Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023495/hb2414sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023495/hb2414Isup2.hkl |
CCDC reference: 650568
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.003 Å
- R factor = 0.025
- wR factor = 0.072
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT148_ALERT_3_B su on the a - Axis is Too Large (x 1000) . 20 Ang.
Alert level C PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.11 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.02 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1 .. 7.49 su PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.11 Ratio
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.30
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
2,2'-Bipyridylamine (5.0 mg, 0.03 mol) dissolved in 90%(v/v) methanol-water solution (2 ml) was reacted with benzoic acid (3.6 mg, 0.03 mol), dissolved in the same solution (2 ml) for 5 min at room temperature. This was followed by the addition of CuCl2.2H2O (5.0 mg, 0.03 mol) dissolved in H2O (1 ml) and reacted for 15 min at room temperature. After several days green plates of (I) appeared from the mother liquor.
All H atoms were located from the difference Fourier maps, and then were placed in idealized positions and treated as riding, with C—H = 0.93 Å, N—H = 0.86Å and Uiso(H) = 1.2Ueq(C,N).
The construction of novel Cu(II) complexes are important for the development of new therapeutic drug design, because some Cu(II) complexes of 1,10-phenanthroline have antitumor activity (Selvakumar et al., 2006; Li et al., 2005; Kelland, 2005; Ranford et al., 1993).
In a previous study, we have reported the structure of the ternary Cu(II) complex with 2,2'-bipyridylamine (bpa) and p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005) in which the bpa ligand has been used as the bidentate N-donor ligand and p-HB as the bidentate O-donor. In this study, we report the structure of the Cu(II) complex with bpa and benzenecarboxylate (BA), (I).
The central Cu atom in (I) (Fig. 1) has a square-pyramidal CuN2O2Cl geometry. Each Cu atom is coordinated by two N atoms from one bpa and two O atoms from one BA and one chloride anion. The bond distances and angles around the Cu atom indicate that the coordination geometry is a slightly distorted square pyramidal (Table 1).
In the complex molecule, the two pyridine rings of the bpa ligand are related by mirror symmetry and distinguished as Ring I (N1/C1—C5) and Ring II (N1i/C1i—C5i) [symmetry code: (i)(x, 1/2 - y, z)]. Four ligand atoms (N1, N1i,O1 and O1i) are neary coplanar, and the Cu atom deviates from the mean square plane towards the apical Cl atom by 0.2986 (1) Å. The bite angle N1—Cu1—N1i is in the range normally observed for the Cu(II) bpa complexes (Wang & Okabe, 2005; Youngme et al., 1999, 2004) The Cu—Cl distance is intermediate between the known values from 2.336 (2) to 2.733 (2) Å (Mao et al., 2004; Brophy et al., 1999). The long Cu—Cl bond distance is explained by the well known Jahn-Teller effect. The molecular structure of (I) is similar to that of the Cu(II) complex with bpa and p-HB (Wang & Okabe, 2005), although the hydrogen bonding and the packing modes of these are different to each other.
As shown in Figs. 2a and 2 b, the crystal structure of (I) is stabilized by hydrogen bonds (Table 2) and by two kinds of π-π stacking interactions with distances between the centroids of the aromatic rings, 3.592 (4) Å between Cg1 (Ring I) and Cg3 (Ring II) at (x, y, 1 + z) and 3.468 (4) Å between Cg2 (N1/C5/N2/C5i/N1i/Cu1) [symmetry code: (i) (x, 1/2 - y, z)] and Cg4 (BA) at (1 - x, 1 - y, 1 - z).
For related literature, see: Brophy et al. (1999); Kelland (2005); Li et al. (2005); Mao et al. (2004); Ranford et al. (1993); Selvakumar et al. (2006); Wang & Okabe (2005); Youngme et al. (2004).
For related literature, see: Youngme (1999).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Betteridge et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997), and PLATON (Spek, 2003); software used to prepare material for publication: CrystalStructure.
