Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010101561X/da1201sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101561X/da1201Isup2.hkl |
CCDC reference: 180147
Disodium naphthalene-1,5-disulfonate (0.17 g, 0.5 mmol) was added to an aqueous solution of cupric chloride (0.09 g, 0.5 mmol). The solution was then treated with tris(2-aminoethyl)amine (0.076 g, 0.5 mmol). The resulting solution was allowed to stand at room temperature. After 10 d, blue block crystals of (I) were collected in 10% yield.
All H atoms of the tren ligands and on the 1,5-nds anions were placed in idealized positions (N—H = 0.90 and 0.89 Å for NH2 and NH3, respectively, and C—H = 0.97 and 0.93 Å for CH2 and CH, respectively) and refined as riding atoms. The H atoms of water molecules O1W and O2W were located from the difference Fourier map and not refined and those of the O3W water molecule were not located.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Cu2(C6H19N4)2Cl2]·2C10H6O6S2·5H2O | Z = 1 |
Mr = 1155.10 | F(000) = 600 |
Triclinic, P1 | Dx = 1.616 Mg m−3 |
a = 9.9348 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.5498 (17) Å | Cell parameters from 843 reflections |
c = 11.9637 (17) Å | θ = 2.3–26.4° |
α = 71.806 (3)° | µ = 1.26 mm−1 |
β = 75.622 (3)° | T = 293 K |
γ = 66.844 (2)° | Block, blue |
V = 1186.6 (3) Å3 | 0.25 × 0.25 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 4786 independent reflections |
Radiation source: fine-focus sealed tube | 4259 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −12→12 |
Tmin = 0.743, Tmax = 0.884 | k = −14→13 |
7629 measured reflections | l = −14→14 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0786P)2 + 0.7132P] where P = (Fo2 + 2Fc2)/3 |
4786 reflections | (Δ/σ)max = 0.001 |
301 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
[Cu2(C6H19N4)2Cl2]·2C10H6O6S2·5H2O | γ = 66.844 (2)° |
Mr = 1155.10 | V = 1186.6 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.9348 (15) Å | Mo Kα radiation |
b = 11.5498 (17) Å | µ = 1.26 mm−1 |
c = 11.9637 (17) Å | T = 293 K |
α = 71.806 (3)° | 0.25 × 0.25 × 0.10 mm |
β = 75.622 (3)° |
Bruker SMART CCD area-detector diffractometer | 4786 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 4259 reflections with I > 2σ(I) |
Tmin = 0.743, Tmax = 0.884 | Rint = 0.017 |
7629 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 1.08 e Å−3 |
4786 reflections | Δρmin = −0.52 e Å−3 |
301 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 | Occ. (<1) | |
Cu1 | −0.99644 (3) | −0.03706 (3) | 0.15407 (2) | 0.03066 (12) | |
