The title complex, {[Cu
2(C
8H
4O
4)
2(C
3H
4N
2)
4(H
2O)]·H
2O}
n, is a three-dimensional polymer formed through bridging by phthalate dianions of two different Cu
II cations and a network of O(N)—H
O hydrogen bonds. The Cu—O and Cu—N interaction distances are in the ranges 2.0020 (16)–2.4835 (17) and 1.968 (2)–1.9855 (19) Å, respectively. The structure is composed of alternating polymer chains parallel to the
c axis, with a shortest Cu
Cu distance of 6.3000 (5) Å.
Supporting information
CCDC reference: 618602
Basic copper(II) carbonate (0.220 g, 1 mmol) was added to a solution of ophthalic acid (0.167 g, 1 mmol) and imidazole (0.14 g, 2 mmol) in water (15 ml). The resulting mixture was stirred and heated at 328 K for 30 min. Then, the resulting solution was cooled to room temperature and filtered. Blue single crystals were obtained from the filtrate after two weeks.
All the water and N-bound H atoms were located in difference Fourier maps and their positional parameters were refined with O—H and N—H distances restrained to 0.82 (2) and 0.86 (2) Å, respectively. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H bond lengths of 0.93 Å and Uiso(H) values of 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Poly[[aquatetraimidazoledi-µ
2-phthalato-dicopper(II)] monohydrate]
top
Crystal data top
[Cu2(C8H4O4)2(C3H4N2)4(H2O)]·H2O | F(000) = 1560 |
Mr = 763.66 | Dx = 1.649 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 9238 reflections |
a = 8.8863 (4) Å | θ = 2.2–26.6° |
b = 22.3787 (10) Å | µ = 1.45 mm−1 |
c = 16.1281 (7) Å | T = 292 K |
β = 106.470 (1)° | Irregular, blue |
V = 3075.7 (2) Å3 | 0.30 × 0.20 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 7066 independent reflections |
Radiation source: fine-focus sealed tube | 5531 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.670, Tmax = 0.893 | k = −28→29 |
35554 measured reflections | l = −20→20 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0519P)2] where P = (Fo2 + 2Fc2)/3 |
7066 reflections | (Δ/σ)max = 0.002 |
457 parameters | Δρmax = 0.50 e Å−3 |
10 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
[Cu2(C8H4O4)2(C3H4N2)4(H2O)]·H2O | V = 3075.7 (2) Å3 |
Mr = 763.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.8863 (4) Å | µ = 1.45 mm−1 |
b = 22.3787 (10) Å | T = 292 K |
c = 16.1281 (7) Å | 0.30 × 0.20 × 0.08 mm |
β = 106.470 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 7066 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 5531 reflections with I > 2σ(I) |
Tmin = 0.670, Tmax = 0.893 | Rint = 0.090 |
35554 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 10 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.50 e Å−3 |
7066 reflections | Δρmin = −0.43 e Å−3 |
457 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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.38368 (3) | 0.702231 (12) | 0.878265 (18) | 0.02598 (9) | |
N1 | 0.5591 (2) | 0.65009 (9) | 0.86917 (12) | 0.0274 (4) | |
N3 | 0.2021 (2) | 0.75450 (9) | 0.87043 (13) | 0.0317 (5) | |
O1 | 0.49842 (19) | 0.77613 (7) | 0.84819 (10) | 0.0281 (4) | |
O3 | 0.2610 (2) | 0.63140 (7) | 0.89838 (10) | 0.0322 (4) | |
Cu2 | 0.70144 (3) | 0.671128 (13) | 0.577869 (18) | 0.02993 (9) | |
