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Acta Cryst. (2007). E63, m1817    [ doi:10.1107/S1600536807026773 ]

(Benzoato-[kappa]2O,O')chlorido(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')copper(II)

X.-P. Xuan, P.-Z. Zhao and S.-X. Zhang

Abstract top

In the title compound, [Cu(C7H5O2)Cl(C14H12N2)], the CuII ion is five-coordinated in a distorted square-pyramidal geometry by two O atoms from one benzoate anion, two N atoms from one 2,9-dimethyl-1,10-phenanthroline ligand (dmphen) and one Cl- anion. The Cu-N bond lengths are 1.990 (3) and 2.111 (3) Å, while the Cu-O bond lengths are 2.031 (2) and 2.069 (2) Å. The crystal packing seems to be determined by interactions between dmphen aromatic rings of neighbouring molecules, with a distance between their ring centroids of 3.978 (5) Å.

Comment top

Copper(II) complexes of 1,10-phenanthroline and its derivatives have attracted much attention because of their peculiar features (Paulovicova et al., 2001; Pallenberg et al., 1995). Recently, we obtained the title mononuclear copper(II) complex, (I), by reaction of copper dichloride, sodium benzoate and 2,9-dimethyl-1,10-phenanthroline (dmphen) in an ethanol/water mixture, and its crystal structure is reported here.

The CuII ion in (I) has a distorted square-pyramidal geometry, with the apical position occupied by one Cl− anion (Fig. 1). Two N atoms of one dmphen molecule and two O atoms of one benzoate anion form the basal plane.

Molecules in the crystal are arranged in chains formed by π–π stacking of the dmphen molecules (Fig. 2). These intermolecular interactions occur between rings C8···C11/N1/C13 and C2···C5/C14/N2 within the staggered conformation. The distance between the ring centroids X(1 A) and X(1B) and the perpendicular distance from X(1 A) to X(1B) rings (symmetry code for symmetry related molecules: 1 + x, 1/2 + y, -z) are 3.978 (5) and 3.614 (5) Å, respectively. The dihedral angle between these planes is 2.8 (5)°.

Related literature top

For related literature, see: Pallenberg et al. (1995); Tian & Long (2000); Paulovicova et al. (2001); Lemoine et al. (2003).

Experimental top

To a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C14H12N2.0.5 H2O, 0.22 g, 1 mmol) and sodium benzoate (0.17 g, 1 mmol) in ethanol/water (20 ml) was added a solution of CuCl2·2H2O (0.18 g, 1 mmol) in distilled water (10 ml). The resulting solution was refluxed for 1 h and then a pale green precipitate was filtered. Blue single crystals of (I) were obtained by slow evaporation of the filtrate after 1 d.

