Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101012914/jz1468sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101012914/jz1468Isup2.hkl |
CCDC reference: 175064
For related literature, see: Attia & Pierpont (1995); Blake et al. (1999); Carlucci et al. (1997); Cheetham et al. (1999); Chippindale et al. (2000); Choudhuy et al. (2000); Dong et al. (2000); Finn & Zubieta (2000); Hagrman et al. (1998, 1999); Janiak (2000); Janiak et al. (1999); Li et al. (2000); Lii & Huang (1999); Moubaraki et al. (1998); Neeraj et al. (1999); Oliver et al. (1998); Orpen et al. (1989); Shi et al. (2000); Subramanian & Zaworotko (1994); Tong et al. (1998, 1999); Wu et al. (1999); Yan et al. (2000); You et al. (2000); Zhang et al. (1999).
Copper nitrate trihydrate (0.241 g, 1.00 mmol) and 4,4'-bipyridine (0.156 g, 1.00 mmol) were mixed in distilled water (25 ml). To this slurry was carefully added a 1 mol l-1 solution of H3PO4 with constant stirring until all the 4,4'-bipy had completely dissolved. The pH was adjusted to 4.3 using tetra-n-butylammonium hydroxide. The mixture was then stirred for 6 h. The solution was left to stand for three days at room temperature and some of the solvent evaporated. After this time, blue crystals of the title compound were collected by filtration (yield 280 mg, 46%). Crystal analysis, IR (KBr): 3444 (br, OH), 1607 (C═C), 1416 (P═O), 963 (P—O); calculated for C20H24CuN4O10P2: C 39.66, H 3.96, N 9.25%; found C 39.21, H 2.95, N 8.90%.
The H atoms on O atoms were found and refined. The O—H bond distances were restrained to a target value of 0.83±0.02 Å with DFIX. Isotropic displacement parameters of U(H) = 1.5Ueq(O) were used. The H atoms on C atoms could also be found and refined but it was preferred to place them at calculated positions and refine them using appropriate riding models (HFIX 43; C—H = 0.94 Å) and isotropic displacement parameters of U(H) = 1.2Ueq(C). The structure could also be solved in a smaller triclinic unit cell with a = 7.707 (1), b = 7.945 (1), c = 10.207 (2) Å, α = 90.839 (3), β = 93.589 (3) and γ = 112.72 (1)°. Solution and refinement in the smaller triclinic cell was succesful to R1 = 0.0405, wR = 0.1122 for 2306 reflections with I > 2σ(I), R1 = 0.0474 and wR = 0.1179 for all data. The superstructure reflections which give rise to the larger unit cell are clearly visible, however. Furthermore, the pyridyl ring C atoms have high displacement parameters perpendicular to the ring plane. This corresponds to an averaged structure of the two bipy ligands where the pyridyl groups are tilted differently. Another example of a 4,4'-bipy complex with pseudosymmetry has been reported recently with the polymeric structure [MnCl2(4,4'-bipy)]n (Chippindale et al., 2000).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) and SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and SHELXTL-Plus; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Cu(H2PO4)2(C10H8N2)2(H2O)2] | Z = 2 |
Mr = 605.91 | F(000) = 622 |
Triclinic, P1 | Dx = 1.750 Mg m−3 |
