Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007451/ob6231sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007451/ob6231Isup2.hkl |
CCDC reference: 214556
A mixture of CuO (0.2 mmol, 0.015 g), 1,10-phenanthroline (0.2 mmol, 0.04 g), orotic acid (0.3 mmol, 0.05 g) and H2O (15 ml) was sealed in a 25 ml Teflon-lined stainless steel reator and heated at 453 K for 72 h. After cooling, blue crystals of (I) were obtained (yield 68%).
The positions of all H atoms were generated geometrically (C—H bond fixed at 0.96 Å), assigned isotropic displacement parameters, and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the molecular structure of (I), showing 50% displacement ellipsoids for non-H atoms. | |
Fig. 2. The crystal structure of (I) along the c axis. |
[Cu(C5H2N2O4)(C12H8N2)] | F(000) = 804 |
Mr = 397.83 | Dx = 1.801 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6703 (2) Å | Cell parameters from 80 reflections |
b = 7.8597 (2) Å | θ = 1.9–25.0° |
c = 21.5279 (2) Å | µ = 1.52 mm−1 |
β = 90.916 (1)° | T = 293 K |
V = 1466.85 (5) Å3 | Block, blue |
Z = 4 | 0.58 × 0.26 × 0.06 mm |
Siemens SMART CCD area-detector diffractometer | 2560 independent reflections |
Radiation source: fine-focus sealed tube | 2127 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→10 |
Tmin = 0.682, Tmax = 0.913 | k = −9→7 |
5179 measured reflections | l = −20→25 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0483P)2 + 1.9946P] where P = (Fo2 + 2Fc2)/3 |
2560 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
[Cu(C5H2N2O4)(C12H8N2)] | V = 1466.85 (5) Å3 |
Mr = 397.83 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.6703 (2) Å | µ = 1.52 mm−1 |
b = 7.8597 (2) Å | T = 293 K |
c = 21.5279 (2) Å | 0.58 × 0.26 × 0.06 mm |
β = 90.916 (1)° |
Siemens SMART CCD area-detector diffractometer | 2560 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2127 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.913 | Rint = 0.024 |
5179 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.43 e Å−3 |
2560 reflections | Δρmin = −0.52 e Å−3 |
235 parameters |
Experimental. empirical from equivalent reflections (XEMP in SHELXTL; Siemens,1994) |
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 | 0.22423 (5) | 0.43152 (5) | −0.034154 (19) | 0.03421 (17) | |
O1 | 0.3815 (3) | 0.3674 (3) | 0.02713 (11) | 0.0408 (6) | |
N2 | 0.1386 (3) | 0.9050 (4) | 0.05854 (14) | 0.0390 (7) | |
H2A | 0.0825 | 0.9941 | 0.0529 | 0.047* | |
N4 | 0.2592 (3) | 0.2062 (4) | −0.07521 (14) | 0.0370 (7) | |
O2 | 0.5312 (3) | 0.4680 (3) | 0.10408 (12) | 0.0502 (7) | |
N1 | 0.2074 (3) | 0.6347 (4) | 0.02113 (13) | 0.0326 (6) | |
N3 | 0.0901 (3) | 0.4664 (4) | −0.11428 (13) | 0.0353 (7) | |
O3 | 0.2549 (4) | 1.0384 (4) | 0.13973 (13) | 0.0559 (8) | |