N5 | 0.5240 (2) | 0.62074 (9) | 0.58464 (14) | 0.0341 (5) | |
N7 | 0.8775 (2) | 0.71926 (9) | 0.56451 (12) | 0.0306 (5) | |
O5 | −0.13405 (19) | 0.60632 (7) | 0.67299 (10) | 0.0327 (4) | |
O7 | 0.65465 (19) | 0.73412 (7) | 0.65622 (10) | 0.0287 (4) | |
O9 | 0.6681 (2) | 0.63837 (8) | 0.45539 (11) | 0.0352 (4) | |
H9A | 0.739 (3) | 0.6222 (12) | 0.4422 (18) | 0.053* | |
H9B | 0.635 (3) | 0.6648 (10) | 0.4201 (16) | 0.053* | |
C1 | 0.6547 (3) | 0.66159 (11) | 0.82204 (15) | 0.0320 (5) | |
H1 | 0.6618 | 0.6984 | 0.7967 | 0.038* | |
C2 | 0.6965 (3) | 0.56865 (12) | 0.85990 (18) | 0.0446 (7) | |
H2 | 0.7356 | 0.5299 | 0.8662 | 0.054* | |
C3 | 0.5854 (3) | 0.59150 (11) | 0.89289 (17) | 0.0380 (6) | |
H3 | 0.5343 | 0.5705 | 0.9267 | 0.046* | |
C4 | 0.2016 (3) | 0.80465 (12) | 0.91175 (18) | 0.0390 (6) | |
H4 | 0.2874 | 0.8198 | 0.9539 | 0.047* | |
C5 | −0.0332 (3) | 0.79600 (14) | 0.82388 (19) | 0.0488 (7) | |
H5 | −0.1375 | 0.8033 | 0.7939 | 0.059* | |
C6 | 0.0537 (3) | 0.74857 (13) | 0.81509 (17) | 0.0420 (7) | |
H6 | 0.0189 | 0.7167 | 0.7775 | 0.050* | |
C7 | 0.4273 (3) | 0.62872 (12) | 0.63158 (16) | 0.0330 (6) | |
H7 | 0.4303 | 0.6615 | 0.6675 | 0.040* | |
C8 | 0.3541 (5) | 0.54609 (15) | 0.5640 (3) | 0.0825 (14) | |
H8 | 0.3008 | 0.5108 | 0.5440 | 0.099* | |
C9 | 0.4752 (4) | 0.56878 (14) | 0.5413 (3) | 0.0760 (13) | |
H9 | 0.5202 | 0.5516 | 0.5016 | 0.091* | |
C10 | 1.0270 (3) | 0.71387 (12) | 0.60444 (16) | 0.0347 (6) | |
H10 | 1.0698 | 0.6843 | 0.6447 | 0.042* | |
C11 | 1.0095 (3) | 0.79167 (12) | 0.52102 (18) | 0.0440 (7) | |
H11 | 1.0347 | 0.8248 | 0.4927 | 0.053* | |
C12 | 0.8653 (3) | 0.76869 (13) | 0.51215 (18) | 0.0441 (7) | |
H12 | 0.7722 | 0.7839 | 0.4762 | 0.053* | |
C13 | 0.4505 (3) | 0.78165 (10) | 0.76600 (14) | 0.0246 (5) | |
C14 | 0.5001 (3) | 0.83598 (10) | 0.72686 (14) | 0.0273 (5) | |
C15 | 0.4891 (3) | 0.89181 (11) | 0.76187 (16) | 0.0371 (6) | |
H15 | 0.4555 | 0.8948 | 0.8113 | 0.045* | |
C16 | 0.5270 (4) | 0.94293 (12) | 0.7248 (2) | 0.0525 (8) | |
H16 | 0.5192 | 0.9802 | 0.7488 | 0.063* | |
C17 | 0.5762 (5) | 0.93809 (14) | 0.6521 (2) | 0.0659 (10) | |
H17 | 0.6038 | 0.9723 | 0.6271 | 0.079* | |
C18 | 0.5852 (4) | 0.88334 (13) | 0.6156 (2) | 0.0527 (8) | |
H18 | 0.6174 | 0.8811 | 0.5657 | 0.063* | |
C19 | −0.0015 (3) | 0.52635 (10) | 0.75601 (14) | 0.0247 (5) | |
C20 | 0.1022 (3) | 0.54924 (10) | 0.83137 (14) | 0.0257 (5) | |
C21 | 0.1268 (3) | 0.51692 (11) | 0.90732 (16) | 0.0356 (6) | |
H21 | 0.1923 | 0.5325 | 0.9583 | 0.043* | |
C22 | 0.0565 (3) | 0.46243 (12) | 0.90900 (18) | 0.0451 (7) | |
H22 | 0.0752 | 0.4415 | 0.9607 | 0.054* | |
C23 | −0.0410 (3) | 0.43879 (12) | 0.83460 (18) | 0.0450 (7) | |
H23 | −0.0867 | 0.4015 | 0.8354 | 0.054* | |
C24 | −0.0712 (3) | 0.47110 (11) | 0.75797 (17) | 0.0373 (6) | |
H24 | −0.1387 | 0.4555 | 0.7076 | 0.045* | |
C25 | 0.1949 (3) | 0.60498 (10) | 0.82795 (15) | 0.0261 (5) | |
C26 | −0.0498 (3) | 0.56143 (10) | 0.67332 (14) | 0.0258 (5) | |
C27 | 0.5476 (3) | 0.83174 (10) | 0.65162 (15) | 0.0304 (5) | |
C28 | 0.5676 (3) | 0.77355 (11) | 0.60908 (15) | 0.0282 (5) | |
N2 | 0.7395 (3) | 0.61428 (11) | 0.81527 (14) | 0.0389 (5) | |
H2A | 0.796 (3) | 0.6112 (14) | 0.7802 (17) | 0.058* | |
N4 | 0.0619 (3) | 0.83122 (11) | 0.88552 (16) | 0.0454 (6) | |