a = 7.948 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.208 (2) Å | Cell parameters from 3065 reflections |
c = 14.362 (3) Å | θ = 1.4–27.5° |
α = 85.693 (5)° | µ = 1.16 mm−1 |
β = 82.008 (5)° | T = 210 K |
γ = 89.172 (5)° | Block, blue |
V = 1150.6 (4) Å3 | 0.15 × 0.14 × 0.05 mm |
Bruker AXS CCD diffractometer | 3065 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 27.5°, θmin = 1.4° |
ω scans | h = −10→10 |
10246 measured reflections | k = −13→13 |
5200 independent reflections | l = −18→18 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0348P)2] where P = (Fo2 + 2Fc2)/3 |
5200 reflections | (Δ/σ)max < 0.001 |
358 parameters | Δρmax = 0.39 e Å−3 |
8 restraints | Δρmin = −0.62 e Å−3 |
[Cu(H2PO4)2(C10H8N2)2(H2O)2] | γ = 89.172 (5)° |
Mr = 605.91 | V = 1150.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.948 (2) Å | Mo Kα radiation |
b = 10.208 (2) Å | µ = 1.16 mm−1 |
c = 14.362 (3) Å | T = 210 K |
α = 85.693 (5)° | 0.15 × 0.14 × 0.05 mm |
β = 82.008 (5)° |
Bruker AXS CCD diffractometer | 3065 reflections with I > 2σ(I) |
10246 measured reflections | Rint = 0.040 |
5200 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 8 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.39 e Å−3 |
5200 reflections | Δρmin = −0.62 e Å−3 |
358 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. Refinement was carried out by using an uncorrected and an absorption- corrected data set (SADABS). With absorption correction (Maximum and minimum effective transmission: 1.000000 0.778807) refinement converged to R-factor-all 0.0746 R-factor-gt 0.0393 wR-factor-ref 0.1101 wR-factor-gt 0.0939 goodness-of-fit-ref 0.996 restrained-S-all 0.996 residual electron density: density-max 0.666 density-min -0.827 density-r.m.s. 0.086 The R-factors and residual electron densities are even somewhat larger than those from the uncorrected data set (see below). Thus, the uncorrected data set was chosen for full refinement. The structure could also be solved in a smaller triclinic unit cell with a = 7.707 (1), b = 7.945 (1), c = 10.207 (2) Å, α = 90.839 (3), β = 93.589 (3), γ = 112.72 (1) °. Solution and refinement in the smaller triclinic cell was succesful to R1 = 0.0405, wR = 0.1122 for 2306 reflections with I > σ(I), R1 = 0.0474, wR = 0.1179 for all data. The superstructure reflections which give rise to the larger unit cell are clearly visible, however. Furthermore, the pyridyl ring carbon atoms have high thermal parameters perpendicular to the ring plane. This corresponds to an averaged structure of the two bipy ligands where the pyridyl groups are tilted differently. Another example of a 4,4'-bipy complex with pseudosymmetry has recently reported with the polymeric structure of [MnCl2(4,4'-bipy)]n (Chippindale et al., 2000). The hydrogen atoms on oxygen were found and refined. The O—H bond distances were restrained to a target value of 0.83±0.02 Å with DFIX. Isotropic temperature factors of U(H) = 1.5 Ueq(O) were used. The hydrogen atoms on carbon could also be found and refined but it was prefered to place them at calculated positions using appropriate riding models (HFIX 43) and isotropic temperature factors of U(H) = 1.2 Ueq(C). |
