Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013324/fr1340sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013324/fr1340Isup2.hkl |
CCDC reference: 174808
To an aqueous solution of sodium 2,6-naphthalenedisulfonate, equimolar amounts of [Cu(en)2]Cl2 and [Ni(en)3]Cl2 were added with stirring. After heating at 333 K for several hours in a water bath, the solution was maintained at room temperature and crystals suitable for data collection were obtained after several days.
The H atoms of the en ligands and the 2,6nds anions were placed in idealized positions (N—H = 0.90 Å, and C–H = 0.97 and 0.93 Å for CH2 and CH, respectively) and refined as riding atoms. The water H atoms were located from a difference Fourier map and were not refined.
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.
[Cu(C2H8N2)2(H2O)2][Ni(C2H8N2)3](C10H6S2O6)3·4H2O | Z = 1 |
Mr = 1628.69 | F(000) = 855 |
Triclinic, P1 | Dx = 1.514 Mg m−3 |
a = 11.8728 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.5961 (17) Å | Cell parameters from 856 reflections |
c = 13.903 (2) Å | θ = 3.6–24.3° |
α = 91.553 (2)° | µ = 1.07 mm−1 |
β = 105.950 (2)° | T = 293 K |
γ = 115.017 (2)° | Plate, brown |
V = 1786.9 (4) Å3 | 0.24 × 0.20 × 0.08 mm |
Bruker CCD area-detector diffractometer | 7625 independent reflections |
Radiation source: fine-focus sealed tube | 6452 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.0° |
Absorption correction: multi-scan (Blessing, 1995) | h = −12→15 |
Tmin = 0.78, Tmax = 0.92 | k = −15→16 |
10504 measured reflections | l = −17→16 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0722P)2 + 0.1603P] where P = (Fo2 + 2Fc2)/3 |
7625 reflections | (Δ/σ)max = 0.001 |
430 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[Cu(C2H8N2)2(H2O)2][Ni(C2H8N2)3](C10H6S2O6)3·4H2O | γ = 115.017 (2)° |
Mr = 1628.69 | V = 1786.9 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.8728 (17) Å | Mo Kα radiation |
b = 12.5961 (17) Å | µ = 1.07 mm−1 |
c = 13.903 (2) Å | T = 293 K |
α = 91.553 (2)° | 0.24 × 0.20 × 0.08 mm |
β = 105.950 (2)° |
Bruker CCD area-detector diffractometer | 7625 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6452 reflections with I > 2σ(I) |
Tmin = 0.78, Tmax = 0.92 | Rint = 0.034 |
10504 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.83 e Å−3 |
7625 reflections | Δρmin = −0.45 e Å−3 |
430 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 | ||
Ni | 0.36628 (3) | 0.21376 (2) | 0.07287 (2) | 0.02656 (9) | |
Cu | 0.0000 | 0.0000 | 0.5000 | 0.03281 (11) | |
N1 | 0.5273 (2) | 0.34898 (18) | 0.04109 (17) | 0.0375 (4) | |
H1A | 0.4985 | 0.3751 | −0.0158 | 0.045* | |
H1B | 0.5703 | 0.4107 | 0.0925 | 0.045* | |
N2 | 0.4427 (2) | 0.10579 (19) | 0.02091 (18) | 0.0428 (5) | |
H2A | 0.4845 | 0.0822 | 0.0737 | 0.051* | |
H2B | 0.3772 | 0.0408 | −0.0219 | 0.051* | |
N3 | 0.4843 (2) | 0.2436 (2) | 0.22753 (17) | 0.0453 (5) | |
H3A | 0.5416 | 0.2133 | 0.2324 | 0.054* | |
H3B | 0.5295 | 0.3220 | 0.2517 | 0.054* | |
N4 | 0.2289 (2) | 0.07636 (19) | 0.12478 (17) | 0.0426 (5) | |
H4A | 0.1646 | 0.0949 | 0.1285 | 0.051* | |
H4B | 0.1926 | 0.0078 | 0.0813 | 0.051* | |
N5 | 0.2933 (2) | 0.33609 (18) | 0.09834 (17) | 0.0392 (5) | |
H5A | 0.2361 | 0.3071 | 0.1332 | 0.047* | |
H5B | 0.3593 | 0.4058 | 0.1338 | 0.047* | |
N6 | 0.2267 (2) | 0.17443 (19) | −0.07312 (16) | 0.0418 (5) | |
H6A | 0.2680 | 0.2016 | −0.1192 | 0.050* | |
