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In title anhydrous
catena-poly[[
trans-bis(ethane-1,2-diamine-
2N,
N')copper(II)]-
-dithionato-
2O:
O'], [Cu(S
2O
6)(C
2H
8N
2)
2]
n or [{H
2N(CH
2)
2NH
2}
2Cu(O·O
2SSO
2·O)]
, successive Cu atoms are bridged by a single doubly charged dithionate group, forming a one-dimensional polymer with inversion centres at the metal atoms and the mid-point of the S-S bond [Cu-O = 2.5744 (15) Å]. In title (hydrated)
trans-diaquabis(propane-1,3-diamine-
2N,
N')copper(II) dithionate, [Cu(C
3H
10N
2)
2(H
2O)
2](S
2O
6) or [{H
2N(CH
2)
3NH
2}
2Cu(OH
2)
2](S
2O
6), both ions have imposed 2/
m symmetry. The `axial' anion components are displaced by a pair of water ligands [Cu-O = 2.439 (3) Å], the shorter Cu-O distance being compensated by the lengthened Cu-N distance [2.0443 (18),
cf. 2.0100 (13) and 2.0122 (16) Å].
Supporting information
CCDC references: 229083; 229084
The title complexes (which appear to be new) were prepared from aqueous solutions of copper(II) chloride with two equivalents of the appropriate diamine, by the addition of lithium dithionate solutions. Crystals were deposited after slow evaporation in the ambience (ambient conditions)?. Bulk materials giving satisfactory analyses were as follows (Kosin University Microanalytical Service): CuS2O6: ethane-1,2-diamine (1:2). For (I), analysis found: C 14.3, H 5.2, N 16.1; C4H16CuN4O6S2 requires: C 13.97, H 4.69, N 16.29%. CuS2O6: propane-1,2-diamine (1:2) dihydrate: For (II), analysis found: C 18.2, H 6.1, N 13.5; C6H24CuN4O8S2 requires: C 17.67, H 5.93, N 13.7%.
H atoms were located from difference Fourier maps and placed at idealized positions (C—H = 0.95 Å), and then their positional and Uiso values were refined.
For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995). Data reduction: Xtal3.5 (Hall et al., 1995) for (I); Xtal3.5 (Hall, King, and Stewart, 1995) for (II). For both compounds, program(s) used to solve structure: Xtal3.5; program(s) used to refine structure: CRYLSQ in Xtal3.5; molecular graphics: Xtal3.5; software used to prepare material for publication: BONDLA and CIFIO in Xtal3.5.
Crystal data top
[Cu(S2O6)(C2H8N2)2] | F(000) = 354 |
Mr = 343.87 | Dx = 1.812 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 3259 reflections |
a = 8.4727 (10) Å | θ = 2.5–28.2° |
b = 10.2699 (10) Å | µ = 2.09 mm−1 |
c = 8.0696 (10) Å | T = 150 K |
β = 116.170 (2)° | Prism, purple |
V = 630.19 (12) Å3 | 0.1 × 0.05 × 0.04 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD diffractometer | 1608 independent reflections |
Radiation source: sealed tube | 1441 reflections with I > 2σ(I ) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 29.2°, θmin = 2.7° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | h = −11→10 |
Tmin = 0.809, Tmax = 0.928 | k = −14→14 |
6260 measured reflections | l = −10→10 |
Refinement top
