

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808022812/fj2128sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808022812/fj2128Isup2.hkl |
CCDC reference: 700381
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.073
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu -- N1 .. 5.95 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Dropwise addition of 2.0 ml (1.0 M) Na2CO3 to an aqueous solution of 0.075 g (0.442 mmol) CuCl2.2H2O in 5.0 ml H2O yielded pale blue deposit, which was separated by centrifugation and washed with doubly distilled water until no Cl- anions are detectable in the supernatant. The precipitate was then added to a solution of 0.100 g (0.442 mmol) 2,9-dimethyl-1,10-phenanthroline in a mixed solvent consisting of 15 ml H2O and 15 ml me thanol. To the mixture 1.77 ml (1.0 M) formic acid was dropped and the precipitate was slowly dissolved under continuous stirring. The resulting blue solution was allowed to stand at room temperature, and slow evaporation for 10 days afforded blue plate crystals.
H atoms attached to C atoms of the dmp ligand were positioned geometrically and refined using a riding model, with C—H = 0.93 and 0.96 Å, and Uiso(H) values set at 1.2 Ueq(C) and 1.5 Ueq(C), respectively. The H atoms of the water molecule and formate anions were located from difference Fourier maps.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu(HCO2)2(C14H12N2)(H2O)] | F(000) = 780 |
Mr = 379.85 | Dx = 1.579 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 10.669 (2) Å | θ = 5.0–12.5° |
b = 7.7677 (16) Å | µ = 1.40 mm−1 |
c = 19.338 (4) Å | T = 295 K |
β = 94.22 (3)° | Plate, blue |
V = 1598.3 (6) Å3 | 0.26 × 0.17 × 0.09 mm |
Z = 4 |
Bruker P4 diffractometer | 3202 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
θ/2θ scans | h = −13→13 |
Absorption correction: multi-scan (XSCANS; Siemens, 1996) | k = −10→9 |
Tmin = 0.749, Tmax = 0.879 | l = −24→25 |
15099 measured reflections | 3 standard reflections every 97 reflections |
3632 independent reflections | intensity decay: none |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.5201P] where P = (Fo2 + 2Fc2)/3 |
3632 reflections | (Δ/σ)max = 0.001 |
219 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
[Cu(HCO2)2(C14H12N2)(H2O)] | V = 1598.3 (6) Å3 |
Mr = 379.85 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.669 (2) Å | µ = 1.40 mm−1 |
b = 7.7677 (16) Å | T = 295 K |
c = 19.338 (4) Å | 0.26 × 0.17 × 0.09 mm |
β = 94.22 (3)° |
Bruker P4 diffractometer | 3202 reflections with I > 2σ(I) |
Absorption correction: multi-scan (XSCANS; Siemens, 1996) | Rint = 0.019 |