H6B | 0.1778 | 0.0953 | −0.0914 | 0.050* | |
N7 | 0.1872 (2) | 0.10808 (19) | 0.50631 (17) | 0.0400 (5) | |
H7A | 0.2359 | 0.1444 | 0.5705 | 0.048* | |
H7B | 0.2230 | 0.0655 | 0.4849 | 0.048* | |
N8 | −0.0402 (2) | 0.12789 (19) | 0.43642 (17) | 0.0411 (5) | |
H8A | −0.0804 | 0.1039 | 0.3692 | 0.049* | |
H8B | −0.0936 | 0.1429 | 0.4636 | 0.049* | |
S1 | 0.21325 (6) | 0.80107 (5) | 0.37848 (5) | 0.03907 (15) | |
S2 | 0.36588 (6) | 0.38926 (5) | −0.24928 (4) | 0.03547 (14) | |
S3 | −0.06277 (6) | 0.19233 (5) | 0.14166 (5) | 0.03416 (14) | |
C1 | 0.6152 (3) | 0.3005 (2) | 0.0279 (3) | 0.0493 (7) | |
H1C | 0.6694 | 0.2984 | 0.0936 | 0.059* | |
H1D | 0.6722 | 0.3504 | −0.0078 | 0.059* | |
C2 | 0.5347 (3) | 0.1775 (3) | −0.0316 (3) | 0.0528 (7) | |
H2C | 0.4864 | 0.1804 | −0.0994 | 0.063* | |
H2D | 0.5913 | 0.1419 | −0.0373 | 0.063* | |
C3 | 0.3949 (3) | 0.1843 (3) | 0.2854 (2) | 0.0562 (7) | |
H3C | 0.3493 | 0.2298 | 0.2951 | 0.067* | |
H3D | 0.4439 | 0.1778 | 0.3516 | 0.067* | |
C4 | 0.2982 (3) | 0.0627 (3) | 0.2265 (2) | 0.0584 (8) | |
H4C | 0.3436 | 0.0158 | 0.2198 | 0.070* | |
H4D | 0.2358 | 0.0222 | 0.2617 | 0.070* | |
C5 | 0.2273 (3) | 0.3521 (2) | −0.0039 (2) | 0.0436 (6) | |
H5C | 0.2922 | 0.4011 | −0.0340 | 0.052* | |
H5D | 0.1739 | 0.3913 | 0.0017 | 0.052* | |
C6 | 0.1426 (3) | 0.2319 (3) | −0.0693 (2) | 0.0472 (6) | |
H6C | 0.0750 | 0.1840 | −0.0410 | 0.057* | |
H6D | 0.1007 | 0.2404 | −0.1371 | 0.057* | |
C7 | 0.1835 (3) | 0.1970 (2) | 0.4401 (2) | 0.0445 (6) | |
H7C | 0.1576 | 0.1624 | 0.3697 | 0.053* | |
H7D | 0.2693 | 0.2644 | 0.4572 | 0.053* | |
C8 | 0.0852 (3) | 0.2363 (2) | 0.4560 (2) | 0.0468 (6) | |
H8C | 0.1146 | 0.2770 | 0.5250 | 0.056* | |
H8D | 0.0745 | 0.2901 | 0.4098 | 0.056* | |
C9 | 0.2037 (3) | 0.6940 (2) | 0.5479 (2) | 0.0430 (6) | |
H9A | 0.2823 | 0.7605 | 0.5806 | 0.052* | |
C10 | 0.1404 (2) | 0.6837 (2) | 0.44358 (19) | 0.0357 (5) | |
C11 | 0.0253 (2) | 0.5882 (2) | 0.3943 (2) | 0.0399 (5) | |
H11A | −0.0164 | 0.5836 | 0.3260 | 0.048* | |
C12 | −0.0322 (2) | 0.4940 (2) | 0.44738 (18) | 0.0352 (5) | |
C13 | −0.1508 (3) | 0.3928 (2) | 0.3990 (2) | 0.0443 (6) | |
H13A | −0.1933 | 0.3850 | 0.3303 | 0.053* | |
C14 | 0.0972 (3) | 0.5439 (2) | 0.1376 (2) | 0.0421 (6) | |
H14A | 0.1561 | 0.6125 | 0.1842 | 0.051* | |
C15 | 0.0622 (3) | 0.4359 (2) | 0.1686 (2) | 0.0424 (6) | |
H15A | 0.0966 | 0.4313 | 0.2361 | 0.051* | |
C16 | −0.0270 (2) | 0.3303 (2) | 0.09771 (18) | 0.0322 (5) | |
C17 | −0.0788 (2) | 0.3362 (2) | −0.00084 (18) | 0.0333 (5) | |
H17A | −0.1373 | 0.2665 | −0.0463 | 0.040* | |
C18 | −0.0450 (2) | 0.44751 (19) | −0.03554 (17) | 0.0305 (5) | |
C19 | 0.5805 (3) | 0.4116 (2) | −0.4331 (2) | 0.0420 (6) | |
H19A | 0.6402 | 0.3842 | −0.4388 | 0.050* | |
C20 | 0.5274 (3) | 0.3859 (2) | −0.35629 (19) | 0.0423 (6) | |
H20A | 0.5509 | 0.3415 | −0.3096 | 0.051* | |
C21 | 0.4364 (2) | 0.4271 (2) | −0.34839 (17) | 0.0328 (5) | |
C22 | 0.4000 (2) | 0.4919 (2) | −0.41517 (18) | 0.0338 (5) | |
H22A | 0.3395 | 0.5177 | −0.4083 | 0.041* | |
C23 | 0.4542 (2) | 0.5205 (2) | −0.49595 (17) | 0.0315 (5) | |
O1 | 0.1108 (2) | 0.78786 (19) | 0.28635 (16) | 0.0584 (5) | |
O2 | 0.2545 (2) | 0.90896 (17) | 0.44618 (17) | 0.0570 (5) | |
O3 | 0.3179 (2) | 0.78567 (19) | 0.3591 (2) | 0.0609 (6) | |
O4 | 0.2938 (2) | 0.4564 (2) | −0.24912 (17) | 0.0647 (6) | |
O5 | 0.2881 (2) | 0.26169 (17) | −0.27142 (15) | 0.0572 (6) | |
