Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033776/tk2180sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033776/tk2180Isup2.hkl |
CCDC reference: 657591
2,2'-Bipyridylamine (5.0 mg, 0.03 mol) dissolved in 90% (v/v) methanol–water solution (2 ml) was mixed with p-nitrobenzoic acid (4.9 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 prismatic crystals of (I) appeared from the mother liquor.
All H atoms were placed in idealized positions and treated as riding, with C—H = 0.93 Å and N—H = 0.86, and with Uiso(H) = 1.2Ueq(C,N).
As part of our studies of new therapeutic drugs, we have reported the structures of ternary Cu(II) complexes with the heterocyclic ligand 2,2'-bipyridylamine (bpa) and various carboxylate ligands, such as p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005), cyclobutane-1,1-dicarboxylate (Yodoshi, Mototsuji & Okabe, 2007), benzenecarboxylate (BA) (Okabe et al., 2007), and glycinate (Yodoshi, Odoko & Okabe, 2007). In this study, we describe the structure of the title Cu(II) complex, (I), containing bpa and 4-nitrobenzoate (p-NBA) and chloride anions.
The overall structure of (I) is similar to those of the ternary Cu(II) complexes with bpa and p-HB (Wang & Okabe, 2005) and BA (Okabe et al., 2007). The central Cu atom in (I) (Fig. 1) has a square pyramidal CuN2O2Cl geometry (Table 1), resulting from its coordination by two N atoms from the bpa molecule, two O atoms from the p-NBA anion and one Cl atom. The four basal atoms (N1, N2, O1 and O2) are neary coplanar and the Cu atom deviates from their least-squares plane towards the apical Cl atom by 0.3274 (1) Å. The O1—Cu1—O2 and N1—Cu1—N2 bite angles of 64.25 (7) and 94.71 (8) Å, respectively, are in the ranges normally observed for these complexes (Wang & Okabe, 2005; Okabe et al., 2007; Yodoshi, Mototsuji & Okabe, 2007; Yodoshi, Odoko & Okabe, 2007; Youngme et al., 2004). The Cu—Cl distance of 2.468 (3)Å is intermediate between the known values from 2.336 (2) to 2.733 (2) Å (Mao et al., 2004; Brophy et al., 1999). Such long Cu—Cl bonds are explained by the well known Jahn-Teller effect.
As shown in Fig. 2, the crystal structure is stabilized by N3—H9···Cl1i hydrogen bonds [i: 2 - x, -y, 1 - z] as well as by three kinds of π-π stacking interactions with the distances between the centroids of the aromatic rings being 3.531 (4) Å for Cg1(N1/C1—C5) and Cg3(N2/C6—C10) at (1 - x, -y, -z), 3.754 (4) Å for Cg2(N1/C5/N3/C6/N2/Cu1) and Cg2 at (1 - x, -y, -z), and 3.549 (4) Å for Cg4(C12—C17) and Cg2 at (-x, -y, -1 - z).
For related literature, see: Brophy et al. (1999); Mao et al. (2004); Okabe et al. (2007); Wang & Okabe (2005); Yodoshi, Mototsuji & Okabe (2007); Yodoshi, Odoko & Okabe (2007); Youngme et al. (2004).