Tmin = 0.749, Tmax = 0.879 | 3 standard reflections every 97 reflections |
15099 measured reflections | intensity decay: none |
3632 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.35 e Å−3 |
3632 reflections | Δρmin = −0.22 e Å−3 |
219 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 | ||
Cu | 0.209657 (18) | 0.90493 (2) | 0.156116 (9) | 0.02440 (7) | |
N1 | 0.21922 (12) | 0.80402 (17) | 0.05966 (6) | 0.0257 (3) | |
N2 | 0.42113 (13) | 0.89494 (17) | 0.14606 (7) | 0.0275 (3) | |
C1 | 0.11886 (17) | 0.7632 (2) | 0.01841 (9) | 0.0325 (4) | |
C2 | 0.1317 (2) | 0.6999 (3) | −0.04910 (10) | 0.0472 (5) | |
H2A | 0.0605 | 0.6741 | −0.0778 | 0.057* | |
C3 | 0.2471 (2) | 0.6765 (3) | −0.07224 (10) | 0.0508 (5) | |
H3A | 0.2552 | 0.6332 | −0.1165 | 0.061* | |
C4 | 0.35505 (19) | 0.7178 (3) | −0.02912 (9) | 0.0393 (4) | |
C5 | 0.4803 (2) | 0.6986 (3) | −0.04949 (11) | 0.0541 (6) | |
H5A | 0.4929 | 0.6540 | −0.0931 | 0.065* | |
C6 | 0.5804 (2) | 0.7435 (3) | −0.00711 (11) | 0.0537 (6) | |
H6A | 0.6609 | 0.7298 | −0.0217 | 0.064* | |
C7 | 0.56433 (17) | 0.8120 (3) | 0.05998 (10) | 0.0397 (4) | |
C8 | 0.66470 (19) | 0.8661 (3) | 0.10598 (12) | 0.0511 (5) | |
H8A | 0.7468 | 0.8577 | 0.0931 | 0.061* | |
C9 | 0.64241 (19) | 0.9302 (3) | 0.16884 (12) | 0.0478 (5) | |
H9A | 0.7091 | 0.9659 | 0.1992 | 0.057* | |
C10 | 0.51845 (17) | 0.9430 (2) | 0.18838 (9) | 0.0350 (4) | |
C11 | 0.44274 (15) | 0.8321 (2) | 0.08260 (8) | 0.0289 (3) | |
C12 | 0.33615 (16) | 0.7831 (2) | 0.03694 (8) | 0.0281 (3) | |
C13 | −0.00801 (18) | 0.7856 (3) | 0.04536 (10) | 0.0438 (4) | |
H13A | −0.0302 | 0.6831 | 0.0694 | 0.066* | |
H13B | −0.0691 | 0.8066 | 0.0073 | 0.066* | |
H13C | −0.0062 | 0.8816 | 0.0767 | 0.066* | |
C14 | 0.4920 (2) | 1.0068 (3) | 0.25888 (10) | 0.0537 (6) | |
H14A | 0.4243 | 1.0884 | 0.2547 | 0.081* | |
H14B | 0.5659 | 1.0614 | 0.2802 | 0.081* | |
H14C | 0.4691 | 0.9116 | 0.2870 | 0.081* | |
O1 | 0.18364 (13) | 0.98991 (18) | 0.24857 (6) | 0.0408 (3) | |
O2 | −0.02000 (15) | 1.0452 (3) | 0.22488 (8) | 0.0613 (4) | |
C15 | 0.0760 (2) | 1.0407 (3) | 0.26275 (10) | 0.0471 (5) | |
O3 | 0.18495 (13) | 1.12747 (15) | 0.10994 (6) | 0.0365 (3) | |
O4 | 0.18327 (18) | 1.41073 (16) | 0.10823 (8) | 0.0530 (4) | |
C16 | 0.19793 (18) | 1.2723 (2) | 0.13792 (9) | 0.0360 (4) | |
O5 | 0.19568 (12) | 0.67025 (15) | 0.19376 (6) | 0.0344 (3) | |
H5B | 0.1958 | 0.5834 | 0.1636 | 0.051* | |
H5C | 0.1416 | 0.6452 | 0.2242 | 0.054* | |
H15 | 0.0751 | 1.0904 | 0.3111 | 0.052* | |
H16 | 0.2383 | 1.2705 | 0.1852 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02683 (11) | 0.02277 (11) | 0.02410 (11) | 0.00161 (7) | 0.00524 (7) | −0.00126 (7) |