H4A | 0.037 (4) | 0.8644 (10) | 0.901 (2) | 0.068* | |
N6 | 0.3244 (3) | 0.58435 (11) | 0.62159 (16) | 0.0442 (6) | |
H6A | 0.259 (3) | 0.5815 (14) | 0.6514 (19) | 0.066* | |
N8 | 1.1098 (3) | 0.75650 (11) | 0.57973 (15) | 0.0403 (5) | |
H8A | 1.206 (2) | 0.7628 (14) | 0.6051 (19) | 0.060* | |
O2 | 0.36521 (19) | 0.74479 (7) | 0.71874 (10) | 0.0309 (4) | |
O4 | 0.2060 (2) | 0.62187 (8) | 0.75677 (10) | 0.0341 (4) | |
O6 | −0.0101 (2) | 0.54151 (8) | 0.60978 (11) | 0.0399 (4) | |
O8 | 0.5061 (2) | 0.76725 (8) | 0.53056 (11) | 0.0417 (4) | |
O10 | 0.0749 (2) | 0.42958 (8) | 0.55832 (12) | 0.0381 (4) | |
H10A | 0.051 (4) | 0.4349 (13) | 0.5062 (11) | 0.057* | |
H10B | 0.057 (4) | 0.4611 (10) | 0.5795 (16) | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.02530 (16) | 0.02619 (16) | 0.02868 (16) | −0.00059 (11) | 0.01127 (12) | −0.00183 (12) |
N1 | 0.0276 (11) | 0.0290 (11) | 0.0252 (10) | 0.0011 (8) | 0.0068 (8) | −0.0038 (8) |
N3 | 0.0294 (11) | 0.0358 (12) | 0.0322 (11) | 0.0026 (9) | 0.0127 (9) | −0.0021 (9) |
O1 | 0.0313 (9) | 0.0300 (9) | 0.0233 (8) | −0.0017 (7) | 0.0080 (7) | 0.0001 (7) |
O3 | 0.0346 (9) | 0.0346 (9) | 0.0281 (9) | −0.0074 (7) | 0.0099 (7) | −0.0036 (7) |
Cu2 | 0.02772 (17) | 0.03472 (18) | 0.03089 (17) | −0.00407 (12) | 0.01406 (13) | −0.00314 (12) |
N5 | 0.0321 (12) | 0.0334 (11) | 0.0411 (12) | −0.0036 (9) | 0.0176 (10) | −0.0058 (9) |
N7 | 0.0247 (11) | 0.0410 (12) | 0.0268 (11) | 0.0000 (9) | 0.0082 (8) | 0.0040 (9) |
O5 | 0.0293 (9) | 0.0384 (10) | 0.0323 (9) | 0.0103 (7) | 0.0119 (7) | 0.0088 (7) |
O7 | 0.0304 (9) | 0.0314 (9) | 0.0248 (8) | 0.0002 (7) | 0.0087 (7) | 0.0003 (7) |
O9 | 0.0357 (10) | 0.0450 (11) | 0.0249 (9) | 0.0073 (8) | 0.0088 (8) | 0.0015 (8) |
C1 | 0.0307 (13) | 0.0370 (14) | 0.0291 (13) | 0.0049 (11) | 0.0098 (11) | 0.0018 (10) |
C2 | 0.0473 (17) | 0.0349 (15) | 0.0525 (17) | 0.0114 (13) | 0.0158 (14) | 0.0015 (13) |
C3 | 0.0426 (16) | 0.0330 (14) | 0.0404 (15) | 0.0021 (12) | 0.0149 (12) | 0.0031 (11) |
C4 | 0.0362 (15) | 0.0374 (15) | 0.0447 (16) | 0.0007 (12) | 0.0136 (12) | −0.0082 (12) |
C5 | 0.0338 (16) | 0.0584 (19) | 0.0496 (18) | 0.0112 (14) | 0.0043 (13) | −0.0006 (15) |
C6 | 0.0357 (15) | 0.0516 (17) | 0.0375 (15) | 0.0008 (13) | 0.0087 (12) | −0.0113 (13) |
C7 | 0.0321 (14) | 0.0396 (14) | 0.0292 (13) | −0.0017 (11) | 0.0117 (11) | −0.0047 (11) |
C8 | 0.094 (3) | 0.049 (2) | 0.137 (4) | −0.039 (2) | 0.086 (3) | −0.045 (2) |
C9 | 0.089 (3) | 0.0497 (19) | 0.121 (3) | −0.0297 (19) | 0.082 (3) | −0.045 (2) |
C10 | 0.0318 (14) | 0.0433 (15) | 0.0283 (13) | 0.0024 (11) | 0.0075 (11) | 0.0037 (11) |
C11 | 0.0482 (17) | 0.0401 (16) | 0.0460 (17) | −0.0044 (13) | 0.0168 (14) | 0.0115 (13) |
C12 | 0.0306 (14) | 0.0556 (18) | 0.0435 (16) | 0.0032 (13) | 0.0062 (12) | 0.0202 (13) |
C13 | 0.0226 (12) | 0.0278 (12) | 0.0251 (12) | 0.0027 (9) | 0.0097 (10) | −0.0006 (9) |
C14 | 0.0253 (12) | 0.0290 (12) | 0.0255 (12) | 0.0005 (9) | 0.0039 (10) | 0.0024 (9) |
C15 | 0.0452 (16) | 0.0316 (13) | 0.0322 (14) | 0.0065 (11) | 0.0070 (12) | −0.0016 (11) |
C16 | 0.073 (2) | 0.0280 (14) | 0.0556 (19) | 0.0015 (14) | 0.0171 (17) | −0.0027 (13) |
C17 | 0.098 (3) | 0.0327 (17) | 0.079 (2) | −0.0069 (17) | 0.045 (2) | 0.0131 (16) |