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(C7H4NO4)Cl(C10H9N3)] | Z = 2 |
Mr = 436.31 | F(000) = 442 |
Triclinic, P1 | Dx = 1.732 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 8.87 (1) Å | Cell parameters from 7938 reflections |
b = 9.085 (8) Å | θ = 3.0–27.5° |
c = 11.23 (1) Å | µ = 1.50 mm−1 |
α = 102.67 (3)° | T = 123 K |
β = 105.34 (3)° | Block, green |
γ = 96.72 (4)° | 0.20 × 0.20 × 0.20 mm |
V = 836.6 (14) Å3 |
Rigaku R-AXIS RAPID diffractometer | 3552 reflections with F2 > 2σ(F2) |
Detector resolution: 10.0 pixels mm-1 | Rint = 0.014 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
Tmin = 0.633, Tmax = 0.740 | k = −11→11 |
8197 measured reflections | l = −14→13 |
3794 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.02P)2 + 1.3275P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max < 0.001 |
S = 1.22 | Δρmax = 0.47 e Å−3 |
3794 reflections | Δρmin = −0.37 e Å−3 |
245 parameters |
[Cu(C7H4NO4)Cl(C10H9N3)] | γ = 96.72 (4)° |
Mr = 436.31 | V = 836.6 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.87 (1) Å | Mo Kα radiation |
b = 9.085 (8) Å | µ = 1.50 mm−1 |
c = 11.23 (1) Å | T = 123 K |
α = 102.67 (3)° | 0.20 × 0.20 × 0.20 mm |
β = 105.34 (3)° |
Rigaku R-AXIS RAPID diffractometer | 3794 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3552 reflections with F2 > 2σ(F2) |
Tmin = 0.633, Tmax = 0.740 | Rint = 0.014 |
8197 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 245 parameters |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.22 | Δρmax = 0.47 e Å−3 |
3794 reflections | Δρmin = −0.37 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 | 0.73294 (3) | 0.07819 (3) | 0.27481 (3) | 0.01278 (8) | |
Cl1 | 0.70600 (6) | 0.23331 (6) | 0.47546 (5) | 0.0173 (1) | |
O1 | 0.6611 (2) | 0.2345 (2) | 0.1668 (2) | 0.0175 (3) | |
O2 | 0.5053 (2) | 0.0288 (2) | 0.1663 (2) | 0.0178 (3) | |
O3 | −0.0260 (2) | 0.4624 (2) | −0.1488 (2) | 0.0236 (4) | |
O4 | −0.1654 (2) | 0.2565 (2) | −0.1366 (2) | 0.0259 (4) | |
N1 | 0.9631 (2) | 0.1289 (2) | 0.3077 (2) | 0.0131 (3) | |
N2 | 0.7358 (2) | −0.1247 (2) | 0.3095 (2) | 0.0139 (3) | |
N3 | 1.0167 (2) | −0.1001 (2) | 0.3660 (2) | 0.0145 (4) | |
N4 | −0.0381 (2) | 0.3401 (2) | −0.1195 (2) | 0.0173 (4) | |
C1 | 1.0206 (3) | 0.2650 (3) | 0.2896 (2) | 0.0161 (4) | |
C2 | 1.1788 (3) | 0.3166 (3) | 0.3095 (2) | 0.0190 (4) | |
C3 | 1.2867 (3) | 0.2236 (3) | 0.3494 (2) | 0.0177 (4) | |
C4 | 1.2313 (3) | 0.0849 (3) | 0.3668 (2) | 0.0159 (4) | |
C5 | 1.0671 (3) | 0.0395 (2) | 0.3462 (2) | 0.0129 (4) | |
C6 | 0.8680 (3) | −0.1814 (2) | 0.3489 (2) | 0.0134 (4) | |
C7 | 0.8602 (3) | −0.3277 (3) | 0.3738 (2) | 0.0165 (4) | |
C8 | 0.7149 (3) | −0.4120 (3) | 0.3600 (2) | 0.0186 (4) | |