O6 | 0.47544 (19) | 0.42403 (18) | −0.15732 (13) | 0.0519 (5) | |
O7 | 0.0621 (2) | 0.18836 (19) | 0.17594 (19) | 0.0585 (6) | |
O8 | −0.1578 (2) | 0.10152 (16) | 0.05693 (15) | 0.0612 (6) | |
O9 | −0.11238 (19) | 0.19707 (17) | 0.22495 (15) | 0.0480 (4) | |
OW1 | 0.5665 (2) | −0.0394 (3) | 0.3649 (2) | 0.0901 (9) | |
HW1 | 0.4837 | −0.0951 | 0.3538 | 0.050* | |
HW2 | 0.6025 | 0.0007 | 0.4317 | 0.050* | |
OW2 | 0.6221 (2) | 0.0891 (2) | 0.21314 (19) | 0.0670 (6) | |
HW3 | 0.7007 | 0.1163 | 0.2156 | 0.050* | |
HW4 | 0.6051 | 0.0442 | 0.2574 | 0.050* | |
OW3 | −0.03042 (19) | −0.08810 (19) | 0.33016 (17) | 0.0581 (5) | |
HW5 | 0.0230 | −0.1215 | 0.3229 | 0.050* | |
HW6 | −0.1119 | −0.1495 | 0.3049 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.02612 (15) | 0.02517 (15) | 0.02772 (15) | 0.01003 (11) | 0.00969 (11) | 0.00644 (11) |
Cu | 0.0296 (2) | 0.0337 (2) | 0.0339 (2) | 0.01425 (17) | 0.00801 (16) | 0.00618 (16) |
N1 | 0.0373 (11) | 0.0336 (10) | 0.0430 (12) | 0.0144 (9) | 0.0169 (9) | 0.0086 (9) |
N2 | 0.0454 (12) | 0.0377 (11) | 0.0469 (13) | 0.0207 (10) | 0.0137 (10) | 0.0062 (9) |
N3 | 0.0449 (12) | 0.0505 (13) | 0.0365 (12) | 0.0198 (10) | 0.0096 (9) | 0.0071 (10) |
N4 | 0.0432 (12) | 0.0365 (11) | 0.0471 (13) | 0.0140 (9) | 0.0191 (10) | 0.0106 (9) |
N5 | 0.0344 (10) | 0.0346 (10) | 0.0484 (13) | 0.0126 (9) | 0.0175 (9) | 0.0062 (9) |
N6 | 0.0426 (12) | 0.0407 (11) | 0.0371 (11) | 0.0150 (10) | 0.0110 (9) | 0.0071 (9) |
N7 | 0.0351 (11) | 0.0410 (11) | 0.0397 (12) | 0.0157 (9) | 0.0083 (9) | 0.0022 (9) |
N8 | 0.0454 (12) | 0.0469 (12) | 0.0370 (11) | 0.0264 (10) | 0.0123 (9) | 0.0094 (9) |
S1 | 0.0414 (3) | 0.0325 (3) | 0.0491 (4) | 0.0175 (3) | 0.0209 (3) | 0.0123 (3) |
S2 | 0.0397 (3) | 0.0358 (3) | 0.0252 (3) | 0.0096 (2) | 0.0136 (2) | 0.0056 (2) |
S3 | 0.0370 (3) | 0.0299 (3) | 0.0380 (3) | 0.0136 (2) | 0.0173 (2) | 0.0106 (2) |
C1 | 0.0377 (14) | 0.0490 (15) | 0.073 (2) | 0.0217 (12) | 0.0301 (13) | 0.0193 (14) |
C2 | 0.0645 (18) | 0.0517 (16) | 0.0649 (19) | 0.0349 (15) | 0.0389 (16) | 0.0135 (14) |
C3 | 0.0601 (18) | 0.077 (2) | 0.0322 (14) | 0.0292 (16) | 0.0180 (13) | 0.0171 (14) |
C4 | 0.0643 (19) | 0.0620 (19) | 0.0605 (19) | 0.0298 (16) | 0.0320 (16) | 0.0375 (16) |
C5 | 0.0438 (14) | 0.0454 (14) | 0.0578 (17) | 0.0282 (12) | 0.0253 (12) | 0.0238 (12) |
C6 | 0.0366 (13) | 0.0657 (18) | 0.0396 (14) | 0.0270 (13) | 0.0054 (11) | 0.0109 (13) |
C7 | 0.0465 (14) | 0.0412 (14) | 0.0382 (14) | 0.0107 (12) | 0.0168 (11) | 0.0040 (11) |
C8 | 0.0588 (17) | 0.0344 (13) | 0.0456 (15) | 0.0209 (12) | 0.0138 (12) | 0.0088 (11) |
C9 | 0.0381 (13) | 0.0384 (13) | 0.0486 (15) | 0.0157 (11) | 0.0103 (11) | 0.0090 (11) |
C10 | 0.0363 (12) | 0.0338 (12) | 0.0437 (13) | 0.0188 (10) | 0.0173 (10) | 0.0107 (10) |
C11 | 0.0404 (13) | 0.0405 (13) | 0.0405 (14) | 0.0199 (11) | 0.0122 (11) | 0.0079 (11) |
C12 | 0.0343 (12) | 0.0367 (12) | 0.0364 (13) | 0.0189 (10) | 0.0089 (10) | 0.0055 (10) |
C13 | 0.0404 (14) | 0.0439 (14) | 0.0401 (14) | 0.0160 (11) | 0.0048 (11) | 0.0054 (11) |
C14 | 0.0451 (14) | 0.0326 (12) | 0.0356 (13) | 0.0120 (11) | 0.0025 (11) | −0.0004 (10) |
C15 | 0.0502 (15) | 0.0396 (13) | 0.0329 (13) | 0.0187 (12) | 0.0088 (11) | 0.0064 (10) |
C16 | 0.0315 (11) | 0.0318 (11) | 0.0383 (12) | 0.0155 (9) | 0.0159 (9) | 0.0105 (9) |
C17 | 0.0292 (11) | 0.0299 (11) | 0.0392 (13) | 0.0119 (9) | 0.0106 (9) | 0.0029 (9) |
