The title compound, [Cu(C4H8N2)4]SO4·0.5CH3CN·1.5H2O, consists of a double chain wherein the Cu centres are octahedrally coordinated by four 1-methylimidazole ligands in the equatorial plane and by two axial sulfate ions which act as bridges between the Cu centres. The Cu—N bond lengths lie between 1.9929 (14) and 2.0226 (14) Å, but the Cu—O bond distances are longer, with values between 2.3496 (13) and 2.8276 (14) Å. The water molecules participate in the formation of a network of hydrogen bonds of significance in maintaining the connectivity of the structure.
Supporting information
CCDC reference: 181976
The title compound was prepared by reaction of an excess of 1-methylimidazole
with (1-propylimidazolidine-2-thionate)copper(I), freshly prepared by an
electrolytic method (Cabaleiro et al., 2000), in refluxing acetonitrile
for 3 h. After this time, a dark-blue precipitate was isolated and
recrystallized from acetonitrile to give crystals of (I) suitable for
structure analysis. Table 2. Classical and non-classical hydrogen bonds and
short contacts (Å, °).
Aryl H atoms were placed in calculated positions and refined using a riding
model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). Methyl
H atoms were located from ΔF syntheses and refined as part of a rigid
rotating group with C—H = 0.96 Å and Uiso(H) =
1.5Ueq(C). Water H atoms were located in ΔF syntheses and refined
freely.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); 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 (Farrugia, 1998); software used to prepare material for publication: SHELXL97.
catena-Poly[[[tetrakis(1-methylimidazole-
κN3)copper(II)]-µ
2-sulfato-O:
O'] acetonitrile hemisolvate sesquihydrate]
top
Crystal data top
[Cu(C4H8N2)4]SO4·0.5C2H3N·1.5H2O | F(000) = 2232 |
Mr = 535.58 | Dx = 1.528 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.6227 (1) Å | Cell parameters from 8192 reflections |
b = 14.2708 (1) Å | θ = 1.1–28.3° |
c = 17.5255 (1) Å | µ = 1.08 mm−1 |
β = 91.650 (1)° | T = 293 K |
V = 4655.66 (5) Å3 | Block, blue |
Z = 8 | 0.20 × 0.16 × 0.12 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 11509 independent reflections |
Radiation source: fine-focus sealed tube | 9721 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.1° |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | h = −24→15 |
Tmin = 0.809, Tmax = 0.881 | k = −18→18 |
31303 measured reflections | l = −23→23 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0318P)2 + 2.923P] where P = (Fo2 + 2Fc2)/3 |
11509 reflections | (Δ/σ)max = 0.001 |
668 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
[Cu(C4H8N2)4]SO4·0.5C2H3N·1.5H2O | V = 4655.66 (5) Å3 |
Mr = 535.58 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.6227 (1) Å | µ = 1.08 mm−1 |
b = 14.2708 (1) Å | T = 293 K |
c = 17.5255 (1) Å | 0.20 × 0.16 × 0.12 mm |
β = 91.650 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 11509 independent reflections |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | 9721 reflections with I > 2σ(I) |
Tmin = 0.809, Tmax = 0.881 | Rint = 0.023 |
31303 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
11509 reflections | Δρmin = −0.70 e Å−3 |
668 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.499829 (11) | −0.364789 (16) | 0.261012 (11) | 0.01963 (6) | |
S1 | 0.43812 (2) | −0.09098 (3) | 0.30505 (2) | 0.01715 (8) | |
O11 | 0.48938 (7) | −0.02287 (9) | 0.27435 (7) | 0.0245 (3) | |
O12 | 0.41140 (8) | −0.05606 (10) | 0.37872 (7) | 0.0293 (3) | |
O13 | 0.47360 (7) | −0.18225 (9) | 0.31642 (9) | 0.0310 (3) | |
O14 | 0.37588 (7) | −0.10075 (9) | 0.25124 (7) | 0.0248 (3) | |
N11 | 0.53634 (7) | −0.39228 (10) | 0.36746 (8) | 0.0189 (3) | |
N12 | 0.55952 (8) | −0.37558 (10) | 0.49020 (8) | 0.0195 (3) | |
N13 | 0.39944 (7) | −0.39084 (10) | 0.29611 (8) | 0.0178 (3) | |
N14 | 0.29024 (8) | −0.37450 (11) | 0.33868 (8) | 0.0201 (3) | |
N15 | 0.46004 (7) | −0.33103 (10) | 0.15786 (8) | 0.0179 (3) | |
N16 | 0.39526 (8) | −0.26715 (10) | 0.06540 (8) | 0.0205 (3) | |
N17 | 0.59807 (8) | −0.31941 (11) | 0.23184 (8) | 0.0203 (3) | |
N18 | 0.70692 (8) | −0.31038 (12) | 0.18733 (9) | 0.0250 (3) | |
C11 | 0.53201 (9) | −0.33536 (13) | 0.42659 (10) | 0.0207 (3) | |
H11 | 0.5125 | −0.2754 | 0.4244 | 0.024 (5)* | |