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.031 | All H-atom parameters refined |
S = 1.07 | w = 1/(σ2(F) + 0.0004F2) |
1441 reflections | (Δ/σ)max = 0.014 |
111 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
0 constraints | |
Crystal data top
[Cu(S2O6)(C2H8N2)2] | V = 630.19 (12) Å3 |
Mr = 343.87 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.4727 (10) Å | µ = 2.09 mm−1 |
b = 10.2699 (10) Å | T = 150 K |
c = 8.0696 (10) Å | 0.1 × 0.05 × 0.04 mm |
β = 116.170 (2)° | |
Data collection top
Bruker SMART CCD diffractometer | 1608 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | 1441 reflections with I > 2σ(I ) |
Tmin = 0.809, Tmax = 0.928 | Rint = 0.023 |
6260 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.031 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.57 e Å−3 |
1441 reflections | Δρmin = −0.41 e Å−3 |
111 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.00000 | 0.00000 | 0.50000 | 0.01700 (14) | |
N1 | 0.2037 (2) | 0.10832 (14) | 0.6731 (2) | 0.0207 (6) | |
C2 | 0.3689 (2) | 0.0416 (2) | 0.7052 (3) | 0.0297 (8) | |
C3 | 0.3417 (3) | −0.1030 (2) | 0.7164 (3) | 0.0317 (9) | |
N4 | 0.1808 (2) | −0.14058 (15) | 0.5501 (2) | 0.0225 (6) | |
S1 | 0.11475 (5) | 0.03080 (4) | 0.11883 (5) | 0.01731 (18) | |
O1 | 0.04766 (16) | 0.09940 (11) | 0.23267 (16) | 0.0221 (5) | |
O2 | 0.20804 (17) | −0.08904 (11) | 0.20022 (17) | 0.0236 (5) | |
O3 | 0.20700 (16) | 0.11519 (12) | 0.04533 (16) | 0.0234 (5) | |
H1a | 0.198 (3) | 0.114 (2) | 0.775 (3) | 0.034 (6)* | |
H1b | 0.201 (2) | 0.188 (2) | 0.625 (3) | 0.025 (5)* | |
H2a | 0.461 (3) | 0.076 (2) | 0.818 (3) | 0.036 (6)* | |
H2b | 0.391 (3) | 0.065 (2) | 0.593 (3) | 0.029 (5)* | |
H3a | 0.327 (3) | −0.122 (2) | 0.824 (3) | 0.039 (6)* | |
H3b | 0.447 (3) | −0.149 (2) | 0.728 (3) | 0.042 (7)* | |
H4a | 0.147 (2) | −0.218 (2) | 0.567 (3) | 0.028 (5)* | |
H4b | 0.203 (3) | −0.141 (2) | 0.449 (3) | 0.039 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.01888 (16) | 0.01545 (16) | 0.01644 (16) | −0.00023 (10) | 0.00759 (12) | −0.00063 (9) |
N1 | 0.0243 (8) | 0.0202 (7) | 0.0183 (7) | −0.0025 (5) | 0.0100 (6) | −0.0010 (5) |
C2 | 0.0210 (9) | 0.0288 (10) | 0.0348 (10) | −0.0035 (7) | 0.0083 (8) | −0.0017 (8) |
C3 | 0.0239 (10) | 0.0269 (10) | 0.0348 (11) | 0.0052 (7) | 0.0044 (8) | 0.0047 (8) |
N4 | 0.0257 (8) | 0.0184 (7) | 0.0225 (8) | 0.0020 (6) | 0.0100 (6) | 0.0029 (5) |
S1 | 0.0210 (2) | 0.0166 (2) | 0.0156 (2) | −0.00119 (14) | 0.00918 (16) | −0.00099 (13) |
O1 | 0.0304 (7) | 0.0198 (6) | 0.0196 (6) | 0.0004 (5) | 0.0143 (5) | −0.0031 (4) |
O2 | 0.0276 (7) | 0.0193 (6) | 0.0231 (6) | 0.0039 (5) | 0.0106 (5) | 0.0015 (4) |
O3 | 0.0290 (7) | 0.0221 (6) | 0.0228 (6) | −0.0075 (5) | 0.0146 (6) | −0.0020 (5) |
Geometric parameters (Å, º) top
Cu—N1 | 2.0100 (13) | C2—H2b | 1.03 (3) |
Cu—N4 | 2.0122 (16) | C3—N4 | 1.481 (2) |
Cu—O1 | 2.5744 (15) | C3—H3a | 0.95 (3) |