C18 | 0.0268 (10) | 0.0308 (11) | 0.0323 (11) | 0.0130 (9) | 0.0072 (9) | 0.0010 (9) |
C19 | 0.0489 (15) | 0.0524 (15) | 0.0428 (14) | 0.0345 (13) | 0.0209 (11) | 0.0201 (12) |
C20 | 0.0532 (15) | 0.0510 (15) | 0.0353 (13) | 0.0307 (13) | 0.0191 (11) | 0.0212 (11) |
C21 | 0.0366 (12) | 0.0310 (11) | 0.0268 (11) | 0.0099 (9) | 0.0124 (9) | 0.0056 (9) |
C22 | 0.0362 (12) | 0.0360 (12) | 0.0327 (12) | 0.0179 (10) | 0.0131 (9) | 0.0060 (9) |
C23 | 0.0347 (11) | 0.0316 (11) | 0.0313 (12) | 0.0164 (9) | 0.0121 (9) | 0.0085 (9) |
O1 | 0.0579 (12) | 0.0558 (12) | 0.0517 (12) | 0.0202 (10) | 0.0102 (10) | 0.0213 (10) |
O2 | 0.0767 (14) | 0.0335 (10) | 0.0634 (13) | 0.0238 (10) | 0.0271 (11) | 0.0089 (9) |
O3 | 0.0574 (12) | 0.0529 (12) | 0.0965 (17) | 0.0304 (10) | 0.0491 (12) | 0.0282 (11) |
O4 | 0.0837 (16) | 0.0909 (17) | 0.0564 (13) | 0.0571 (14) | 0.0454 (12) | 0.0313 (12) |
O5 | 0.0588 (12) | 0.0400 (10) | 0.0462 (11) | −0.0061 (9) | 0.0239 (10) | 0.0010 (8) |
O6 | 0.0509 (11) | 0.0562 (11) | 0.0256 (9) | 0.0060 (9) | 0.0072 (8) | 0.0073 (8) |
O7 | 0.0547 (12) | 0.0620 (13) | 0.0869 (16) | 0.0393 (11) | 0.0396 (11) | 0.0412 (12) |
O8 | 0.0817 (15) | 0.0317 (10) | 0.0450 (12) | 0.0065 (10) | 0.0135 (11) | 0.0034 (8) |
O9 | 0.0506 (11) | 0.0542 (11) | 0.0459 (11) | 0.0220 (9) | 0.0268 (9) | 0.0161 (9) |
OW1 | 0.0604 (15) | 0.101 (2) | 0.0660 (17) | −0.0027 (14) | 0.0201 (13) | 0.0177 (15) |
OW2 | 0.0408 (11) | 0.0915 (17) | 0.0729 (15) | 0.0320 (12) | 0.0181 (10) | 0.0380 (13) |
OW3 | 0.0413 (10) | 0.0541 (12) | 0.0645 (14) | 0.0162 (9) | 0.0056 (9) | −0.0082 (10) |
Ni—N1 | 2.122 (2) | C3—C4 | 1.504 (5) |
Ni—N4 | 2.122 (2) | C3—H3C | 0.9700 |
Ni—N6 | 2.124 (2) | C3—H3D | 0.9700 |
Ni—N5 | 2.126 (2) | C4—H4C | 0.9700 |
Ni—N2 | 2.132 (2) | C4—H4D | 0.9700 |
Ni—N3 | 2.141 (2) | C5—C6 | 1.505 (4) |
Cu—N8 | 2.025 (2) | C5—H5C | 0.9700 |
Cu—N8i | 2.025 (2) | C5—H5D | 0.9700 |
Cu—N7i | 2.032 (2) | C6—H6C | 0.9700 |
Cu—N7 | 2.032 (2) | C6—H6D | 0.9700 |
Cu—OW3 | 2.447 (2) | C7—C8 | 1.510 (4) |
N1—C1 | 1.461 (3) | C7—H7C | 0.9700 |
N1—H1A | 0.9000 | C7—H7D | 0.9700 |
N1—H1B | 0.9000 | C8—H8C | 0.9700 |
N2—C2 | 1.478 (3) | C8—H8D | 0.9700 |
N2—H2A | 0.9000 | C9—C13ii | 1.361 (4) |
N2—H2B | 0.9000 | C9—C10 | 1.412 (4) |
N3—C3 | 1.471 (4) | C9—H9A | 0.9300 |
N3—H3A | 0.9000 | C10—C11 | 1.355 (3) |
N3—H3B | 0.9000 | C11—C12 | 1.434 (4) |
N4—C4 | 1.484 (4) | C11—H11A | 0.9300 |
N4—H4A | 0.9000 | C12—C13 | 1.405 (3) |
N4—H4B | 0.9000 | C12—C12ii | 1.423 (5) |
N5—C5 | 1.487 (3) | C13—C9ii | 1.361 (4) |
N5—H5A | 0.9000 | C13—H13A | 0.9300 |
N5—H5B | 0.9000 | C14—C15 | 1.364 (4) |
N6—C6 | 1.471 (3) | C14—C18iii | 1.411 (3) |
N6—H6A | 0.9000 | C14—H14A | 0.9300 |
N6—H6B | 0.9000 | C15—C16 | 1.423 (3) |
N7—C7 | 1.476 (3) | C15—H15A | 0.9300 |
N7—H7A | 0.9000 | C16—C17 | 1.357 (3) |
N7—H7B | 0.9000 | C17—C18 | 1.424 (3) |
N8—C8 | 1.481 (3) | C17—H17A | 0.9300 |
N8—H8A | 0.9000 | C18—C14iii | 1.411 (3) |
N8—H8B | 0.9000 | C18—C18iii | 1.421 (4) |
S1—O3 | 1.428 (2) | C19—C20 | 1.363 (4) |
S1—O2 | 1.445 (2) | C19—C23iv | 1.412 (3) |
S1—O1 | 1.452 (2) | C19—H19A | 0.9300 |
S1—C10 | 1.781 (2) | C20—C21 | 1.410 (4) |
S2—O4 | 1.435 (2) | C20—H20A | 0.9300 |
S2—O5 | 1.4463 (19) | C21—C22 | 1.353 (3) |
S2—O6 | 1.4464 (19) | C22—C23 | 1.424 (3) |
S2—C21 | 1.777 (2) | C22—H22A | 0.9300 |
S3—O8 | 1.440 (2) | C23—C19iv | 1.412 (3) |
S3—O9 | 1.4465 (19) | C23—C23iv | 1.415 (4) |
S3—O7 | 1.451 (2) | OW1—HW1 | 0.9002 |