[Cu(C7H5O2)Cl(C10H9N3)] | F(000) = 796.0 |
Mr = 391.31 | Dx = 1.644 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 13658 reflections |
a = 19.31 (2) Å | θ = 3.1–27.5° |
b = 11.77 (1) Å | µ = 1.57 mm−1 |
c = 6.958 (6) Å | T = 123 K |
V = 1581 (3) Å3 | Plate, green |
Z = 4 | 0.40 × 0.40 × 0.10 mm |
Rigaku R-AXIS RAPID diffractometer | 1746 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.015 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR : Higashi,1995) | h = −25→25 |
Tmin = 0.587, Tmax = 0.840 | k = −15→15 |
15128 measured reflections | l = −8→9 |
1893 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0341P)2 + 1.7191P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.072 | (Δ/σ)max < 0.001 |
S = 1.12 | Δρmax = 0.34 e Å−3 |
1893 reflections | Δρmin = −1.17 e Å−3 |
119 parameters |
[Cu(C7H5O2)Cl(C10H9N3)] | V = 1581 (3) Å3 |
Mr = 391.31 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 19.31 (2) Å | µ = 1.57 mm−1 |
b = 11.77 (1) Å | T = 123 K |
c = 6.958 (6) Å | 0.40 × 0.40 × 0.10 mm |
Rigaku R-AXIS RAPID diffractometer | 1893 independent reflections |
Absorption correction: multi-scan (ABSCOR : Higashi,1995) | 1746 reflections with F2 > 2.0σ(F2) |
Tmin = 0.587, Tmax = 0.840 | Rint = 0.015 |
15128 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 119 parameters |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.34 e Å−3 |
1893 reflections | Δρmin = −1.17 e Å−3 |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.61824 (1) | 0.2500 | 0.18707 (4) | 0.0144 (1) | |
Cl1 | 0.50045 (3) | 0.2500 | 0.03740 (8) | 0.0198 (1) | |
O1 | 0.67196 (6) | 0.3426 (1) | −0.0121 (2) | 0.0190 (3) | |
N1 | 0.60171 (7) | 0.3723 (1) | 0.3734 (2) | 0.0148 (3) | |
N2 | 0.5622 (1) | 0.2500 | 0.6194 (3) | 0.0166 (4) | |
C1 | 0.61517 (9) | 0.4801 (2) | 0.3141 (3) | 0.0201 (4) | |
C2 | 0.6049 (1) | 0.5735 (2) | 0.4273 (3) | 0.0238 (4) | |
C3 | 0.57907 (9) | 0.5576 (1) | 0.6132 (3) | 0.0210 (4) | |
C4 | 0.56524 (9) | 0.4495 (2) | 0.6754 (2) | 0.0183 (3) | |
C5 | 0.57716 (8) | 0.3570 (1) | 0.5513 (2) | 0.0146 (3) | |
C6 | 0.6903 (1) | 0.2500 | −0.0902 (3) | 0.0153 (4) | |
C7 | 0.7299 (1) | 0.2500 | −0.2737 (3) | 0.0144 (4) | |
C8 | 0.74776 (9) | 0.1475 (1) | −0.3616 (3) | 0.0178 (3) | |
C9 | 0.78256 (9) | 0.1476 (1) | −0.5363 (3) | 0.0203 (3) | |
C10 | 0.7993 (1) | 0.2500 | −0.6228 (4) | 0.0208 (5) | |
H1 | 0.6322 | 0.4908 | 0.1905 | 0.024* | |
H2 | 0.6148 | 0.6460 | 0.3816 | 0.028* | |
H3 | 0.5714 | 0.6195 | 0.6935 | 0.025* | |
H4 | 0.5481 | 0.4373 | 0.7986 | 0.022* | |
H5 | 0.5391 | 0.2500 | 0.7250 | 0.020* | |
H6 | 0.7363 | 0.0791 | −0.3030 | 0.021* | |
H7 | 0.7945 | 0.0793 | −0.5948 | 0.024* | |
H8 | 0.8221 | 0.2500 | −0.7405 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0185 (2) | 0.0141 (2) | 0.0105 (2) | 0.0000 | 0.0030 (1) | 0.0000 |
Cl1 | 0.0175 (3) | 0.0296 (3) | 0.0125 (3) | 0.0000 | 0.0023 (2) | 0.0000 |
O1 | 0.0228 (6) | 0.0191 (6) | 0.0150 (6) | 0.0009 (5) | 0.0050 (5) | −0.0011 (5) |
N1 | 0.0159 (6) | 0.0150 (6) | 0.0136 (6) | −0.0010 (5) | 0.0010 (5) | −0.0012 (5) |
N2 | 0.020 (1) | 0.021 (1) | 0.0092 (9) | 0.0000 | 0.0052 (8) | 0.0000 |