C18 | 0.075 (2) | 0.0416 (17) | 0.0533 (19) | −0.0036 (15) | 0.0370 (17) | 0.0088 (14) |
C19 | 0.0255 (12) | 0.0237 (11) | 0.0275 (12) | 0.0027 (9) | 0.0119 (10) | 0.0005 (9) |
C20 | 0.0250 (12) | 0.0270 (12) | 0.0266 (12) | 0.0028 (9) | 0.0097 (10) | 0.0023 (9) |
C21 | 0.0354 (14) | 0.0396 (15) | 0.0307 (13) | −0.0005 (11) | 0.0076 (11) | 0.0063 (11) |
C22 | 0.0548 (18) | 0.0407 (16) | 0.0422 (16) | 0.0015 (13) | 0.0175 (14) | 0.0189 (13) |
C23 | 0.0558 (18) | 0.0298 (14) | 0.0514 (17) | −0.0084 (13) | 0.0183 (15) | 0.0085 (12) |
C24 | 0.0420 (15) | 0.0316 (14) | 0.0375 (14) | −0.0050 (11) | 0.0101 (12) | −0.0008 (11) |
C25 | 0.0224 (12) | 0.0285 (12) | 0.0281 (12) | 0.0029 (9) | 0.0086 (10) | 0.0010 (10) |
C26 | 0.0240 (12) | 0.0276 (12) | 0.0263 (12) | −0.0045 (9) | 0.0077 (10) | −0.0004 (9) |
C27 | 0.0332 (13) | 0.0304 (13) | 0.0276 (12) | 0.0006 (10) | 0.0083 (10) | 0.0025 (10) |
C28 | 0.0262 (12) | 0.0340 (13) | 0.0270 (13) | −0.0042 (10) | 0.0116 (10) | 0.0020 (10) |
N2 | 0.0371 (13) | 0.0471 (14) | 0.0364 (13) | 0.0099 (10) | 0.0168 (10) | 0.0003 (10) |
N4 | 0.0484 (15) | 0.0390 (14) | 0.0527 (15) | 0.0127 (11) | 0.0205 (12) | −0.0034 (11) |
N6 | 0.0422 (14) | 0.0420 (13) | 0.0595 (16) | −0.0089 (11) | 0.0323 (12) | −0.0081 (11) |
N8 | 0.0243 (11) | 0.0518 (14) | 0.0407 (13) | −0.0067 (10) | 0.0025 (10) | 0.0009 (11) |
O2 | 0.0301 (9) | 0.0327 (9) | 0.0297 (9) | −0.0069 (7) | 0.0085 (7) | −0.0047 (7) |
O4 | 0.0370 (10) | 0.0399 (10) | 0.0269 (9) | −0.0109 (8) | 0.0112 (8) | 0.0029 (7) |
O6 | 0.0553 (12) | 0.0398 (10) | 0.0285 (9) | 0.0047 (9) | 0.0181 (9) | −0.0011 (8) |
O8 | 0.0501 (11) | 0.0477 (11) | 0.0244 (9) | 0.0015 (9) | 0.0059 (8) | 0.0003 (8) |
O10 | 0.0492 (11) | 0.0300 (10) | 0.0361 (10) | 0.0012 (9) | 0.0136 (9) | 0.0038 (8) |
Geometric parameters (Å, º) top
Cu1—N3 | 1.968 (2) | C9—H9 | 0.9300 |
Cu1—N1 | 1.9855 (19) | C10—N8 | 1.333 (3) |
Cu1—O3 | 2.0020 (16) | C10—H10 | 0.9300 |
Cu1—O1 | 2.0712 (16) | C11—C12 | 1.350 (4) |
Cu1—O8i | 2.4835 (17) | C11—N8 | 1.354 (3) |
N1—C1 | 1.316 (3) | C11—H11 | 0.9300 |
N1—C3 | 1.367 (3) | C12—H12 | 0.9300 |
N3—C4 | 1.306 (3) | C13—O2 | 1.228 (3) |
N3—C6 | 1.373 (3) | C13—C14 | 1.493 (3) |
O1—C13 | 1.278 (3) | C14—C15 | 1.386 (3) |
O3—C25 | 1.267 (3) | C14—C27 | 1.396 (3) |
Cu2—N7 | 1.961 (2) | C15—C16 | 1.376 (4) |
Cu2—N5 | 1.967 (2) | C15—H15 | 0.9300 |
Cu2—O7 | 2.0137 (16) | C16—C17 | 1.366 (4) |
Cu2—O9 | 2.0483 (17) | C16—H16 | 0.9300 |
Cu2—O5ii | 2.3070 (16) | C17—C18 | 1.371 (4) |
N5—C7 | 1.308 (3) | C17—H17 | 0.9300 |
N5—C9 | 1.362 (4) | C18—C27 | 1.376 (4) |
N7—C10 | 1.307 (3) | C18—H18 | 0.9300 |
N7—C12 | 1.377 (3) | C19—C24 | 1.387 (3) |
O5—C26 | 1.252 (3) | C19—C20 | 1.398 (3) |
O5—Cu2iii | 2.3070 (16) | C19—C26 | 1.502 (3) |
O7—C28 | 1.273 (3) | C20—C21 | 1.385 (3) |
O9—H9A | 0.806 (16) | C20—C25 | 1.504 (3) |
O9—H9B | 0.817 (16) | C21—C22 | 1.374 (4) |
C1—N2 | 1.322 (3) | C21—H21 | 0.9300 |
C1—H1 | 0.9300 | C22—C23 | 1.372 (4) |
C2—C3 | 1.348 (4) | C22—H22 | 0.9300 |
C2—N2 | 1.365 (4) | C23—C24 | 1.391 (3) |
C2—H2 | 0.9300 | C23—H23 | 0.9300 |
C3—H3 | 0.9300 | C24—H24 | 0.9300 |
C4—N4 | 1.332 (3) | C25—O4 | 1.239 (3) |
C4—H4 | 0.9300 | C26—O6 | 1.256 (3) |