S3—C16 | 1.775 (2) | OW1—HW2 | 0.9353 |
C1—C2 | 1.497 (4) | OW2—HW3 | 0.8374 |
C1—H1C | 0.9700 | OW2—HW4 | 0.8542 |
C1—H1D | 0.9700 | OW3—HW5 | 0.9208 |
C2—H2C | 0.9700 | OW3—HW6 | 0.9073 |
C2—H2D | 0.9700 | ||
N1—Ni—N4 | 170.59 (9) | C2—C1—H1D | 109.9 |
N1—Ni—N6 | 97.23 (9) | H1C—C1—H1D | 108.3 |
N4—Ni—N6 | 91.59 (9) | N2—C2—C1 | 108.8 (2) |
N1—Ni—N5 | 91.25 (8) | N2—C2—H2C | 109.9 |
N4—Ni—N5 | 93.20 (8) | C1—C2—H2C | 109.9 |
N6—Ni—N5 | 82.13 (9) | N2—C2—H2D | 109.9 |
N1—Ni—N2 | 81.24 (8) | C1—C2—H2D | 109.9 |
N4—Ni—N2 | 95.49 (9) | H2C—C2—H2D | 108.3 |
N6—Ni—N2 | 90.42 (9) | N3—C3—C4 | 108.0 (2) |
N5—Ni—N2 | 168.70 (8) | N3—C3—H3C | 110.1 |
N1—Ni—N3 | 89.98 (9) | C4—C3—H3C | 110.1 |
N4—Ni—N3 | 81.40 (9) | N3—C3—H3D | 110.1 |
N6—Ni—N3 | 172.13 (9) | C4—C3—H3D | 110.1 |
N5—Ni—N3 | 94.62 (9) | H3C—C3—H3D | 108.4 |
N2—Ni—N3 | 93.81 (9) | N4—C4—C3 | 108.4 (2) |
N8—Cu—N8i | 180.0 | N4—C4—H4C | 110.0 |
N8—Cu—N7i | 95.51 (9) | C3—C4—H4C | 110.0 |
N8i—Cu—N7i | 84.49 (9) | N4—C4—H4D | 110.0 |
N8—Cu—N7 | 84.49 (9) | C3—C4—H4D | 110.0 |
N8i—Cu—N7 | 95.51 (9) | H4C—C4—H4D | 108.4 |
N7i—Cu—N7 | 180.0 | N5—C5—C6 | 108.7 (2) |
N8—Cu—OW3 | 88.00 (8) | N5—C5—H5C | 109.9 |
N8i—Cu—OW3 | 92.00 (8) | C6—C5—H5C | 109.9 |
N7i—Cu—OW3 | 93.13 (8) | N5—C5—H5D | 109.9 |
N7—Cu—OW3 | 86.87 (8) | C6—C5—H5D | 109.9 |
C1—N1—Ni | 108.87 (15) | H5C—C5—H5D | 108.3 |
C1—N1—H1A | 109.9 | N6—C6—C5 | 108.1 (2) |
Ni—N1—H1A | 109.9 | N6—C6—H6C | 110.1 |
C1—N1—H1B | 109.9 | C5—C6—H6C | 110.1 |
Ni—N1—H1B | 109.9 | N6—C6—H6D | 110.1 |
H1A—N1—H1B | 108.3 | C5—C6—H6D | 110.1 |
C2—N2—Ni | 107.76 (15) | H6C—C6—H6D | 108.4 |
C2—N2—H2A | 110.2 | N7—C7—C8 | 107.7 (2) |
Ni—N2—H2A | 110.2 | N7—C7—H7C | 110.2 |
C2—N2—H2B | 110.2 | C8—C7—H7C | 110.2 |
Ni—N2—H2B | 110.2 | N7—C7—H7D | 110.2 |
H2A—N2—H2B | 108.5 | C8—C7—H7D | 110.2 |
C3—N3—Ni | 107.12 (17) | H7C—C7—H7D | 108.5 |
C3—N3—H3A | 110.3 | N8—C8—C7 | 107.0 (2) |
Ni—N3—H3A | 110.3 | N8—C8—H8C | 110.3 |
C3—N3—H3B | 110.3 | C7—C8—H8C | 110.3 |
Ni—N3—H3B | 110.3 | N8—C8—H8D | 110.3 |
H3A—N3—H3B | 108.5 | C7—C8—H8D | 110.3 |
C4—N4—Ni | 108.51 (17) | H8C—C8—H8D | 108.6 |
C4—N4—H4A | 110.0 | C13ii—C9—C10 | 120.6 (2) |
Ni—N4—H4A | 110.0 | C13ii—C9—H9A | 119.7 |
C4—N4—H4B | 110.0 | C10—C9—H9A | 119.7 |
Ni—N4—H4B | 110.0 | C11—C10—C9 | 120.9 (2) |
H4A—N4—H4B | 108.4 | C11—C10—S1 | 120.5 (2) |
C5—N5—Ni | 105.90 (15) | C9—C10—S1 | 118.53 (19) |
C5—N5—H5A | 110.6 | C10—C11—C12 | 120.0 (2) |
Ni—N5—H5A | 110.6 | C10—C11—H11A | 120.0 |
C5—N5—H5B | 110.6 | C12—C11—H11A | 120.0 |
Ni—N5—H5B | 110.6 | C13—C12—C12ii | 119.7 (3) |
H5A—N5—H5B | 108.7 | C13—C12—C11 | 121.9 (2) |
C6—N6—Ni | 108.55 (16) | C12ii—C12—C11 | 118.4 (3) |
C6—N6—H6A | 110.0 | C9ii—C13—C12 | 120.4 (2) |
Ni—N6—H6A | 110.0 | C9ii—C13—H13A | 119.8 |
C6—N6—H6B | 110.0 | C12—C13—H13A | 119.8 |
Ni—N6—H6B | 110.0 | C15—C14—C18iii | 120.6 (2) |
H6A—N6—H6B | 108.4 | C15—C14—H14A | 119.7 |
C7—N7—Cu | 107.69 (16) | C18iii—C14—H14A | 119.7 |
C7—N7—H7A | 110.2 | C14—C15—C16 | 120.1 (2) |
Cu—N7—H7A | 110.2 | C14—C15—H15A | 119.9 |
C7—N7—H7B | 110.2 | C16—C15—H15A | 119.9 |
Cu—N7—H7B | 110.2 | C17—C16—C15 | 120.4 (2) |
H7A—N7—H7B | 108.5 | C17—C16—S3 | 121.67 (18) |
C8—N8—Cu | 108.02 (16) | C15—C16—S3 | 117.86 (18) |
C8—N8—H8A | 110.1 | C16—C17—C18 | 120.9 (2) |
Cu—N8—H8A | 110.1 | C16—C17—H17A | 119.6 |
C8—N8—H8B | 110.1 | C18—C17—H17A | 119.6 |
Cu—N8—H8B | 110.1 | C14iii—C18—C18iii | 119.6 (3) |
