Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034253/hg2260sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034253/hg2260Isup2.hkl |
CCDC reference: 657595
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.037
- wR factor = 0.106
- Data-to-parameter ratio = 14.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.75 mm PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 600 Deg. PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.10 PLAT480_ALERT_4_C Long H...A H-Bond Reported H2WB .. O5 .. 2.62 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6 PLAT731_ALERT_1_C Bond Calc 0.84(4), Rep 0.842(18) ...... 2.22 su-Ra O1W -H1WB 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.850(18) ...... 2.22 su-Ra O2W -H2WB 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.84(4), Rep 0.842(18) ...... 2.22 su-Ra O1W -H2# 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.850(18) ...... 2.22 su-Ra O2W -H3# 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.850(18) ...... 2.22 su-Ra O2W -H3# 1.555 1.555
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.11 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 15
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Li et al. (1997); Rodriguez-Martin et al. (2001); Simpson et al. (1963).
Copper malonate (Li et al., 1997) and Z-1,2-dipyridylethylene-bis-N-oxide were prepared via published procedures (Simpson et al., 1963). Copper malonate (202 mg, 1.0 mmol) was dissolved in 30 ml H2O. To this solution was added a solution of Z-1,2-dipyridylethylene-bis-N-oxide (107 mg, 0.5 mmol) in 10 ml e thanol. The mixture was then heated under autogenous pressure at 373 K for 5 min. Large green blocks of the title compound were isolated after cooling and standing for 7 d.
All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 (2) Å and refined in riding mode with Uiso = 1.2Ueq(C). All H atoms bound to O atoms were placed in calculated positions. The H atoms bound to O were found via Fourier difference map, restrained with O—H = 0.89 (2) Å, and refined with Uiso = 1.2Ueq(N).
The title compound was prepared during an attempt to synthesize a copper malonate coordination polymer incorporating Z-1,2-di-4-pyridylethylene-bis-N-oxide (bpeno), inspired by a report of the ferromagnetically coupled two-dimensional material [Cu2(malonate)2(H2O)2(4,4'-bipyridine)] (Rodriguez-Martin et al., 2001). Its asymmetric unit consists of a single [Cu(malonate)(bpeno)(H2O)2] molecule along with three water molecules of crystallization (Figure 1). The bond distances about the Cu atom are consistent with a "4 + 1" Jahn-Teller distorted square pyramidal coordination sphere (Table 1). The ligated water molecules are oriented in a cis fashion with respect to each other; one (O8) lies in the axial position of the square pyramid while the other (O7) rests in the equatorial plane. The oxygen donor atom belonging to the pendant, monodentate bpeno is oriented cis to both aqua ligands. The malonate ligand serves only as a chelating ligand to a single Cu atom.
Individual [Cu(malonate)(bpeno)(H2O)2] molecules aggregate into pairs through O—H···O hydrogen bonding between aqua ligands (O8) and the unligated oxygen atom of the monodentate bpeno ligands (O2) as well as π-π stacking between bpeno pyridyl rings. In turn, these form one-dimensional supramolecular chains through O—H···O hydrogen bonding between aquo ligands (O7) and unligated malonate oxygen atoms (O6). These further aggregate into pseudo two-dimensional layers (Figure 2) that course parallel to the bc crystallographic planes, through hydrogen bonding between the water molecules of crystallization and aquo ligands (O8) and unligated malonate oxygen atoms (O6). The water molecules of crystallization form discrete trimeric units. The pseudo two-dimensional layers stack into the three-dimensional crystal structure of I through additional hydrogen bonding patterns. Metrical parameters for the supramolecular interactions are given in Table 2.
For related literature, see: Li et al. (1997); Rodriguez-Martin et al. (2001); Simpson et al. (1963).
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: SHELXL97.