C1 | 0.0234 (9) | 0.0182 (9) | 0.0187 (9) | −0.0028 (6) | 0.0043 (6) | −0.0000 (7) |
C2 | 0.0264 (9) | 0.0156 (8) | 0.0292 (9) | −0.0030 (7) | 0.0046 (8) | −0.0017 (7) |
C3 | 0.0201 (8) | 0.0197 (8) | 0.0233 (9) | 0.0006 (7) | −0.0007 (7) | −0.0085 (7) |
C4 | 0.0167 (7) | 0.0236 (9) | 0.0146 (8) | 0.0020 (6) | −0.0001 (6) | −0.0040 (6) |
C5 | 0.0124 (7) | 0.0182 (8) | 0.0133 (7) | 0.0000 (6) | −0.0011 (6) | −0.0010 (6) |
C6 | 0.014 (1) | 0.020 (1) | 0.012 (1) | 0.0000 | −0.0014 (9) | 0.0000 |
C7 | 0.0120 (9) | 0.018 (1) | 0.013 (1) | 0.0000 | −0.0004 (9) | 0.0000 |
C8 | 0.0182 (7) | 0.0167 (8) | 0.0185 (8) | −0.0010 (6) | 0.0023 (6) | 0.0009 (7) |
C9 | 0.0212 (8) | 0.0206 (8) | 0.0190 (8) | 0.0002 (6) | 0.0036 (7) | −0.0053 (7) |
C10 | 0.020 (1) | 0.030 (1) | 0.012 (1) | 0.0000 | 0.0054 (9) | 0.0000 |
Cu1—Cl1 | 2.502 (3) | C3—C4 | 1.370 (3) |
Cu1—O1 | 2.046 (1) | C3—H3 | 0.9300 |
Cu1—O1i | 2.046 (1) | C4—C5 | 1.409 (2) |
Cu1—N1 | 1.963 (1) | C4—H4 | 0.9300 |
Cu1—N1i | 1.963 (1) | C6—O1i | 1.269 (2) |
C6—O1 | 1.269 (2) | C6—C7 | 1.488 (3) |
N1—C1 | 1.359 (2) | C7—C8 | 1.396 (2) |
N1—C5 | 1.338 (2) | C7—C8i | 1.396 (2) |
N2—C5 | 1.377 (2) | C8—C9 | 1.389 (2) |
N2—C5i | 1.377 (2) | C8—H6 | 0.9300 |
N2—H5 | 0.8600 | C9—C10 | 1.386 (2) |
C1—C2 | 1.367 (3) | C9—H7 | 0.9300 |
C1—H1 | 0.9300 | C10—C9i | 1.386 (2) |
C2—C3 | 1.399 (3) | C10—H8 | 0.9300 |
C2—H2 | 0.9299 | ||
Cl1—Cu1—O1 | 100.32 (4) | H2—C2—C1 | 120.7624 |
Cl1—Cu1—O1i | 100.32 (4) | C4—C3—C2 | 119.0 (2) |
Cl1—Cu1—N1 | 97.30 (4) | C4—C3—H3 | 120.4892 |
Cl1—Cu1—N1i | 97.30 (4) | H3—C3—C2 | 120.4784 |
O1—Cu1—O1i | 64.43 (5) | C5—C4—C3 | 119.5 (2) |
O1—Cu1—N1 | 97.97 (5) | C5—C4—H4 | 120.2397 |
O1—Cu1—N1i | 156.99 (5) | H4—C4—C3 | 120.2411 |
O1i—Cu1—N1 | 156.99 (5) | O1i—C6—O1 | 118.5 (2) |
O1i—Cu1—N1i | 97.97 (5) | O1i—C6—C7 | 120.7 (1) |
N1—Cu1—N1i | 94.33 (6) | C7—C6—O1 | 120.7 (1) |
C6—O1—Cu1 | 88.5 (1) | C8—C7—C6 | 120.2 (1) |
C1—N1—Cu1 | 117.0 (1) | C8—C7—C8i | 119.6 (2) |
C1—N1—C5 | 118.3 (1) | C8i—C7—C6 | 120.2 (1) |
C5—N1—Cu1 | 124.7 (1) | C9—C8—C7 | 120.2 (2) |
C5—N2—C5i | 132.5 (2) | C9—C8—H6 | 119.9074 |
C5—N2—H5 | 113.7538 | H6—C8—C7 | 119.9042 |
C5i—N2—H5 | 113.7538 | C10—C9—C8 | 119.5 (2) |
C2—C1—N1 | 123.3 (2) | C10—C9—H7 | 120.2314 |
C2—C1—H1 | 118.3538 | H7—C9—C8 | 120.2290 |
H1—C1—N1 | 118.3581 | C9i—C10—C9 | 120.9 (2) |
C3—C2—C1 | 118.5 (2) | C9i—C10—H8 | 119.5321 |
C3—C2—H2 | 120.7669 | H8—C10—C9 | 119.5321 |
Cl1—Cu1—O1—C6 | −94.68 (11) | C1—C2—C3—C4 | 0.1 (2) |
Cl1—Cu1—N1—C1 | −89.35 (12) | C2—C3—C4—C5 | −0.0 (2) |
Cu1—O1—C6—C7 | 174.32 (17) | C3—C4—C5—N1 | −0.1 (2) |
Cu1—N1—C1—C2 | 178.8 (1) | C3—C4—C5—N2 | −179.67 (17) |
Cu1—N1—C5—N2 | 1.0 (2) | O1—C6—C7—C8 | −177.83 (18) |
Cu1—N1—C5—C4 | −178.6 (1) | C6—C7—C8—C9 | 177.7 (3) |
H5—N2—C5—N1 | −168.0 | C7—C8—C9—C10 | −0.1 (2) |
H5—N2—C5—C4 | 11.6 | C8—C9—C10—H8 | −179.2 |
N1—C1—C2—C3 | −0.1 (2) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···Cl1ii | 0.86 | 2.3 | 3.144 (2) | 168 |
Symmetry code: (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H5O2)Cl(C10H9N3)] |
Mr | 391.31 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 123 |