C5—C6 | 1.344 (4) | C27—C28 | 1.506 (3) |
C5—N4 | 1.359 (4) | C28—O8 | 1.237 (3) |
C5—H5 | 0.9300 | N2—H2A | 0.856 (17) |
C6—H6 | 0.9300 | N4—H4A | 0.833 (18) |
C7—N6 | 1.328 (3) | N6—H6A | 0.854 (18) |
C7—H7 | 0.9300 | N8—H8A | 0.851 (18) |
C8—C9 | 1.331 (4) | O10—H10A | 0.815 (16) |
C8—N6 | 1.343 (4) | O10—H10B | 0.817 (17) |
C8—H8 | 0.9300 | | |
| | | |
N3—Cu1—N1 | 172.39 (8) | C12—C11—H11 | 127.2 |
N3—Cu1—O3 | 90.38 (8) | N8—C11—H11 | 127.2 |
N1—Cu1—O3 | 91.25 (8) | C11—C12—N7 | 109.5 (2) |
N3—Cu1—O1 | 87.67 (8) | C11—C12—H12 | 125.2 |
N1—Cu1—O1 | 90.17 (7) | N7—C12—H12 | 125.2 |
O3—Cu1—O1 | 175.61 (6) | O2—C13—O1 | 123.0 (2) |
C1—N1—C3 | 105.2 (2) | O2—C13—C14 | 119.3 (2) |
C1—N1—Cu1 | 125.22 (17) | O1—C13—C14 | 117.8 (2) |
C3—N1—Cu1 | 128.19 (17) | C15—C14—C27 | 119.3 (2) |
C4—N3—C6 | 105.8 (2) | C15—C14—C13 | 119.9 (2) |
C4—N3—Cu1 | 126.84 (19) | C27—C14—C13 | 120.7 (2) |
C6—N3—Cu1 | 127.09 (17) | C16—C15—C14 | 121.2 (3) |
C13—O1—Cu1 | 106.19 (14) | C16—C15—H15 | 119.4 |
C25—O3—Cu1 | 111.06 (14) | C14—C15—H15 | 119.4 |
N7—Cu2—N5 | 176.65 (8) | C17—C16—C15 | 119.0 (3) |
N7—Cu2—O7 | 89.86 (8) | C17—C16—H16 | 120.5 |
N5—Cu2—O7 | 93.16 (7) | C15—C16—H16 | 120.5 |
N7—Cu2—O9 | 89.56 (8) | C16—C17—C18 | 120.7 (3) |
N5—Cu2—O9 | 87.10 (8) | C16—C17—H17 | 119.6 |
O7—Cu2—O9 | 148.94 (7) | C18—C17—H17 | 119.6 |
N7—Cu2—O5ii | 92.49 (7) | C17—C18—C27 | 121.2 (3) |
N5—Cu2—O5ii | 88.26 (8) | C17—C18—H18 | 119.4 |
O7—Cu2—O5ii | 103.15 (6) | C27—C18—H18 | 119.4 |
O9—Cu2—O5ii | 107.90 (7) | C24—C19—C20 | 119.7 (2) |
C7—N5—C9 | 104.3 (2) | C24—C19—C26 | 118.0 (2) |
C7—N5—Cu2 | 128.47 (18) | C20—C19—C26 | 122.2 (2) |
C9—N5—Cu2 | 127.18 (18) | C21—C20—C19 | 118.5 (2) |
C10—N7—C12 | 105.6 (2) | C21—C20—C25 | 121.0 (2) |
C10—N7—Cu2 | 128.77 (18) | C19—C20—C25 | 120.3 (2) |
C12—N7—Cu2 | 125.61 (17) | C22—C21—C20 | 121.5 (2) |
C26—O5—Cu2iii | 140.59 (15) | C22—C21—H21 | 119.3 |
C28—O7—Cu2 | 108.00 (14) | C20—C21—H21 | 119.3 |
Cu2—O9—H9A | 120 (2) | C23—C22—C21 | 120.2 (2) |
Cu2—O9—H9B | 110 (2) | C23—C22—H22 | 119.9 |
H9A—O9—H9B | 107 (2) | C21—C22—H22 | 119.9 |
N1—C1—N2 | 111.6 (2) | C22—C23—C24 | 119.4 (2) |
N1—C1—H1 | 124.2 | C22—C23—H23 | 120.3 |
N2—C1—H1 | 124.2 | C24—C23—H23 | 120.3 |
C3—C2—N2 | 105.7 (2) | C19—C24—C23 | 120.6 (2) |
C3—C2—H2 | 127.2 | C19—C24—H24 | 119.7 |
N2—C2—H2 | 127.2 | C23—C24—H24 | 119.7 |
C2—C3—N1 | 109.9 (2) | O4—C25—O3 | 123.3 (2) |
C2—C3—H3 | 125.1 | O4—C25—C20 | 118.4 (2) |
N1—C3—H3 | 125.1 | O3—C25—C20 | 118.2 (2) |
N3—C4—N4 | 111.1 (2) | O5—C26—O6 | 125.9 (2) |
N3—C4—H4 | 124.5 | O5—C26—C19 | 116.30 (19) |
N4—C4—H4 | 124.5 | O6—C26—C19 | 117.6 (2) |
C6—C5—N4 | 106.2 (2) | C18—C27—C14 | 118.6 (2) |
C6—C5—H5 | 126.9 | C18—C27—C28 | 117.3 (2) |
N4—C5—H5 | 126.9 | C14—C27—C28 | 124.0 (2) |
C5—C6—N3 | 109.3 (2) | O8—C28—O7 | 123.3 (2) |
C5—C6—H6 | 125.4 | O8—C28—C27 | 119.3 (2) |
N3—C6—H6 | 125.4 | O7—C28—C27 | 117.2 (2) |
N5—C7—N6 | 111.7 (2) | C1—N2—C2 | 107.7 (2) |
N5—C7—H7 | 124.1 | C1—N2—H2A | 125 (2) |
N6—C7—H7 | 124.1 | C2—N2—H2A | 126 (2) |
C9—C8—N6 | 106.2 (3) | C4—N4—C5 | 107.7 (2) |
C9—C8—H8 | 126.9 | C4—N4—H4A | 127 (3) |
N6—C8—H8 | 126.9 | C5—N4—H4A | 125 (2) |
C8—C9—N5 | 110.4 (3) | C7—N6—C8 | 107.3 (2) |
C8—C9—H9 | 124.8 | C7—N6—H6A | 123 (2) |