x | y | z | Uiso*/Ueq | ||
Cu | 0.24669 (6) | −0.00412 (4) | −0.25266 (3) | 0.02267 (11) | |
O1 | −0.0633 (3) | −0.1516 (2) | −0.43557 (16) | 0.0275 (5) | |
H01 | −0.105 (4) | −0.084 (2) | −0.457 (2) | 0.041* | |
O2 | 0.2209 (3) | −0.0425 (2) | −0.49030 (15) | 0.0258 (5) | |
O3 | 0.1871 (3) | −0.2874 (2) | −0.44940 (16) | 0.0303 (6) | |
H03 | 0.271 (3) | −0.319 (3) | −0.427 (2) | 0.046* | |
O4 | 0.1455 (3) | −0.13335 (19) | −0.32069 (14) | 0.0247 (5) | |
O5 | 0.2842 (3) | 0.0415 (2) | −0.01461 (15) | 0.0255 (5) | |
O6 | 0.3490 (3) | 0.12572 (19) | −0.18587 (14) | 0.0254 (5) | |
O7 | 0.5707 (3) | 0.1408 (2) | −0.07926 (16) | 0.0276 (5) | |
H07 | 0.612 (4) | 0.081 (3) | −0.047 (2) | 0.041* | |
O8 | 0.3272 (3) | 0.2852 (2) | −0.06202 (16) | 0.0279 (5) | |
H08 | 0.233 (3) | 0.309 (3) | −0.072 (3) | 0.042* | |
O9 | 0.4469 (3) | 0.0994 (2) | −0.40621 (16) | 0.0312 (5) | |
H9A | 0.388 (4) | 0.063 (3) | −0.439 (2) | 0.047* | |
H9B | 0.545 (3) | 0.098 (4) | −0.431 (2) | 0.047* | |
O10 | 0.0402 (3) | −0.0799 (2) | −0.10176 (16) | 0.0309 (6) | |
H10A | −0.058 (3) | −0.076 (4) | −0.076 (2) | 0.046* | |
H10B | 0.087 (4) | −0.037 (3) | −0.065 (2) | 0.046* | |
P1 | 0.12817 (10) | −0.14690 (7) | −0.42277 (5) | 0.01881 (18) | |
P2 | 0.37670 (10) | 0.14133 (7) | −0.08597 (5) | 0.01842 (18) | |
N1 | 0.4186 (3) | −0.1405 (2) | −0.21717 (17) | 0.0219 (6) | |
N2 | 1.0355 (3) | −0.6089 (2) | −0.09874 (18) | 0.0245 (6) | |
N3 | 0.0771 (3) | 0.1324 (2) | −0.28698 (17) | 0.0217 (6) | |
N4 | −0.5286 (3) | 0.6117 (2) | −0.40124 (19) | 0.0268 (6) | |
C1 | 0.3787 (4) | −0.2359 (3) | −0.1480 (2) | 0.0257 (7) | |
H1 | 0.2675 | −0.2389 | −0.1155 | 0.031* | |
C2 | 0.4943 (4) | −0.3295 (3) | −0.1230 (2) | 0.0235 (7) | |
H2 | 0.4612 | −0.3943 | −0.0742 | 0.028* | |
C3 | 0.6587 (4) | −0.3284 (3) | −0.1695 (2) | 0.0197 (7) | |
C4 | 0.6992 (4) | −0.2292 (3) | −0.2406 (2) | 0.0261 (7) | |
H4 | 0.8097 | −0.2232 | −0.2739 | 0.031* | |
C5 | 0.5765 (4) | −0.1399 (3) | −0.2618 (2) | 0.0282 (7) | |
H5 | 0.6061 | −0.0746 | −0.3108 | 0.034* | |
C6 | 0.7878 (4) | −0.4263 (3) | −0.1447 (2) | 0.0197 (7) | |
C7 | 0.7444 (4) | −0.5545 (3) | −0.1103 (2) | 0.0223 (7) | |
H7 | 0.6305 | −0.5818 | −0.1021 | 0.027* | |
C8 | 0.8714 (4) | −0.6411 (3) | −0.0885 (2) | 0.0259 (7) | |
H8 | 0.8404 | −0.7272 | −0.0651 | 0.031* | |
C9 | 1.0756 (4) | −0.4863 (3) | −0.1329 (2) | 0.0277 (7) | |
H9 | 1.1908 | −0.4622 | −0.1413 | 0.033* | |
C10 | 0.9592 (4) | −0.3933 (3) | −0.1565 (2) | 0.0267 (7) | |
H10 | 0.9948 | −0.3084 | −0.1803 | 0.032* | |
C11 | −0.0890 (4) | 0.1073 (3) | −0.2754 (2) | 0.0252 (7) | |
H11 | −0.1254 | 0.0223 | −0.2524 | 0.030* | |
C12 | −0.2105 (4) | 0.1991 (3) | −0.2953 (2) | 0.0232 (7) | |
H12 | −0.3263 | 0.1769 | −0.2851 | 0.028* | |
C13 | −0.1595 (4) | 0.3246 (3) | −0.33077 (19) | 0.0201 (7) | |
C14 | 0.0128 (4) | 0.3509 (3) | −0.3432 (2) | 0.0238 (7) | |
H14 | 0.0525 | 0.4348 | −0.3670 | 0.029* | |