C12 | 0.58244 (10) | −0.46325 (13) | 0.47032 (10) | 0.0233 (4) | |
H12 | 0.6036 | −0.5076 | 0.5027 | 0.044 (7)* | |
C13 | 0.56829 (9) | −0.47298 (13) | 0.39436 (10) | 0.0218 (3) | |
H13 | 0.5785 | −0.5256 | 0.3653 | 0.028 (6)* | |
C14 | 0.56646 (11) | −0.33389 (14) | 0.56580 (10) | 0.0274 (4) | |
H14A | 0.5494 | −0.2704 | 0.5639 | 0.043 (7)* | |
H14B | 0.5386 | −0.3692 | 0.6009 | 0.039 (7)* | |
H14C | 0.6160 | −0.3344 | 0.5825 | 0.040 (7)* | |
C15 | 0.34909 (9) | −0.33014 (12) | 0.31491 (10) | 0.0197 (3) | |
H15 | 0.3539 | −0.2654 | 0.3120 | 0.026 (5)* | |
C16 | 0.30355 (10) | −0.46856 (13) | 0.33476 (11) | 0.0261 (4) | |
H16 | 0.2725 | −0.5167 | 0.3478 | 0.046 (7)* | |
C17 | 0.37101 (10) | −0.47787 (13) | 0.30812 (11) | 0.0249 (4) | |
H17 | 0.3942 | −0.5344 | 0.2994 | 0.036 (6)* | |
C18 | 0.22391 (10) | −0.33023 (16) | 0.36372 (12) | 0.0320 (4) | |
H18A | 0.2276 | −0.2635 | 0.3580 | 0.061 (9)* | |
H18B | 0.1840 | −0.3529 | 0.3332 | 0.059 (8)* | |
H18C | 0.2167 | −0.3452 | 0.4163 | 0.069 (9)* | |
C19 | 0.41537 (9) | −0.26232 (12) | 0.13968 (9) | 0.0189 (3) | |
H19 | 0.3999 | −0.2169 | 0.1735 | 0.027 (6)* | |
C110 | 0.42908 (10) | −0.34320 (13) | 0.03436 (10) | 0.0231 (4) | |
H110 | 0.4253 | −0.3638 | −0.0159 | 0.033 (6)* | |
C111 | 0.46922 (10) | −0.38217 (13) | 0.09217 (10) | 0.0214 (3) | |
H111 | 0.4982 | −0.4349 | 0.0880 | 0.025 (5)* | |
C112 | 0.34355 (11) | −0.20616 (15) | 0.02593 (12) | 0.0330 (4) | |
H11A | 0.3241 | −0.1626 | 0.0617 | 0.046 (7)* | |
H11B | 0.3671 | −0.1723 | −0.0136 | 0.048 (7)* | |
H11C | 0.3054 | −0.2433 | 0.0037 | 0.057 (8)* | |
C113 | 0.64755 (10) | −0.36325 (13) | 0.19260 (10) | 0.0239 (4) | |
H113 | 0.6420 | −0.4227 | 0.1715 | 0.024 (5)* | |
C114 | 0.69444 (11) | −0.22825 (14) | 0.22447 (11) | 0.0297 (4) | |
H114 | 0.7259 | −0.1779 | 0.2299 | 0.036 (6)* | |
C115 | 0.62721 (10) | −0.23415 (13) | 0.25195 (11) | 0.0263 (4) | |
H115 | 0.6045 | −0.1879 | 0.2799 | 0.036 (6)* | |
C116 | 0.77291 (11) | −0.33598 (19) | 0.14854 (14) | 0.0409 (5) | |
H11D | 0.7776 | −0.2977 | 0.1039 | 0.051 (8)* | |
H11E | 0.8136 | −0.3262 | 0.1825 | 0.044 (7)* | |
H11F | 0.7707 | −0.4007 | 0.1338 | 0.063 (9)* | |
Cu2 | 0.013919 (11) | −0.416559 (16) | 0.264011 (11) | 0.02063 (6) | |
S2 | 0.07097 (2) | −0.15721 (3) | 0.29701 (2) | 0.01561 (8) | |
O21 | 0.06826 (7) | −0.25479 (9) | 0.27022 (7) | 0.0236 (3) | |
O23 | 0.02589 (7) | −0.09634 (9) | 0.24730 (7) | 0.0236 (3) | |
O22 | 0.14642 (6) | −0.12274 (9) | 0.29653 (8) | 0.0249 (3) | |
O24 | 0.04528 (7) | −0.15361 (9) | 0.37623 (7) | 0.0229 (3) | |
N21 | −0.02357 (8) | −0.37777 (10) | 0.16061 (8) | 0.0188 (3) | |
N22 | −0.06946 (8) | −0.38306 (10) | 0.04398 (8) | 0.0216 (3) | |
N23 | 0.10588 (8) | −0.45830 (10) | 0.21926 (8) | 0.0192 (3) | |
N24 | 0.20856 (7) | −0.44650 (10) | 0.16179 (8) | 0.0194 (3) | |
N25 | 0.05209 (7) | −0.44348 (10) | 0.37098 (8) | 0.0189 (3) | |
N26 | 0.08916 (8) | −0.41929 (11) | 0.48961 (8) | 0.0214 (3) | |
N27 | −0.08021 (8) | −0.38241 (10) | 0.30791 (8) | 0.0190 (3) | |
N28 | −0.19043 (8) | −0.39301 (11) | 0.34700 (9) | 0.0215 (3) | |
C21 | −0.04812 (10) | −0.43304 (12) | 0.10547 (10) | 0.0211 (3) | |
H21 | −0.0504 | −0.4980 | 0.1087 | 0.020 (5)* | |
C22 | −0.05756 (11) | −0.29040 (13) | 0.06113 (11) | 0.0269 (4) | |
H22 | −0.0670 | −0.2393 | 0.0294 | 0.037 (6)* | |
C23 | −0.02939 (10) | −0.28785 (13) | 0.13308 (10) | 0.0244 (4) | |
H23 | −0.0161 | −0.2339 | 0.1597 | 0.031 (6)* | |
C24 | −0.10045 (12) | −0.41974 (15) | −0.02705 (11) | 0.0315 (4) | |
H24A | −0.1031 | −0.4868 | −0.0242 | 0.036 (6)* | |
H24B | −0.1479 | −0.3946 | −0.0352 | 0.047 (7)* | |
H24C | −0.0709 | −0.4020 | −0.0687 | 0.041 (7)* | |
C25 | 0.15110 (9) | −0.40038 (13) | 0.18670 (10) | 0.0205 (3) | |
H25 | 0.1440 | −0.3361 | 0.1817 | 0.021 (5)* | |
C26 | 0.19960 (9) | −0.53949 (13) | 0.17914 (10) | 0.0223 (4) | |
H26 | 0.2309 | −0.5883 | 0.1687 | 0.041 (7)* | |
C27 | 0.13586 (9) | −0.54608 (12) | 0.21454 (10) | 0.0210 (3) | |
H27 | 0.1157 | −0.6011 | 0.2327 | 0.044 (7)* | |
C28 | 0.26920 (10) | −0.40369 (15) | 0.12410 (12) | 0.0293 (4) | |
H28A | 0.2641 | −0.3368 | 0.1246 | 0.034 (6)* | |
H28B | 0.3131 | −0.4209 | 0.1506 | 0.027 (6)* | |
H28C | 0.2704 | −0.4253 | 0.0723 | 0.037 (6)* | |
C29 | 0.06346 (9) | −0.37973 (12) | 0.42501 (9) | 0.0194 (3) | |
H29 | 0.0548 | −0.3160 | 0.4189 | 0.021 (5)* | |