N5—C9—H9 | 124.8 | C8—N6—H6A | 130 (2) |
N7—C10—N8 | 110.9 (2) | C10—N8—C11 | 108.4 (2) |
N7—C10—H10 | 124.5 | C10—N8—H8A | 123 (2) |
N8—C10—H10 | 124.5 | C11—N8—H8A | 128 (2) |
C12—C11—N8 | 105.6 (2) | H10A—O10—H10B | 106 (2) |
| | | |
O3—Cu1—N1—C1 | 149.9 (2) | O1—C13—C14—C15 | −46.7 (3) |
O1—Cu1—N1—C1 | −26.0 (2) | O2—C13—C14—C27 | −42.9 (3) |
O3—Cu1—N1—C3 | −14.6 (2) | O1—C13—C14—C27 | 137.7 (2) |
O1—Cu1—N1—C3 | 169.6 (2) | C27—C14—C15—C16 | −1.3 (4) |
O3—Cu1—N3—C4 | 129.9 (2) | C13—C14—C15—C16 | −176.9 (2) |
O1—Cu1—N3—C4 | −54.1 (2) | C14—C15—C16—C17 | 0.0 (5) |
O3—Cu1—N3—C6 | −56.3 (2) | C15—C16—C17—C18 | 1.1 (5) |
O1—Cu1—N3—C6 | 119.7 (2) | C16—C17—C18—C27 | −1.0 (6) |
N3—Cu1—O1—C13 | −81.68 (15) | C24—C19—C20—C21 | −2.9 (3) |
N1—Cu1—O1—C13 | 91.02 (14) | C26—C19—C20—C21 | 172.7 (2) |
N3—Cu1—O3—C25 | 93.33 (16) | C24—C19—C20—C25 | 171.9 (2) |
N1—Cu1—O3—C25 | −79.24 (16) | C26—C19—C20—C25 | −12.4 (3) |
O7—Cu2—N5—C7 | −4.5 (2) | C19—C20—C21—C22 | 2.5 (4) |
O9—Cu2—N5—C7 | −153.4 (2) | C25—C20—C21—C22 | −172.3 (2) |
O5ii—Cu2—N5—C7 | 98.5 (2) | C20—C21—C22—C23 | −0.3 (4) |
O7—Cu2—N5—C9 | 176.2 (3) | C21—C22—C23—C24 | −1.5 (4) |
O9—Cu2—N5—C9 | 27.3 (3) | C20—C19—C24—C23 | 1.2 (4) |
O5ii—Cu2—N5—C9 | −80.8 (3) | C26—C19—C24—C23 | −174.7 (2) |
O7—Cu2—N7—C10 | 98.8 (2) | C22—C23—C24—C19 | 1.1 (4) |
O9—Cu2—N7—C10 | −112.3 (2) | Cu1—O3—C25—O4 | −0.3 (3) |
O5ii—Cu2—N7—C10 | −4.4 (2) | Cu1—O3—C25—C20 | 177.78 (15) |
O7—Cu2—N7—C12 | −77.9 (2) | C21—C20—C25—O4 | 158.1 (2) |
O9—Cu2—N7—C12 | 71.0 (2) | C19—C20—C25—O4 | −16.7 (3) |
O5ii—Cu2—N7—C12 | 178.9 (2) | C21—C20—C25—O3 | −20.1 (3) |
N7—Cu2—O7—C28 | 85.36 (15) | C19—C20—C25—O3 | 165.2 (2) |
N5—Cu2—O7—C28 | −93.17 (15) | Cu2iii—O5—C26—O6 | 12.6 (4) |
O9—Cu2—O7—C28 | −3.5 (2) | Cu2iii—O5—C26—C19 | −163.10 (16) |
O5ii—Cu2—O7—C28 | 177.89 (14) | C24—C19—C26—O5 | 107.4 (3) |
C3—N1—C1—N2 | −0.4 (3) | C20—C19—C26—O5 | −68.3 (3) |
Cu1—N1—C1—N2 | −167.82 (16) | C24—C19—C26—O6 | −68.6 (3) |
N2—C2—C3—N1 | 0.2 (3) | C20—C19—C26—O6 | 115.6 (2) |
C1—N1—C3—C2 | 0.1 (3) | C17—C18—C27—C14 | −0.3 (5) |
Cu1—N1—C3—C2 | 167.01 (19) | C17—C18—C27—C28 | −177.5 (3) |
C6—N3—C4—N4 | −0.5 (3) | C15—C14—C27—C18 | 1.4 (4) |
Cu1—N3—C4—N4 | 174.41 (18) | C13—C14—C27—C18 | 177.0 (2) |
N4—C5—C6—N3 | −0.4 (3) | C15—C14—C27—C28 | 178.4 (2) |
C4—N3—C6—C5 | 0.6 (3) | C13—C14—C27—C28 | −6.0 (4) |
Cu1—N3—C6—C5 | −174.31 (19) | Cu2—O7—C28—O8 | 10.1 (3) |
C9—N5—C7—N6 | 1.5 (3) | Cu2—O7—C28—C27 | −166.44 (16) |
Cu2—N5—C7—N6 | −177.95 (19) | C18—C27—C28—O8 | −52.5 (3) |
N6—C8—C9—N5 | 0.7 (5) | C14—C27—C28—O8 | 130.5 (3) |
C7—N5—C9—C8 | −1.3 (4) | C18—C27—C28—O7 | 124.2 (3) |
Cu2—N5—C9—C8 | 178.1 (3) | C14—C27—C28—O7 | −52.8 (3) |
C12—N7—C10—N8 | −0.7 (3) | N1—C1—N2—C2 | 0.6 (3) |
Cu2—N7—C10—N8 | −177.85 (17) | C3—C2—N2—C1 | −0.5 (3) |
N8—C11—C12—N7 | −0.6 (3) | N3—C4—N4—C5 | 0.2 (3) |
C10—N7—C12—C11 | 0.8 (3) | C6—C5—N4—C4 | 0.1 (3) |
Cu2—N7—C12—C11 | 178.12 (19) | N5—C7—N6—C8 | −1.1 (4) |
Cu1—O1—C13—O2 | −6.4 (3) | C9—C8—N6—C7 | 0.2 (5) |
Cu1—O1—C13—C14 | 172.95 (15) | N7—C10—N8—C11 | 0.3 (3) |
O2—C13—C14—C15 | 132.6 (2) | C12—C11—N8—C10 | 0.2 (3) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9A···O10iv | 0.81 (3) | 2.02 (3) | 2.804 (3) | 164 (3) |