C9 | 0.5780 (3) | −0.3515 (3) | 0.3211 (2) | 0.0198 (5) | |
C10 | 0.5934 (3) | −0.2102 (3) | 0.2967 (2) | 0.0177 (4) | |
C11 | 0.5245 (3) | 0.1524 (3) | 0.1326 (2) | 0.0140 (4) | |
C12 | 0.3807 (3) | 0.2005 (3) | 0.0586 (2) | 0.0131 (4) | |
C13 | 0.2366 (3) | 0.0967 (3) | 0.0131 (2) | 0.0144 (4) | |
C14 | 0.0990 (3) | 0.1430 (3) | −0.0461 (2) | 0.0148 (4) | |
C15 | 0.1099 (3) | 0.2917 (3) | −0.0591 (2) | 0.0142 (4) | |
C16 | 0.2522 (3) | 0.3956 (3) | −0.0182 (2) | 0.0162 (4) | |
C17 | 0.3891 (3) | 0.3480 (3) | 0.0422 (2) | 0.0157 (4) | |
H1 | 0.9487 | 0.3262 | 0.2624 | 0.019* | |
H2 | 1.2136 | 0.4109 | 0.2968 | 0.023* | |
H3 | 1.3951 | 0.2556 | 0.3640 | 0.021* | |
H4 | 1.3016 | 0.0214 | 0.3921 | 0.019* | |
H5 | 0.9527 | −0.3664 | 0.3993 | 0.020* | |
H6 | 0.7077 | −0.5082 | 0.3763 | 0.022* | |
H7 | 0.4783 | −0.4061 | 0.3120 | 0.024* | |
H8 | 0.5017 | −0.1708 | 0.2699 | 0.021* | |
H9 | 1.0932 | −0.1453 | 0.3947 | 0.017* | |
H10 | 0.2329 | −0.0028 | 0.0223 | 0.017* | |
H11 | 0.0016 | 0.0758 | −0.0763 | 0.018* | |
H12 | 0.2561 | 0.4937 | −0.0306 | 0.019* | |
H13 | 0.4865 | 0.4152 | 0.0716 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0089 (1) | 0.0130 (1) | 0.0164 (1) | 0.00345 (9) | 0.0011 (1) | 0.0062 (1) |
Cl1 | 0.0161 (3) | 0.0200 (3) | 0.0166 (3) | 0.0094 (2) | 0.0029 (2) | 0.0057 (2) |
O1 | 0.0115 (7) | 0.0191 (8) | 0.0210 (8) | 0.0032 (6) | 0.0013 (6) | 0.0079 (7) |
O2 | 0.0121 (7) | 0.0184 (8) | 0.0230 (8) | 0.0045 (6) | 0.0006 (6) | 0.0101 (7) |
O3 | 0.0251 (9) | 0.0277 (9) | 0.0240 (9) | 0.0142 (7) | 0.0067 (7) | 0.0149 (8) |
O4 | 0.0121 (8) | 0.0298 (9) | 0.033 (1) | 0.0061 (7) | 0.0015 (7) | 0.0083 (8) |
N1 | 0.0107 (8) | 0.0150 (9) | 0.0128 (8) | 0.0037 (7) | 0.0015 (7) | 0.0040 (7) |
N2 | 0.0134 (9) | 0.0136 (8) | 0.0139 (9) | 0.0031 (7) | 0.0021 (7) | 0.0041 (7) |
N3 | 0.0118 (8) | 0.0158 (9) | 0.0163 (9) | 0.0069 (7) | 0.0015 (7) | 0.0062 (7) |
N4 | 0.0161 (9) | 0.023 (1) | 0.0137 (9) | 0.0096 (8) | 0.0030 (7) | 0.0046 (8) |
C1 | 0.014 (1) | 0.017 (1) | 0.018 (1) | 0.0049 (8) | 0.0027 (8) | 0.0075 (9) |
C2 | 0.017 (1) | 0.021 (1) | 0.021 (1) | 0.0023 (9) | 0.0048 (9) | 0.0101 (9) |
C3 | 0.011 (1) | 0.026 (1) | 0.017 (1) | 0.0030 (9) | 0.0032 (8) | 0.0064 (9) |
C4 | 0.012 (1) | 0.021 (1) | 0.015 (1) | 0.0071 (8) | 0.0021 (8) | 0.0046 (9) |
C5 | 0.013 (1) | 0.016 (1) | 0.0095 (9) | 0.0046 (8) | 0.0019 (8) | 0.0024 (8) |
C6 | 0.016 (1) | 0.013 (1) | 0.0103 (9) | 0.0042 (8) | 0.0030 (8) | 0.0025 (8) |
C7 | 0.020 (1) | 0.015 (1) | 0.015 (1) | 0.0074 (8) | 0.0043 (9) | 0.0046 (8) |
C8 | 0.026 (1) | 0.013 (1) | 0.016 (1) | 0.0039 (9) | 0.0053 (9) | 0.0041 (9) |