C7 | 0.3429 (5) | 0.0775 (5) | −0.0530 (2) | 0.0448 (9) | |
H7A | 0.3925 | 0.0898 | −0.0147 | 0.054* | |
C6 | 0.1874 (4) | 0.1869 (5) | −0.13119 (16) | 0.0353 (8) | |
O4 | −0.0025 (3) | 0.7776 (4) | −0.01688 (13) | 0.0604 (9) | |
C2 | 0.3174 (4) | 0.6363 (5) | 0.06778 (15) | 0.0324 (7) | |
C3 | 0.3390 (4) | 0.7599 (5) | 0.10965 (16) | 0.0375 (8) | |
H3A | 0.4138 | 0.7476 | 0.1408 | 0.045* | |
C4 | 0.2468 (4) | 0.9118 (5) | 0.10664 (15) | 0.0374 (8) | |
C17 | 0.0965 (4) | 0.3280 (4) | −0.15231 (15) | 0.0337 (8) | |
C1 | 0.4198 (4) | 0.4781 (5) | 0.06788 (16) | 0.0364 (8) | |
C5 | 0.1115 (4) | 0.7706 (5) | 0.01878 (16) | 0.0388 (9) | |
C10 | 0.1974 (5) | 0.0377 (5) | −0.16661 (18) | 0.0432 (9) | |
C16 | 0.0050 (4) | 0.5973 (5) | −0.13386 (18) | 0.0430 (9) | |
H16A | −0.0010 | 0.6933 | −0.1088 | 0.052* | |
C15 | −0.0762 (5) | 0.5964 (5) | −0.19078 (18) | 0.0496 (10) | |
H15A | −0.1340 | 0.6909 | −0.2027 | 0.059* | |
C13 | 0.0165 (4) | 0.3164 (5) | −0.20972 (16) | 0.0392 (8) | |
C11 | 0.1159 (5) | 0.0301 (6) | −0.22480 (19) | 0.0516 (11) | |
H11A | 0.1225 | −0.0673 | −0.2491 | 0.062* | |
C9 | 0.2867 (5) | −0.0958 (5) | −0.1410 (2) | 0.0509 (10) | |
H9A | 0.2961 | −0.1980 | −0.1624 | 0.061* | |
C14 | −0.0708 (5) | 0.4584 (5) | −0.22854 (18) | 0.0490 (10) | |
H14A | −0.1242 | 0.4578 | −0.2664 | 0.059* | |
C12 | 0.0295 (5) | 0.1624 (6) | −0.24490 (18) | 0.0503 (10) | |
H12A | −0.0232 | 0.1535 | −0.2827 | 0.060* | |
C8 | 0.3591 (5) | −0.0748 (5) | −0.0851 (2) | 0.0539 (11) | |
H8A | 0.4191 | −0.1619 | −0.0683 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0353 (3) | 0.0364 (3) | 0.0306 (3) | 0.00821 (18) | −0.00960 (17) | −0.00646 (19) |
O1 | 0.0507 (15) | 0.0358 (13) | 0.0353 (13) | 0.0091 (12) | −0.0158 (11) | −0.0044 (12) |
N2 | 0.0365 (16) | 0.0432 (18) | 0.0370 (16) | 0.0151 (13) | −0.0099 (13) | −0.0123 (14) |
N4 | 0.0390 (16) | 0.0342 (16) | 0.0376 (16) | 0.0037 (13) | −0.0060 (13) | −0.0025 (13) |
O2 | 0.0602 (18) | 0.0445 (16) | 0.0448 (15) | 0.0150 (13) | −0.0289 (13) | −0.0024 (13) |
N1 | 0.0291 (14) | 0.0384 (16) | 0.0300 (15) | 0.0061 (13) | −0.0080 (11) | −0.0069 (13) |
N3 | 0.0381 (16) | 0.0356 (16) | 0.0320 (15) | 0.0037 (13) | −0.0042 (12) | −0.0029 (13) |
O3 | 0.070 (2) | 0.0505 (17) | 0.0462 (16) | 0.0142 (14) | −0.0250 (14) | −0.0216 (14) |
C7 | 0.051 (2) | 0.0327 (19) | 0.050 (2) | 0.0062 (17) | −0.0097 (18) | 0.0006 (18) |
C6 | 0.0330 (18) | 0.039 (2) | 0.0336 (18) | −0.0034 (15) | 0.0004 (15) | −0.0045 (16) |
O4 | 0.0473 (16) | 0.072 (2) | 0.0613 (18) | 0.0302 (15) | −0.0312 (14) | −0.0330 (16) |
C2 | 0.0347 (18) | 0.0346 (18) | 0.0279 (17) | 0.0017 (15) | −0.0028 (14) | 0.0001 (15) |
C3 | 0.041 (2) | 0.042 (2) | 0.0289 (18) | 0.0067 (16) | −0.0143 (15) | −0.0004 (16) |
C4 | 0.042 (2) | 0.045 (2) | 0.0249 (17) | 0.0051 (17) | −0.0077 (14) | −0.0036 (16) |