Cu—N1 | 2.0100 (13) | C3—H3b | 0.98 (3) |
Cu—N4 | 2.0122 (16) | N4—H4a | 0.88 (2) |
Cu—O1 | 2.5744 (15) | N4—H4b | 0.92 (3) |
N1—C2 | 1.476 (3) | S1—O1 | 1.4573 (16) |
N1—H1a | 0.85 (3) | S1—O2 | 1.4536 (12) |
N1—H1b | 0.90 (2) | S1—O3 | 1.4569 (16) |
C2—C3 | 1.511 (3) | S1—S1i | 2.1378 (5) |
C2—H2a | 0.97 (2) | | |
| | | |
N1—Cu—N4 | 85.02 (6) | N1—C2—H2b | 105.1 (11) |
N1—Cu—O1 | 87.64 (6) | C3—C2—H2a | 112.5 (14) |
N1—Cu—N1 | 180.0000 | C3—C2—H2b | 112.0 (12) |
N1—Cu—N4 | 94.98 (6) | H2a—C2—H2b | 111 (2) |
N1—Cu—O1 | 92.36 (6) | C2—C3—N4 | 107.83 (15) |
N4—Cu—O1 | 93.78 (6) | C2—C3—H3a | 110.0 (13) |
N4—Cu—N1 | 94.98 (6) | C2—C3—H3b | 109.1 (15) |
N4—Cu—N4 | 180.0000 | N4—C3—H3a | 109.5 (13) |
N4—Cu—O1 | 86.22 (6) | N4—C3—H3b | 113.1 (13) |
O1—Cu—N1 | 92.36 (6) | H3a—C3—H3b | 107 (2) |
O1—Cu—N4 | 86.22 (6) | Cu—N4—C3 | 108.05 (12) |
O1—Cu—O1 | 180.0000 | Cu—N4—H4a | 114.2 (14) |
N1—Cu—N4 | 85.02 (6) | Cu—N4—H4b | 105.2 (14) |
N1—Cu—O1 | 87.64 (6) | C3—N4—H4a | 109.2 (10) |
N4—Cu—O1 | 93.78 (6) | C3—N4—H4b | 109.9 (13) |
Cu—N1—C2 | 108.81 (11) | H4a—N4—H4b | 110 (2) |
Cu—N1—H1a | 108.2 (15) | O1—S1—O2 | 114.21 (8) |
Cu—N1—H1b | 110.6 (10) | O1—S1—O3 | 113.42 (8) |
C2—N1—H1a | 108.5 (14) | O1—S1—S1i | 104.79 (5) |
C2—N1—H1b | 109.9 (14) | O2—S1—O3 | 113.90 (9) |
H1a—N1—H1b | 111 (2) | O2—S1—S1i | 104.65 (5) |
N1—C2—C3 | 107.98 (17) | O3—S1—S1i | 104.47 (5) |
N1—C2—H2a | 107.9 (16) | Cu—O1—S1 | 125.84 (7) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4b···O2 | 0.92 (2) | 2.09 (3) | 2.980 (2) | 162 (2) |
N1—H1a···O3ii | 0.85 (3) | 2.15 (3) | 2.993 (2) | 174 (2) |
N1—H1b···O3iii | 0.90 (2) | 2.13 (2) | 3.025 (2) | 173 (2) |
N4—H4a···O2iv | 0.88 (2) | 2.20 (2) | 2.997 (2) | 152 (2) |
Symmetry codes: (ii) x, y, z+1; (iii) x, −y+1/2, z+1/2; (iv) x, −y−1/2, z+1/2. |
Crystal data top
[Cu(C3H10N2)2(H2O)2](S2O6) | F(000) = 426 |
Mr = 407.96 | Dx = 1.705 Mg m−3 |
Orthorhombic, Pnnm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2 2n | Cell parameters from 3669 reflections |
a = 15.500 (2) Å | θ = 2.4–28.2° |
b = 7.098 (1) Å | µ = 1.68 mm−1 |
c = 7.224 (1) Å | T = 150 K |
V = 794.78 (19) Å3 | Plate, blue |
Z = 2 | 0.4 × 0.4 × 0.09 mm |
Data collection top
Bruker SMART CCD diffractometer | 1104 independent reflections |
Radiation source: sealed tube | 1002 reflections with I > 2σ(I ) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 29.0°, θmin = 2.6° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | h = −20→20 |
Tmin = 0.605, Tmax = 0.894 | k = −9→9 |
7799 measured reflections | l = −9→9 |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.035 | All H-atom parameters refined |
wR(F2) = 0.041 | w = 1/(σ2(F) + 0.0003F2) |
S = 1.18 | (Δ/σ)max = 0.017 |
1002 reflections | Δρmax = 1.14 e Å−3 |
82 parameters | Δρmin = −0.88 e Å−3 |
Crystal data top
[Cu(C3H10N2)2(H2O)2](S2O6) | V = 794.78 (19) Å3 |
Mr = 407.96 | Z = 2 |