H8A—N8—H8B | 108.4 | C14iii—C18—C17 | 122.1 (2) |
O3—S1—O2 | 114.41 (14) | C18iii—C18—C17 | 118.3 (3) |
O3—S1—O1 | 112.90 (15) | C20—C19—C23iv | 120.7 (2) |
O2—S1—O1 | 111.12 (13) | C20—C19—H19A | 119.7 |
O3—S1—C10 | 106.09 (12) | C23iv—C19—H19A | 119.7 |
O2—S1—C10 | 105.12 (12) | C19—C20—C21 | 119.4 (2) |
O1—S1—C10 | 106.43 (12) | C19—C20—H20A | 120.3 |
O4—S2—O5 | 115.23 (15) | C21—C20—H20A | 120.3 |
O4—S2—O6 | 111.94 (14) | C22—C21—C20 | 121.7 (2) |
O5—S2—O6 | 111.02 (13) | C22—C21—S2 | 119.89 (19) |
O4—S2—C21 | 106.75 (12) | C20—C21—S2 | 118.36 (18) |
O5—S2—C21 | 105.70 (11) | C21—C22—C23 | 120.2 (2) |
O6—S2—C21 | 105.42 (11) | C21—C22—H22A | 119.9 |
O8—S3—O9 | 113.13 (13) | C23—C22—H22A | 119.9 |
O8—S3—O7 | 113.79 (15) | C19iv—C23—C23iv | 119.7 (3) |
O9—S3—O7 | 111.48 (13) | C19iv—C23—C22 | 122.0 (2) |
O8—S3—C16 | 106.56 (12) | C23iv—C23—C22 | 118.3 (3) |
O9—S3—C16 | 106.27 (11) | HW1—OW1—HW2 | 110.3 |
O7—S3—C16 | 104.83 (11) | HW3—OW2—HW4 | 112.1 |
N1—C1—C2 | 108.8 (2) | Cu—OW3—HW5 | 118.7 |
N1—C1—H1C | 109.9 | Cu—OW3—HW6 | 109.5 |
C2—C1—H1C | 109.9 | HW5—OW3—HW6 | 103.1 |
N1—C1—H1D | 109.9 | ||
N6—Ni—N1—C1 | −103.40 (19) | N7—C7—C8—N8 | −55.4 (3) |
N5—Ni—N1—C1 | 174.38 (19) | C13ii—C9—C10—C11 | 0.6 (4) |
N2—Ni—N1—C1 | −14.10 (18) | C13ii—C9—C10—S1 | 179.1 (2) |
N3—Ni—N1—C1 | 79.76 (19) | O3—S1—C10—C11 | −103.2 (2) |
N1—Ni—N2—C2 | −15.14 (19) | O2—S1—C10—C11 | 135.2 (2) |
N4—Ni—N2—C2 | 173.75 (19) | O1—S1—C10—C11 | 17.2 (2) |
N6—Ni—N2—C2 | 82.11 (19) | O3—S1—C10—C9 | 78.2 (2) |
N5—Ni—N2—C2 | 33.6 (5) | O2—S1—C10—C9 | −43.4 (2) |
N3—Ni—N2—C2 | −104.54 (19) | O1—S1—C10—C9 | −161.3 (2) |
N1—Ni—N3—C3 | 165.4 (2) | C9—C10—C11—C12 | −1.7 (4) |
N4—Ni—N3—C3 | −18.38 (19) | S1—C10—C11—C12 | 179.79 (18) |
N5—Ni—N3—C3 | 74.2 (2) | C10—C11—C12—C13 | −179.4 (2) |
N6—Ni—N4—C4 | 171.79 (19) | C10—C11—C12—C12ii | 2.1 (4) |
N5—Ni—N4—C4 | −106.01 (19) | C12ii—C12—C13—C9ii | −0.4 (4) |
N2—Ni—N4—C4 | 81.2 (2) | C11—C12—C13—C9ii | −178.9 (3) |
N3—Ni—N4—C4 | −11.81 (19) | C18iii—C14—C15—C16 | 0.5 (4) |
N1—Ni—N5—C5 | 78.36 (16) | C14—C15—C16—C17 | −0.7 (4) |
N4—Ni—N5—C5 | −109.94 (16) | C14—C15—C16—S3 | 177.2 (2) |
N6—Ni—N5—C5 | −18.77 (15) | O8—S3—C16—C17 | −4.2 (2) |
N2—Ni—N5—C5 | 30.3 (5) | O9—S3—C16—C17 | −125.1 (2) |
N3—Ni—N5—C5 | 168.44 (15) | O7—S3—C16—C17 | 116.7 (2) |
N1—Ni—N6—C6 | −101.46 (17) | O8—S3—C16—C15 | 177.9 (2) |
N4—Ni—N6—C6 | 81.81 (18) | O9—S3—C16—C15 | 57.0 (2) |
N5—Ni—N6—C6 | −11.20 (17) | O7—S3—C16—C15 | −61.1 (2) |
N2—Ni—N6—C6 | 177.31 (17) | C15—C16—C17—C18 | 0.3 (3) |
N8—Cu—N7—C7 | −14.53 (16) | S3—C16—C17—C18 | −177.52 (17) |
N8i—Cu—N7—C7 | 165.47 (16) | C16—C17—C18—C14iii | 179.8 (2) |
OW3—Cu—N7—C7 | 73.76 (16) | C16—C17—C18—C18iii | 0.3 (4) |
N7i—Cu—N8—C8 | 164.64 (17) | C23iv—C19—C20—C21 | 0.4 (4) |
N7—Cu—N8—C8 | −15.36 (17) | C19—C20—C21—C22 | 0.0 (4) |
OW3—Cu—N8—C8 | −102.41 (17) | C19—C20—C21—S2 | 178.6 (2) |
Ni—N1—C1—C2 | 40.9 (3) | O4—S2—C21—C22 | −10.0 (2) |
Ni—N2—C2—C1 | 41.6 (3) | O5—S2—C21—C22 | 113.2 (2) |
N1—C1—C2—N2 | −55.8 (3) | O6—S2—C21—C22 | −129.2 (2) |
Ni—N3—C3—C4 | 45.3 (3) | O4—S2—C21—C20 | 171.4 (2) |
Ni—N4—C4—C3 | 39.8 (3) | O5—S2—C21—C20 | −65.4 (2) |
N3—C3—C4—N4 | −57.7 (3) | O6—S2—C21—C20 | 52.2 (2) |
Ni—N5—C5—C6 | 45.8 (2) | C20—C21—C22—C23 | −0.2 (4) |
Ni—N6—C6—C5 | 39.1 (2) | S2—C21—C22—C23 | −178.77 (17) |
N5—C5—C6—N6 | −57.9 (3) | C21—C22—C23—C19iv | −179.6 (2) |
Cu—N7—C7—C8 | 41.2 (2) | C21—C22—C23—C23iv | 0.1 (4) |