S1 | −0.33042 (8) | −0.29981 (7) | 0.01995 (7) | 0.04172 (18) | |
S2 | −0.30605 (8) | −0.22336 (7) | 0.49481 (6) | 0.04280 (18) | |
Cl1 | −1.18179 (7) | 0.01126 (8) | 0.04844 (6) | 0.04496 (19) | |
O1 | −0.4340 (3) | −0.1793 (2) | −0.0328 (3) | 0.0655 (7) | |
O2 | −0.1974 (2) | −0.3501 (2) | −0.0575 (2) | 0.0567 (6) | |
O3 | −0.2965 (3) | −0.2938 (3) | 0.1295 (2) | 0.0621 (6) | |
O4 | −0.2518 (2) | −0.1551 (2) | 0.37776 (19) | 0.0515 (5) | |
O5 | −0.4109 (2) | −0.2776 (2) | 0.4876 (2) | 0.0558 (6) | |
O6 | −0.3611 (3) | −0.1457 (3) | 0.5810 (2) | 0.0719 (8) | |
O1W | 0.0678 (3) | −0.3620 (2) | 0.0099 (3) | 0.0605 (6) | |
H1WA | 0.1142 | −0.4446 | 0.0218 | 0.050* | |
H1WB | −0.0155 | −0.3591 | 0.0039 | 0.050* | |
O2W | −0.2953 (3) | 0.1065 (3) | 0.4091 (3) | 0.0697 (7) | |
H2WA | −0.3048 | 0.0129 | 0.4178 | 0.050* | |
H2WB | −0.3844 | 0.1579 | 0.4084 | 0.050* | |
N1 | −1.0797 (3) | 0.1350 (3) | 0.1925 (2) | 0.0441 (5) | |
H1A | −1.0810 | 0.1976 | 0.1249 | 0.053* | |
H1B | −1.1735 | 0.1483 | 0.2291 | 0.053* | |
N2 | −0.9530 (3) | −0.2261 (2) | 0.1912 (2) | 0.0473 (6) | |
H2A | −1.0292 | −0.2464 | 0.2408 | 0.057* | |
H2B | −0.9407 | −0.2508 | 0.1240 | 0.057* | |
N3 | −0.8449 (2) | −0.0830 (3) | 0.26754 (19) | 0.0380 (5) | |
N4 | −0.4608 (2) | −0.0608 (2) | 0.2062 (2) | 0.0371 (5) | |
H4B | −0.4017 | −0.0627 | 0.2523 | 0.071 (12)* | |
H4C | −0.4830 | 0.0152 | 0.1530 | 0.062 (11)* | |
H4D | −0.4149 | −0.1246 | 0.1688 | 0.057 (10)* | |
C1 | −0.4691 (3) | −0.4500 (3) | −0.0183 (2) | 0.0374 (6) | |
C2 | −0.4168 (3) | −0.4199 (3) | 0.0643 (3) | 0.0402 (6) | |
C3 | −0.4241 (4) | −0.4872 (3) | 0.1803 (3) | 0.0488 (7) | |
H3A | −0.3897 | −0.4665 | 0.2345 | 0.059* | |
C4 | −0.4831 (4) | −0.5872 (3) | 0.2186 (3) | 0.0542 (8) | |
H4A | −0.4864 | −0.6329 | 0.2979 | 0.065* | |
C5 | −0.5354 (4) | −0.6184 (3) | 0.1423 (3) | 0.0489 (7) | |
H5A | −0.5748 | −0.6849 | 0.1698 | 0.059* | |
C6 | −0.0199 (3) | −0.5411 (3) | 0.3105 (2) | 0.0417 (6) | |
H6A | −0.0464 | −0.5380 | 0.2401 | 0.050* | |
C7 | −0.1050 (3) | −0.4509 (3) | 0.3727 (2) | 0.0372 (6) | |
H7A | −0.1911 | −0.3881 | 0.3457 | 0.045* | |
C8 | −0.0649 (3) | −0.4506 (2) | 0.4787 (2) | 0.0309 (5) | |
C9 | −0.1483 (3) | −0.3554 (3) | 0.5453 (2) | 0.0342 (5) | |
C10 | −0.1082 (3) | −0.3606 (3) | 0.6485 (2) | 0.0397 (6) | |
H10A | −0.1658 | −0.2989 | 0.6918 | 0.048* | |
C11 | −0.9260 (3) | 0.0087 (4) | 0.3453 (3) | 0.0585 (10) | |
H11A | −0.8589 | 0.0092 | 0.3916 | 0.070* | |
H11B | −1.0041 | −0.0187 | 0.3998 | 0.070* | |
C12 | −0.9914 (4) | 0.1425 (4) | 0.2700 (3) | 0.0584 (9) | |
H12A | −1.0533 | 0.2013 | 0.3201 | 0.070* | |