Refinement top

H atoms were positioned geometrically and treated as riding, with C—H distances in the range 0.95–0.99 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The π–π interactions between dmphen ligands in the crystal structure of (I). H atoms have been omitted for clarity.
(Benzoato-κ2O,O')chlorido(2,9-dimethyl-1,10-phenanthroline- κ2N,N')copper(II) top
Crystal data top
[Cu(C7H5O2)Cl(C14H12N2)]F000 = 876
Mr = 428.36Dx = 1.514 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4230 reflections
a = 8.0991 (8) Åθ = 2.6–22.1º
b = 15.9385 (15) ŵ = 1.32 mm−1
c = 15.0440 (14) ÅT = 291 (2) K
β = 104.6100 (10)ºBlock, blue
V = 1879.2 (3) Å30.36 × 0.27 × 0.24 mm
Z = 4
Data collection top
SMART CCD area-detector
diffractometer		3499 independent reflections
Radiation source: fine-focus sealed tube2627 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −9→9
Tmin = 0.634, Tmax = 0.727k = −19→19
14114 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.118  w = 1/[σ2(Fo2) + (0.0601P)2 + 0.8256P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3499 reflectionsΔρmax = 0.55 e Å−3
246 parametersΔρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C7H5O2)Cl(C14H12N2)]V = 1879.2 (3) Å3
Mr = 428.36Z = 4
Monoclinic, P21/nMo Kα
a = 8.0991 (8) ŵ = 1.32 mm−1
b = 15.9385 (15) ÅT = 291 (2) K
c = 15.0440 (14) Å0.36 × 0.27 × 0.24 mm
β = 104.6100 (10)º
Data collection top
SMART CCD area-detector
diffractometer		3499 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		2627 reflections with I > 2σ(I)
Tmin = 0.634, Tmax = 0.727Rint = 0.021
14114 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040246 parameters
wR(F2) = 0.118H-atom parameters constrained
S = 1.03Δρmax = 0.55 e Å−3
3499 reflectionsΔρmin = −0.28 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.25490 (5)0.18713 (2)0.62658 (3)0.06726 (17)
Cl10.51574 (12)0.20729 (7)0.72554 (7)0.0892 (3)
O10.0325 (3)0.23262 (14)0.6526 (2)0.0883 (7)
O20.1888 (4)0.30772 (16)0.5907 (2)0.1047 (9)
N10.2118 (3)0.06795 (16)0.6532 (2)0.0692 (7)
N20.2893 (3)0.13257 (18)0.50468 (17)0.0654 (7)
C10.3686 (5)0.2577 (3)0.4339 (3)0.0989 (13)
H1A0.26190.28720.41910.148*
H1B0.43060.27040.38900.148*
H1C0.43440.27470.49360.148*
C20.3361 (4)0.1660 (3)0.4340 (2)0.0798 (10)
C30.3579 (5)0.1140 (4)0.3609 (3)0.1068 (15)
H30.39250.13750.31200.128*
C40.3290 (5)0.0311 (4)0.3621 (3)0.1126 (17)
H40.3411−0.00190.31320.135*
C50.2808 (4)−0.0064 (3)0.4361 (3)0.0914 (12)
C60.2490 (6)−0.0936 (3)0.4431 (4)0.1109 (17)
H60.2599−0.12950.39610.133*