C210 | 0.09426 (11) | −0.51411 (13) | 0.47659 (11) | 0.0281 (4) | |
H210 | 0.1101 | −0.5596 | 0.5111 | 0.044 (7)* | |
C211 | 0.07140 (10) | −0.52773 (13) | 0.40300 (10) | 0.0252 (4) | |
H211 | 0.0692 | −0.5853 | 0.3782 | 0.032 (6)* | |
C212 | 0.10936 (11) | −0.37097 (14) | 0.56068 (11) | 0.0295 (4) | |
H21A | 0.1043 | −0.3046 | 0.5536 | 0.043 (7)* | |
H21B | 0.0786 | −0.3912 | 0.6005 | 0.041 (7)* | |
H21C | 0.1584 | −0.3854 | 0.5746 | 0.053 (8)* | |
C213 | −0.13776 (9) | −0.43609 (12) | 0.30975 (10) | 0.0203 (3) | |
H213 | −0.1414 | −0.4955 | 0.2882 | 0.019 (5)* | |
C214 | −0.16489 (10) | −0.30720 (13) | 0.37052 (11) | 0.0246 (4) | |
H214 | −0.1895 | −0.2622 | 0.3979 | 0.036 (6)* | |
C215 | −0.09651 (10) | −0.30119 (13) | 0.34576 (10) | 0.0229 (4) | |
H215 | −0.0658 | −0.2504 | 0.3532 | 0.031 (6)* | |
C216 | −0.26156 (10) | −0.43117 (15) | 0.36292 (13) | 0.0330 (5) | |
H21D | −0.2632 | −0.4483 | 0.4158 | 0.058 (8)* | |
H21E | −0.2976 | −0.3847 | 0.3516 | 0.061 (9)* | |
H21F | −0.2704 | −0.4855 | 0.3318 | 0.065 (9)* | |
O1 | 0.24702 (9) | −0.17514 (13) | 0.19041 (10) | 0.0390 (4) | |
H1A | 0.2141 (16) | −0.162 (2) | 0.2180 (17) | 0.053 (8)* | |
H1B | 0.2791 (16) | −0.156 (2) | 0.2094 (16) | 0.045 (8)* | |
O2 | 0.26049 (12) | −0.07596 (18) | 0.40307 (12) | 0.0617 (6) | |
H2A | 0.300 (2) | −0.074 (2) | 0.3877 (19) | 0.073 (11)* | |
H2B | 0.2352 (19) | −0.083 (2) | 0.365 (2) | 0.069 (11)* | |
O3 | 0.14936 (13) | −0.15637 (14) | 0.49416 (10) | 0.0463 (4) | |
H3A | 0.1183 (17) | −0.154 (2) | 0.4596 (18) | 0.059 (9)* | |
H3B | 0.1812 (16) | −0.137 (2) | 0.4760 (16) | 0.044 (9)* | |
N1 | −0.29741 (12) | −0.21602 (19) | 0.47097 (14) | 0.0586 (6) | |
C1 | −0.33913 (12) | −0.15952 (17) | 0.46150 (14) | 0.0393 (5) | |
C2 | −0.39318 (14) | −0.08688 (17) | 0.44966 (17) | 0.0502 (6) | |
H2C | −0.4400 | −0.1150 | 0.4464 | 0.075* | |
H2D | −0.3842 | −0.0540 | 0.4031 | 0.075* | |
H2E | −0.3910 | −0.0437 | 0.4917 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01330 (10) | 0.03227 (12) | 0.01324 (10) | −0.00135 (8) | −0.00083 (7) | 0.00205 (8) |
S1 | 0.01751 (19) | 0.01566 (19) | 0.01822 (18) | −0.00269 (15) | −0.00046 (15) | 0.00357 (15) |
O11 | 0.0242 (6) | 0.0235 (6) | 0.0259 (6) | −0.0081 (5) | 0.0020 (5) | 0.0054 (5) |
O12 | 0.0382 (8) | 0.0324 (7) | 0.0175 (6) | −0.0051 (6) | 0.0046 (5) | 0.0019 (5) |
O13 | 0.0265 (7) | 0.0208 (7) | 0.0455 (8) | 0.0018 (5) | −0.0029 (6) | 0.0099 (6) |
O14 | 0.0191 (6) | 0.0264 (7) | 0.0285 (7) | −0.0020 (5) | −0.0049 (5) | −0.0026 (5) |
N11 | 0.0159 (7) | 0.0239 (7) | 0.0167 (7) | −0.0002 (6) | −0.0008 (5) | 0.0002 (6) |
N12 | 0.0219 (7) | 0.0211 (7) | 0.0156 (6) | 0.0019 (6) | −0.0003 (5) | −0.0016 (5) |
N13 | 0.0154 (7) | 0.0217 (7) | 0.0163 (6) | −0.0005 (5) | −0.0009 (5) | 0.0011 (5) |
N14 | 0.0149 (7) | 0.0254 (8) | 0.0200 (7) | −0.0006 (6) | 0.0003 (5) | −0.0006 (6) |
N15 | 0.0171 (7) | 0.0219 (7) | 0.0147 (6) | −0.0018 (5) | 0.0008 (5) | −0.0002 (5) |
N16 | 0.0215 (7) | 0.0224 (7) | 0.0173 (7) | −0.0010 (6) | −0.0026 (5) | 0.0019 (6) |
N17 | 0.0166 (7) | 0.0263 (8) | 0.0179 (7) | −0.0010 (6) | −0.0014 (5) | 0.0005 (6) |
N18 | 0.0167 (7) | 0.0340 (9) | 0.0244 (7) | −0.0022 (6) | 0.0015 (6) | 0.0027 (7) |
C11 | 0.0220 (8) | 0.0213 (9) | 0.0188 (8) | 0.0028 (7) | −0.0019 (6) | 0.0006 (6) |
C12 | 0.0266 (9) | 0.0219 (9) | 0.0213 (8) | 0.0065 (7) | −0.0006 (7) | 0.0013 (7) |
C13 | 0.0222 (8) | 0.0226 (9) | 0.0208 (8) | 0.0026 (7) | 0.0008 (7) | −0.0029 (7) |
C14 | 0.0355 (11) | 0.0294 (10) | 0.0171 (8) | 0.0048 (8) | −0.0031 (7) | −0.0042 (7) |
C15 | 0.0181 (8) | 0.0200 (8) | 0.0209 (8) | −0.0014 (6) | 0.0009 (6) | 0.0011 (6) |
C16 | 0.0247 (9) | 0.0227 (9) | 0.0309 (10) | −0.0069 (7) | 0.0033 (7) | 0.0022 (8) |
C17 | 0.0261 (9) | 0.0201 (9) | 0.0287 (9) | 0.0012 (7) | 0.0026 (7) | 0.0023 (7) |
C18 | 0.0179 (9) | 0.0448 (13) | 0.0335 (10) | 0.0054 (8) | 0.0035 (8) | −0.0046 (9) |
C19 | 0.0186 (8) | 0.0210 (8) | 0.0171 (8) | −0.0018 (6) | 0.0004 (6) | −0.0014 (6) |
C110 | 0.0298 (9) | 0.0249 (9) | 0.0146 (7) | −0.0022 (7) | −0.0001 (7) | −0.0019 (7) |
C111 | 0.0255 (9) | 0.0206 (8) | 0.0183 (8) | 0.0002 (7) | 0.0022 (7) | −0.0019 (6) |
C112 | 0.0340 (11) | 0.0336 (11) | 0.0307 (10) | 0.0041 (9) | −0.0089 (8) | 0.0097 (9) |