H12B | −0.9132 | 0.1748 | 0.2224 | 0.070* | |
C13 | −0.8221 (4) | −0.2211 (4) | 0.3319 (3) | 0.0640 (10) | |
H13A | −0.9020 | −0.2258 | 0.3970 | 0.077* | |
H13B | −0.7298 | −0.2591 | 0.3646 | 0.077* | |
C14 | −0.8181 (4) | −0.2943 (3) | 0.2470 (4) | 0.0651 (10) | |
H14A | −0.7316 | −0.2984 | 0.1869 | 0.078* | |
H14B | −0.8134 | −0.3822 | 0.2891 | 0.078* | |
C15 | −0.7044 (3) | −0.0642 (3) | 0.2012 (2) | 0.0350 (6) | |
H15A | −0.7275 | 0.0214 | 0.1476 | 0.042* | |
H15B | −0.6557 | −0.1273 | 0.1532 | 0.042* | |
C16 | −0.5978 (3) | −0.0776 (4) | 0.2800 (2) | 0.0463 (7) | |
H16A | −0.6435 | −0.0126 | 0.3262 | 0.056* | |
H16B | −0.5745 | −0.1625 | 0.3347 | 0.056* | |
O3W | −0.5574 (19) | −0.4587 (12) | 0.4874 (16) | 0.200 (7) | 0.52 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02304 (17) | 0.0402 (2) | 0.02803 (17) | −0.01173 (13) | −0.00347 (12) | −0.00629 (13) |
S1 | 0.0317 (3) | 0.0366 (4) | 0.0538 (4) | −0.0120 (3) | −0.0006 (3) | −0.0108 (3) |
S2 | 0.0335 (3) | 0.0433 (4) | 0.0390 (4) | −0.0037 (3) | −0.0083 (3) | −0.0029 (3) |
Cl1 | 0.0272 (3) | 0.0796 (5) | 0.0297 (3) | −0.0265 (3) | −0.0029 (2) | −0.0056 (3) |
O1 | 0.0579 (14) | 0.0404 (12) | 0.0882 (19) | −0.0139 (11) | −0.0202 (13) | 0.0014 (12) |
O2 | 0.0373 (11) | 0.0627 (14) | 0.0719 (15) | −0.0221 (10) | 0.0135 (10) | −0.0290 (12) |
O3 | 0.0771 (17) | 0.0619 (15) | 0.0581 (14) | −0.0325 (13) | −0.0105 (12) | −0.0171 (12) |
O4 | 0.0450 (12) | 0.0469 (12) | 0.0478 (12) | −0.0119 (10) | −0.0121 (9) | 0.0078 (9) |
O5 | 0.0321 (10) | 0.0681 (15) | 0.0554 (13) | −0.0151 (10) | −0.0119 (9) | 0.0026 (11) |
O6 | 0.0679 (16) | 0.0636 (15) | 0.0633 (16) | 0.0141 (13) | −0.0183 (13) | −0.0280 (13) |
O1W | 0.0417 (12) | 0.0442 (12) | 0.0936 (19) | −0.0108 (10) | −0.0156 (12) | −0.0147 (12) |
O2W | 0.0385 (12) | 0.0605 (15) | 0.0806 (18) | −0.0089 (11) | 0.0113 (12) | −0.0033 (13) |
N1 | 0.0370 (12) | 0.0486 (14) | 0.0466 (13) | −0.0146 (11) | 0.0009 (10) | −0.0167 (11) |
N2 | 0.0433 (14) | 0.0448 (14) | 0.0494 (14) | −0.0183 (11) | −0.0032 (11) | −0.0042 (11) |
N3 | 0.0255 (10) | 0.0610 (15) | 0.0252 (10) | −0.0184 (10) | −0.0019 (8) | −0.0040 (10) |
N4 | 0.0243 (10) | 0.0492 (14) | 0.0372 (12) | −0.0131 (10) | −0.0050 (9) | −0.0088 (10) |
C1 | 0.0286 (12) | 0.0348 (13) | 0.0413 (14) | −0.0097 (11) | 0.0006 (10) | −0.0050 (11) |
C2 | 0.0338 (13) | 0.0378 (14) | 0.0417 (14) | −0.0113 (11) | 0.0000 (11) | −0.0051 (11) |
C3 | 0.0477 (17) | 0.0509 (17) | 0.0424 (16) | −0.0184 (14) | −0.0071 (13) | −0.0017 (13) |
C4 | 0.063 (2) | 0.062 (2) | 0.0333 (14) | −0.0306 (17) | −0.0081 (14) | 0.0076 (14) |