[Cu(C3H2O4)(C12H10N2O2)(H2O)2]·3H2O | Z = 2 |
Mr = 469.89 | F(000) = 486 |
Triclinic, P1 | Dx = 1.623 Mg m−3 |
a = 7.526 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.781 (4) Å | Cell parameters from 10713 reflections |
c = 12.723 (5) Å | θ = 1.8–28.2° |
α = 111.701 (6)° | µ = 1.20 mm−1 |
β = 99.270 (6)° | T = 293 K |
γ = 106.219 (6)° | Block, green |
V = 961.2 (6) Å3 | 0.75 × 0.12 × 0.12 mm |
Bruker SMART 1 K diffractometer | 4273 independent reflections |
Radiation source: fine-focus sealed tube | 3606 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 28.2°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.635, Tmax = 0.866 | k = −15→14 |
10713 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.057P)2 + 0.2918P] where P = (Fo2 + 2Fc2)/3 |
4273 reflections | (Δ/σ)max = 0.001 |
292 parameters | Δρmax = 0.57 e Å−3 |
15 restraints | Δρmin = −0.41 e Å−3 |
[Cu(C3H2O4)(C12H10N2O2)(H2O)2]·3H2O | γ = 106.219 (6)° |
Mr = 469.89 | V = 961.2 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.526 (3) Å | Mo Kα radiation |
b = 11.781 (4) Å | µ = 1.20 mm−1 |
c = 12.723 (5) Å | T = 293 K |
α = 111.701 (6)° | 0.75 × 0.12 × 0.12 mm |
β = 99.270 (6)° |
Bruker SMART 1 K diffractometer | 4273 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3606 reflections with I > 2σ(I) |
Tmin = 0.635, Tmax = 0.866 | Rint = 0.034 |
10713 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 15 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.57 e Å−3 |
4273 reflections | Δρmin = −0.41 e Å−3 |
292 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.08675 (4) | −0.18865 (2) | 0.66333 (2) | 0.03131 (11) | |
O1 | 0.2763 (2) | −0.02081 (15) | 0.78449 (16) | 0.0368 (4) | |
O1W | 0.7376 (3) | 0.1511 (2) | 0.5214 (3) | 0.0659 (7) | |
H1WA | 0.617 (3) | 0.139 (4) | 0.510 (4) | 0.079* | |
H1WB | 0.755 (5) | 0.085 (3) | 0.525 (4) | 0.079* | |
O2 | 0.3440 (3) | 1.08288 (16) | 1.16265 (19) | 0.0479 (5) | |
O2W | 0.8976 (4) | 0.4226 (2) | 0.6538 (2) | 0.0615 (6) | |
H2WB | 0.952 (5) | 0.455 (3) | 0.612 (3) | 0.074* | |
H2WA | 0.862 (6) | 0.3382 (18) | 0.615 (3) | 0.074* | |
O3 | −0.0695 (3) | −0.10789 (16) | 0.60478 (17) | 0.0387 (4) | |
O3W | 0.6847 (3) | 0.5529 (2) | 0.76154 (17) | 0.0512 (5) | |
H3WB | 0.573 (3) | 0.539 (3) | 0.718 (3) | 0.061* | |
H3WA | 0.742 (4) | 0.503 (3) | 0.724 (3) | 0.061* | |
O4 | −0.3436 (3) | −0.10490 (17) | 0.51713 (16) | 0.0405 (4) | |
O5 | −0.0721 (2) | −0.36467 (15) | 0.54332 (15) | 0.0346 (4) | |
O6 | −0.3333 (3) | −0.50656 (16) | 0.39468 (16) | 0.0425 (4) | |
O7 | 0.2857 (3) | −0.25608 (17) | 0.70707 (17) | 0.0394 (4) | |
H7A | 0.288 (4) | −0.330 (2) | 0.659 (2) | 0.047* | |
H7B | 0.399 (3) | −0.198 (2) | 0.746 (2) | 0.047* | |
O8 | −0.0726 (3) | −0.1970 (2) | 0.80628 (19) | 0.0457 (5) | |
H8A | −0.153 (4) | −0.155 (3) | 0.817 (3) | 0.055* | |
H8B | −0.153 (4) | −0.275 (2) | 0.795 (3) | 0.055* | |