N1 | 0.0280 (7) | 0.0227 (6) | 0.0263 (6) | −0.0003 (5) | 0.0021 (5) | −0.0001 (5) |
N2 | 0.0267 (7) | 0.0283 (7) | 0.0276 (6) | −0.0012 (5) | 0.0032 (5) | 0.0011 (5) |
C1 | 0.0353 (9) | 0.0304 (8) | 0.0313 (8) | −0.0023 (7) | −0.0011 (7) | −0.0003 (7) |
C2 | 0.0495 (12) | 0.0554 (12) | 0.0350 (9) | −0.0055 (10) | −0.0086 (8) | −0.0096 (9) |
C3 | 0.0627 (14) | 0.0601 (13) | 0.0297 (9) | −0.0010 (11) | 0.0040 (9) | −0.0158 (9) |
C4 | 0.0467 (11) | 0.0421 (10) | 0.0300 (8) | 0.0022 (8) | 0.0093 (7) | −0.0060 (8) |
C5 | 0.0587 (14) | 0.0690 (15) | 0.0373 (10) | 0.0073 (11) | 0.0227 (9) | −0.0110 (10) |
C6 | 0.0430 (12) | 0.0737 (15) | 0.0474 (11) | 0.0080 (10) | 0.0234 (9) | −0.0016 (11) |
C7 | 0.0319 (9) | 0.0479 (11) | 0.0408 (9) | 0.0023 (8) | 0.0126 (7) | 0.0052 (9) |
C8 | 0.0246 (9) | 0.0722 (14) | 0.0575 (12) | −0.0005 (9) | 0.0102 (8) | 0.0079 (11) |
C9 | 0.0306 (10) | 0.0592 (13) | 0.0526 (12) | −0.0096 (9) | −0.0033 (8) | 0.0047 (10) |
C10 | 0.0323 (9) | 0.0346 (9) | 0.0374 (9) | −0.0041 (7) | −0.0018 (7) | 0.0021 (7) |
C11 | 0.0292 (8) | 0.0288 (8) | 0.0295 (7) | 0.0007 (6) | 0.0077 (6) | 0.0020 (7) |
C12 | 0.0327 (8) | 0.0264 (7) | 0.0258 (7) | 0.0020 (6) | 0.0070 (6) | 0.0006 (6) |
C13 | 0.0308 (9) | 0.0564 (12) | 0.0434 (10) | −0.0056 (9) | −0.0033 (8) | 0.0005 (9) |
C14 | 0.0484 (12) | 0.0687 (15) | 0.0426 (11) | −0.0057 (11) | −0.0066 (9) | −0.0160 (11) |
O1 | 0.0475 (8) | 0.0463 (8) | 0.0293 (6) | 0.0104 (6) | 0.0073 (5) | −0.0055 (6) |
O2 | 0.0465 (9) | 0.0904 (13) | 0.0485 (8) | 0.0135 (9) | 0.0128 (7) | −0.0072 (9) |
C15 | 0.0577 (13) | 0.0534 (12) | 0.0319 (9) | 0.0127 (10) | 0.0159 (9) | −0.0061 (9) |
O3 | 0.0529 (8) | 0.0249 (6) | 0.0319 (6) | 0.0037 (5) | 0.0045 (5) | 0.0000 (5) |
O4 | 0.0859 (12) | 0.0259 (7) | 0.0479 (8) | 0.0012 (7) | 0.0098 (8) | 0.0004 (6) |
C16 | 0.0443 (10) | 0.0292 (9) | 0.0346 (8) | −0.0012 (7) | 0.0028 (7) | −0.0013 (7) |
O5 | 0.0415 (7) | 0.0271 (6) | 0.0359 (6) | −0.0028 (5) | 0.0122 (5) | 0.0032 (5) |
Cu—O1 | 1.9450 (12) | C7—C11 | 1.408 (2) |
Cu—O3 | 1.9546 (12) | C8—C9 | 1.351 (3) |
Cu—O5 | 1.9726 (12) | C8—H8A | 0.9300 |
Cu—N1 | 2.0328 (13) | C9—C10 | 1.405 (3) |
Cu—N2 | 2.2801 (15) | C9—H9A | 0.9300 |
N1—C1 | 1.326 (2) | C10—C14 | 1.497 (3) |
N1—C12 | 1.363 (2) | C11—C12 | 1.439 (2) |
N2—C10 | 1.327 (2) | C13—H13A | 0.9600 |
N2—C11 | 1.356 (2) | C13—H13B | 0.9600 |
C1—C2 | 1.411 (2) | C13—H13C | 0.9600 |
C1—C13 | 1.496 (3) | C14—H14A | 0.9600 |
C2—C3 | 1.353 (3) | C14—H14B | 0.9600 |
C2—H2A | 0.9300 | C14—H14C | 0.9600 |
C3—C4 | 1.408 (3) | O1—C15 | 1.264 (2) |