a, b, c (Å) | 19.31 (2), 11.77 (1), 6.958 (6) |
V (Å3) | 1581 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.57 |
Crystal size (mm) | 0.40 × 0.40 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR : Higashi,1995) |
Tmin, Tmax | 0.587, 0.840 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 15128, 1893, 1746 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.072, 1.12 |
No. of reflections | 1893 |
No. of parameters | 119 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −1.17 |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Betteridge et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), and PLATON (Spek, 2003), CrystalStructure.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···Cl1i | 0.86 | 2.3 | 3.144 (2) | 168 |
Symmetry code: (i) x, y, z+1. |
The construction of novel Cu(II) complexes are important for the development of new therapeutic drug design, because some Cu(II) complexes of 1,10-phenanthroline have antitumor activity (Selvakumar et al., 2006; Li et al., 2005; Kelland, 2005; Ranford et al., 1993).
In a previous study, we have reported the structure of the ternary Cu(II) complex with 2,2'-bipyridylamine (bpa) and p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005) in which the bpa ligand has been used as the bidentate N-donor ligand and p-HB as the bidentate O-donor. In this study, we report the structure of the Cu(II) complex with bpa and benzenecarboxylate (BA), (I).
The central Cu atom in (I) (Fig. 1) has a square-pyramidal CuN2O2Cl geometry. Each Cu atom is coordinated by two N atoms from one bpa and two O atoms from one BA and one chloride anion. The bond distances and angles around the Cu atom indicate that the coordination geometry is a slightly distorted square pyramidal (Table 1).
In the complex molecule, the two pyridine rings of the bpa ligand are related by mirror symmetry and distinguished as Ring I (N1/C1—C5) and Ring II (N1i/C1i—C5i) [symmetry code: (i)(x, 1/2 - y, z)]. Four ligand atoms (N1, N1i,O1 and O1i) are neary coplanar, and the Cu atom deviates from the mean square plane towards the apical Cl atom by 0.2986 (1) Å. The bite angle N1—Cu1—N1i is in the range normally observed for the Cu(II) bpa complexes (Wang & Okabe, 2005; Youngme et al., 1999, 2004) The Cu—Cl distance is intermediate between the known values from 2.336 (2) to 2.733 (2) Å (Mao et al., 2004; Brophy et al., 1999). The long Cu—Cl bond distance is explained by the well known Jahn-Teller effect. The molecular structure of (I) is similar to that of the Cu(II) complex with bpa and p-HB (Wang & Okabe, 2005), although the hydrogen bonding and the packing modes of these are different to each other.
As shown in Figs. 2a and 2 b, the crystal structure of (I) is stabilized by hydrogen bonds (Table 2) and by two kinds of π-π stacking interactions with distances between the centroids of the aromatic rings, 3.592 (4) Å between Cg1 (Ring I) and Cg3 (Ring II) at (x, y, 1 + z) and 3.468 (4) Å between Cg2 (N1/C5/N2/C5i/N1i/Cu1) [symmetry code: (i) (x, 1/2 - y, z)] and Cg4 (BA) at (1 - x, 1 - y, 1 - z).