N1 | 0.2473 (3) | 0.09267 (17) | 0.80976 (17) | 0.0297 (4) | |
N2 | 0.3096 (3) | 0.95500 (18) | 1.1263 (2) | 0.0359 (5) | |
C1 | 0.2451 (4) | 0.1434 (2) | 0.7312 (2) | 0.0381 (6) | |
H1 | 0.2506 | 0.0948 | 0.6541 | 0.046* | |
C2 | 0.2349 (4) | 0.2655 (2) | 0.7624 (2) | 0.0396 (6) | |
H2 | 0.2323 | 0.3003 | 0.7059 | 0.047* | |
C3 | 0.2283 (4) | 0.3391 (2) | 0.8746 (2) | 0.0312 (5) | |
C4 | 0.2247 (4) | 0.2804 (2) | 0.9519 (2) | 0.0356 (5) | |
H4 | 0.2161 | 0.3259 | 1.0289 | 0.043* | |
C5 | 0.2334 (4) | 0.1579 (2) | 0.9179 (2) | 0.0356 (5) | |
H5 | 0.2296 | 0.1188 | 0.9712 | 0.043* | |
C6 | 0.2314 (4) | 0.4725 (2) | 0.9081 (2) | 0.0357 (5) | |
H6 | 0.2235 | 0.5019 | 0.8479 | 0.043* | |
C7 | 0.2444 (4) | 0.5558 (2) | 1.0156 (2) | 0.0328 (5) | |
H7 | 0.2447 | 0.5246 | 1.0746 | 0.039* | |
C8 | 0.2975 (4) | 0.9014 (2) | 1.2024 (2) | 0.0426 (6) | |
H8 | 0.3059 | 0.9539 | 1.2818 | 0.051* | |
C9 | 0.2728 (4) | 0.7710 (2) | 1.1669 (2) | 0.0383 (6) | |
H9 | 0.2656 | 0.7348 | 1.2223 | 0.046* | |
C10 | 0.2583 (3) | 0.6916 (2) | 1.0509 (2) | 0.0302 (5) | |
C11 | 0.2640 (4) | 0.7503 (2) | 0.9737 (2) | 0.0388 (6) | |
H11 | 0.2491 | 0.6991 | 0.8928 | 0.047* | |
C12 | 0.2907 (4) | 0.8806 (2) | 1.0125 (2) | 0.0401 (6) | |
H12 | 0.2959 | 0.9188 | 0.9585 | 0.048* | |
C13 | −0.2471 (3) | −0.1632 (2) | 0.54898 (19) | 0.0283 (5) | |
C14 | −0.3532 (3) | −0.3063 (2) | 0.5211 (2) | 0.0339 (5) | |
H14A | −0.3874 | −0.3089 | 0.5924 | 0.041* | |
H14B | −0.4760 | −0.3409 | 0.4575 | 0.041* | |
C15 | −0.2454 (3) | −0.3987 (2) | 0.4829 (2) | 0.0290 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03120 (17) | 0.01942 (15) | 0.03551 (18) | 0.01190 (11) | 0.00088 (12) | 0.00577 (12) |
O1 | 0.0372 (9) | 0.0175 (7) | 0.0463 (10) | 0.0139 (7) | 0.0017 (7) | 0.0057 (7) |
O1W | 0.0503 (13) | 0.0477 (13) | 0.1030 (19) | 0.0219 (11) | 0.0188 (13) | 0.0354 (13) |
O2 | 0.0389 (10) | 0.0188 (8) | 0.0728 (13) | 0.0125 (7) | 0.0051 (9) | 0.0096 (9) |
O2W | 0.0680 (15) | 0.0591 (14) | 0.0599 (14) | 0.0263 (13) | 0.0297 (12) | 0.0219 (12) |
O3 | 0.0340 (9) | 0.0234 (8) | 0.0532 (11) | 0.0110 (7) | 0.0022 (8) | 0.0151 (8) |
O3W | 0.0559 (13) | 0.0497 (12) | 0.0379 (11) | 0.0215 (10) | 0.0057 (9) | 0.0106 (9) |
O4 | 0.0445 (10) | 0.0365 (9) | 0.0466 (10) | 0.0237 (8) | 0.0083 (8) | 0.0202 (8) |
O5 | 0.0316 (9) | 0.0234 (8) | 0.0413 (9) | 0.0136 (7) | 0.0029 (7) | 0.0071 (7) |
O6 | 0.0404 (10) | 0.0225 (8) | 0.0453 (10) | 0.0125 (7) | −0.0002 (8) | −0.0003 (8) |
O7 | 0.0346 (9) | 0.0238 (8) | 0.0479 (10) | 0.0148 (7) | 0.0008 (8) | 0.0051 (8) |
O8 | 0.0414 (11) | 0.0498 (12) | 0.0553 (12) | 0.0237 (9) | 0.0181 (9) | 0.0262 (10) |
N1 | 0.0293 (10) | 0.0178 (8) | 0.0357 (10) | 0.0092 (7) | 0.0043 (8) | 0.0070 (8) |
N2 | 0.0310 (10) | 0.0189 (9) | 0.0484 (12) | 0.0107 (8) | 0.0044 (9) | 0.0070 (9) |