C15 | 0.1269 (4) | 0.2538 (3) | −0.3206 (2) | 0.0236 (7) | |
H15 | 0.2434 | 0.2738 | −0.3291 | 0.028* | |
C16 | −0.2864 (4) | 0.4263 (3) | −0.3536 (2) | 0.0201 (7) | |
C17 | −0.4547 (4) | 0.4163 (3) | −0.3125 (2) | 0.0265 (7) | |
H17 | −0.4900 | 0.3464 | −0.2680 | 0.032* | |
C18 | −0.5696 (4) | 0.5104 (3) | −0.3378 (2) | 0.0281 (7) | |
H18 | −0.6830 | 0.5029 | −0.3089 | 0.034* | |
C19 | −0.3660 (4) | 0.6228 (3) | −0.4387 (2) | 0.0294 (8) | |
H19 | −0.3342 | 0.6941 | −0.4826 | 0.035* | |
C20 | −0.2419 (4) | 0.5347 (3) | −0.4160 (2) | 0.0252 (7) | |
H20 | −0.1281 | 0.5480 | −0.4427 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0246 (2) | 0.01727 (17) | 0.0289 (2) | 0.00607 (13) | −0.01192 (15) | −0.00526 (14) |
O1 | 0.0210 (13) | 0.0258 (12) | 0.0360 (13) | 0.0009 (10) | −0.0093 (10) | 0.0064 (10) |
O2 | 0.0166 (12) | 0.0292 (12) | 0.0311 (12) | 0.0005 (9) | −0.0054 (9) | 0.0039 (10) |
O3 | 0.0337 (15) | 0.0260 (12) | 0.0355 (13) | 0.0125 (10) | −0.0165 (11) | −0.0105 (10) |
O4 | 0.0299 (13) | 0.0195 (11) | 0.0259 (11) | 0.0011 (9) | −0.0077 (10) | −0.0030 (9) |
O5 | 0.0165 (12) | 0.0281 (12) | 0.0314 (12) | 0.0010 (9) | −0.0055 (9) | 0.0054 (10) |
O6 | 0.0349 (14) | 0.0192 (11) | 0.0241 (11) | −0.0019 (9) | −0.0102 (10) | −0.0028 (9) |
O7 | 0.0178 (12) | 0.0262 (12) | 0.0380 (13) | 0.0003 (10) | −0.0085 (10) | 0.0116 (10) |
O8 | 0.0297 (14) | 0.0201 (11) | 0.0372 (13) | 0.0085 (10) | −0.0146 (11) | −0.0078 (10) |
O9 | 0.0255 (14) | 0.0385 (14) | 0.0296 (13) | 0.0025 (11) | −0.0022 (11) | −0.0064 (11) |
O10 | 0.0257 (14) | 0.0368 (14) | 0.0305 (13) | 0.0001 (11) | −0.0001 (11) | −0.0112 (11) |
P1 | 0.0169 (4) | 0.0171 (4) | 0.0232 (4) | 0.0026 (3) | −0.0066 (3) | −0.0006 (3) |
P2 | 0.0168 (4) | 0.0161 (4) | 0.0232 (4) | 0.0020 (3) | −0.0067 (3) | 0.0001 (3) |
N1 | 0.0220 (15) | 0.0176 (13) | 0.0272 (14) | 0.0023 (11) | −0.0069 (11) | −0.0022 (11) |
N2 | 0.0245 (16) | 0.0213 (14) | 0.0285 (14) | 0.0062 (11) | −0.0065 (12) | −0.0022 (11) |
N3 | 0.0231 (15) | 0.0182 (13) | 0.0250 (13) | 0.0025 (11) | −0.0066 (11) | −0.0033 (11) |
N4 | 0.0278 (17) | 0.0198 (14) | 0.0351 (16) | 0.0072 (12) | −0.0104 (13) | −0.0062 (12) |
C1 | 0.0206 (17) | 0.0256 (17) | 0.0297 (17) | 0.0025 (13) | −0.0011 (14) | 0.0005 (14) |
C2 | 0.0220 (17) | 0.0220 (16) | 0.0251 (16) | 0.0020 (13) | −0.0023 (13) | 0.0045 (13) |
C3 | 0.0202 (17) | 0.0171 (15) | 0.0228 (16) | 0.0020 (13) | −0.0053 (13) | −0.0041 (13) |
C4 | 0.0191 (17) | 0.0270 (17) | 0.0307 (18) | 0.0035 (13) | −0.0018 (14) | 0.0029 (14) |
C5 | 0.0289 (19) | 0.0234 (16) | 0.0308 (18) | 0.0016 (14) | −0.0038 (14) | 0.0059 (14) |
C6 | 0.0210 (17) | 0.0182 (15) | 0.0202 (15) | 0.0029 (13) | −0.0038 (13) | −0.0024 (12) |
C7 | 0.0196 (17) | 0.0222 (15) | 0.0248 (16) | 0.0001 (12) | −0.0029 (13) | 0.0004 (13) |
C8 | 0.0280 (19) | 0.0200 (16) | 0.0299 (17) | 0.0037 (13) | −0.0067 (14) | 0.0008 (13) |
C9 | 0.0187 (17) | 0.0238 (17) | 0.0410 (19) | 0.0035 (13) | −0.0062 (14) | −0.0024 (15) |
C10 | 0.0214 (17) | 0.0186 (15) | 0.0403 (19) | −0.0005 (13) | −0.0062 (14) | 0.0003 (14) |