C9 | 0.018 (1) | 0.018 (1) | 0.021 (1) | −0.0015 (9) | 0.0037 (9) | 0.0050 (9) |
C10 | 0.015 (1) | 0.019 (1) | 0.019 (1) | 0.0034 (8) | 0.0034 (9) | 0.0057 (9) |
C11 | 0.012 (1) | 0.016 (1) | 0.013 (1) | 0.0049 (8) | 0.0030 (8) | 0.0030 (8) |
C12 | 0.011 (1) | 0.017 (1) | 0.0112 (9) | 0.0051 (8) | 0.0030 (8) | 0.0047 (8) |
C13 | 0.015 (1) | 0.014 (1) | 0.015 (1) | 0.0039 (8) | 0.0038 (8) | 0.0055 (8) |
C14 | 0.011 (1) | 0.018 (1) | 0.014 (1) | 0.0022 (8) | 0.0023 (8) | 0.0040 (8) |
C15 | 0.012 (1) | 0.020 (1) | 0.012 (1) | 0.0083 (8) | 0.0033 (8) | 0.0056 (8) |
C16 | 0.018 (1) | 0.016 (1) | 0.018 (1) | 0.0065 (8) | 0.0057 (9) | 0.0084 (9) |
C17 | 0.013 (1) | 0.017 (1) | 0.017 (1) | 0.0022 (8) | 0.0034 (8) | 0.0055 (9) |
Cu1—Cl1 | 2.468 (3) | C3—H3 | 0.9300 |
Cu1—O1 | 2.110 (2) | C4—C5 | 1.408 (3) |
Cu1—O2 | 2.002 (3) | C4—H4 | 0.9300 |
Cu1—N1 | 1.955 (2) | C6—C7 | 1.415 (3) |
Cu1—N2 | 1.967 (2) | C7—C8 | 1.372 (3) |
O1—C11 | 1.260 (3) | C7—H5 | 0.9300 |
O2—C11 | 1.269 (3) | C8—C9 | 1.395 (4) |
O3—N4 | 1.226 (3) | C8—H6 | 0.9300 |
O4—N4 | 1.228 (3) | C9—C10 | 1.370 (4) |
N1—C1 | 1.359 (3) | C9—H7 | 0.9300 |
N1—C5 | 1.347 (3) | C10—H8 | 0.9300 |
N2—C6 | 1.342 (3) | C11—C12 | 1.495 (3) |
N2—C10 | 1.358 (3) | C12—C13 | 1.395 (3) |
N3—C5 | 1.379 (3) | C12—C17 | 1.388 (3) |
N3—C6 | 1.378 (3) | C13—C14 | 1.386 (3) |
N3—H9 | 0.8600 | C13—H10 | 0.9301 |
N4—C15 | 1.474 (3) | C14—C15 | 1.385 (3) |
C1—C2 | 1.368 (3) | C14—H11 | 0.9299 |
C1—H1 | 0.9299 | C15—C16 | 1.385 (3) |
C2—C3 | 1.400 (4) | C16—C17 | 1.392 (3) |
C2—H2 | 0.9300 | C16—H12 | 0.9299 |
C3—C4 | 1.372 (4) | C17—H13 | 0.9300 |
Cu1···N3 | 3.213 (2) | C5···H1 | 3.1569 |
Cu1···C1 | 2.838 (2) | C5···H3 | 3.2461 |
Cu1···C5 | 2.942 (2) | C5···H4 | 2.0415 |
Cu1···C6 | 2.947 (2) | C5···H9 | 1.8960 |
Cu1···C10 | 2.853 (2) | C5···H9ii | 3.5623 |
Cu1···C11 | 2.371 (2) | C5···H11i | 2.8517 |
Cu1···C13i | 3.370 (2) | C6···N3ii | 3.450 (3) |
Cu1···H1 | 2.8330 | C6···N4i | 3.454 (3) |
Cu1···H8 | 2.8508 | C6···C4ii | 3.489 (3) |
Cu1···H9ii | 3.5040 | C6···C5ii | 3.250 (3) |
Cu1···H10i | 3.3583 | C6···C8 | 2.405 (3) |
Cl1···O1 | 3.385 (2) | C6···C9 | 2.744 (3) |
Cl1···O2 | 3.435 (2) | C6···C10 | 2.317 (3) |
Cl1···N1 | 3.412 (2) | C6···C14i | 3.577 (4) |
Cl1···N2 | 3.454 (2) | C6···C15i | 3.254 (3) |
Cl1···N3ii | 3.163 (2) | C6···H5 | 2.0484 |
Cl1···C3iii | 3.594 (2) | C6···H6 | 3.2513 |
Cl1···H2iv | 3.5169 | C6···H8 | 3.1516 |
Cl1···H3iii | 2.7616 | C6···H9 | 1.8947 |
Cl1···H4ii | 3.0162 | C6···H9ii | 3.5643 |
Cl1···H5ii | 2.9570 | C7···O3i | 3.328 (3) |
Cl1···H6v | 2.8114 | C7···N1ii | 3.471 (3) |
Cl1···H7vi | 3.4427 | C7···N4i | 3.597 (4) |
Cl1···H9ii | 2.3252 | C7···C1ii | 3.539 (3) |
O1···O2 | 2.188 (2) | C7···C4ii | 3.586 (3) |