C5 | 0.0485 (17) | 0.0520 (17) | 0.0423 (16) | −0.0241 (14) | −0.0017 (13) | −0.0008 (13) |
C6 | 0.0470 (16) | 0.0483 (16) | 0.0335 (13) | −0.0170 (13) | −0.0157 (12) | −0.0062 (12) |
C7 | 0.0352 (13) | 0.0429 (14) | 0.0322 (13) | −0.0131 (11) | −0.0138 (10) | −0.0008 (11) |
C8 | 0.0301 (12) | 0.0344 (12) | 0.0279 (11) | −0.0145 (10) | −0.0075 (9) | −0.0001 (9) |
C9 | 0.0296 (12) | 0.0360 (13) | 0.0320 (12) | −0.0102 (10) | −0.0064 (10) | −0.0014 (10) |
C10 | 0.0420 (15) | 0.0422 (15) | 0.0352 (13) | −0.0138 (12) | −0.0076 (11) | −0.0090 (11) |
C11 | 0.0306 (14) | 0.120 (3) | 0.0361 (15) | −0.0290 (17) | 0.0063 (12) | −0.0378 (18) |
C12 | 0.0424 (17) | 0.083 (3) | 0.069 (2) | −0.0303 (17) | 0.0125 (15) | −0.049 (2) |
C13 | 0.0454 (18) | 0.085 (3) | 0.0509 (19) | −0.0340 (18) | −0.0211 (15) | 0.0248 (18) |
C14 | 0.0391 (17) | 0.0441 (17) | 0.088 (3) | −0.0122 (14) | −0.0102 (17) | 0.0139 (17) |
C15 | 0.0230 (11) | 0.0565 (16) | 0.0254 (11) | −0.0159 (11) | −0.0027 (9) | −0.0076 (11) |
C16 | 0.0254 (12) | 0.083 (2) | 0.0310 (13) | −0.0200 (14) | −0.0034 (10) | −0.0125 (14) |
O3W | 0.245 (19) | 0.131 (11) | 0.253 (15) | −0.061 (11) | −0.146 (15) | −0.005 (11) |
Cu1—N2 | 1.975 (3) | C1—C5ii | 1.445 (4) |
Cu1—N1 | 1.983 (2) | C2—C3 | 1.362 (4) |
Cu1—N3 | 2.081 (2) | C3—C4 | 1.399 (5) |
Cu1—Cl1 | 2.2818 (7) | C3—H3A | 0.9300 |
Cu1—Cl1i | 2.6320 (7) | C4—C5 | 1.351 (5) |
Cu1—Cu1i | 3.5269 (8) | C4—H4A | 0.9300 |
S1—O1 | 1.429 (3) | C5—C1ii | 1.445 (4) |
S1—O2 | 1.438 (2) | C5—H5A | 0.9300 |
S1—O3 | 1.459 (3) | C6—C7 | 1.355 (4) |
S1—C2 | 1.787 (3) | C6—C10iii | 1.405 (4) |
S2—O6 | 1.442 (3) | C6—H6A | 0.9300 |
S2—O5 | 1.442 (2) | C7—C8 | 1.421 (3) |
S2—O4 | 1.464 (2) | C7—H7A | 0.9300 |
S2—C9 | 1.778 (3) | C8—C8iii | 1.425 (5) |
Cl1—Cu1i | 2.6320 (7) | C8—C9 | 1.426 (4) |
O1W—H1WA | 0.8623 | C9—C10 | 1.366 (4) |
O1W—H1WB | 0.8346 | C10—C6iii | 1.405 (4) |
O2W—H2WA | 1.0922 | C10—H10A | 0.9300 |
O2W—H2WB | 0.8502 | C11—C12 | 1.501 (6) |
N1—C12 | 1.467 (4) | C11—H11A | 0.9700 |
N1—H1A | 0.9000 | C11—H11B | 0.9700 |
N1—H1B | 0.9000 | C12—H12A | 0.9700 |
N2—C14 | 1.465 (4) | C12—H12B | 0.9700 |
N2—H2A | 0.9000 | C13—C14 | 1.496 (6) |
N2—H2B | 0.9000 | C13—H13A | 0.9700 |
N3—C15 | 1.485 (3) | C13—H13B | 0.9700 |
N3—C11 | 1.486 (4) | C14—H14A | 0.9700 |
N3—C13 | 1.491 (4) | C14—H14B | 0.9700 |
N4—C16 | 1.474 (3) | C15—C16 | 1.520 (3) |
N4—H4B | 0.8900 | C15—H15A | 0.9700 |
N4—H4C | 0.8900 | C15—H15B | 0.9700 |
N4—H4D | 0.8900 | C16—H16A | 0.9700 |
C1—C2 | 1.407 (4) | C16—H16B | 0.9700 |
C1—C1ii | 1.419 (5) | O3W—O3Wiv | 1.20 (3) |
N2—Cu1—N1 | 154.12 (11) | C2—C3—C4 | 120.5 (3) |