C113 | 0.0199 (8) | 0.0261 (9) | 0.0260 (9) | −0.0033 (7) | 0.0031 (7) | −0.0020 (7) |
C114 | 0.0296 (10) | 0.0308 (10) | 0.0285 (10) | −0.0106 (8) | −0.0023 (8) | 0.0014 (8) |
C115 | 0.0300 (10) | 0.0248 (9) | 0.0239 (9) | −0.0011 (8) | −0.0005 (7) | −0.0024 (7) |
C116 | 0.0198 (10) | 0.0600 (16) | 0.0434 (12) | 0.0024 (10) | 0.0097 (9) | 0.0061 (11) |
Cu2 | 0.01570 (10) | 0.03257 (13) | 0.01369 (10) | 0.00705 (8) | 0.00166 (7) | 0.00454 (8) |
S2 | 0.01471 (18) | 0.01463 (18) | 0.01745 (18) | 0.00082 (14) | −0.00026 (14) | −0.00087 (14) |
O21 | 0.0262 (7) | 0.0182 (6) | 0.0263 (6) | 0.0016 (5) | −0.0012 (5) | −0.0058 (5) |
O23 | 0.0216 (6) | 0.0237 (6) | 0.0252 (6) | 0.0048 (5) | −0.0034 (5) | 0.0031 (5) |
O22 | 0.0154 (6) | 0.0262 (7) | 0.0330 (7) | −0.0031 (5) | −0.0009 (5) | 0.0021 (5) |
O24 | 0.0286 (7) | 0.0218 (6) | 0.0185 (6) | −0.0015 (5) | 0.0042 (5) | −0.0024 (5) |
N21 | 0.0186 (7) | 0.0203 (7) | 0.0175 (7) | 0.0014 (6) | 0.0008 (5) | 0.0032 (5) |
N22 | 0.0272 (8) | 0.0206 (7) | 0.0169 (7) | −0.0025 (6) | −0.0033 (6) | 0.0018 (6) |
N23 | 0.0180 (7) | 0.0232 (7) | 0.0164 (6) | 0.0023 (6) | 0.0011 (5) | 0.0005 (6) |
N24 | 0.0155 (7) | 0.0239 (7) | 0.0189 (7) | 0.0015 (6) | 0.0009 (5) | −0.0013 (6) |
N25 | 0.0171 (7) | 0.0224 (7) | 0.0171 (7) | 0.0014 (6) | 0.0004 (5) | 0.0039 (6) |
N26 | 0.0224 (7) | 0.0236 (8) | 0.0179 (7) | −0.0017 (6) | −0.0026 (6) | 0.0018 (6) |
N27 | 0.0170 (7) | 0.0219 (7) | 0.0179 (7) | 0.0031 (6) | 0.0008 (5) | 0.0012 (6) |
N28 | 0.0159 (7) | 0.0223 (7) | 0.0265 (8) | −0.0005 (6) | 0.0020 (6) | −0.0002 (6) |
C21 | 0.0261 (9) | 0.0185 (8) | 0.0185 (8) | 0.0004 (7) | −0.0004 (7) | 0.0031 (6) |
C22 | 0.0356 (10) | 0.0194 (9) | 0.0251 (9) | −0.0032 (8) | −0.0078 (8) | 0.0062 (7) |
C23 | 0.0302 (10) | 0.0194 (9) | 0.0234 (9) | −0.0016 (7) | −0.0050 (7) | 0.0016 (7) |
C24 | 0.0410 (12) | 0.0322 (11) | 0.0210 (9) | −0.0053 (9) | −0.0059 (8) | −0.0039 (8) |
C25 | 0.0187 (8) | 0.0220 (9) | 0.0209 (8) | 0.0021 (7) | 0.0023 (6) | 0.0001 (7) |
C26 | 0.0213 (8) | 0.0224 (9) | 0.0232 (8) | 0.0052 (7) | 0.0001 (7) | −0.0026 (7) |
C27 | 0.0227 (8) | 0.0191 (8) | 0.0214 (8) | 0.0007 (7) | 0.0001 (7) | −0.0003 (7) |
C28 | 0.0186 (9) | 0.0376 (11) | 0.0321 (10) | −0.0018 (8) | 0.0066 (7) | 0.0032 (8) |
C29 | 0.0186 (8) | 0.0208 (8) | 0.0188 (8) | 0.0014 (6) | 0.0009 (6) | 0.0039 (6) |
C210 | 0.0381 (11) | 0.0217 (9) | 0.0241 (9) | −0.0006 (8) | −0.0058 (8) | 0.0058 (7) |
C211 | 0.0323 (10) | 0.0202 (9) | 0.0229 (9) | −0.0002 (7) | −0.0036 (7) | 0.0017 (7) |
C212 | 0.0363 (11) | 0.0311 (10) | 0.0207 (9) | −0.0027 (8) | −0.0062 (8) | −0.0018 (8) |
C213 | 0.0197 (8) | 0.0194 (8) | 0.0217 (8) | 0.0027 (6) | 0.0001 (6) | −0.0006 (7) |
C214 | 0.0211 (9) | 0.0222 (9) | 0.0307 (9) | 0.0032 (7) | 0.0033 (7) | −0.0046 (7) |
C215 | 0.0204 (8) | 0.0210 (9) | 0.0273 (9) | −0.0010 (7) | 0.0007 (7) | −0.0020 (7) |
C216 | 0.0186 (9) | 0.0354 (11) | 0.0452 (12) | −0.0053 (8) | 0.0063 (8) | 0.0014 (9) |
O1 | 0.0235 (8) | 0.0548 (10) | 0.0386 (9) | −0.0005 (7) | −0.0011 (7) | −0.0171 (8) |
O2 | 0.0362 (10) | 0.1040 (18) | 0.0451 (11) | −0.0228 (11) | 0.0044 (9) | −0.0135 (11) |
O3 | 0.0564 (12) | 0.0508 (11) | 0.0310 (9) | −0.0105 (9) | −0.0108 (9) | 0.0058 (8) |
N1 | 0.0422 (12) | 0.0749 (17) | 0.0588 (14) | 0.0162 (12) | 0.0061 (11) | −0.0174 (12) |
C1 | 0.0327 (11) | 0.0441 (13) | 0.0418 (12) | −0.0041 (10) | 0.0123 (9) | −0.0087 (10) |
C2 | 0.0436 (14) | 0.0362 (13) | 0.0715 (18) | −0.0005 (11) | 0.0156 (13) | 0.0053 (12) |
Geometric parameters (Å, º) top
Cu1—N11 | 2.0059 (14) | Cu2—O23iii | 2.6764 (13) |
Cu1—N13 | 2.0193 (14) | S2—O21 | 1.4700 (12) |
Cu1—N15 | 1.9930 (14) | S2—O22 | 1.4889 (13) |
Cu1—N17 | 2.0203 (14) | S2—O23 | 1.4753 (13) |
Cu1—O11i | 2.3496 (13) | S2—O24 | 1.4824 (12) |
Cu1—O13 | 2.8276 (14) | N21—C21 | 1.319 (2) |
S1—O11 | 1.4748 (12) | N21—C23 | 1.374 (2) |
S1—O12 | 1.4833 (13) | N22—C21 | 1.343 (2) |
S1—O13 | 1.4714 (14) | N22—C22 | 1.373 (2) |
S1—O14 | 1.4796 (13) | N22—C24 | 1.454 (2) |
O11—Cu1ii | 2.3497 (13) | N23—C25 | 1.321 (2) |
N11—C11 | 1.321 (2) | N23—C27 | 1.375 (2) |
N11—C13 | 1.373 (2) | N24—C25 | 1.340 (2) |
N12—C11 | 1.342 (2) | N24—C26 | 1.373 (2) |
N12—C12 | 1.370 (2) | N24—C28 | 1.459 (2) |
N12—C14 | 1.455 (2) | N25—C29 | 1.326 (2) |
N13—C15 | 1.325 (2) | N25—C211 | 1.370 (2) |
N13—C17 | 1.369 (2) | N26—C29 | 1.341 (2) |