C3—H3A | 0.9300 | O2—C15 | 1.215 (3) |
C4—C12 | 1.403 (2) | C15—H15 | 1.0122 |
C4—C5 | 1.429 (3) | O3—C16 | 1.252 (2) |
C5—C6 | 1.343 (3) | O4—C16 | 1.223 (2) |
C5—H5A | 0.9300 | C16—H16 | 0.9821 |
C6—C7 | 1.424 (3) | O5—H5B | 0.8914 |
C6—H6A | 0.9300 | O5—H5C | 0.8760 |
C7—C8 | 1.405 (3) | ||
O1—Cu—O3 | 95.53 (6) | C9—C8—H8A | 119.9 |
O1—Cu—O5 | 87.40 (6) | C7—C8—H8A | 119.9 |
O1—Cu—N1 | 174.06 (6) | C8—C9—C10 | 119.97 (19) |
O1—Cu—N2 | 107.40 (6) | C8—C9—H9A | 120.0 |
O3—Cu—O5 | 167.05 (6) | C10—C9—H9A | 120.0 |
O3—Cu—N1 | 86.33 (5) | N2—C10—C9 | 121.54 (18) |
O3—Cu—N2 | 95.28 (6) | N2—C10—C14 | 117.62 (17) |
O5—Cu—N1 | 89.57 (5) | C9—C10—C14 | 120.81 (18) |
O5—Cu—N2 | 95.87 (5) | N2—C11—C7 | 122.89 (16) |
N1—Cu—N2 | 77.98 (6) | N2—C11—C12 | 118.11 (14) |
C1—N1—C12 | 119.71 (14) | C7—C11—C12 | 119.01 (15) |
C1—N1—Cu | 123.47 (11) | N1—C12—C4 | 122.22 (16) |
C12—N1—Cu | 116.80 (11) | N1—C12—C11 | 118.15 (14) |
C10—N2—C11 | 118.80 (15) | C4—C12—C11 | 119.63 (16) |
C10—N2—Cu | 132.20 (12) | C1—C13—H13A | 109.5 |
C11—N2—Cu | 108.95 (11) | C1—C13—H13B | 109.5 |
N1—C1—C2 | 120.71 (17) | H13A—C13—H13B | 109.5 |
N1—C1—C13 | 118.29 (15) | C1—C13—H13C | 109.5 |
C2—C1—C13 | 121.00 (17) | H13A—C13—H13C | 109.5 |
C3—C2—C1 | 120.38 (18) | H13B—C13—H13C | 109.5 |
C3—C2—H2A | 119.8 | C10—C14—H14A | 109.5 |
C1—C2—H2A | 119.8 | C10—C14—H14B | 109.5 |
C2—C3—C4 | 119.86 (17) | H14A—C14—H14B | 109.5 |
C2—C3—H3A | 120.1 | C10—C14—H14C | 109.5 |
C4—C3—H3A | 120.1 | H14A—C14—H14C | 109.5 |
C12—C4—C3 | 117.10 (18) | H14B—C14—H14C | 109.5 |
C12—C4—C5 | 119.28 (18) | C15—O1—Cu | 119.93 (13) |
C3—C4—C5 | 123.61 (18) | O2—C15—O1 | 128.13 (18) |
C6—C5—C4 | 121.48 (18) | O2—C15—H15 | 118.8 |
C6—C5—H5A | 119.3 | O1—C15—H15 | 112.9 |
C4—C5—H5A | 119.3 | C16—O3—Cu | 126.20 (12) |
C5—C6—C7 | 120.61 (18) | O4—C16—O3 | 125.51 (17) |
C5—C6—H6A | 119.7 | O4—C16—H16 | 118.8 |
C7—C6—H6A | 119.7 | O3—C16—H16 | 114.6 |
C8—C7—C11 | 116.55 (17) | Cu—O5—H5B | 117.0 |
C8—C7—C6 | 123.44 (18) | Cu—O5—H5C | 121.6 |
C11—C7—C6 | 119.99 (19) | H5B—O5—H5C | 107.7 |
C9—C8—C7 | 120.23 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···O2i | 0.88 | 1.86 | 2.714 (2) | 166 |
O5—H5B···O4ii | 0.89 | 1.72 | 2.605 (2) | 175 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(HCO2)2(C14H12N2)(H2O)] |
Mr | 379.85 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.669 (2), 7.7677 (16), 19.338 (4) |
β (°) | 94.22 (3) |
V (Å3) | 1598.3 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.26 × 0.17 × 0.09 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Multi-scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.749, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15099, 3632, 3202 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.072, 1.06 |