C11 | 0.0244 (18) | 0.0192 (15) | 0.0327 (17) | −0.0010 (12) | −0.0073 (14) | −0.0002 (13) |
C12 | 0.0209 (17) | 0.0208 (15) | 0.0288 (17) | 0.0012 (12) | −0.0069 (13) | −0.0005 (13) |
C13 | 0.0222 (17) | 0.0222 (16) | 0.0167 (15) | 0.0043 (13) | −0.0048 (13) | −0.0034 (13) |
C14 | 0.0233 (17) | 0.0197 (15) | 0.0281 (17) | −0.0012 (12) | −0.0046 (13) | 0.0025 (13) |
C15 | 0.0186 (16) | 0.0235 (16) | 0.0282 (17) | 0.0001 (13) | −0.0025 (13) | −0.0007 (13) |
C16 | 0.0228 (18) | 0.0190 (16) | 0.0203 (15) | 0.0037 (13) | −0.0085 (13) | −0.0036 (13) |
C17 | 0.0218 (18) | 0.0238 (17) | 0.0335 (18) | 0.0025 (13) | −0.0055 (14) | 0.0029 (14) |
C18 | 0.0200 (17) | 0.0271 (17) | 0.0380 (19) | 0.0023 (13) | −0.0064 (14) | −0.0028 (15) |
C19 | 0.034 (2) | 0.0225 (17) | 0.0304 (18) | 0.0052 (14) | −0.0027 (15) | 0.0046 (14) |
C20 | 0.0203 (17) | 0.0250 (17) | 0.0289 (17) | 0.0049 (13) | 0.0004 (13) | −0.0008 (14) |
Cu—O6 | 1.9435 (19) | C1—H1 | 0.9400 |
Cu—O4 | 1.9452 (19) | C2—C3 | 1.381 (4) |
Cu—N3 | 2.007 (3) | C2—H2 | 0.9400 |
Cu—N1 | 2.024 (3) | C3—C4 | 1.392 (4) |
Cu—O10 | 2.605 (2) | C3—C6 | 1.482 (4) |
Cu—O9 | 2.690 (3) | C4—C5 | 1.374 (4) |
O1—P1 | 1.560 (2) | C4—H4 | 0.9400 |
O1—H01 | 0.822 (18) | C5—H5 | 0.9400 |
O2—P1 | 1.513 (2) | C6—C10 | 1.392 (4) |
O3—P1 | 1.561 (2) | C6—C7 | 1.394 (4) |
O3—H03 | 0.828 (18) | C7—C8 | 1.386 (4) |
O4—P1 | 1.508 (2) | C7—H7 | 0.9400 |
O5—P2 | 1.511 (2) | C8—H8 | 0.9400 |
O6—P2 | 1.502 (2) | C9—C10 | 1.374 (4) |
O7—P2 | 1.558 (2) | C9—H9 | 0.9400 |
O7—H07 | 0.827 (18) | C10—H10 | 0.9400 |
O8—P2 | 1.565 (2) | C11—C12 | 1.379 (4) |
O8—H08 | 0.812 (18) | C11—H11 | 0.9400 |
O9—H9A | 0.819 (18) | C12—C13 | 1.388 (4) |
O9—H9B | 0.809 (18) | C12—H12 | 0.9400 |
O10—H10A | 0.815 (18) | C13—C14 | 1.384 (4) |
O10—H10B | 0.836 (18) | C13—C16 | 1.487 (4) |
P1—O2 | 1.513 (2) | C14—C15 | 1.384 (4) |
P2—O5 | 1.511 (2) | C14—H14 | 0.9400 |
N1—C5 | 1.327 (4) | C15—H15 | 0.9400 |
N1—C1 | 1.346 (4) | C16—C17 | 1.387 (4) |
N2—C8 | 1.335 (4) | C16—C20 | 1.389 (4) |
N2—C9 | 1.336 (4) | C17—C18 | 1.379 (4) |
N3—C11 | 1.334 (4) | C17—H17 | 0.9400 |
N3—C15 | 1.341 (4) | C18—H18 | 0.9400 |
N4—C19 | 1.332 (4) | C19—C20 | 1.381 (4) |
N4—C18 | 1.339 (4) | C19—H19 | 0.9400 |
C1—C2 | 1.379 (4) | C20—H20 | 0.9400 |
O6—Cu—O4 | 179.42 (10) | C1—C2—C3 | 120.3 (3) |
O6—Cu—N3 | 88.77 (9) | C1—C2—H2 | 119.8 |
O4—Cu—N3 | 91.15 (9) | C3—C2—H2 | 119.8 |
O6—Cu—N1 | 90.65 (9) | C2—C3—C4 | 116.7 (3) |
O4—Cu—N1 | 89.43 (9) | C2—C3—C6 | 122.3 (3) |
N3—Cu—N1 | 179.41 (10) | C4—C3—C6 | 120.9 (3) |
O6—Cu—O10 | 91.53 (8) | C5—C4—C3 | 119.5 (3) |
O4—Cu—O10 | 89.04 (8) | C5—C4—H4 | 120.3 |
N3—Cu—O10 | 89.89 (9) | C3—C4—H4 | 120.3 |
N1—Cu—O10 | 90.05 (10) | N1—C5—C4 | 123.9 (3) |
O6—Cu—O9 | 85.15 (8) | N1—C5—H5 | 118.0 |
O4—Cu—O9 | 94.28 (8) | C4—C5—H5 | 118.0 |
N3—Cu—O9 | 85.10 (9) | C10—C6—C7 | 117.4 (3) |
N1—Cu—O9 | 94.93 (9) | C10—C6—C3 | 120.6 (3) |
O10—Cu—O9 | 174.04 (8) | C7—C6—C3 | 122.0 (3) |
P1—O1—H01 | 117 (2) | C8—C7—C6 | 119.1 (3) |