N14—C15 | 1.342 (2) | N26—C210 | 1.376 (2) |
N14—C16 | 1.367 (2) | N26—C212 | 1.463 (2) |
N14—C18 | 1.466 (2) | N27—C213 | 1.318 (2) |
N15—C19 | 1.319 (2) | N27—C215 | 1.374 (2) |
N15—C111 | 1.378 (2) | N28—C213 | 1.343 (2) |
N16—C19 | 1.346 (2) | N28—C214 | 1.373 (2) |
N16—C110 | 1.375 (2) | N28—C216 | 1.466 (2) |
N16—C112 | 1.458 (2) | C21—H21 | 0.9300 |
N17—C113 | 1.323 (2) | C22—C23 | 1.352 (2) |
N17—C115 | 1.374 (2) | C22—H22 | 0.9299 |
N18—C113 | 1.344 (2) | C23—H23 | 0.9300 |
N18—C114 | 1.364 (3) | C24—H24A | 0.9601 |
N18—C116 | 1.468 (2) | C24—H24B | 0.9600 |
C11—H11 | 0.9300 | C24—H24C | 0.9600 |
C12—C13 | 1.357 (2) | C25—H25 | 0.9301 |
C12—H12 | 0.9301 | C26—C27 | 1.358 (2) |
C13—H13 | 0.9301 | C26—H26 | 0.9301 |
C14—H14A | 0.9600 | C27—H27 | 0.9300 |
C14—H14B | 0.9599 | C28—H28A | 0.9600 |
C14—H14C | 0.9599 | C28—H28B | 0.9601 |
C15—H15 | 0.9300 | C28—H28C | 0.9600 |
C16—C17 | 1.359 (3) | C29—H29 | 0.9300 |
C16—H16 | 0.9300 | C210—C211 | 1.360 (3) |
C17—H17 | 0.9298 | C210—H210 | 0.9301 |
C18—H18A | 0.9600 | C211—H211 | 0.9300 |
C18—H18B | 0.9599 | C212—H21A | 0.9599 |
C18—H18C | 0.9600 | C212—H21B | 0.9600 |
C19—H19 | 0.9300 | C212—H21C | 0.9600 |
C110—C111 | 1.361 (2) | C213—H213 | 0.9300 |
C110—H110 | 0.9299 | C214—C215 | 1.360 (2) |
C111—H111 | 0.9300 | C214—H214 | 0.9301 |
C112—H11A | 0.9600 | C215—H215 | 0.9301 |
C112—H11B | 0.9600 | C216—H21D | 0.9600 |
C112—H11C | 0.9599 | C216—H21E | 0.9599 |
C113—H113 | 0.9300 | C216—H21F | 0.9601 |
C114—C115 | 1.357 (3) | O1—H1A | 0.81 (3) |
C114—H114 | 0.9299 | O1—H1B | 0.73 (3) |
C115—H115 | 0.9299 | O2—H2A | 0.79 (4) |
C116—H11D | 0.9599 | O2—H2B | 0.81 (4) |
C116—H11E | 0.9601 | O3—H3A | 0.83 (3) |
C116—H11F | 0.9600 | O3—H3B | 0.73 (3) |
Cu2—N21 | 2.0012 (14) | N1—C1 | 1.129 (3) |
Cu2—N23 | 1.9951 (14) | C1—C2 | 1.456 (3) |
Cu2—N25 | 2.0225 (14) | C2—H2C | 0.9600 |
Cu2—N27 | 1.9950 (14) | C2—H2D | 0.9600 |
Cu2—O21 | 2.5216 (13) | C2—H2E | 0.9600 |
| | | |
N11—Cu1—N13 | 88.44 (6) | N23—Cu2—N25 | 91.43 (6) |
N11—Cu1—N15 | 176.48 (6) | N23—Cu2—N27 | 176.65 (6) |
N11—Cu1—N17 | 90.74 (6) | N23—Cu2—O21 | 86.70 (5) |
N11—Cu1—O11i | 91.62 (5) | N23—Cu2—O23iii | 85.62 (5) |
N11—Cu1—O13 | 85.30 (5) | N25—Cu2—N27 | 88.75 (6) |
N13—Cu1—N15 | 89.86 (6) | N25—Cu2—O21 | 90.23 (5) |
N13—Cu1—O11i | 89.46 (5) | N25—Cu2—O23iii | 88.61 (5) |
N13—Cu1—O13 | 83.94 (5) | N27—Cu2—O21 | 96.64 (5) |
N13—Cu1—N17 | 171.55 (6) | N27—Cu2—O23iii | 91.04 (5) |
N15—Cu1—N17 | 90.49 (6) | O21—Cu2—O23iii | 172.20 (4) |
N15—Cu1—O11i | 91.45 (5) | O21—S2—O23 | 110.81 (8) |
N15—Cu1—O13 | 91.46 (5) | O21—S2—O24 | 108.84 (7) |
N17—Cu1—O11i | 98.98 (5) | O23—S2—O24 | 109.82 (8) |
N17—Cu1—O13 | 87.61 (5) | O21—S2—O22 | 109.57 (8) |
O11i—Cu1—O13 | 172.78 (4) | O23—S2—O22 | 108.86 (8) |
O13—S1—O11 | 109.88 (8) | O24—S2—O22 | 108.91 (8) |
O13—S1—O14 | 110.08 (8) | S2—O21—Cu2 | 153.01 (8) |
O11—S1—O14 | 109.45 (8) | C21—N21—C23 | 106.20 (14) |
O13—S1—O12 | 109.88 (8) | C21—N21—Cu2 | 127.05 (12) |
O11—S1—O12 | 109.45 (8) | C23—N21—Cu2 | 126.74 (12) |
O14—S1—O12 | 108.07 (8) | C21—N22—C22 | 107.09 (15) |
S1—O11—Cu1ii | 142.21 (8) | C21—N22—C24 | 126.63 (16) |
C11—N11—C13 | 106.38 (14) | C22—N22—C24 | 126.28 (15) |
C11—N11—Cu1 | 125.64 (12) | C25—N23—C27 | 106.21 (14) |
C13—N11—Cu1 | 127.96 (12) | C25—N23—Cu2 | 123.22 (12) |
C11—N12—C12 | 107.07 (14) | C27—N23—Cu2 | 130.57 (12) |
C11—N12—C14 | 127.10 (15) | C25—N24—C26 | 107.42 (14) |
C12—N12—C14 | 125.80 (15) | C25—N24—C28 | 125.28 (16) |
C15—N13—C17 | 105.98 (14) | C26—N24—C28 | 127.29 (15) |
C15—N13—Cu1 | 128.56 (12) | C29—N25—C211 | 105.96 (14) |
C17—N13—Cu1 | 125.42 (12) | C29—N25—Cu2 | 125.19 (12) |
C15—N14—C16 | 107.26 (14) | C211—N25—Cu2 | 128.85 (12) |
C15—N14—C18 | 126.32 (16) | C29—N26—C210 | 107.38 (15) |
C16—N14—C18 | 126.42 (16) | C29—N26—C212 | 126.65 (16) |
C19—N15—C111 | 106.52 (14) | C210—N26—C212 | 125.97 (16) |
C19—N15—Cu1 | 127.90 (12) | C213—N27—C215 | 106.70 (14) |
C111—N15—Cu1 | 125.31 (12) | C213—N27—Cu2 | 126.25 (12) |
C19—N16—C110 | 107.77 (14) | C215—N27—Cu2 | 126.95 (12) |
C19—N16—C112 | 126.16 (16) | C213—N28—C214 | 107.62 (14) |
C110—N16—C112 | 125.98 (16) | C213—N28—C216 | 126.80 (16) |
C113—N17—C115 | 106.03 (15) | C214—N28—C216 | 125.54 (16) |
C113—N17—Cu1 | 129.01 (13) | N21—C21—N22 | 111.02 (15) |