C17 | 0.0328 (18) | 0.040 (2) | 0.0286 (17) | −0.0030 (15) | 0.0007 (14) | −0.0033 (15) |
C1 | 0.042 (2) | 0.0357 (19) | 0.0311 (18) | 0.0049 (16) | −0.0069 (15) | 0.0025 (16) |
C5 | 0.0342 (19) | 0.047 (2) | 0.0350 (19) | 0.0086 (16) | −0.0061 (15) | −0.0130 (17) |
C10 | 0.046 (2) | 0.042 (2) | 0.041 (2) | −0.0050 (17) | 0.0068 (17) | −0.0108 (18) |
C16 | 0.047 (2) | 0.043 (2) | 0.039 (2) | 0.0083 (17) | −0.0096 (17) | −0.0026 (17) |
C15 | 0.059 (3) | 0.049 (2) | 0.040 (2) | 0.011 (2) | −0.0126 (18) | 0.0042 (19) |
C13 | 0.040 (2) | 0.049 (2) | 0.0285 (18) | −0.0080 (17) | −0.0037 (15) | −0.0018 (16) |
C11 | 0.060 (3) | 0.052 (3) | 0.043 (2) | −0.008 (2) | 0.0028 (19) | −0.018 (2) |
C9 | 0.056 (3) | 0.034 (2) | 0.063 (3) | 0.0011 (18) | 0.006 (2) | −0.0127 (19) |
C14 | 0.053 (2) | 0.063 (3) | 0.0310 (19) | −0.001 (2) | −0.0146 (17) | 0.0037 (19) |
C12 | 0.057 (2) | 0.062 (3) | 0.032 (2) | −0.015 (2) | −0.0034 (18) | −0.0091 (19) |
C8 | 0.057 (3) | 0.035 (2) | 0.069 (3) | 0.0102 (19) | −0.007 (2) | −0.002 (2) |
Cu—O1 | 1.949 (2) | C2—C3 | 1.336 (5) |
Cu—N1 | 1.998 (3) | C2—C1 | 1.528 (5) |
Cu—N4 | 2.004 (3) | C3—C4 | 1.438 (5) |
Cu—N3 | 2.083 (3) | C3—H3A | 0.9300 |
O1—C1 | 1.276 (4) | C17—C13 | 1.410 (5) |
N2—C5 | 1.377 (4) | C10—C9 | 1.411 (6) |
N2—C4 | 1.387 (4) | C10—C11 | 1.430 (6) |
N2—H2A | 0.8600 | C16—C15 | 1.403 (5) |
N4—C7 | 1.329 (5) | C16—H16A | 0.9300 |
N4—C6 | 1.356 (4) | C15—C14 | 1.356 (6) |
O2—C1 | 1.234 (4) | C15—H15A | 0.9300 |
N1—C5 | 1.354 (4) | C13—C14 | 1.405 (6) |
N1—C2 | 1.374 (4) | C13—C12 | 1.433 (6) |
N3—C16 | 1.331 (5) | C11—C12 | 1.349 (6) |
N3—C17 | 1.363 (4) | C11—H11A | 0.9300 |
O3—C4 | 1.225 (4) | C9—C8 | 1.360 (6) |
C7—C8 | 1.389 (5) | C9—H9A | 0.9300 |
C7—H7A | 0.9300 | C14—H14A | 0.9300 |
C6—C10 | 1.402 (5) | C12—H12A | 0.9300 |
C6—C17 | 1.431 (5) | C8—H8A | 0.9300 |
O4—C5 | 1.243 (4) | ||
O1—Cu—N1 | 81.97 (10) | N3—C17—C6 | 117.1 (3) |
O1—Cu—N4 | 87.76 (11) | C13—C17—C6 | 119.3 (3) |
N1—Cu—N4 | 168.99 (12) | O2—C1—O1 | 125.6 (3) |
O1—Cu—N3 | 165.97 (11) | O2—C1—C2 | 120.2 (3) |
N1—Cu—N3 | 110.06 (11) | O1—C1—C2 | 114.1 (3) |
N4—Cu—N3 | 80.65 (11) | O4—C5—N1 | 122.7 (3) |
C1—O1—Cu | 117.4 (2) | O4—C5—N2 | 118.4 (3) |
C5—N2—C4 | 126.9 (3) | N1—C5—N2 | 118.9 (3) |
C5—N2—H2A | 116.6 | C6—C10—C9 | 116.6 (4) |
C4—N2—H2A | 116.6 | C6—C10—C11 | 118.5 (4) |
C7—N4—C6 | 118.3 (3) | C9—C10—C11 | 124.8 (4) |
C7—N4—Cu | 126.9 (3) | N3—C16—C15 | 122.7 (4) |
C6—N4—Cu | 114.9 (2) | N3—C16—H16A | 118.6 |
C5—N1—C2 | 116.0 (3) | C15—C16—H16A | 118.6 |
C5—N1—Cu | 131.2 (2) | C14—C15—C16 | 120.4 (4) |
C2—N1—Cu | 112.7 (2) | C14—C15—H15A | 119.8 |
C16—N3—C17 | 117.0 (3) | C16—C15—H15A | 119.8 |
C16—N3—Cu | 131.6 (2) | C14—C13—C17 | 117.2 (3) |
C17—N3—Cu | 111.4 (2) | C14—C13—C12 | 124.4 (3) |
N4—C7—C8 | 122.4 (4) | C17—C13—C12 | 118.4 (4) |