N2—Cu1—N3 | 85.23 (11) | C2—C3—H3A | 119.8 |
N1—Cu1—N3 | 85.38 (10) | C4—C3—H3A | 119.8 |
N2—Cu1—Cl1 | 93.80 (8) | C5—C4—C3 | 121.0 (3) |
N1—Cu1—Cl1 | 92.84 (8) | C5—C4—H4A | 119.5 |
N3—Cu1—Cl1 | 173.53 (6) | C3—C4—H4A | 119.5 |
N2—Cu1—Cl1i | 98.89 (8) | C4—C5—C1ii | 120.9 (3) |
N1—Cu1—Cl1i | 106.26 (8) | C4—C5—H5A | 119.6 |
N3—Cu1—Cl1i | 97.93 (6) | C1ii—C5—H5A | 119.6 |
Cl1—Cu1—Cl1i | 88.54 (3) | C7—C6—C10iii | 120.6 (2) |
N2—Cu1—Cu1i | 99.11 (8) | C7—C6—H6A | 119.7 |
N1—Cu1—Cu1i | 103.94 (8) | C10iii—C6—H6A | 119.7 |
N3—Cu1—Cu1i | 138.22 (6) | C6—C7—C8 | 121.1 (2) |
Cl1—Cu1—Cu1i | 48.246 (18) | C6—C7—H7A | 119.5 |
Cl1i—Cu1—Cu1i | 40.297 (16) | C8—C7—H7A | 119.5 |
O1—S1—O2 | 115.50 (17) | C7—C8—C8iii | 119.1 (3) |
O1—S1—O3 | 111.16 (16) | C7—C8—C9 | 123.2 (2) |
O2—S1—O3 | 111.10 (16) | C8iii—C8—C9 | 117.7 (3) |
O1—S1—C2 | 107.97 (15) | C10—C9—C8 | 121.3 (2) |
O2—S1—C2 | 105.09 (13) | C10—C9—S2 | 117.6 (2) |
O3—S1—C2 | 105.28 (15) | C8—C9—S2 | 120.99 (19) |
O6—S2—O5 | 112.52 (17) | C9—C10—C6iii | 120.2 (3) |
O6—S2—O4 | 112.88 (17) | C9—C10—H10A | 119.9 |
O5—S2—O4 | 111.88 (14) | C6iii—C10—H10A | 119.9 |
O6—S2—C9 | 106.41 (14) | N3—C11—C12 | 109.5 (2) |
O5—S2—C9 | 107.18 (13) | N3—C11—H11A | 109.8 |
O4—S2—C9 | 105.38 (12) | C12—C11—H11A | 109.8 |
Cu1—Cl1—Cu1i | 91.46 (3) | N3—C11—H11B | 109.8 |
H1WA—O1W—H1WB | 99.8 | C12—C11—H11B | 109.8 |
H2WA—O2W—H2WB | 102.9 | H11A—C11—H11B | 108.2 |
C12—N1—Cu1 | 110.7 (2) | N1—C12—C11 | 108.0 (3) |
C12—N1—H1A | 109.5 | N1—C12—H12A | 110.1 |
Cu1—N1—H1A | 109.5 | C11—C12—H12A | 110.1 |
C12—N1—H1B | 109.5 | N1—C12—H12B | 110.1 |
Cu1—N1—H1B | 109.5 | C11—C12—H12B | 110.1 |
H1A—N1—H1B | 108.1 | H12A—C12—H12B | 108.4 |
C14—N2—Cu1 | 109.5 (2) | N3—C13—C14 | 109.0 (3) |
C14—N2—H2A | 109.8 | N3—C13—H13A | 109.9 |
Cu1—N2—H2A | 109.8 | C14—C13—H13A | 109.9 |
C14—N2—H2B | 109.8 | N3—C13—H13B | 109.9 |
Cu1—N2—H2B | 109.8 | C14—C13—H13B | 109.9 |
H2A—N2—H2B | 108.2 | H13A—C13—H13B | 108.3 |
C15—N3—C11 | 112.3 (2) | N2—C14—C13 | 107.9 (3) |
C15—N3—C13 | 112.0 (2) | N2—C14—H14A | 110.1 |
C11—N3—C13 | 113.0 (3) | C13—C14—H14A | 110.1 |
C15—N3—Cu1 | 111.72 (15) | N2—C14—H14B | 110.1 |
C11—N3—Cu1 | 102.17 (17) | C13—C14—H14B | 110.1 |
C13—N3—Cu1 | 104.97 (18) | H14A—C14—H14B | 108.4 |
C16—N4—H4B | 109.5 | N3—C15—C16 | 114.1 (2) |
C16—N4—H4C | 109.5 | N3—C15—H15A | 108.7 |
H4B—N4—H4C | 109.5 | C16—C15—H15A | 108.7 |
C16—N4—H4D | 109.5 | N3—C15—H15B | 108.7 |
H4B—N4—H4D | 109.5 | C16—C15—H15B | 108.7 |
H4C—N4—H4D | 109.5 | H15A—C15—H15B | 107.6 |
C2—C1—C1ii | 120.4 (3) | N4—C16—C15 | 110.0 (2) |