C115—N17—Cu1 | 124.95 (12) | N21—C21—H21 | 124.5 |
C113—N18—C114 | 107.33 (15) | N22—C21—H21 | 124.5 |
C113—N18—C116 | 126.41 (18) | C23—C22—N22 | 106.61 (16) |
C114—N18—C116 | 126.26 (17) | C23—C22—H22 | 126.7 |
N11—C11—N12 | 110.98 (15) | N22—C22—H22 | 126.7 |
N11—C11—H11 | 124.5 | C22—C23—N21 | 109.08 (16) |
N12—C11—H11 | 124.5 | C22—C23—H23 | 125.5 |
C13—C12—N12 | 106.84 (15) | N21—C23—H23 | 125.5 |
C13—C12—H12 | 126.6 | N22—C24—H24A | 109.5 |
N12—C12—H12 | 126.6 | N22—C24—H24B | 109.5 |
C12—C13—N11 | 108.72 (15) | H24A—C24—H24B | 109.5 |
C12—C13—H13 | 125.6 | N22—C24—H24C | 109.5 |
N11—C13—H13 | 125.6 | H24A—C24—H24C | 109.5 |
N12—C14—H14A | 109.5 | H24B—C24—H24C | 109.5 |
N12—C14—H14B | 109.5 | N23—C25—N24 | 110.99 (16) |
H14A—C14—H14B | 109.5 | N23—C25—H25 | 124.5 |
N12—C14—H14C | 109.5 | N24—C25—H25 | 124.5 |
H14A—C14—H14C | 109.5 | C27—C26—N24 | 106.35 (15) |
H14B—C14—H14C | 109.5 | C27—C26—H26 | 126.8 |
N13—C15—N14 | 111.03 (15) | N24—C26—H26 | 126.8 |
N13—C15—H15 | 124.5 | C26—C27—N23 | 109.03 (16) |
N14—C15—H15 | 124.5 | C26—C27—H27 | 125.5 |
C17—C16—N14 | 106.50 (16) | N23—C27—H27 | 125.5 |
C17—C16—H16 | 126.8 | N24—C28—H28A | 109.5 |
N14—C16—H16 | 126.7 | N24—C28—H28B | 109.5 |
C16—C17—N13 | 109.24 (16) | H28A—C28—H28B | 109.5 |
C16—C17—H17 | 125.4 | N24—C28—H28C | 109.5 |
N13—C17—H17 | 125.4 | H28A—C28—H28C | 109.5 |
N14—C18—H18A | 109.5 | H28B—C28—H28C | 109.5 |
N14—C18—H18B | 109.5 | N25—C29—N26 | 111.09 (15) |
H18A—C18—H18B | 109.5 | N25—C29—H29 | 124.5 |
N14—C18—H18C | 109.5 | N26—C29—H29 | 124.5 |
H18A—C18—H18C | 109.5 | C211—C210—N26 | 106.05 (16) |
H18B—C18—H18C | 109.5 | C211—C210—H210 | 127.0 |
N15—C19—N16 | 110.59 (15) | N26—C210—H210 | 127.0 |
N15—C19—H19 | 124.7 | C210—C211—N25 | 109.52 (16) |
N16—C19—H19 | 124.7 | C210—C211—H211 | 125.2 |
C111—C110—N16 | 106.03 (15) | N25—C211—H211 | 125.2 |
C111—C110—H110 | 127.0 | N26—C212—H21A | 109.5 |
N16—C110—H110 | 127.0 | N26—C212—H21B | 109.5 |
C110—C111—N15 | 109.08 (16) | H21A—C212—H21B | 109.5 |
C110—C111—H111 | 125.5 | N26—C212—H21C | 109.5 |
N15—C111—H111 | 125.5 | H21A—C212—H21C | 109.5 |
N16—C112—H11A | 109.5 | H21B—C212—H21C | 109.5 |
N16—C112—H11B | 109.5 | N27—C213—N28 | 110.59 (16) |
H11A—C112—H11B | 109.5 | N27—C213—H213 | 124.7 |
N16—C112—H11C | 109.5 | N28—C213—H213 | 124.7 |
H11A—C112—H11C | 109.5 | C215—C214—N28 | 106.26 (15) |
H11B—C112—H11C | 109.5 | C215—C214—H214 | 126.9 |
N17—C113—N18 | 110.92 (17) | N28—C214—H214 | 126.9 |
N17—C113—H113 | 124.5 | C214—C215—N27 | 108.83 (16) |
N18—C113—H113 | 124.5 | C214—C215—H215 | 125.6 |
C115—C114—N18 | 106.72 (17) | N27—C215—H215 | 125.6 |
C115—C114—H114 | 126.6 | N28—C216—H21D | 109.5 |
N18—C114—H114 | 126.6 | N28—C216—H21E | 109.5 |
C114—C115—N17 | 109.00 (17) | H21D—C216—H21E | 109.5 |
C114—C115—H115 | 125.5 | N28—C216—H21F | 109.5 |
N17—C115—H115 | 125.5 | H21D—C216—H21F | 109.5 |
N18—C116—H11D | 109.5 | H21E—C216—H21F | 109.5 |
N18—C116—H11E | 109.5 | N1—C1—C2 | 179.7 (3) |
H11D—C116—H11E | 109.5 | C1—C2—H2C | 109.5 |
N18—C116—H11F | 109.5 | C1—C2—H2D | 109.5 |
H11D—C116—H11F | 109.5 | H2C—C2—H2D | 109.5 |
H11E—C116—H11F | 109.5 | C1—C2—H2E | 109.5 |
N21—Cu2—N23 | 90.44 (6) | H2C—C2—H2E | 109.5 |
N21—Cu2—N25 | 174.89 (6) | H2D—C2—H2E | 109.5 |
N21—Cu2—N27 | 89.67 (6) | H1A—O1—H1B | 105 (3) |
N21—Cu2—O21 | 85.12 (5) | H3A—O3—H3B | 103 (3) |
N21—Cu2—O23iii | 96.28 (5) | H2A—O2—H2B | 104 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O22 | 0.81 (3) | 1.97 (3) | 2.780 (2) | 171 (3) |
O1—H1B···O14 | 0.73 (3) | 2.08 (3) | 2.806 (2) | 173 (3) |
O2—H2A···O14 | 0.79 (4) | 2.84 (3) | 3.486 (2) | 141 (3) |
O2—H2A···O12 | 0.79 (4) | 2.10 (4) | 2.869 (3) | 164 (3) |
O2—H2B···O22 | 0.81 (4) | 2.09 (4) | 2.866 (3) | 159 (3) |
O3—H3B···O2 | 0.73 (3) | 2.17 (3) | 2.888 (3) | 168 (3) |
O3—H3A···O24 | 0.83 (3) | 1.97 (3) | 2.793 (2) | 177 (3) |
O3—H3A···O22 | 0.83 (3) | 2.95 (3) | 3.496 (2) | 125 (2) |
C13—H13···O14i | 0.93 | 2.48 | 3.327 (2) | 152 |
C13—H13···O11i | 0.93 | 2.72 | 3.197 (2) | 112 |
C17—H17···O11i | 0.93 | 2.56 | 3.078 (2) | 115 |
C110—H110···O12iv | 0.93 | 2.18 | 3.092 (2) | 166 |
C111—H111···O12i | 0.93 | 2.47 | 3.361 (2) | 160 |
C113—H113···O12i | 0.93 | 2.31 | 3.203 (2) | 161 |
C212—H21A···O3 | 0.96 | 2.51 | 3.368 (3) | 148 |
C23—H23···O21 | 0.93 | 2.48 | 3.009 (2) | 116 |