C70.2039 (6)−0.1248 (3)0.5157 (4)0.1129 (17)
H70.1829−0.18210.51780.135*
C80.1869 (4)−0.0736 (2)0.5896 (3)0.0878 (12)
C90.1446 (5)−0.1015 (3)0.6678 (4)0.1085 (15)
H90.1211−0.15800.67380.130*
C100.1370 (6)−0.0480 (3)0.7348 (4)0.1115 (15)
H100.1088−0.06790.78720.134*
C110.1711 (5)0.0386 (2)0.7277 (3)0.0916 (11)
C120.1657 (7)0.0984 (3)0.8021 (3)0.1284 (19)
H12A0.26450.13400.81350.193*
H12B0.16470.06800.85700.193*
H12C0.06450.13210.78420.193*
C130.2195 (4)0.0140 (2)0.5848 (3)0.0703 (9)
C140.2637 (4)0.0475 (2)0.5068 (2)0.0702 (9)
C150.0574 (4)0.30065 (18)0.6177 (2)0.0618 (7)
C16−0.0696 (4)0.36993 (19)0.60953 (19)0.0636 (7)
C17−0.2333 (4)0.3520 (3)0.6138 (2)0.0802 (10)
H17−0.26440.29720.62340.096*
C18−0.3518 (5)0.4165 (3)0.6036 (3)0.1022 (13)
H18−0.46410.40440.60370.123*
C19−0.3057 (7)0.4971 (3)0.5935 (3)0.1080 (14)
H19−0.38580.53990.58820.130*
C20−0.1434 (7)0.5157 (3)0.5911 (3)0.1134 (15)
H20−0.11130.57120.58590.136*
C21−0.0254 (5)0.4515 (2)0.5965 (3)0.0924 (11)
H210.08400.46370.59120.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0660 (3)0.0575 (2)0.0816 (3)0.00553 (17)0.0248 (2)0.00678 (18)
Cl10.0797 (6)0.0941 (7)0.0833 (6)−0.0101 (5)0.0008 (4)−0.0077 (5)
O10.0784 (15)0.0559 (14)0.136 (2)0.0059 (11)0.0374 (15)0.0078 (14)
O20.104 (2)0.0773 (17)0.156 (3)0.0294 (14)0.0753 (19)0.0437 (16)
N10.0591 (14)0.0613 (15)0.0919 (19)0.0120 (12)0.0276 (13)0.0080 (14)
N20.0464 (13)0.0868 (19)0.0587 (15)0.0011 (12)0.0053 (11)−0.0053 (13)
C10.088 (3)0.136 (4)0.073 (2)−0.009 (3)0.0217 (19)0.023 (2)
C20.0550 (18)0.120 (3)0.0585 (19)−0.0011 (18)0.0035 (15)−0.005 (2)
C30.070 (2)0.185 (5)0.061 (2)0.000 (3)0.0065 (17)−0.010 (3)
C40.075 (3)0.166 (5)0.083 (3)0.019 (3)−0.005 (2)−0.051 (3)
C50.056 (2)0.114 (3)0.088 (3)0.0143 (19)−0.0118 (18)−0.034 (2)
C60.082 (3)0.095 (3)0.129 (4)0.019 (2)−0.022 (3)−0.055 (3)
C70.078 (3)0.077 (3)0.154 (5)0.007 (2)−0.027 (3)−0.029 (3)
C80.0470 (17)0.070 (2)0.130 (3)0.0055 (15)−0.008 (2)−0.008 (2)
C90.068 (2)0.082 (3)0.166 (5)−0.002 (2)0.012 (3)0.030 (3)
C100.096 (3)0.096 (3)0.154 (4)0.013 (3)0.054 (3)0.046 (3)
C110.086 (2)0.080 (2)0.121 (3)0.018 (2)0.049 (2)0.028 (2)
C120.176 (5)0.116 (4)0.123 (4)0.040 (3)0.095 (4)0.039 (3)
C130.0426 (15)0.065 (2)0.095 (2)0.0062 (13)0.0038 (15)−0.0020 (18)
C140.0411 (15)0.081 (2)0.077 (2)0.0106 (14)−0.0052 (14)−0.0212 (18)
C150.0630 (18)0.0551 (18)0.0635 (18)−0.0012 (13)0.0090 (14)−0.0038 (14)
C160.0710 (19)0.0636 (18)0.0524 (16)0.0075 (15)0.0087 (14)−0.0029 (13)
C170.071 (2)0.082 (2)0.087 (2)0.0052 (18)0.0190 (18)−0.0189 (19)