O9—H9B···O1v | 0.82 (2) | 1.94 (2) | 2.729 (2) | 162 (3) |
N2—H2A···O5ii | 0.86 (3) | 2.00 (3) | 2.832 (3) | 163 (3) |
N4—H4A···O10vi | 0.83 (3) | 1.98 (3) | 2.787 (3) | 163 (3) |
N6—H6A···O4 | 0.85 (3) | 2.09 (2) | 2.805 (3) | 140 (3) |
N6—H6A···O6 | 0.85 (3) | 2.46 (3) | 3.078 (3) | 130 (3) |
N8—H8A···O2ii | 0.85 (2) | 2.01 (2) | 2.713 (3) | 139 (3) |
O10—H10A···O6vii | 0.82 (2) | 1.88 (2) | 2.686 (2) | 171 (3) |
O10—H10B···O6 | 0.82 (2) | 2.00 (2) | 2.809 (3) | 170 (3) |
Symmetry codes: (ii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) x, −y+3/2, z−1/2; (vi) −x, y+1/2, −z+3/2; (vii) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Cu2(C8H4O4)2(C3H4N2)4(H2O)]·H2O |
Mr | 763.66 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 292 |
a, b, c (Å) | 8.8863 (4), 22.3787 (10), 16.1281 (7) |
β (°) | 106.470 (1) |
V (Å3) | 3075.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.30 × 0.20 × 0.08 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.670, 0.893 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35554, 7066, 5531 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.096, 0.95 |
No. of reflections | 7066 |
No. of parameters | 457 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.50, −0.43 |
Selected geometric parameters (Å, º) topCu1—N3 | 1.968 (2) | Cu2—N7 | 1.961 (2) |
Cu1—N1 | 1.9855 (19) | Cu2—N5 | 1.967 (2) |
Cu1—O3 | 2.0020 (16) | Cu2—O7 | 2.0137 (16) |
Cu1—O1 | 2.0712 (16) | Cu2—O9 | 2.0483 (17) |
Cu1—O8i | 2.4835 (17) | Cu2—O5ii | 2.3070 (16) |
O1—C13 | 1.278 (3) | O5—C26 | 1.252 (3) |
O3—C25 | 1.267 (3) | O7—C28 | 1.273 (3) |
| | | |
N3—Cu1—N1 | 172.39 (8) | N5—Cu2—O7 | 93.16 (7) |
N3—Cu1—O3 | 90.38 (8) | N5—Cu2—O9 | 87.10 (8) |
N3—Cu1—O1 | 87.67 (8) | N7—Cu2—O5ii | 92.49 (7) |
O3—Cu1—O1 | 175.61 (6) | N5—Cu2—O5ii | 88.26 (8) |
N7—Cu2—N5 | 176.65 (8) | | |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9A···O10iii | 0.81 (3) | 2.02 (3) | 2.804 (3) | 164 (3) |
O9—H9B···O1iv | 0.82 (2) | 1.94 (2) | 2.729 (2) | 162 (3) |
N2—H2A···O5ii | 0.86 (3) | 2.00 (3) | 2.832 (3) | 163 (3) |
N4—H4A···O10v | 0.83 (3) | 1.98 (3) | 2.787 (3) | 163 (3) |
N6—H6A···O4 | 0.85 (3) | 2.09 (2) | 2.805 (3) | 140 (3) |
N6—H6A···O6 | 0.85 (3) | 2.46 (3) | 3.078 (3) | 130 (3) |
N8—H8A···O2ii | 0.85 (2) | 2.01 (2) | 2.713 (3) | 139 (3) |
O10—H10A···O6vi | 0.815 (18) | 1.878 (18) | 2.686 (2) | 171 (3) |
O10—H10B···O6 | 0.82 (2) | 2.00 (2) | 2.809 (3) | 170 (3) |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z−1/2; (v) −x, y+1/2, −z+3/2; (vi) −x, −y+1, −z+1. |
There has been considerable interest in the design and synthesis of transition metal complexes with carboxylate ligands in coordination chemistry, owing to the fact that this type complex has potential applications in molecular-based magnets, catalysis, supramolecular chemistry and biological systems (Li et al., 2002; Shi et al., 2000; Devereux et al., 2000). It is known that the phthalate dianion is a versatile ligand able to chelate to, as well as bridge, metal ions. The variety of its coordination modes provides the possibility of preparing new metal phthalates with diverse topological structures and interesting physical properties (Biagini Cingi et al., 1979; Squire et al., 1995; Whitcomb & Rogers, 1997).