C1 | 0.0545 (16) | 0.0245 (11) | 0.0309 (12) | 0.0141 (11) | 0.0143 (11) | 0.0074 (10) |
C2 | 0.0603 (17) | 0.0276 (12) | 0.0327 (12) | 0.0153 (12) | 0.0151 (12) | 0.0154 (10) |
C3 | 0.0382 (13) | 0.0204 (10) | 0.0315 (12) | 0.0116 (9) | 0.0074 (10) | 0.0082 (9) |
C4 | 0.0528 (15) | 0.0268 (12) | 0.0304 (12) | 0.0200 (11) | 0.0136 (11) | 0.0117 (10) |
C5 | 0.0471 (15) | 0.0287 (12) | 0.0334 (12) | 0.0163 (11) | 0.0096 (11) | 0.0152 (10) |
C6 | 0.0472 (15) | 0.0251 (11) | 0.0364 (13) | 0.0154 (10) | 0.0098 (11) | 0.0146 (10) |
C7 | 0.0442 (14) | 0.0223 (11) | 0.0336 (12) | 0.0135 (10) | 0.0097 (10) | 0.0140 (10) |
C8 | 0.0516 (16) | 0.0280 (12) | 0.0391 (14) | 0.0154 (11) | 0.0129 (12) | 0.0050 (11) |
C9 | 0.0510 (16) | 0.0257 (12) | 0.0368 (13) | 0.0142 (11) | 0.0146 (11) | 0.0116 (10) |
C10 | 0.0306 (12) | 0.0228 (11) | 0.0343 (12) | 0.0103 (9) | 0.0074 (9) | 0.0102 (9) |
C11 | 0.0554 (16) | 0.0270 (12) | 0.0322 (12) | 0.0185 (11) | 0.0086 (11) | 0.0106 (10) |
C12 | 0.0488 (15) | 0.0287 (12) | 0.0429 (14) | 0.0155 (11) | 0.0058 (12) | 0.0182 (11) |
C13 | 0.0372 (13) | 0.0255 (11) | 0.0249 (10) | 0.0171 (9) | 0.0111 (9) | 0.0092 (9) |
C14 | 0.0299 (12) | 0.0257 (11) | 0.0417 (13) | 0.0127 (9) | 0.0088 (10) | 0.0093 (10) |
C15 | 0.0340 (12) | 0.0204 (10) | 0.0344 (12) | 0.0118 (9) | 0.0101 (10) | 0.0125 (9) |
Cu1—O3 | 1.9263 (17) | C1—C2 | 1.372 (3) |
Cu1—O5 | 1.9357 (17) | C1—H1 | 0.9500 |
Cu1—O1 | 1.9450 (17) | C2—C3 | 1.387 (3) |
Cu1—O7 | 1.9766 (18) | C2—H2 | 0.9500 |
Cu1—O8 | 2.350 (2) | C3—C4 | 1.395 (3) |
O1—N1 | 1.344 (2) | C3—C6 | 1.461 (3) |
O1W—H1WA | 0.857 (18) | C4—C5 | 1.369 (3) |
O1W—H1WB | 0.842 (18) | C4—H4 | 0.9500 |
O2—N2 | 1.334 (2) | C5—H5 | 0.9500 |
O2W—H2WB | 0.850 (18) | C6—C7 | 1.324 (3) |
O2W—H2WA | 0.866 (18) | C6—H6 | 0.9500 |
O3—C13 | 1.257 (3) | C7—C10 | 1.460 (3) |
O3W—H3WB | 0.861 (18) | C7—H7 | 0.9500 |
O3W—H3WA | 0.871 (17) | C8—C9 | 1.379 (3) |
O4—C13 | 1.246 (3) | C8—H8 | 0.9500 |
O5—C15 | 1.268 (3) | C9—C10 | 1.391 (3) |
O6—C15 | 1.245 (3) | C9—H9 | 0.9500 |
O7—H7A | 0.867 (17) | C10—C11 | 1.395 (3) |
O7—H7B | 0.852 (17) | C11—C12 | 1.369 (3) |
O8—H8A | 0.881 (17) | C11—H11 | 0.9500 |
O8—H8B | 0.889 (17) | C12—H12 | 0.9500 |
N1—C1 | 1.341 (3) | C13—C14 | 1.524 (3) |
N1—C5 | 1.343 (3) | C14—C15 | 1.519 (3) |
N2—C8 | 1.339 (4) | C14—H14A | 0.9900 |
N2—C12 | 1.346 (3) | C14—H14B | 0.9900 |
O3—Cu1—O5 | 93.99 (8) | C5—C4—H4 | 119.7 |
O3—Cu1—O1 | 93.20 (8) | C3—C4—H4 | 119.7 |
O5—Cu1—O1 | 171.90 (7) | N1—C5—C4 | 120.4 (2) |
O3—Cu1—O7 | 167.73 (8) | N1—C5—H5 | 119.8 |
O5—Cu1—O7 | 89.06 (8) | C4—C5—H5 | 119.8 |
O1—Cu1—O7 | 83.14 (8) | C7—C6—C3 | 125.2 (2) |
O3—Cu1—O8 | 92.76 (8) | C7—C6—H6 | 117.4 |
O5—Cu1—O8 | 95.96 (8) | C3—C6—H6 | 117.4 |
O1—Cu1—O8 | 87.42 (8) | C6—C7—C10 | 125.4 (2) |
O7—Cu1—O8 | 98.75 (8) | C6—C7—H7 | 117.3 |
N1—O1—Cu1 | 122.35 (13) | C10—C7—H7 | 117.3 |
H1WA—O1W—H1WB | 109 (3) | N2—C8—C9 | 120.8 (2) |