Orthorhombic, Pnnm | Mo Kα radiation |
a = 15.500 (2) Å | µ = 1.68 mm−1 |
b = 7.098 (1) Å | T = 150 K |
c = 7.224 (1) Å | 0.4 × 0.4 × 0.09 mm |
Data collection top
Bruker SMART CCD diffractometer | 1104 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | 1002 reflections with I > 2σ(I ) |
Tmin = 0.605, Tmax = 0.894 | Rint = 0.040 |
7799 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.041 | All H-atom parameters refined |
S = 1.18 | Δρmax = 1.14 e Å−3 |
1002 reflections | Δρmin = −0.88 e Å−3 |
82 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.00000 | 1.00000 | 0.50000 | 0.0169 (3) | |
O | 0.0688 (2) | 1.3091 (4) | 0.50000 | 0.0363 (14) | |
N1 | 0.08427 (12) | 0.9287 (3) | 0.2939 (3) | 0.0200 (9) | |
C2 | 0.17888 (14) | 0.9215 (3) | 0.3248 (3) | 0.0242 (11) | |
C3 | 0.2007 (2) | 0.8131 (5) | 0.50000 | 0.0237 (16) | |
S1 | −0.06388 (5) | 0.55611 (10) | 0.00000 | 0.0160 (3) | |
O1 | −0.10257 (10) | 0.4842 (2) | 0.1690 (2) | 0.0206 (7) | |
O2 | −0.05117 (14) | 0.7598 (3) | 0.00000 | 0.0200 (10) | |
H1a | 0.0691 (17) | 0.821 (4) | 0.255 (4) | 0.027 (7)* | |
H1b | 0.0740 (17) | 1.010 (4) | 0.209 (4) | 0.028 (7)* | |
H2a | 0.1997 (15) | 1.055 (4) | 0.333 (4) | 0.015 (6)* | |
H2b | 0.2068 (16) | 0.864 (4) | 0.219 (4) | 0.023 (7)* | |
H3a | 0.261 (3) | 0.789 (5) | 0.50000 | 0.022 (9)* | |
H3b | 0.173 (2) | 0.690 (5) | 0.50000 | 0.019 (9)* | |
H | 0.083 (2) | 1.376 (5) | 0.419 (5) | 0.059 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0237 (3) | 0.0151 (3) | 0.0118 (2) | 0.00060 (18) | 0.00000 | 0.00000 |
O | 0.073 (2) | 0.0180 (12) | 0.0180 (12) | −0.0134 (12) | 0.00000 | 0.00000 |
N1 | 0.0282 (10) | 0.0164 (8) | 0.0155 (9) | −0.0006 (7) | −0.0000 (7) | −0.0005 (7) |
C2 | 0.0252 (11) | 0.0260 (11) | 0.0214 (10) | −0.0031 (9) | 0.0046 (9) | 0.0012 (9) |
C3 | 0.0230 (15) | 0.0249 (16) | 0.0231 (15) | −0.0001 (12) | 0.00000 | 0.00000 |
S1 | 0.0223 (4) | 0.0137 (3) | 0.0119 (3) | −0.0001 (3) | 0.00000 | 0.00000 |
O1 | 0.0270 (8) | 0.0199 (7) | 0.0150 (7) | −0.0012 (6) | 0.0040 (6) | 0.0030 (6) |
O2 | 0.0295 (11) | 0.0118 (10) | 0.0186 (10) | 0.0003 (8) | 0.00000 | 0.00000 |
Geometric parameters (Å, º) top
Cu—O | 2.439 (3) | N1—H1b | 0.86 (3) |
Cu—N1 | 2.0443 (18) | C2—C3 | 1.520 (3) |
Cu—O | 2.439 (3) | C2—H2a | 1.00 (2) |
Cu—N1 | 2.0443 (18) | C2—H2b | 0.97 (3) |
Cu—N1 | 2.0443 (18) | C3—H3a | 0.95 (4) |
Cu—N1 | 2.0443 (18) | C3—H3b | 0.97 (4) |
O—H | 0.79 (3) | S1—O1 | 1.4530 (16) |
O—H | 0.79 (3) | S1—O2 | 1.459 (2) |
N1—C2 | 1.484 (3) | S1—S1 | 2.1346 (11) |
N1—H1a | 0.85 (3) | S1—O1i | 1.4530 (16) |
| | | |
O—Cu—N1 | 86.75 (8) | C2—N1—H1a | 107.1 (18) |
O—Cu—O | 180.0000 | C2—N1—H1b | 108.3 (18) |
O—Cu—N1 | 93.25 (8) | H1a—N1—H1b | 108 (3) |
O—Cu—N1 | 93.25 (8) | N1—C2—C3 | 111.3 (2) |
O—Cu—N1 | 86.75 (7) | N1—C2—H2a | 107.1 (13) |
N1—Cu—O | 93.25 (8) | N1—C2—H2b | 109.8 (15) |
N1—Cu—N1 | 86.50 (7) | C3—C2—H2a | 110.9 (15) |