Several structures of CuII complexes with the phthalate ligand (pht) have been reported, viz. [Cu(pht)(4-MeIm)2(H2O)]n (4-MeIm is 4-methylimidazole; Baca, Filippova et al., 2004 or Baca, Malinovskii et al., 2004), [Cu(pht)(phen)2(H2O)]n.nH2O (phen is 1,10-phenanthroline; Ye et al., 2005), [CuNa2(pht)2(H2O)2]n (Liu et al., 2003), [Cu(pht)(1-MeIm)2]n (Baca, Filippova et al., 2004 or Baca, Malinovskii et al., 2004) and [Cu(pht)2(pic)4(H2O)] (pic is 4-methylpyridine; Gerbeleu et al., 1999). In these structures, the CuII ions are all found to have the same stereochemistry. In only one structure, to the best of our knowledge, have different CuII coordination sites been found, namely [(Cudien)2(Cudien·H2O)TCB(ClO4)2·H2O]n (TCB is tetracarboxylatobenzene; dien is 3-azapentane-1,5-diamine; Zou et al., 1998). We report here another novel three-dimensional copper phthalate, {[Cu2(pht)2(Im)4(H2O)]·H2O}n, (I), in which two different copper(II) environments are observed.
The molecular structure of (I) (Fig 1 and Table 1) can be described as a three-dimensional network of CuII ions, which are linked by phthalate dianions into columns, lying approximately parallel to the c axis, cross-linked by an extensive network of hydrogen bonds including water molecules of crystallization (Fig 2 and Table 2).
The Cu1II ion adopts a distorted square-pyramidal N2O3 environment, with the basal plane defined by atoms O1 and O3 from two phthalate ligands, and atoms N1 and N3 from two imidazole ligands, and with a long Cu—O8(carboxylate)i apical interaction (Table 1). The Cu2II ion is also coordinated in a square-pyramidal geometry, in this case by two imidazole ligands (N5 and N7), a phthalate ligand (O7) and a water molecule (O9) in the basal plane, with the apical position occupied by carboxylate atom O5. The equatorial Cu—N, Cu—O(pht) and Cu—O(water) distances are in agreement with the corresponding distances observed in [Cu(pht)(4-MeIm)2(H2O)]n (Baca, Filippova et al., 2004 or Baca, Malinovskii et al., 2004) and [Cu(pht)2(pic)4(H2O)] (Gerbeleu et al., 1999). The axial Cu2—O5 distance is longer than that in the related complex [Cu(pht)2(pic)4(H2O)] [2.240 (4) Å; Gerbeleu et al., 1999] but shorter than that in [Cu(pht)(4-MeIm)2(H2O)]n [2.353 (2) Å; Baca, Filippova et al., 2004 or Baca, Malinovskii et al., 2004]. The C—O bond distances of the carboxylate groups are normal, with coordinated C—O bond distances slightly longer [0.004 (3)–0.050 (3) Å] than the uncoordinated C—O bond distances.
Each phthalate dianion acts as a bidentate ligand, bridging two different CuII ions through O atoms from both carboxylate groups (1,6-bridging mode). Based on this coordination mode of phthalate including the weak interaction between the atoms Cu1 and O8, an infinite polymeric network is formed parallel to the c axis (Fig. 2), with a shortest inter-column Cu—Cu distance of 6.3005 (5) Å. All available H atoms are involved in the hydrogen-bond interactions (Table 2). The coordinated and solvent water molecules (atoms O9 and O10), and uncoordinated imidazole N atoms (atoms N2, N4, N6 and N8) are linked through hydrogen bonds to uncoordinated carboxylate O atoms (atoms O2, O4 and O6). Thus the alternating infinite chains are linked to each other through these hydrogen-bond interactions to form a stable three-dimensional coordination polymer.