O1···N1 | 3.102 (2) | C7···C5ii | 3.476 (3) |
O1···C1 | 3.073 (3) | C7···C9 | 2.387 (3) |
O1···C8v | 3.360 (3) | C7···C10 | 2.721 (3) |
O1···C12 | 2.411 (2) | C7···H1xii | 3.3823 |
O1···C13i | 3.592 (3) | C7···H6 | 2.0098 |
O1···C17 | 2.876 (3) | C7···H7 | 3.2304 |
O1···H1 | 2.4514 | C7···H9 | 2.4167 |
O1···H6v | 2.8321 | C8···O1xii | 3.360 (3) |
O1···H10i | 3.0638 | C8···C2ii | 3.458 (3) |
O1···H12vii | 3.2862 | C8···C3ii | 3.341 (3) |
O1···H13 | 2.5930 | C8···C10 | 2.378 (4) |
O2···N2 | 2.936 (3) | C8···H1xii | 3.5177 |
O2···C3iii | 3.526 (3) | C8···H3ii | 3.5456 |
O2···C10 | 2.942 (3) | C8···H5 | 2.0094 |
O2···C11i | 3.325 (3) | C8···H7 | 2.0336 |
O2···C12 | 2.375 (3) | C8···H8 | 3.2136 |
O2···C12i | 3.358 (3) | C8···H13xii | 3.2572 |
O2···C13 | 2.768 (3) | C9···C3ii | 3.452 (3) |
O2···C13i | 3.555 (3) | C9···C17xii | 3.532 (3) |
O2···H3iii | 3.1214 | C9···H2xiii | 3.5802 |
O2···H4iii | 3.4882 | C9···H3ii | 3.3874 |
O2···H8 | 2.3613 | C9···H5 | 3.2319 |
O2···H10 | 2.4701 | C9···H6 | 2.0311 |
O2···H10i | 3.5278 | C9···H8 | 1.9878 |
O3···O3viii | 3.155 (3) | C9···H13xii | 2.9652 |
O3···O4 | 2.169 (3) | C10···C4ii | 3.547 (3) |
O3···O4viii | 3.492 (2) | C10···H4ii | 3.3617 |
O3···N4viii | 3.017 (3) | C10···H6 | 3.2220 |
O3···C1vii | 3.221 (3) | C10···H7 | 2.0100 |
O3···C2vii | 3.171 (3) | C11···O2i | 3.325 (3) |
O3···C7i | 3.328 (3) | C11···C11i | 3.486 (3) |
O3···C14 | 3.539 (3) | C11···C13 | 2.482 (3) |
O3···C15 | 2.314 (3) | C11···C17 | 2.505 (3) |
O3···C15viii | 3.165 (3) | C11···H3iii | 3.1151 |
O3···C16 | 2.726 (3) | C11···H6v | 3.5229 |
O3···C16viii | 3.277 (3) | C11···H10 | 2.6259 |
O3···H1vii | 2.6489 | C11···H10i | 3.3375 |
O3···H2vii | 2.5847 | C11···H13 | 2.6580 |
O3···H5i | 3.0205 | C12···O2i | 3.358 (3) |
O3···H9i | 3.3943 | C12···C3iii | 3.547 (4) |
O3···H12 | 2.4516 | C12···C14 | 2.402 (3) |
O3···H12viii | 3.2237 | C12···C15 | 2.733 (3) |
O4···O3viii | 3.492 (2) | C12···C16 | 2.410 (3) |
O4···N3i | 3.320 (3) | C12···H3iii | 3.3206 |
O4···C4i | 3.450 (3) | C12···H10 | 2.0291 |
O4···C5i | 3.519 (3) | C12···H11 | 3.2474 |
O4···C14 | 2.712 (3) | C12···H12 | 3.2553 |
O4···C15 | 2.321 (3) | C12···H13 | 2.0196 |
O4···C16 | 3.555 (3) | C13···Cu1i | 3.370 (2) |
O4···C16viii | 3.532 (3) | C13···O1i | 3.592 (3) |
O4···H4i | 3.2153 | C13···O2i | 3.555 (3) |
O4···H7ix | 3.5488 | C13···N1i | 3.585 (2) |
O4···H8ix | 2.8854 | C13···C3iii | 3.588 (3) |
O4···H9i | 3.1116 | C13···C15 | 2.381 (3) |
O4···H10ix | 2.9493 | C13···C16 | 2.806 (3) |
O4···H11 | 2.4230 | C13···C17 | 2.421 (3) |
O4···H12viii | 2.9466 | C13···H11 | 2.0259 |
N1···N2 | 2.885 (3) | C13···H11ix | 2.8158 |
N1···N3 | 2.377 (3) | C13···H13 | 3.2570 |