No. of reflections | 3632 |
No. of parameters | 219 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.22 |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
Cu—O1 | 1.9450 (12) | Cu—N1 | 2.0328 (13) |
Cu—O3 | 1.9546 (12) | Cu—N2 | 2.2801 (15) |
Cu—O5 | 1.9726 (12) | ||
O1—Cu—O3 | 95.53 (6) | O3—Cu—N1 | 86.33 (5) |
O1—Cu—O5 | 87.40 (6) | O3—Cu—N2 | 95.28 (6) |
O1—Cu—N1 | 174.06 (6) | O5—Cu—N1 | 89.57 (5) |
O1—Cu—N2 | 107.40 (6) | O5—Cu—N2 | 95.87 (5) |
O3—Cu—O5 | 167.05 (6) | N1—Cu—N2 | 77.98 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···O2i | 0.88 | 1.86 | 2.714 (2) | 166 |
O5—H5B···O4ii | 0.89 | 1.72 | 2.605 (2) | 175 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z. |
We reported a structure of the copper-dmp complex aqua-(2,9-dimethyl-1,10-phenanthroline-κ2N:N')-diromato-copper(II) previously, which crystallizes in space group Pna21 (Pan, et al.,2005). On repeating the experiment recently, to our surprise, we found a new polyporph, (I), that had crystallized in the space group P21/c.
The crystal structure of the title compound is very similar to the previously reported complex, built up by the [Cu(dmp)(H2O)(HCOO)2] complex molecules. The Cu atoms are each square pyramidally coordinated by two N atoms of one dmp ligand, three O atoms of two formate anions and one water molecule with the N2 atom of the dmp ligand at the apical position. The apical and basal Cu—N bond distances are 2.280 (1) and 2.033 (2) Å, respectively. The Cu—O bond distances to the formate anions are 1.945 (1) and 1.955 (1) Å, slightly longer than that to the water molecule (1.973 (1) Å). Suggesting that the formate anions possess better coordinating capability to the water molecule in the structure, which also show no significant difference from the isomer crystal structure that reported by us. The Cu atom is shifted by 0.153 (1) Å from the equatorial plane through N1, O1, O3 and O5 atoms towards the apical N2 atom. Through the intermolecular hydrogen bond the complex molecules are link into double chains with the chelating dmp ligands extending parallelly on one side along [010]. The substituted phenanthroline ligands of one double chain protrude into the grooves between adjacent aromatic planes of the neighboring double chain, yielding two-dimensional layers parallel to (100). It is found that the assembly of the double chains is due to interchain π-π stacking interactions between the dmp ligands (mean interplanar distance: 3.59 Å).