N1—Cu—N1 | 180.0000 | C3—C2—H2b | 110.0 (16) |
N1—Cu—N1 | 93.50 (7) | H2a—C2—H2b | 108 (2) |
O—Cu—N1 | 86.75 (7) | C2—C3—H3a | 108.0 (11) |
O—Cu—N1 | 86.75 (7) | C2—C3—H3b | 110.9 (10) |
O—Cu—N1 | 93.25 (7) | C2—C3—C2 | 112.8 (2) |
N1—Cu—N1 | 93.50 (7) | H3a—C3—H3b | 106 (3) |
N1—Cu—N1 | 180.0000 | H3a—C3—C2 | 108.0 (11) |
N1—Cu—N1 | 86.50 (7) | H3b—C3—C2 | 110.9 (10) |
Cu—O—H | 132 (2) | O1—S1—O2 | 113.82 (7) |
Cu—O—H | 132 (2) | O1—S1—S1 | 104.58 (7) |
H—O—H | 96 (4) | O1—S1—O1i | 114.36 (10) |
Cu—N1—C2 | 122.03 (14) | O2—S1—S1 | 104.15 (10) |
Cu—N1—H1a | 106.8 (18) | O2—S1—O1i | 113.82 (7) |
Cu—N1—H1b | 103.9 (19) | S1—S1—O1i | 104.58 (7) |
Symmetry code: (i) x, y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H···O1ii | 0.79 (4) | 2.08 (4) | 2.854 (2) | 167 (3) |
N1—H1b···O2ii | 0.86 (3) | 2.25 (3) | 3.108 (2) | 176 (3) |
N1—H1a···O1iii | 0.85 (3) | 2.31 (3) | 3.080 (3) | 151 (2) |
N1—H1b···O2iv | 0.86 (3) | 2.25 (3) | 3.108 (3) | 176 (3) |
Symmetry codes: (ii) −x, −y+2, z; (iii) −x, −y+1, z; (iv) −x, −y+2, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu(S2O6)(C2H8N2)2] | [Cu(C3H10N2)2(H2O)2](S2O6) |
Mr | 343.87 | 407.96 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pnnm |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 8.4727 (10), 10.2699 (10), 8.0696 (10) | 15.500 (2), 7.098 (1), 7.224 (1) |
α, β, γ (°) | 90, 116.170 (2), 90 | 90, 90, 90 |
V (Å3) | 630.19 (12) | 794.78 (19) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.09 | 1.68 |
Crystal size (mm) | 0.1 × 0.05 × 0.04 | 0.4 × 0.4 × 0.09 |
|
Data collection |
Diffractometer | Bruker SMART CCD diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan SADABS; Sheldrick, 1996 | Multi-scan SADABS; Sheldrick, 1996 |
Tmin, Tmax | 0.809, 0.928 | 0.605, 0.894 |
No. of measured, independent and observed [I > 2σ(I )] reflections | 6260, 1608, 1441 | 7799, 1104, 1002 |
Rint | 0.023 | 0.040 |
(sin θ/λ)max (Å−1) | 0.686 | 0.682 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.031, 1.07 | 0.035, 0.041, 1.18 |
No. of reflections | 1441 | 1002 |
No. of parameters | 111 | 82 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.57, −0.41 | 1.14, −0.88 |
Selected geometric parameters (Å, º) for (I) topCu—N1 | 2.0100 (13) | Cu—O1 | 2.5744 (15) |
Cu—N4 | 2.0122 (16) | | |
| | | |
N1—Cu—N4 | 85.02 (6) | Cu—N1—C2 | 108.81 (11) |
N1—Cu—O1 | 87.64 (6) | Cu—N4—C3 | 108.05 (12) |
N4—Cu—O1 | 93.78 (6) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4b···O2 | 0.92 (2) | 2.09 (3) | 2.980 (2) | 162 (2) |
N1—H1a···O3i | 0.85 (3) | 2.15 (3) | 2.993 (2) | 174 (2) |
N1—H1b···O3ii | 0.90 (2) | 2.13 (2) | 3.025 (2) | 173 (2) |
N4—H4a···O2iii | 0.88 (2) | 2.20 (2) | 2.997 (2) | 152 (2) |
Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z+1/2. |
Selected geometric parameters (Å, º) for (II) topCu—O | 2.439 (3) | Cu—N1 | 2.0443 (18) |
| | | |
O—Cu—N1 | 86.75 (8) | Cu—N1—C2 | 122.03 (14) |