C2—C1—C5ii | 122.7 (3) | N4—C16—H16A | 109.7 |
C1ii—C1—C5ii | 116.9 (3) | C15—C16—H16A | 109.7 |
C3—C2—C1 | 120.3 (3) | N4—C16—H16B | 109.7 |
C3—C2—S1 | 118.0 (2) | C15—C16—H16B | 109.7 |
C1—C2—S1 | 121.6 (2) | H16A—C16—H16B | 108.2 |
N2—Cu1—Cl1—Cu1i | −98.82 (8) | C1—C2—C3—C4 | 0.2 (5) |
N1—Cu1—Cl1—Cu1i | 106.21 (8) | S1—C2—C3—C4 | −176.4 (3) |
N2—Cu1—N1—C12 | 72.3 (3) | C2—C3—C4—C5 | −0.7 (5) |
N3—Cu1—N1—C12 | 3.3 (2) | C3—C4—C5—C1ii | 0.5 (5) |
Cl1—Cu1—N1—C12 | 177.1 (2) | C10iii—C6—C7—C8 | 2.0 (4) |
Cl1i—Cu1—N1—C12 | −93.6 (2) | C6—C7—C8—C8iii | −1.7 (4) |
Cu1i—Cu1—N1—C12 | −135.4 (2) | C6—C7—C8—C9 | 178.0 (3) |
N1—Cu1—N2—C14 | −83.9 (3) | C7—C8—C9—C10 | 178.2 (3) |
N3—Cu1—N2—C14 | −14.9 (2) | C8iii—C8—C9—C10 | −2.1 (4) |
Cl1—Cu1—N2—C14 | 171.5 (2) | C7—C8—C9—S2 | −3.3 (4) |
Cl1i—Cu1—N2—C14 | 82.4 (2) | C8iii—C8—C9—S2 | 176.4 (2) |
Cu1i—Cu1—N2—C14 | 123.3 (2) | O6—S2—C9—C10 | −0.3 (3) |
N2—Cu1—N3—C15 | 107.9 (2) | O5—S2—C9—C10 | −120.9 (2) |
N1—Cu1—N3—C15 | −96.2 (2) | O4—S2—C9—C10 | 119.8 (2) |
Cl1i—Cu1—N3—C15 | 9.60 (19) | O6—S2—C9—C8 | −178.9 (2) |
Cu1i—Cu1—N3—C15 | 9.6 (3) | O5—S2—C9—C8 | 60.5 (2) |
N2—Cu1—N3—C11 | −131.8 (2) | O4—S2—C9—C8 | −58.8 (2) |
N1—Cu1—N3—C11 | 24.1 (2) | C8—C9—C10—C6iii | 1.9 (4) |
Cl1i—Cu1—N3—C11 | 129.89 (19) | S2—C9—C10—C6iii | −176.7 (2) |
Cu1i—Cu1—N3—C11 | 129.90 (17) | C15—N3—C11—C12 | 72.3 (3) |
N2—Cu1—N3—C13 | −13.6 (2) | C13—N3—C11—C12 | −159.8 (2) |
N1—Cu1—N3—C13 | 142.2 (2) | Cu1—N3—C11—C12 | −47.6 (3) |
Cl1i—Cu1—N3—C13 | −111.96 (19) | Cu1—N1—C12—C11 | −30.4 (3) |
Cu1i—Cu1—N3—C13 | −111.95 (19) | N3—C11—C12—N1 | 53.7 (3) |
C1ii—C1—C2—C3 | 0.5 (5) | C15—N3—C13—C14 | −82.1 (3) |
C5ii—C1—C2—C3 | 179.8 (3) | C11—N3—C13—C14 | 149.9 (3) |
C1ii—C1—C2—S1 | 177.0 (3) | Cu1—N3—C13—C14 | 39.3 (3) |
C5ii—C1—C2—S1 | −3.7 (4) | Cu1—N2—C14—C13 | 40.7 (3) |
O1—S1—C2—C3 | −124.0 (3) | N3—C13—C14—N2 | −54.0 (3) |
O2—S1—C2—C3 | 112.3 (3) | C11—N3—C15—C16 | 57.6 (3) |
O3—S1—C2—C3 | −5.1 (3) | C13—N3—C15—C16 | −70.9 (3) |
O1—S1—C2—C1 | 59.4 (3) | Cu1—N3—C15—C16 | 171.7 (2) |
O2—S1—C2—C1 | −64.3 (3) | N3—C15—C16—N4 | 178.5 (3) |
O3—S1—C2—C1 | 178.3 (2) |
Symmetry codes: (i) −x−2, −y, −z; (ii) −x−1, −y−1, −z; (iii) −x, −y−1, −z+1; (iv) −x−1, −y−1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2v | 0.86 | 2.12 | 2.975 (3) | 172 |
O1W—H1WB···O2 | 0.83 | 2.07 | 2.883 (3) | 165 |
O2W—H2WA···O4 | 1.09 | 1.98 | 3.009 (4) | 156 |
O2W—H2WB···O5vi | 0.85 | 2.28 | 3.025 (3) | 146 |
O2W—H2WB···O6vi | 0.85 | 2.56 | 3.238 (4) | 138 |
N1—H1A···O1Wvii | 0.90 | 2.10 | 2.982 (4) | 167 |
N1—H1B···O2Wviii | 0.90 | 2.20 | 2.945 (4) | 140 |