P1—O3—H03 | 117 (3) | C8—C7—H7 | 120.5 |
P1—O4—Cu | 134.82 (13) | C6—C7—H7 | 120.5 |
P2—O6—Cu | 136.53 (13) | N2—C8—C7 | 123.5 (3) |
P2—O7—H07 | 120 (2) | N2—C8—H8 | 118.2 |
P2—O8—H08 | 116 (3) | C7—C8—H8 | 118.2 |
Cu—O9—H9A | 88 (3) | N2—C9—C10 | 124.1 (3) |
Cu—O9—H9B | 140 (3) | N2—C9—H9 | 117.9 |
H9A—O9—H9B | 109 (3) | C10—C9—H9 | 117.9 |
Cu—O10—H10A | 144 (3) | C9—C10—C6 | 119.1 (3) |
Cu—O10—H10B | 95 (3) | C9—C10—H10 | 120.4 |
H10A—O10—H10B | 99 (3) | C6—C10—H10 | 120.4 |
O4—P1—O2 | 114.07 (12) | N3—C11—C12 | 123.7 (3) |
O4—P1—O2 | 114.07 (12) | N3—C11—H11 | 118.1 |
O2—P1—O2 | 0.00 (18) | C12—C11—H11 | 118.1 |
O4—P1—O1 | 110.14 (13) | C11—C12—C13 | 119.1 (3) |
O2—P1—O1 | 110.91 (12) | C11—C12—H12 | 120.4 |
O2—P1—O1 | 110.91 (12) | C13—C12—H12 | 120.4 |
O4—P1—O3 | 109.09 (12) | C14—C13—C12 | 117.3 (3) |
O2—P1—O3 | 111.09 (13) | C14—C13—C16 | 121.9 (3) |
O2—P1—O3 | 111.09 (13) | C12—C13—C16 | 120.8 (3) |
O1—P1—O3 | 100.73 (12) | C13—C14—C15 | 120.1 (3) |
O6—P2—O5 | 114.16 (12) | C13—C14—H14 | 119.9 |
O6—P2—O5 | 114.16 (12) | C15—C14—H14 | 119.9 |
O5—P2—O5 | 0.0 (3) | N3—C15—C14 | 122.3 (3) |
O6—P2—O7 | 109.76 (13) | N3—C15—H15 | 118.8 |
O5—P2—O7 | 111.14 (12) | C14—C15—H15 | 118.8 |
O5—P2—O7 | 111.14 (12) | C17—C16—C20 | 117.4 (3) |
O6—P2—O8 | 108.33 (12) | C17—C16—C13 | 120.9 (3) |
O5—P2—O8 | 111.55 (13) | C20—C16—C13 | 121.8 (3) |
O5—P2—O8 | 111.55 (13) | C18—C17—C16 | 119.1 (3) |
O7—P2—O8 | 101.09 (12) | C18—C17—H17 | 120.5 |
C5—N1—C1 | 116.9 (3) | C16—C17—H17 | 120.5 |
C5—N1—Cu | 121.1 (2) | N4—C18—C17 | 123.7 (3) |
C1—N1—Cu | 121.9 (2) | N4—C18—H18 | 118.2 |
C8—N2—C9 | 116.8 (3) | C17—C18—H18 | 118.2 |
C11—N3—C15 | 117.4 (3) | N4—C19—C20 | 123.1 (3) |
C11—N3—Cu | 121.7 (2) | N4—C19—H19 | 118.4 |
C15—N3—Cu | 120.9 (2) | C20—C19—H19 | 118.4 |
C19—N4—C18 | 117.1 (3) | C19—C20—C16 | 119.6 (3) |
N1—C1—C2 | 122.6 (3) | C19—C20—H20 | 120.2 |
N1—C1—H1 | 118.7 | C16—C20—H20 | 120.2 |
C2—C1—H1 | 118.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01···O2i | 0.82 (2) | 1.76 (2) | 2.570 (3) | 170 (4) |
O3—H03···N4ii | 0.83 (2) | 1.81 (2) | 2.627 (3) | 170 (4) |
O7—H07···O5iii | 0.83 (2) | 1.74 (2) | 2.570 (3) | 175 (4) |
O8—H08···N2iv | 0.81 (2) | 1.84 (2) | 2.646 (3) | 170 (4) |
O9—H9A···O2 | 0.82 (2) | 1.97 (2) | 2.780 (3) | 168 (4) |
O9—H9B···O2v | 0.81 (2) | 2.13 (2) | 2.918 (3) | 163 (3) |
O10—H10A···O5vi | 0.82 (2) | 2.11 (2) | 2.909 (3) | 166 (3) |
O10—H10B···O5 | 0.84 (2) | 2.02 (2) | 2.800 (3) | 156 (3) |
Symmetry codes: (i) −x, −y, −z−1; (ii) x+1, y−1, z; (iii) −x+1, −y, −z; (iv) x−1, y+1, z; (v) −x+1, −y, −z−1; (vi) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(H2PO4)2(C10H8N2)2(H2O)2] |
Mr | 605.91 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 210 |
a, b, c (Å) | 7.948 (2), 10.208 (2), 14.362 (3) |
α, β, γ (°) | 85.693 (5), 82.008 (5), 89.172 (5) |
V (Å3) | 1150.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.15 × 0.14 × 0.05 |
Data collection | |
Diffractometer | Bruker AXS CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10246, 5200, 3065 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.096, 1.01 |