H2WB—O2W—H2WA | 106 (3) | N2—C8—H8 | 119.6 |
C13—O3—Cu1 | 125.26 (15) | C9—C8—H8 | 119.6 |
H3WB—O3W—H3WA | 113 (3) | C8—C9—C10 | 120.8 (2) |
C15—O5—Cu1 | 124.50 (14) | C8—C9—H9 | 119.6 |
Cu1—O7—H7A | 121 (2) | C10—C9—H9 | 119.6 |
Cu1—O7—H7B | 115 (2) | C9—C10—C11 | 116.4 (2) |
H7A—O7—H7B | 113 (3) | C9—C10—C7 | 120.6 (2) |
Cu1—O8—H8A | 117 (2) | C11—C10—C7 | 123.0 (2) |
Cu1—O8—H8B | 118 (2) | C12—C11—C10 | 121.1 (2) |
H8A—O8—H8B | 98 (2) | C12—C11—H11 | 119.4 |
C1—N1—C5 | 121.0 (2) | C10—C11—H11 | 119.4 |
C1—N1—O1 | 120.4 (2) | N2—C12—C11 | 120.6 (2) |
C5—N1—O1 | 118.5 (2) | N2—C12—H12 | 119.7 |
O2—N2—C8 | 120.5 (2) | C11—C12—H12 | 119.7 |
O2—N2—C12 | 119.2 (2) | O4—C13—O3 | 122.8 (2) |
C8—N2—C12 | 120.2 (2) | O4—C13—C14 | 117.6 (2) |
N1—C1—C2 | 119.9 (2) | O3—C13—C14 | 119.6 (2) |
N1—C1—H1 | 120.1 | C15—C14—C13 | 116.6 (2) |
C2—C1—H1 | 120.1 | C15—C14—H14A | 108.1 |
C1—C2—C3 | 121.3 (2) | C13—C14—H14A | 108.1 |
C1—C2—H2 | 119.3 | C15—C14—H14B | 108.1 |
C3—C2—H2 | 119.3 | C13—C14—H14B | 108.1 |
C2—C3—C4 | 116.6 (2) | H14A—C14—H14B | 107.3 |
C2—C3—C6 | 120.1 (2) | O6—C15—O5 | 122.7 (2) |
C4—C3—C6 | 123.2 (2) | O6—C15—C14 | 118.2 (2) |
C5—C4—C3 | 120.7 (2) | O5—C15—C14 | 119.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.86 (2) | 1.93 (2) | 2.786 (3) | 178 (4) |
O1W—H1WB···O4ii | 0.84 (2) | 2.11 (2) | 2.883 (3) | 152 (3) |
O2W—H2WB···O5iii | 0.85 (2) | 2.33 (3) | 2.963 (3) | 131 (3) |
O2W—H2WB···O5iv | 0.85 (2) | 2.62 (3) | 3.271 (3) | 134 (3) |
O2W—H2WA···O1W | 0.87 (2) | 1.92 (2) | 2.780 (4) | 170 (4) |
O3W—H3WB···O6i | 0.86 (2) | 1.96 (2) | 2.818 (3) | 174 (3) |
O3W—H3WA···O2W | 0.87 (2) | 1.85 (2) | 2.707 (3) | 171 (3) |
O7—H7A···O6v | 0.87 (2) | 1.94 (2) | 2.767 (3) | 159 (3) |
O7—H7B···O2vi | 0.85 (2) | 1.89 (2) | 2.741 (3) | 174 (3) |
O8—H8A···O2vii | 0.88 (2) | 1.87 (2) | 2.745 (3) | 174 (3) |
O8—H8B···O3Wviii | 0.89 (2) | 1.90 (2) | 2.786 (3) | 175 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) x+1, y+1, z; (v) −x, −y−1, −z+1; (vi) −x+1, −y+1, −z+2; (vii) −x, −y+1, −z+2; (viii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H2O4)(C12H10N2O2)(H2O)2]·3H2O |
Mr | 469.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.526 (3), 11.781 (4), 12.723 (5) |
α, β, γ (°) | 111.701 (6), 99.270 (6), 106.219 (6) |
V (Å3) | 961.2 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.20 |
Crystal size (mm) | 0.75 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART 1 K |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.635, 0.866 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10713, 4273, 3606 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.106, 1.07 |
No. of reflections | 4273 |
No. of parameters | 292 |
No. of restraints | 15 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.41 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalMaker (Palmer, 2005), SHELXL97.
