Orotato(1,10-phenanthroline)copper(II)

Li, X.; Cao, R.; Bi, W.; Sun, D.; Hong, M.

doi:10.1107/S1600536803007451

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Orotato(1,10-phenanthroline)copper(II)

X. Li, R. Cao, W. Bi, D. Sun and M. Hong

Hydrothermal reaction of CuO, orotic acid and 1,10-phenanthroline in an aqueous solution resulted in the title compound, [Cu(orotate)(phen)] or [Cu(C₅H₂N₂O₄)(C₁₂H₈N₂)], with a mononuclear structure. The coordination geometry around the Cu^II atom is distorted square planar. Through weak intermolecular Cu

O interactions and N—H

O hydrogen bonds, the crystal structure extends into a two-dimensional framework.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007451/ob6231sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007451/ob6231Isup2.hkl Contains datablock I

CCDC reference: 214556

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.038
wR factor = 0.106
Data-to-parameter ratio = 10.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C(1)   -   C(2)   =       1.53 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

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.

Experimental top

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%).

Computing details top

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.

Figures top

	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.

Orotato(1,10-phenanthroline)copper(II) top

Crystal data top

[Cu(C₅H₂N₂O₄)(C₁₂H₈N₂)]	F(000) = 804
M_r = 397.83	D_x = 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

Data collection top

Siemens SMART CCD area-detector diffractometer	2560 independent reflections
Radiation source: fine-focus sealed tube	2127 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.682, T_max = 0.913	k = −9→7
5179 measured reflections	l = −20→25

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0483P)² + 1.9946P] where P = (F_o² + 2F_c²)/3
2560 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

[Cu(C₅H₂N₂O₄)(C₁₂H₈N₂)]	V = 1466.85 (5) Å³
M_r = 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)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2560 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	2127 reflections with I > 2σ(I)
T_min = 0.682, T_max = 0.913	R_int = 0.024
5179 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.08	Δρ_max = 0.43 e Å⁻³
2560 reflections	Δρ_min = −0.52 e Å⁻³
235 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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)]
M_r	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)
T_min, T_max	0.682, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	5179, 2560, 2127
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.52

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1994), SHELXTL (Siemens, 1994), SHELXTL.

Selected geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

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