C23—H23···O23 | 0.93 | 2.60 | 3.524 (2) | 173 |
C25—H25···O21 | 0.93 | 2.42 | 2.995 (2) | 120 |
C29—H29···O24 | 0.93 | 2.44 | 3.353 (2) | 167 |
C215—H215···O24 | 0.93 | 2.51 | 3.408 (2) | 162 |
C11—H11···O13 | 0.93 | 2.41 | 3.093 (2) | 130 |
C15—H15···O13 | 0.93 | 2.52 | 3.135 (2) | 123 |
C15—H15···O14 | 0.93 | 2.62 | 3.499 (2) | 159 |
C19—H19···O13 | 0.93 | 2.86 | 3.447 (2) | 122 |
C19—H19···O14 | 0.93 | 2.20 | 3.125 (2) | 173 |
C21—H21···O24iii | 0.93 | 2.24 | 3.164 (2) | 174 |
C21—H21···O23iii | 0.93 | 2.91 | 3.493 (2) | 122 |
C24—H24A···O3iii | 0.96 | 2.63 | 3.549 (3) | 161 |
C24—H24C···O24iv | 0.96 | 2.52 | 3.406 (2) | 153 |
C212—H21B···O23v | 0.96 | 2.79 | 3.691 (2) | 158 |
C212—H21C···O1v | 0.96 | 2.72 | 3.441 (3) | 132 |
C213—H213···O23iii | 0.93 | 2.68 | 3.270 (2) | 122 |
C213—H213···O22iii | 0.93 | 2.35 | 3.252 (2) | 164 |
C214—H214···N1 | 0.93 | 2.50 | 3.337 (3) | 149 |
C215—H215···O21 | 0.93 | 2.93 | 3.441 (2) | 116 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) x, −y−1/2, z−1/2; (v) x, −y−1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C4H8N2)4]SO4·0.5C2H3N·1.5H2O |
Mr | 535.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 18.6227 (1), 14.2708 (1), 17.5255 (1) |
β (°) | 91.650 (1) |
V (Å3) | 4655.66 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.08 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Siemens, 1996) |
Tmin, Tmax | 0.809, 0.881 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31303, 11509, 9721 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.05 |
No. of reflections | 11509 |
No. of parameters | 668 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.70 |
Selected geometric parameters (Å, º) topCu1—N11 | 2.0059 (14) | Cu2—N21 | 2.0012 (14) |
Cu1—N13 | 2.0193 (14) | Cu2—N23 | 1.9951 (14) |
Cu1—N15 | 1.9930 (14) | Cu2—N25 | 2.0225 (14) |
Cu1—N17 | 2.0203 (14) | Cu2—N27 | 1.9950 (14) |
Cu1—O11i | 2.3496 (13) | Cu2—O21 | 2.5216 (13) |
Cu1—O13 | 2.8276 (14) | Cu2—O23ii | 2.6764 (13) |
S1—O11 | 1.4748 (12) | S2—O21 | 1.4700 (12) |
S1—O12 | 1.4833 (13) | S2—O22 | 1.4889 (13) |
S1—O13 | 1.4714 (14) | S2—O23 | 1.4753 (13) |
S1—O14 | 1.4796 (13) | S2—O24 | 1.4824 (12) |
| | | |
N11—Cu1—N13 | 88.44 (6) | N21—Cu2—N23 | 90.44 (6) |
N11—Cu1—N15 | 176.48 (6) | N21—Cu2—N25 | 174.89 (6) |
N11—Cu1—N17 | 90.74 (6) | N21—Cu2—N27 | 89.67 (6) |
N11—Cu1—O11i | 91.62 (5) | N21—Cu2—O21 | 85.12 (5) |
N11—Cu1—O13 | 85.30 (5) | N21—Cu2—O23ii | 96.28 (5) |
N13—Cu1—N15 | 89.86 (6) | N23—Cu2—N25 | 91.43 (6) |
N13—Cu1—O11i | 89.46 (5) | N23—Cu2—N27 | 176.65 (6) |
N13—Cu1—O13 | 83.94 (5) | N23—Cu2—O21 | 86.70 (5) |
N13—Cu1—N17 | 171.55 (6) | N23—Cu2—O23ii | 85.62 (5) |
N15—Cu1—N17 | 90.49 (6) | N25—Cu2—N27 | 88.75 (6) |
N15—Cu1—O11i | 91.45 (5) | N25—Cu2—O21 | 90.23 (5) |
N15—Cu1—O13 | 91.46 (5) | N25—Cu2—O23ii | 88.61 (5) |
N17—Cu1—O11i | 98.98 (5) | N27—Cu2—O21 | 96.64 (5) |
N17—Cu1—O13 | 87.61 (5) | N27—Cu2—O23ii | 91.04 (5) |
O11i—Cu1—O13 | 172.78 (4) | O21—Cu2—O23ii | 172.20 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O22 | 0.81 (3) | 1.97 (3) | 2.780 (2) | 171 (3) |
O1—H1B···O14 | 0.73 (3) | 2.08 (3) | 2.806 (2) | 173 (3) |
O2—H2A···O14 | 0.79 (4) | 2.84 (3) | 3.486 (2) | 141 (3) |
O2—H2A···O12 | 0.79 (4) | 2.10 (4) | 2.869 (3) | 164 (3) |
O2—H2B···O22 | 0.81 (4) | 2.09 (4) | 2.866 (3) | 159 (3) |
O3—H3B···O2 | 0.73 (3) | 2.17 (3) | 2.888 (3) | 168 (3) |
O3—H3A···O24 | 0.83 (3) | 1.97 (3) | 2.793 (2) | 177 (3) |
O3—H3A···O22 | 0.83 (3) | 2.95 (3) | 3.496 (2) | 125 (2) |
C13—H13···O14i | 0.93 | 2.48 | 3.327 (2) | 152 |
C110—H110···O12iii | 0.93 | 2.18 | 3.092 (2) | 166 |
C111—H111···O12i | 0.93 | 2.47 | 3.361 (2) | 160 |
C113—H113···O12i | 0.93 | 2.31 | 3.203 (2) | 161 |
C212—H21A···O3 | 0.96 | 2.51 | 3.368 (3) | 148 |
C29—H29···O24 | 0.93 | 2.44 | 3.353 (2) | 167 |
C11—H11···O13 | 0.93 | 2.41 | 3.093 (2) | 130 |
C19—H19···O14 | 0.93 | 2.20 | 3.125 (2) | 173 |
C21—H21···O24ii | 0.93 | 2.24 | 3.164 (2) | 174 |
C213—H213···O22ii | 0.93 | 2.35 | 3.252 (2) | 164 |
C214—H214···N1 | 0.93 | 2.50 | 3.337 (3) | 149 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x, −y−1/2, z−1/2. |