No. of reflections | 5200 |
No. of parameters | 358 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.62 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997) and SHELXTL-Plus (Sheldrick, 1998), SHELXL97 (Sheldrick, 1997) and SHELXTL-Plus, ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Cu—O6 | 1.9435 (19) | Cu—N1 | 2.024 (3) |
Cu—O4 | 1.9452 (19) | Cu—O10 | 2.605 (2) |
Cu—N3 | 2.007 (3) | Cu—O9 | 2.690 (3) |
O6—Cu—O4 | 179.42 (10) | N3—Cu—O10 | 89.89 (9) |
O6—Cu—N3 | 88.77 (9) | N1—Cu—O10 | 90.05 (10) |
O4—Cu—N3 | 91.15 (9) | O6—Cu—O9 | 85.15 (8) |
O6—Cu—N1 | 90.65 (9) | O4—Cu—O9 | 94.28 (8) |
O4—Cu—N1 | 89.43 (9) | N3—Cu—O9 | 85.10 (9) |
N3—Cu—N1 | 179.41 (10) | N1—Cu—O9 | 94.93 (9) |
O6—Cu—O10 | 91.53 (8) | O10—Cu—O9 | 174.04 (8) |
O4—Cu—O10 | 89.04 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01···O2i | 0.82 (2) | 1.76 (2) | 2.570 (3) | 170 (4) |
O3—H03···N4ii | 0.83 (2) | 1.81 (2) | 2.627 (3) | 170 (4) |
O7—H07···O5iii | 0.83 (2) | 1.74 (2) | 2.570 (3) | 175 (4) |
O8—H08···N2iv | 0.81 (2) | 1.84 (2) | 2.646 (3) | 170 (4) |
O9—H9A···O2 | 0.82 (2) | 1.97 (2) | 2.780 (3) | 168 (4) |
O9—H9B···O2v | 0.81 (2) | 2.13 (2) | 2.918 (3) | 163 (3) |
O10—H10A···O5vi | 0.82 (2) | 2.11 (2) | 2.909 (3) | 166 (3) |
O10—H10B···O5 | 0.84 (2) | 2.02 (2) | 2.800 (3) | 156 (3) |
Symmetry codes: (i) −x, −y, −z−1; (ii) x+1, y−1, z; (iii) −x+1, −y, −z; (iv) x−1, y+1, z; (v) −x+1, −y, −z−1; (vi) −x, −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
There is widespread interest in achieving control of the aggregation of organic ligands and metal ions into oligo- or polynuclear coordination structures via covalent metal–ligand bonds and non-covalent interactions (Wu et al., 1999; Janiak et al., 1999). Recent years have seen an appreciable number of studies on the coordination of phosphate ions to transition metals (Choudhuy et al., 2000; Finn & Zubieta, 2000; Neeraji et al., 2000; Shi et al., 2000; Yan et al., 2000). Amine phosphates, for example, react with metal ions under hydrothermal conditions to give open-framework metal phosphates (Neeraj et al., 1999; Cheetham et al., 1999; Oliver et al., 1998). Mono- and dihydrogenphosphate ligands are good candidates for participation in structure-directing hydrogen-bonding interactions (Subramanian & Zaworotko, 1994). Moreover, 4,4'-bipyridine (4,4'-bipy) is an often used building block and excellent bridging ligand for the construction of coordination polymeric frameworks (Hagrman et al., 1999; Li et al., 2000; Janiak et al., 1999; Wu et al., 1999, and references therein). Little work has been carried out on the simultaneous coordination of 4,4'-bipy and phosphate with metals (Hagrman et al., 1999). Hydrothermal reaction of In(NO3)2.5H2O, H3PO4 and 4,4'-bipy in n-butanol produced [In4(4,4'-bipy)4(H2PO4)4(HPO4)4].4H4O (Lii & Huang, 1999). The extended inorganic–organic hybrid material [M(4,4'-bipy)2(VO2)2(HPO4)4] (M = Co, Ni) was also obtained by a hydrothermal reaction (Shi et al., 2000).