C180.080 (3)0.117 (4)0.112 (3)0.020 (2)0.027 (2)−0.019 (3)
C190.112 (4)0.102 (3)0.110 (3)0.046 (3)0.030 (3)−0.001 (3)
C200.123 (4)0.077 (3)0.145 (4)0.033 (3)0.042 (3)0.029 (3)
C210.090 (3)0.071 (2)0.120 (3)0.0204 (19)0.035 (2)0.022 (2)
Geometric parameters (Å, °) top
Cu1—N11.990 (3)C7—C81.414 (6)
Cu1—O22.031 (2)C7—H70.9300
Cu1—O12.069 (2)C8—C91.379 (6)
Cu1—N22.111 (3)C8—C131.426 (5)
Cu1—Cl12.2795 (10)C9—C101.334 (7)
Cu1—C152.396 (3)C9—H90.9300
O1—C151.243 (4)C10—C111.417 (6)
O2—C151.236 (4)C10—H100.9300
N1—C111.330 (5)C11—C121.480 (6)
N1—C131.356 (4)C12—H12A0.9600
N2—C21.328 (4)C12—H12B0.9600
N2—C141.374 (4)C12—H12C0.9600
C1—C21.485 (5)C13—C141.414 (5)
C1—H1A0.9600C15—C161.493 (4)
C1—H1B0.9600C16—C171.374 (5)
C1—H1C0.9600C16—C211.376 (5)
C2—C31.424 (6)C17—C181.389 (5)
C3—C41.342 (7)C17—H170.9300
C3—H30.9300C18—C191.357 (6)
C4—C51.402 (7)C18—H180.9300
C4—H40.9300C19—C201.357 (6)
C5—C141.401 (5)C19—H190.9300
C5—C61.423 (6)C20—C211.388 (5)
C6—C71.333 (7)C20—H200.9300
C6—H60.9300C21—H210.9300
N1—Cu1—O2155.33 (11)C9—C8—C13116.6 (4)
N1—Cu1—O195.23 (10)C7—C8—C13117.9 (5)
O2—Cu1—O162.29 (10)C10—C9—C8120.5 (4)
N1—Cu1—N281.37 (12)C10—C9—H9119.8
O2—Cu1—N2104.05 (12)C8—C9—H9119.8
O1—Cu1—N2128.40 (10)C9—C10—C11121.3 (5)
N1—Cu1—Cl1100.58 (8)C9—C10—H10119.4
O2—Cu1—Cl1100.31 (11)C11—C10—H10119.4
O1—Cu1—Cl1122.31 (8)N1—C11—C10120.0 (4)
N2—Cu1—Cl1108.78 (7)N1—C11—C12118.2 (4)
N1—Cu1—C15125.70 (10)C10—C11—C12121.8 (4)
O2—Cu1—C1531.05 (10)C11—C12—H12A109.5
O1—Cu1—C1531.25 (9)C11—C12—H12B109.5
N2—Cu1—C15119.69 (10)H12A—C12—H12B109.5
Cl1—Cu1—C15115.18 (8)C11—C12—H12C109.5
C15—O1—Cu189.06 (19)H12A—C12—H12C109.5
C15—O2—Cu191.0 (2)H12B—C12—H12C109.5
C11—N1—C13119.1 (3)N1—C13—C14117.4 (3)
C11—N1—Cu1126.7 (3)N1—C13—C8122.5 (4)
C13—N1—Cu1114.1 (2)C14—C13—C8120.1 (4)
C2—N2—C14119.4 (3)N2—C14—C5122.8 (4)
C2—N2—Cu1131.1 (3)N2—C14—C13117.6 (3)
C14—N2—Cu1109.4 (2)C5—C14—C13119.5 (4)
C2—C1—H1A109.5O2—C15—O1117.6 (3)
C2—C1—H1B109.5O2—C15—C16122.5 (3)
H1A—C1—H1B109.5O1—C15—C16119.9 (3)
C2—C1—H1C109.5O2—C15—Cu157.96 (16)
H1A—C1—H1C109.5O1—C15—Cu159.69 (16)
H1B—C1—H1C109.5C16—C15—Cu1178.1 (2)
N2—C2—C3120.0 (4)C17—C16—C21119.5 (3)
N2—C2—C1118.9 (3)C17—C16—C15119.7 (3)
C3—C2—C1121.1 (4)C21—C16—C15120.8 (3)
C4—C3—C2120.5 (4)C16—C17—C18119.2 (4)
C4—C3—H3119.8C16—C17—H17120.4
C2—C3—H3119.8C18—C17—H17120.4
C3—C4—C5121.0 (4)C19—C18—C17120.8 (4)
C3—C4—H4119.5C19—C18—H18119.6
C5—C4—H4119.5C17—C18—H18119.6
C14—C5—C4116.3 (4)C20—C19—C18120.3 (4)
C14—C5—C6119.2 (5)C20—C19—H19119.8
C4—C5—C6124.5 (5)C18—C19—H19119.8
C7—C6—C5121.2 (5)C19—C20—C21119.6 (4)
