengths are similar to those in the anion, and the conformations of the three dpa ligands in the asymmetric unit differ slightly. The dihedral angle between the two pyridyl rings of the dpa ligand in the anion is 19.2 (2)°, while the corresponding angles in the cation are 23.9 (3) and 15.3 (4)°. The N1···N3, N4···N6 and N7···N9 distances are 2.855 (5), 2.891 (6) and 2.955 (6) Å, respectively.
The anions and water molecules form one-dimensional hydrogen-bonded chain through N—H···O1W and O1W—H···O(SO3−) interactions (Fig. 3 and Table 2). These chains are linked into a two-dimensional hydrogen-bonded network by the cations through N—H···O(–COO−) and N—H···O(SO3−) interactions (Fig. 4). Therefore, in the solid state, the stability of (I) is enhanced by hydrogen-bonding interactions.