N2—H2A···O4viii | 0.90 | 2.48 | 3.226 (4) | 141 |
N2—H2B···O1Wviii | 0.90 | 2.11 | 2.977 (4) | 160 |
N4—H4B···O4 | 0.89 | 2.11 | 2.941 (3) | 154 |
N4—H4C···O1vii | 0.89 | 2.00 | 2.879 (3) | 170 |
N4—H4D···O3 | 0.89 | 1.98 | 2.845 (4) | 164 |
Symmetry codes: (v) −x, −y−1, −z; (vi) −x−1, −y, −z+1; (vii) −x−1, −y, −z; (viii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C6H19N4)2Cl2]·2C10H6O6S2·5H2O |
Mr | 1155.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.9348 (15), 11.5498 (17), 11.9637 (17) |
α, β, γ (°) | 71.806 (3), 75.622 (3), 66.844 (2) |
V (Å3) | 1186.6 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.25 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.743, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7629, 4786, 4259 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.118, 1.01 |
No. of reflections | 4786 |
No. of parameters | 301 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.08, −0.52 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2i | 0.86 | 2.12 | 2.975 (3) | 172 |
O1W—H1WB···O2 | 0.83 | 2.07 | 2.883 (3) | 165 |
O2W—H2WA···O4 | 1.09 | 1.98 | 3.009 (4) | 156 |
O2W—H2WB···O5ii | 0.85 | 2.28 | 3.025 (3) | 146 |
O2W—H2WB···O6ii | 0.85 | 2.56 | 3.238 (4) | 138 |
N1—H1A···O1Wiii | 0.90 | 2.10 | 2.982 (4) | 167 |
N1—H1B···O2Wiv | 0.90 | 2.20 | 2.945 (4) | 140 |
N2—H2A···O4iv | 0.90 | 2.48 | 3.226 (4) | 141 |
N2—H2B···O1Wiv | 0.90 | 2.11 | 2.977 (4) | 160 |
N4—H4B···O4 | 0.89 | 2.11 | 2.941 (3) | 154 |
N4—H4C···O1iii | 0.89 | 2.00 | 2.879 (3) | 170 |
N4—H4D···O3 | 0.89 | 1.98 | 2.845 (4) | 164 |
Symmetry codes: (i) −x, −y−1, −z; (ii) −x−1, −y, −z+1; (iii) −x−1, −y, −z; (iv) x−1, y, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Copper(II) complexes with the formula [Cu2(tren)2X2](BPh4)2, where X is CN-, NCO-, NCS- or Cl-, have been studied from both structural and magnetic points of view (Duggan & Hendrickson, 1974a,b; Duggan et al., 1974; Laskowski et al., 1975). Each CuII ion in these compounds is five-coordinate in a trigonal-bipyramidal geometry, with tren as a tetradentate ligand and the X- anion in the axial position. These [Cu2(tren)2X2]2+ ions dimerize via a hydrogen bond between the X group and a primary amine of tren coordinated to the second CuII ion. Herein, we report a novel dimeric CuII cation with the same basic formula as the above but with a different structure, [Cu2(tren)2Cl2](1,5-nds)2·5H2O, (I) (1,5-nds is naphthalene-1,5-disulfonate). \sch