C7—C6—H6119.4C19—C20—H20120.2
C5—C6—H6119.4C21—C20—H20120.2
C6—C7—C8122.1 (5)C16—C21—C20120.3 (4)
C6—C7—H7119.0C16—C21—H21119.8
C8—C7—H7119.0C20—C21—H21119.8
C9—C8—C7125.4 (5)
N1—Cu1—O1—C15−168.1 (2)Cu1—N1—C11—C12−3.8 (5)
O2—Cu1—O1—C151.2 (2)C9—C10—C11—N1−0.1 (7)
N2—Cu1—O1—C15−85.0 (2)C9—C10—C11—C12−179.1 (5)
Cl1—Cu1—O1—C1585.9 (2)C11—N1—C13—C14−179.8 (3)
N1—Cu1—O2—C1525.0 (5)Cu1—N1—C13—C142.8 (3)
O1—Cu1—O2—C15−1.2 (2)C11—N1—C13—C8−0.5 (5)
N2—Cu1—O2—C15125.1 (2)Cu1—N1—C13—C8−177.9 (2)
Cl1—Cu1—O2—C15−122.4 (2)C9—C8—C13—N10.7 (5)
O2—Cu1—N1—C11−74.0 (4)C7—C8—C13—N1−178.0 (3)
O1—Cu1—N1—C11−50.8 (3)C9—C8—C13—C14−180.0 (3)
N2—Cu1—N1—C11−178.9 (3)C7—C8—C13—C141.3 (4)
Cl1—Cu1—N1—C1173.4 (3)C2—N2—C14—C5−1.6 (4)
C15—Cu1—N1—C11−58.4 (3)Cu1—N2—C14—C5−178.7 (2)
O2—Cu1—N1—C13103.2 (3)C2—N2—C14—C13177.9 (3)
O1—Cu1—N1—C13126.3 (2)Cu1—N2—C14—C130.8 (3)
N2—Cu1—N1—C13−1.8 (2)C4—C5—C14—N21.0 (4)
Cl1—Cu1—N1—C13−109.4 (2)C6—C5—C14—N2−178.9 (3)
C15—Cu1—N1—C13118.8 (2)C4—C5—C14—C13−178.5 (3)
N1—Cu1—N2—C2−176.2 (3)C6—C5—C14—C131.6 (5)
O2—Cu1—N2—C228.4 (3)N1—C13—C14—N2−2.4 (4)
O1—Cu1—N2—C294.0 (3)C8—C13—C14—N2178.3 (3)
Cl1—Cu1—N2—C2−77.9 (3)N1—C13—C14—C5177.2 (3)
C15—Cu1—N2—C257.5 (3)C8—C13—C14—C5−2.2 (4)
N1—Cu1—N2—C140.52 (18)Cu1—O2—C15—O12.0 (3)
O2—Cu1—N2—C14−154.91 (19)Cu1—O2—C15—C16−177.8 (3)
O1—Cu1—N2—C14−89.3 (2)Cu1—O1—C15—O2−2.0 (3)
Cl1—Cu1—N2—C1498.83 (17)Cu1—O1—C15—C16177.8 (2)
C15—Cu1—N2—C14−125.84 (18)N1—Cu1—C15—O2−167.4 (2)
C14—N2—C2—C30.5 (4)O1—Cu1—C15—O2177.9 (4)
Cu1—N2—C2—C3177.0 (2)N2—Cu1—C15—O2−66.1 (3)
C14—N2—C2—C1−178.1 (3)Cl1—Cu1—C15—O266.6 (3)
Cu1—N2—C2—C1−1.7 (4)N1—Cu1—C15—O114.6 (2)
N2—C2—C3—C41.0 (6)O2—Cu1—C15—O1−177.9 (4)
C1—C2—C3—C4179.6 (4)N2—Cu1—C15—O1116.0 (2)
C2—C3—C4—C5−1.6 (6)Cl1—Cu1—C15—O1−111.34 (19)
C3—C4—C5—C140.6 (6)O2—C15—C16—C17160.2 (3)
C3—C4—C5—C6−179.5 (4)O1—C15—C16—C17−19.6 (4)
C14—C5—C6—C7−0.2 (6)O2—C15—C16—C21−18.9 (5)
C4—C5—C6—C7179.9 (4)O1—C15—C16—C21161.3 (3)
C5—C6—C7—C8−0.7 (7)C21—C16—C17—C180.9 (5)
C6—C7—C8—C9−178.5 (4)C15—C16—C17—C18−178.3 (3)
C6—C7—C8—C130.1 (6)C16—C17—C18—C19−2.8 (6)
C7—C8—C9—C10178.0 (4)C17—C18—C19—C201.5 (7)
C13—C8—C9—C10−0.6 (6)C18—C19—C20—C211.8 (8)
C8—C9—C10—C110.3 (7)C17—C16—C21—C202.4 (6)
C13—N1—C11—C100.2 (5)C15—C16—C21—C20−178.5 (4)
Cu1—N1—C11—C10177.2 (3)C19—C20—C21—C16−3.8 (7)
C13—N1—C11—C12179.2 (3)
Acknowledgements top

Financial support by the Science Fund of Henan Province for Distinguished Young Scholar (No. 074100510005) is gratefully acknowledged.

references
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