Cu—N8—C8—C7 | 41.7 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x+1, −y+1, −z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O6 | 0.90 | 2.06 | 2.929 (3) | 162 |
N1—H1B···O4v | 0.90 | 2.39 | 3.274 (3) | 166 |
N1—H1B···O6v | 0.90 | 2.56 | 3.262 (3) | 135 |
N2—H2A···OW2 | 0.90 | 2.14 | 3.001 (3) | 161 |
N2—H2B···O8vi | 0.90 | 2.35 | 3.130 (3) | 144 |
N3—H3A···OW2 | 0.90 | 2.19 | 3.059 (3) | 161 |
N4—H4A···O7 | 0.90 | 2.22 | 3.081 (3) | 161 |
N4—H4B···O8vi | 0.90 | 2.17 | 3.006 (3) | 155 |
N5—H5A···O7 | 0.90 | 2.23 | 3.095 (3) | 161 |
N5—H5B···O6v | 0.90 | 2.15 | 2.992 (3) | 156 |
N6—H6A···O5 | 0.90 | 2.31 | 3.151 (3) | 156 |
N6—H6B···O8vi | 0.90 | 2.46 | 3.246 (3) | 146 |
N7—H7A···O5vii | 0.90 | 2.39 | 3.226 (3) | 155 |
N7—H7B···O2viii | 0.90 | 2.23 | 3.094 (3) | 160 |
N8—H8A···O9 | 0.90 | 2.37 | 3.086 (3) | 136 |
N8—H8B···O2ii | 0.90 | 2.44 | 3.268 (3) | 153 |
OW1—HW1···O3viii | 0.90 | 1.93 | 2.817 (3) | 168 |
OW1—HW2···O2ix | 0.94 | 1.93 | 2.804 (4) | 154 |
OW2—HW3···O9x | 0.84 | 1.98 | 2.809 (3) | 174 |
OW2—HW4···OW1 | 0.85 | 1.90 | 2.748 (3) | 173 |
OW3—HW5···O1viii | 0.92 | 1.98 | 2.889 (3) | 170 |
OW3—HW6···O5vi | 0.91 | 1.88 | 2.771 (3) | 169 |
Symmetry codes: (ii) −x, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x, −y, −z; (vii) x, y, z+1; (viii) x, y−1, z; (ix) −x+1, −y+1, −z+1; (x) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H8N2)2(H2O)2][Ni(C2H8N2)3](C10H6S2O6)3·4H2O |
Mr | 1628.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.8728 (17), 12.5961 (17), 13.903 (2) |
α, β, γ (°) | 91.553 (2), 105.950 (2), 115.017 (2) |
V (Å3) | 1786.9 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.24 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.78, 0.92 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10504, 7625, 6452 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.111, 1.07 |
No. of reflections | 7625 |
No. of parameters | 430 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.45 |
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 |
N1—H1A···O6 | 0.90 | 2.06 | 2.929 (3) | 162 |
N1—H1B···O4i | 0.90 | 2.39 | 3.274 (3) | 166 |
N1—H1B···O6i | 0.90 | 2.56 | 3.262 (3) | 135 |
N2—H2A···OW2 | 0.90 | 2.14 | 3.001 (3) | 161 |
N2—H2B···O8ii | 0.90 | 2.35 | 3.130 (3) | 144 |
N3—H3A···OW2 | 0.90 | 2.19 | 3.059 (3) | 161 |
N4—H4A···O7 | 0.90 | 2.22 | 3.081 (3) | 161 |
N4—H4B···O8ii | 0.90 | 2.17 | 3.006 (3) | 155 |
N5—H5A···O7 | 0.90 | 2.23 | 3.095 (3) | 161 |
N5—H5B···O6i | 0.90 | 2.15 | 2.992 (3) | 156 |
N6—H6A···O5 | 0.90 | 2.31 | 3.151 (3) | 156 |
N6—H6B···O8ii | 0.90 | 2.46 | 3.246 (3) | 146 |
N7—H7A···O5iii | 0.90 | 2.39 | 3.226 (3) | 155 |
N7—H7B···O2iv | 0.90 | 2.23 | 3.094 (3) | 160 |
N8—H8A···O9 | 0.90 | 2.37 | 3.086 (3) | 136 |
N8—H8B···O2v | 0.90 | 2.44 | 3.268 (3) | 153 |
OW1—HW1···O3iv | 0.90 | 1.93 | 2.817 (3) | 168 |
OW1—HW2···O2vi | 0.94 | 1.93 | 2.804 (4) | 154 |
OW2—HW3···O9vii | 0.84 | 1.98 | 2.809 (3) | 174 |
OW2—HW4···OW1 | 0.85 | 1.90 | 2.748 (3) | 173 |
OW3—HW5···O1iv | 0.92 | 1.98 | 2.889 (3) | 170 |
OW3—HW6···O5ii | 0.91 | 1.88 | 2.771 (3) | 169 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z; (iii) x, y, z+1; (iv) x, y−1, z; (v) −x, −y+1, −z+1; (vi) −x+1, −y+1, −z+1; (vii) x+1, y, z. |