Crystals of (I) are comprised of discrete [Cu2(tren)2Cl2]2+ cations, 1,5-nds anions and water molecules, as shown in Fig. 1. Two Cl- anions bridge two CuII ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligands, leaving two free ethylamine arms. A search of the Cambridge Structural Database (Release?; Allen & Kennard, 1993) indicates no previous observation of this kind of coordination mode of tren with CuII.
The coordination geometry of CuII can be described as a distorted square pyramid, as ascertained by Reedijk's τ factor (Addison et al., 1984) of 0.313 for Cu1 and 0.331 for Cu1A (τ = 0 for a square pyramid and 1 for a trigonal bipyramid). Atoms N1, N2 and N3 of the tren ligand and atom Cl1 are nearly coplanar, constituting the base of one pyramid, while Cl1A occupies the apical position. As a result, the geometry of the complex consists of two square pyramids sharing one common base-to-apex edge, with the two bases nearly parallel to each other (dihedral angle of 1.6°).
The reported geometry of CuII dimers with the general formula [N3Cu(µ-Cl)2CuN3] has been classified into three types (Rodríguez & Llobet, 1999). The arrangement in (I) belongs to type II. The Cu—N distances are 1.975 (3), 1.983 (2) and 2.081 (2) Å. Obviously, the Cu—N bonds in which N is cis to the basal Cl are slightly shorter than that in which N is trans to the basal Cl. This phenomenon is different from that in [Cu2(dien)2Cl2](ClO4)2 (dien is diethylenetriamine?; Hoffmann et al., 1984), with the same geometry and N3Cl2 coordination environment, but similar to that in [Cu2(dpt)2Cl2]Cl2 (dpt is ?; Rodríguez & Llobet, 1999).
With regard to the [Cu(µ-Cl)2Cu] core, the dimeric unit has unsymmetrical Cu—Cl bridging distances of 2.2819 (7) and 2.6320 (7) Å. The bridging Cu—Cl—Cu angle is 91.46 (3)° and Cl—Cu—Cl is 88.54 (3)°. All of the bond distances and angles are close to those found in [Cu2(dien)2Cl2](ClO4)2 (Hoffmann et al., 1984). The Cu···Cu separation is 3.5269 (8) Å, which is slightly shorter than the values reported in analogous compounds (Hoffmann et al., 1984; Rodrí guez & Llobet, 1999).
The coordination mode of tren, the mode of dimerization and the coordination geometry in (I) are quite different from those in [Cu2(tren)2Cl2](BPh4)2, (II) (Laskowski et al., 1975), although the two compounds have the same cation formula, [Cu2(tren)2Cl2]2+. In (II), each CuII centre is coordinated by a Cl- ligand and all four amino N atoms of tren, and the CuII centres are dimerized by two complementary hydrogen bonds between Cl- and a primary amine of tren. Moreover, the local copper environment in (II) is a distorted trigonal bipyramid (N4Cl), while in (I) it is a distorted square pyramid (N3Cl2).