Our research group is interested in the synthesis and characterization of thione complexes (García-Vázquez et al., 1999). However, the pronounced tendency of S to bridge metal centres often produces insoluble polymers. In these cases, one strategy for the synthesis of low molecular weight compounds involves the incorporation of co-ligands to block some coordination sites. This technique has previously been successfully employed in the preparation of mixed thionate complexes (García-Vázquez et al., 1999). As a continuation of this work, we attempted to synthesize a copper(I) complex incorporating a heterocyclic thionate and 1-methylimidazole as co-ligand. However, in the reaction of (1-propylimidazolidine-2-thionate)copper(I) with 1-methylimidazole, instead of the expected mixed-ligand copper(I) complex, the title compound, (I), was obtained. This compound is probably formed by oxidation of copper(I) and further replacement of the heterocyclic thionate ligand by 1-methylimidazole and sulfate ions, the latter formed by oxidation of the thionate sulfur in accord with the process previously described by Raper (1994). \sch
The coordination chemistry of tetrakis(imidazole)copper(II) and its alkyl ligand derivatives has been widely studied and crystal structures have been obtained, mainly in the case of the halides, and also for oxoanions (Pan et al., 1998 and references therein; Kohout et al., 1999; Su et al., 1995). Moreover, tetrakis(imidazole) copper(II) sulfate has been studied by X-ray diffraction (Fransson & Lundberg, 1972) and its structure shows a chain structure, but there are some differences from the compound described in the present paper (apart from the methyl group in the ligand). These differences are, in part, related to the supramolecular structure arising from the presence of water molecules and to the absence of an inversion centre at Cu and the resulting lack of local symmetry (see below).
The structure of (I) is shown in Fig. 1 and selected bond distances and angles are given in Table 1. Compound (I) crystallizes as a linear polymer (Fig. 2). The asymmetric unit contains two formula units belonging to two different chains. The sulfate dianion acts as a bridge (O:O') between the Cu centres. In addition, the other O atoms of the sulfate anions are involved in hydrogen-bond formation. Indeed, the framework is maintained by hydrogen bonds between the water molecules labelled O1 and O2 and sulfate anions of different chains, and the water molecule O3 linking a sulfate ion and the water molecule O2. Therefore, all H atoms in the water molecules are involved in hydrogen bonds. In the same way, all O atoms of the sulfate anions are involved in short interactions, either with Cu centres or water molecules, or through non-classical hydrogen bonds (Table 2).
The environment of both Cu atoms is octahedral, with the four 1-methylimidazole ligands in the equatorial plane and the O atoms of two symmetry-related sulfate ions in the axial positions. The bond lengths in the equatorial positions are similar to those found in the literature [see, for example, Su et al. (1995) or Potenza et al. (1988)] and do not merit further discussion. Each imidazole ring is planar to within ±0.003 (1) Å, while the methyl C atoms deviate by between 0.007 (3) and 0.069 (3) Å from these planes.
For the molecule labelled 1, the dihedral angles between each imidazole plane and the planar [±0.046 (1) Å] donor N4 unit are 81.87 (6), 77.10 (6), 69.66 (5) and 78.80 (6)°, respectively, and for the other four with their planar [±0.071 (1) Å] donor N4 unit the dihedral angles are 77.75 (6), 67.12 (6), 66.27 (7) and 80.18 (6)°, respectively. The two N4Cu units are slightly different: that centred on Cu1 has the metal 0.102 (1) Å out of the best plane defined by the four N donor atoms, while this distance is only 0.013 (1) Å for Cu2. This deviation is due to the different coordination of the sulfate groups. Indeed, the Cu2—O distances have similar values, 2.5216 (13) and 2.6764 (13) Å, but the Cu1—O distances are 2.3496 (13) and 2.8276 (14) Å. This behaviour is not observed in the compound studied by Fransson & Lundberg (1972), where the value found is 2.574 (4) Å for both Cu—O distances, since the metal lies on a centre of inversion. These longer distances for the axial positions are well documented in the literature, mainly when the ligands in these positions are as poorly coordinating as sulfate.