N1···C2 | 2.401 (3) | C14···N1i | 3.268 (3) |
N1···C3 | 2.780 (3) | C14···N3i | 3.385 (3) |
N1···C4 | 2.400 (3) | C14···C5i | 3.260 (3) |
N1···C6 | 3.016 (3) | C14···C6i | 3.577 (4) |
N1···C7ii | 3.471 (3) | C14···C14ix | 3.461 (4) |
N1···C13i | 3.585 (2) | C14···C16 | 2.438 (3) |
N1···C14i | 3.268 (3) | C14···C17 | 2.791 (3) |
N1···H1 | 1.9771 | C14···H10 | 2.0211 |
N1···H2 | 3.2347 | C14···H10ix | 3.1686 |
N1···H4 | 3.2326 | C14···H11ix | 2.8401 |
N1···H5ii | 3.3535 | C14···H12 | 3.2734 |
N1···H9 | 3.1038 | C15···O3viii | 3.165 (3) |
N1···H9ii | 3.4809 | C15···N2i | 3.568 (3) |
N1···H10i | 3.5119 | C15···N3i | 3.322 (3) |
N1···H11i | 2.9588 | C15···C6i | 3.254 (3) |
N2···N3 | 2.372 (3) | C15···C17 | 2.376 (3) |
N2···C4ii | 3.502 (3) | C15···H9i | 3.5874 |
N2···C5 | 3.015 (3) | C15···H10 | 3.2263 |
N2···C7 | 2.404 (3) | C15···H11 | 2.0252 |
N2···C8 | 2.786 (3) | C15···H12 | 2.0295 |
N2···C9 | 2.401 (3) | C15···H13 | 3.2209 |
N2···C15i | 3.568 (3) | C16···O3viii | 3.277 (3) |
N2···H4ii | 3.3917 | C16···O4viii | 3.532 (3) |
N2···H5 | 3.2359 | C16···N4viii | 3.571 (3) |
N2···H7 | 3.2328 | C16···H11 | 3.2709 |
N2···H8 | 1.9776 | C16···H13 | 2.0231 |
N2···H9 | 3.0993 | C16···H13vii | 2.9901 |
N2···H9ii | 3.4982 | C17···C9v | 3.532 (3) |
N3···Cl1ii | 3.163 (2) | C17···H2iii | 3.5736 |
N3···O4i | 3.320 (3) | C17···H7v | 3.1858 |
N3···N3ii | 3.263 (3) | C17···H10 | 3.2582 |
N3···N4i | 3.191 (3) | C17···H12 | 2.0356 |
N3···C4 | 2.384 (3) | C17···H12vii | 3.3505 |
N3···C5ii | 3.448 (3) | C17···H13vii | 2.9793 |
N3···C6ii | 3.450 (3) | H1···O3vii | 2.6489 |
N3···C7 | 2.383 (3) | H1···C7v | 3.3823 |
N3···C10 | 3.596 (3) | H1···C8v | 3.5177 |
N3···C14i | 3.385 (3) | H2···Cl1iv | 3.5169 |
N3···C15i | 3.322 (3) | H2···O3vii | 2.5847 |
N3···H4 | 2.5498 | H2···N4vii | 3.5583 |
N3···H5 | 2.5496 | H2···C9x | 3.5802 |
N3···H9ii | 3.5220 | H2···C17xi | 3.5736 |
N3···H11i | 3.2717 | H3···Cl1xi | 2.7616 |
N4···O3viii | 3.017 (3) | H3···O2xi | 3.1214 |
N4···N3i | 3.191 (3) | H3···C8ii | 3.5456 |
N4···N4viii | 3.356 (3) | H3···C9ii | 3.3874 |
N4···C6i | 3.454 (3) | H3···C11xi | 3.1151 |
N4···C7i | 3.597 (4) | H3···C12xi | 3.3206 |
N4···C14 | 2.448 (3) | H4···Cl1ii | 3.0162 |
N4···C16 | 2.464 (3) | H4···O2xi | 3.4882 |
N4···C16viii | 3.571 (3) | H4···O4i | 3.2153 |
N4···H2vii | 3.5583 | H4···N2ii | 3.3917 |
N4···H5i | 3.4709 | H4···C10ii | 3.3617 |
N4···H9i | 3.0861 | H5···Cl1ii | 2.9570 |
N4···H11 | 2.5975 | H5···O3i | 3.0205 |
N4···H12 | 2.6282 | H5···N1ii | 3.3535 |
N4···H12viii | 3.1857 | H5···N4i | 3.4709 |
C1···O3vii | 3.221 (3) | H5···C1xii | 3.4865 |
C1···C3 | 2.375 (3) | H5···C1ii | 3.3473 |
C1···C4 | 2.720 (3) | H6···Cl1xii | 2.8114 |
C1···C5 | 2.323 (3) | H6···O1xii | 2.8321 |