N1—Cu—N1 | 93.50 (7) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H···O1i | 0.79 (4) | 2.08 (4) | 2.854 (2) | 167 (3) |
N1—H1b···O2i | 0.86 (3) | 2.25 (3) | 3.108 (2) | 176 (3) |
N1—H1a···O1ii | 0.85 (3) | 2.31 (3) | 3.080 (3) | 151 (2) |
N1—H1b···O2iii | 0.86 (3) | 2.25 (3) | 3.108 (3) | 176 (3) |
Symmetry codes: (i) −x, −y+2, z; (ii) −x, −y+1, z; (iii) −x, −y+2, −z. |
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Copper(II) in the presence of the dithionate counterion crystallizes from an aqueous solution of ethane-1,2-diamine to yield an anhydrous complex, catena-trans-(O-dithionato-O')bis(ethane-1,2-diamine)copper(II), (I), the propane-1,3-diamine counterpart is a dihydrate, trans-diaquabis(propane-1,3-diamine)copper(II) dithionate, (II). In both cases, the Cu atom lies on a crystallographic inversion centre [actual symmetry in (II), is 2/m] in a typical (Melnik et al., 1998) trans six-coordinate Cu(II)(N2)2O2 environment.
In (I), the trans O-donors form successive ends of the doubly charged dithionate anion as −O·O2SSO2·O−, linking successive translation-related Cu atoms into a single-stranded polymer parallel to c, with inversion centres, also now lying at the centres of the S—S bonds (Fig. 1). The Cu—N distances are 2.010 (1) and 2.012 (2) Å, the Cu—O distance is 2.574 (1) Å, and the Cu—O—S angle is 125.84 (7)°, the coordinated O—S distance being comparable to the uncoordinated distance (Table 1). Both ligand conformations are necessarily the same and of the δλ form, with quasi-twofold? symmetry about the line through the C—C bonds, the angles in the chelating rings (outwardly from the Cu atom) being 12.7 (4), 15.7 (2), −38.1 (2), −40.5 (2) and 52.2 (3)°.
Compound (II), by contrast, is a dihydrate in which a pair of aqua ligands now coordinate in the trans monodentate sites, supplanting the anionic moieties so that the complex is now ionic rather than polymeric [trans-diaquabis(propane-1,3-diamine)copper(II) dithionate], with both the anion and the cation centrosymmetric. In (II), Cu—N increases to 2.044 (2), compensating the shorter Cu—O distance [2.439 (3) Å] associated with the stronger oxygen donor; this distance is appreciably shorter than those recorded for other examples of this cation that are also centrosymmetric [2.637 (6) (Emsley et al., 1988), 2.587 (8) and 2.555 (7) (Sundberg & Klinga, 1994), and 2.618 (2) Å (Sundberg & Uggla, 1997)]. The water molecule H atoms are hydrogen bonded to the anion O atoms, as shown in Fig. 2 [H···O = 2.08 (3) Å]. The O-atom environment is (obligate) planar, but in the present circumstances, the elongated displacement envelope of the O atom may be a foil for the unresolved disorder or off-axis displacement. The chelate rings are of the low-energy C3-chair form (Niketic et al., 1976); the torsion angles (outward from the Cu atom) are −22.5 (2), 47.7 (3) and −72.8 (3)°.