Cu1—O3 | 1.9263 (17) | Cu1—O7 | 1.9766 (18) |
Cu1—O5 | 1.9357 (17) | Cu1—O8 | 2.350 (2) |
Cu1—O1 | 1.9450 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.857 (18) | 1.929 (19) | 2.786 (3) | 178 (4) |
O1W—H1WB···O4ii | 0.842 (18) | 2.11 (2) | 2.883 (3) | 152 (3) |
O2W—H2WB···O5iii | 0.850 (18) | 2.33 (3) | 2.963 (3) | 131 (3) |
O2W—H2WB···O5iv | 0.850 (18) | 2.62 (3) | 3.271 (3) | 134 (3) |
O2W—H2WA···O1W | 0.866 (18) | 1.923 (19) | 2.780 (4) | 170 (4) |
O3W—H3WB···O6i | 0.861 (18) | 1.960 (19) | 2.818 (3) | 174 (3) |
O3W—H3WA···O2W | 0.871 (17) | 1.845 (18) | 2.707 (3) | 171 (3) |
O7—H7A···O6v | 0.867 (17) | 1.94 (2) | 2.767 (3) | 159 (3) |
O7—H7B···O2vi | 0.852 (17) | 1.892 (18) | 2.741 (3) | 174 (3) |
O8—H8A···O2vii | 0.881 (17) | 1.869 (18) | 2.745 (3) | 174 (3) |
O8—H8B···O3Wviii | 0.889 (17) | 1.899 (18) | 2.786 (3) | 175 (3) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) x+1, y+1, z; (v) −x, −y−1, −z+1; (vi) −x+1, −y+1, −z+2; (vii) −x, −y+1, −z+2; (viii) x−1, y−1, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The title compound was prepared during an attempt to synthesize a copper malonate coordination polymer incorporating Z-1,2-di-4-pyridylethylene-bis-N-oxide (bpeno), inspired by a report of the ferromagnetically coupled two-dimensional material [Cu2(malonate)2(H2O)2(4,4'-bipyridine)] (Rodriguez-Martin et al., 2001). Its asymmetric unit consists of a single [Cu(malonate)(bpeno)(H2O)2] molecule along with three water molecules of crystallization (Figure 1). The bond distances about the Cu atom are consistent with a "4 + 1" Jahn-Teller distorted square pyramidal coordination sphere (Table 1). The ligated water molecules are oriented in a cis fashion with respect to each other; one (O8) lies in the axial position of the square pyramid while the other (O7) rests in the equatorial plane. The oxygen donor atom belonging to the pendant, monodentate bpeno is oriented cis to both aqua ligands. The malonate ligand serves only as a chelating ligand to a single Cu atom.
Individual [Cu(malonate)(bpeno)(H2O)2] molecules aggregate into pairs through O—H···O hydrogen bonding between aqua ligands (O8) and the unligated oxygen atom of the monodentate bpeno ligands (O2) as well as π-π stacking between bpeno pyridyl rings. In turn, these form one-dimensional supramolecular chains through O—H···O hydrogen bonding between aquo ligands (O7) and unligated malonate oxygen atoms (O6). These further aggregate into pseudo two-dimensional layers (Figure 2) that course parallel to the bc crystallographic planes, through hydrogen bonding between the water molecules of crystallization and aquo ligands (O8) and unligated malonate oxygen atoms (O6). The water molecules of crystallization form discrete trimeric units. The pseudo two-dimensional layers stack into the three-dimensional crystal structure of I through additional hydrogen bonding patterns. Metrical parameters for the supramolecular interactions are given in Table 2.