We describe here the structure of the monomeric complex [Cu(4,4'-bipy)2(H2PO4)2(H2O)2], (I) (Fig. 1). The molecular symmetry is D2 h when H2PO4 is treated as a point ligand and C2 h when the latter is taken into account as a full group. The coordination geometry around the CuII atom is a Jahn–Teller-distorted elongated octahedron. The two bipy N atoms and the two phosphate O atoms form the equatorial plane around copper. The two aqua ligands comprise the elongated axial coordination. There are intramolecular hydrogen bonds between the aqua and phosphate ligands (Fig. 2). The in-plane distances for Cu—N1 [2.024 (3) Å], Cu—N3 [2.007 (3) Å], Cu—O4 [1.945 (2) Å] and Cu—O6 [1.944 (2) Å] are normal. For Cu—Npy, the expected range is 2.046±0.032 Å (Orpen et al., 1989). There are few examples of copper–phosphate bonds. Nevertheless, the copper–phosphate distances are comparable to those in [{Cu(2,2'-bipy)}2(VO)3(PO4)2(HPO4)2].2H2O [average Cu—Ophosphate = 1.975 (4) Å], in [{Cu(terpy)}2(VO2)3(PO4)(HPO4)2] [Cu—Ophosphate = 1.921 (4) Å; Finn & Zubieta, 2000], and in [{Cu2(HL)(H2PO4)2}2](NO3)2.2H2O [H2L = bis(pyridine-2-aldehyde) thiocarbohydrazone; Cu—Ophosphate = 1.890 (3) and 1.933 (3) Å; Moubaraki et al., 1998]. The axial distances from Cu to the aqua ligands with O9 [2.690 (3) Å] and O10 [2.605 (2) Å] lie at the top end of the expected range. For the terminal Cu—OH2 bonds, the range is 2.399±0.154 Å (Orpen et al., 1989).
The 4,4'-bipy group functions as a monodentate ligand towards a metal atom in (I). This appears to be a rare phenomenon. Two known examples of monodentate 4,4'-bipy binding involve coordination to manganese (Attia & Pierpont, 1995; Tong et al., 1999). Much more common for 4,4'-bipy is a bidentate bridging coordination between metal atoms, thereby usually giving rise to extended metal–ligand structures, such as chains or grids. This is normally also observed in copper compounds with 4,4'-bipy (Blake et al., 1999; Hagrman et al., 1998; You et al., 2000; Tong et al., 1998; Zhang et al., 1999). In (I), one of the N-donor atoms of 4,4'-bipy is, however, engaged in intermolecular hydrogen bonding to a dihydrogenphosphate ligand of an adjacent complex (cf. Fig. 1). Without the protonated phosphate group, an extended copper–4,4'-bipy chain could have been envisioned, as found in [Cu(4,4'-bipy)(SO4)(H2O)3].2H2O and compounds with related bipyridine ligands (Hagrman et al., 1998). Hydrogen bonding from metal–aqua ligands to both N atoms of uncoordinated 4,4'-bipy molecules has been observed in [Co(4,4'-bipy)(H2O)4](PF6)2.(4,4'-bipy)3 (Dong et al., 2000), in [Mn(4,4'-bipy)2(H2O)4](ClO4)2.(4,4'-bipy)4 (Tong et al., 1999), and in a series of [M(4,4'-bipy)(H2O)m]X2.(4,4'-bipy)n compounds (M = Fe, Zn; m = 3, 4; X = ClO4, NO3, O3SCF3; n = 1, 1.5, 2; Carlucci et al., 1997). An example with metal coordination to one end of 4,4'-bipy and hydrogen bonding from an aqua ligand to the other end is [Cd2(4,4-bipy)5(H2O)4(NO3)2(PF6)2] (Dong et al., 2000). The pyridyl rings of the 4,4'-bipy molecules are non-coplanar and are twisted by interplanar angles of 30.6 (1) (rings with N1 and N2) and 22.6 (1)° (rings with N3 and N4).
The crystal packing is further controlled by hydrogen bonding among the phosphate ligands and between the aqua and phosphate ligands, as shown in Fig. 2. Hydrogen bonding between the phosphate ligands gives rise to a ring with inversion symmetry. The sole hydrogen-bond acceptor is the formally P═O double-bonded O atom. It accepts three hydrogen bonds, one intra- and two intermolecular. These hydrogen-bonding interactions create two-dimensional networks parallel to the xz plane, which then are connected by the bipyridine ligands. The crystal packing seems also to be influenced by π-stacking between the 4,4'-bipy ligands. They feature offset or slipped π–π interactions, with an interplanar separation of about 3.64 Å (Janiak, 2000). These latter packing interactions can be seen in Fig. 1.