Promising applications of porous crystalline materials include separation, shape-selective catalysis, trapping and storage of toxic materials, off-peak energy storage and heterogeneous catalysis (Thompson, 1994; Endo et al., 1997). The general approach toward the construction of porous coordination network is the use of coordination polymerization to align inorganic complexes (Munakata et al., 1996; Hunter, 1995). Recently, the ability to design and control the assembly of coordination networks through both coordination and hydrogen-bonding interactions, by employing organic ligands with hydrogen–bonding functionality combined with coordination sites for transition metal, has been of great interest for both perspectives of crystal engineering and searching for functional materials (MacDonald et al., 2000). We have been exploring an approach, namely using the amino-coordinated metal complex cation and large naphthalenedisulfonate anion as building blocks, to construct porous crystalline materials and mixed-metal systems. The amino H atoms of the metal complex can form strong ionic hydrogen bonds with the sulfonate O atoms. If the hydrogen bonds are directive, a porous framework can be built which can accommodate guest molecules with diverse nature. Indeed this is what observed in the adduct [Co(trien)(phen)](1,5nds)1.5.2(phen).8(H2O) (trien is triethylenetetraamine, phen is 1, 10-phenanthroline and nds is naphthalenedisulfonate; Cai, Feng & Hu, 2001). We report here the crystal structure of the title mixed-metal compound, [Cu(en)2(H2O)2][Ni(en)3]2(2,6nds)3.4H2O, (I), where en is ethylenediamine.
Fig. 1 shows the structure of (I). The coordination geometries of the elongated octahedral [Cu(en)2(H2O)2]2+ and octahedral [Ni(en)3]2+ are regular and compatible with the reported analogues (Kovbasyuk et al., 1997; Emsley et al., 1988, 1990; Urrutigoity et al., 1996). The Cu atom and all the three independent 2,6-naphthalenedisulfonate anions are located on inversion centers. The OW3 water molecule forms weak coordination with Cu2+ in axial positions [Cu···O 2.448 (2) Å]. The amino H atoms of the [Cu(en)2(H2O)2]2+ fragment are involved in hydrogen-bonding interactions with the sulfonate O atoms, as shown in Fig. 2 [the N···O distances are in the range 3.086 (3)–3.246 (3) Å and the N–H···O angles are in the range 136.2–159.6°], resulting in an extended porous two-dimensional network. The cavities along the c axis, each constructed by four [Cu(en)2(H2O)2]2+ and four 2,6nds anions, are filled by the [Ni(en)3]2+ cations. The amino H atoms of the [Ni(en)3]2+ fragments are also involved in extensive hydrogen bonds with the sulfonate O atoms. The other two water molecules exist as a dimer with strong intermolecular hydrogen bonds [OW2···OW1 2.751 (4) Å and OW2–H···OW1 173.8°], and also reside in the cavities hydrogen bonded to the sulfonate O atoms. During our previous investigation of the coordination behavior of sulfonate anions with transition metal atoms (Cai et al., 2001), we demonstrated that the coordination strength of sulfonate could be tailored chemically. In the structures of Cu(en)2(1,5nds).2H2O and Cu(N-meen)2(2,6nds).2H2O (N–meen is N-methylethylenediamine; Cai, Chen et al., 2001), the Cu atom is weakly coordinated in the axial positions by the sulfonate O atoms instead of water O atoms. In the title compound, there is no direct interaction between the Cu and sulfonate O atoms. This observation further illustrates that metal sulfonates display a wide range of structural chemistry that calls for extensive investigation.