C1···C7ii | 3.539 (3) | H6···C2ii | 3.3923 |
C1···H2 | 2.0107 | H6···C3ii | 3.5455 |
C1···H3 | 3.2191 | H6···C11xii | 3.5229 |
C1···H5v | 3.4865 | H7···Cl1vi | 3.4427 |
C1···H5ii | 3.3473 | H7···O4ix | 3.5488 |
C1···H11i | 3.4228 | H7···C2xiii | 3.4306 |
C2···O3vii | 3.171 (3) | H7···C17xii | 3.1858 |
C2···C4 | 2.393 (4) | H8···O4ix | 2.8854 |
C2···C5 | 2.752 (3) | H9···Cu1ii | 3.5040 |
C2···C8ii | 3.458 (3) | H9···Cl1ii | 2.3252 |
C2···H1 | 1.9855 | H9···O3i | 3.3943 |
C2···H3 | 2.0341 | H9···O4i | 3.1116 |
C2···H4 | 3.2373 | H9···N1ii | 3.4809 |
C2···H6ii | 3.3923 | H9···N2ii | 3.4982 |
C2···H7x | 3.4306 | H9···N3ii | 3.5220 |
C3···Cl1xi | 3.594 (2) | H9···N4i | 3.0861 |
C3···O2xi | 3.526 (3) | H9···C5ii | 3.5623 |
C3···C5 | 2.401 (3) | H9···C6ii | 3.5643 |
C3···C8ii | 3.341 (3) | H9···C15i | 3.5874 |
C3···C9ii | 3.452 (3) | H10···Cu1i | 3.3583 |
C3···C12xi | 3.547 (4) | H10···O1i | 3.0638 |
C3···C13xi | 3.588 (3) | H10···O2i | 3.5278 |
C3···H1 | 3.2117 | H10···O4ix | 2.9493 |
C3···H2 | 2.0398 | H10···N1i | 3.5119 |
C3···H4 | 2.0081 | H10···C11i | 3.3375 |
C3···H6ii | 3.5455 | H10···C14ix | 3.1686 |
C4···O4i | 3.450 (3) | H11···N1i | 2.9588 |
C4···N2ii | 3.502 (3) | H11···N3i | 3.2717 |
C4···C6ii | 3.489 (3) | H11···C1i | 3.4228 |
C4···C7ii | 3.586 (3) | H11···C4i | 3.2677 |
C4···C10ii | 3.547 (3) | H11···C5i | 2.8517 |
C4···H2 | 3.2371 | H11···C13ix | 2.8158 |
C4···H3 | 2.0085 | H11···C14ix | 2.8401 |
C4···H9 | 2.4215 | H12···O1vii | 3.2862 |
C4···H11i | 3.2677 | H12···O3viii | 3.2237 |
C5···O4i | 3.519 (3) | H12···O4viii | 2.9466 |
C5···N3ii | 3.448 (3) | H12···N4viii | 3.1857 |
C5···C6 | 2.525 (3) | H13···C8v | 3.2572 |
C5···C6ii | 3.250 (3) | H13···C9v | 2.9652 |
C5···C7ii | 3.476 (3) | H13···C16vii | 2.9901 |
C5···C14i | 3.260 (3) | H13···C17vii | 2.9793 |
Cl1—Cu1—O1 | 95.05 (5) | C5—C4—H4 | 120.2593 |
Cl1—Cu1—O2 | 99.92 (5) | H4—C4—C3 | 120.2604 |
Cl1—Cu1—N1 | 100.33 (5) | C7—C6—N2 | 121.4 (2) |
Cl1—Cu1—N2 | 101.67 (6) | C7—C6—N3 | 117.2 (2) |
O1—Cu1—O2 | 64.25 (7) | C8—C7—C6 | 119.3 (2) |
O1—Cu1—N1 | 99.41 (8) | C8—C7—H5 | 120.3604 |
O1—Cu1—N2 | 155.79 (6) | H5—C7—C6 | 120.3492 |
O2—Cu1—N1 | 154.99 (8) | C9—C8—C7 | 119.2 (2) |
O2—Cu1—N2 | 95.41 (7) | C9—C8—H6 | 120.4173 |
N1—Cu1—N2 | 94.71 (8) | H6—C8—C7 | 120.4118 |
C11—O1—Cu1 | 85.5 (1) | C10—C9—C8 | 118.7 (2) |
C11—O2—Cu1 | 90.1 (1) | C10—C9—H7 | 120.6607 |
C1—N1—Cu1 | 116.7 (2) | H7—C9—C8 | 120.6708 |
C1—N1—C5 | 118.3 (2) | H8—C10—N2 | 118.3692 |
C5—N1—Cu1 | 125.0 (2) | H8—C10—C9 | 118.3655 |
C6—N2—Cu1 | 124.8 (2) | C12—C11—O1 | 121.8 (2) |
C6—N2—C10 | 118.2 (2) | C12—C11—O2 | 118.3 (2) |
C10—N2—Cu1 | 117.0 (2) | C13—C12—C11 | 118.4 (2) |