N4—C7—H7A | 118.8 | C12—C11—C10 | 120.9 (4) |
C8—C7—H7A | 118.8 | C12—C11—H11A | 119.6 |
N4—C6—C10 | 123.1 (3) | C10—C11—H11A | 119.6 |
N4—C6—C17 | 116.0 (3) | C8—C9—C10 | 119.9 (4) |
C10—C6—C17 | 120.9 (3) | C8—C9—H9A | 120.1 |
C3—C2—N1 | 126.1 (3) | C10—C9—H9A | 120.1 |
C3—C2—C1 | 121.0 (3) | C15—C14—C13 | 119.1 (3) |
N1—C2—C1 | 113.0 (3) | C15—C14—H14A | 120.5 |
C2—C3—C4 | 120.1 (3) | C13—C14—H14A | 120.5 |
C2—C3—H3A | 120.0 | C11—C12—C13 | 122.0 (4) |
C4—C3—H3A | 120.0 | C11—C12—H12A | 119.0 |
O3—C4—N2 | 119.8 (3) | C13—C12—H12A | 119.0 |
O3—C4—C3 | 128.5 (3) | C9—C8—C7 | 119.7 (4) |
N2—C4—C3 | 111.7 (3) | C9—C8—H8A | 120.1 |
N3—C17—C13 | 123.6 (3) | C7—C8—H8A | 120.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4i | 0.86 | 2.07 | 2.895 (4) | 161 |
Symmetry code: (i) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C5H2N2O4)(C12H8N2)] |
Mr | 397.83 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.6703 (2), 7.8597 (2), 21.5279 (2) |
β (°) | 90.916 (1) |
V (Å3) | 1466.85 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.58 × 0.26 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.682, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5179, 2560, 2127 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.08 |
No. of reflections | 2560 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.52 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1994), SHELXTL (Siemens, 1994), SHELXTL.
Cu—O1 | 1.949 (2) | Cu—N4 | 2.004 (3) |
Cu—N1 | 1.998 (3) | Cu—N3 | 2.083 (3) |
O1—Cu—N1 | 81.97 (10) | O1—Cu—N3 | 165.97 (11) |
O1—Cu—N4 | 87.76 (11) | N1—Cu—N3 | 110.06 (11) |
N1—Cu—N4 | 168.99 (12) | N4—Cu—N3 | 80.65 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O4i | 0.86 | 2.07 | 2.895 (4) | 161 |
Symmetry code: (i) −x, −y+2, −z. |
The design and synthesis of novel inorganic-organic hybrid coordination complexes have attracted the attention of many chemists in recent years owing to their potential applications, such as selective guest absorption (Gardner et al., 1995), gas storage (Li et al., 1999), and heterogeneous catalysis (Dong et al., 2000). In the past, many complexes have been synthesized and characterized (Harvey et al., 2000). In this paper, we report the title compound, (I), which is a new cuprum coordination compound, [Cu(orotate)(phen)].
The Cu atom is four coordinated by two N atoms from phenanthroline, carboxylato O and N atoms from orotate (Fig. 1). The coordination geometry of the Cu atom can be regarded as a distorted square planar (Table 1). Through weak intermolecular Cu···O interactions and N—H···O hydrogen bonds, the crystal structure extends into a two-dimensional framework (Fig. 2). The distances Cu—O2(1 − x,1 − y,-z) and Cu—O4(2 − x,1 − y,-z) are 2.737 (3) and 2.771 (3) Å, respectively.