C5—N3—C6 | 132.6 (2) | C13—C12—C17 | 120.9 (2) |
C5—N3—H9 | 113.6855 | C17—C12—C11 | 120.6 (2) |
C6—N3—H9 | 113.6935 | C14—C13—C12 | 119.5 (2) |
C15—N4—O3 | 117.7 (2) | C14—C13—H10 | 120.2585 |
C15—N4—O4 | 118.1 (2) | H10—C13—C12 | 120.2528 |
C2—C1—N1 | 123.4 (2) | C15—C14—C13 | 118.5 (2) |
C2—C1—H1 | 118.2880 | C15—C14—H11 | 120.7658 |
H1—C1—N1 | 118.2784 | H11—C14—C13 | 120.7685 |
C3—C2—C1 | 118.2 (2) | C16—C15—N4 | 119.0 (2) |
C3—C2—H2 | 120.8938 | C16—C15—C14 | 123.2 (2) |
H2—C2—C1 | 120.8914 | C17—C16—C15 | 117.6 (2) |
C4—C3—C2 | 119.4 (2) | C17—C16—H12 | 121.1990 |
C4—C3—H3 | 120.2966 | H12—C16—C15 | 121.1987 |
H3—C3—C2 | 120.2991 | H13—C17—C12 | 119.8929 |
C5—C4—C3 | 119.5 (2) | H13—C17—C16 | 119.8888 |
Cl1—Cu1—O1—C11 | −95.2 (1) | N1—C1—C2—C3 | 0.6 (4) |
Cl1—Cu1—O2—C11 | 87.5 (1) | C1—C2—C3—C4 | 0.2 (3) |
Cl1—Cu1—N1—C1 | −79.9 (2) | C2—C3—C4—C5 | −1.0 (3) |
Cl1—Cu1—N2—C6 | −98.4 (2) | C3—C4—C5—N1 | 1.0 (3) |
Cu1—O1—C11—O2 | −5.5 (2) | C3—C4—C5—N3 | −179.4 (2) |
Cu1—O2—C11—O1 | 5.8 (2) | N2—C6—C7—C8 | −1.4 (3) |
Cu1—N1—C1—C2 | 179.6 (2) | C6—C7—C8—C9 | 0.3 (3) |
Cu1—N1—C5—N3 | −0.0 (2) | C7—C8—C9—C10 | 0.7 (4) |
Cu1—N1—C5—C4 | 179.6 (2) | C8—C9—C10—N2 | −0.7 (4) |
Cu1—N2—C6—N3 | −1.5 (3) | O1—C11—C12—C13 | 173.5 (2) |
Cu1—N2—C10—C9 | −178.1 (2) | C11—C12—C13—C14 | 174.4 (2) |
C6—N3—C5—N1 | 3.5 (4) | C11—C12—C17—C16 | −175.0 (2) |
C6—N3—C5—C4 | −176.2 (2) | C12—C13—C14—C15 | 0.6 (4) |
C5—N3—C6—N2 | −2.7 (4) | C13—C14—C15—N4 | −178.6 (2) |
O3—N4—C15—C14 | −169.1 (2) | N4—C15—C16—C17 | 178.0 (2) |
O4—N4—C15—C14 | 11.4 (3) | C15—C16—C17—C12 | 0.6 (4) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z; (viii) −x, −y+1, −z; (ix) −x, −y, −z; (x) x+1, y+1, z; (xi) x+1, y, z; (xii) x, y−1, z; (xiii) x−1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···Cl1ii | 0.86 | 2.33 | 3.163 (2) | 165 |
Symmetry code: (ii) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H4NO4)Cl(C10H9N3)] |
Mr | 436.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 8.87 (1), 9.085 (8), 11.23 (1) |
α, β, γ (°) | 102.67 (3), 105.34 (3), 96.72 (4) |
V (Å3) | 836.6 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.50 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.633, 0.740 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 8197, 3794, 3552 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.078, 1.22 |
No. of reflections | 3794 |
No. of parameters | 245 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.37 |
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.
Cu1—Cl1 | 2.468 (3) | Cu1—N1 | 1.955 (2) |
Cu1—O1 | 2.110 (2) | Cu1—N2 | 1.967 (2) |
Cu1—O2 | 2.002 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···Cl1i | 0.86 | 2.33 | 3.163 (2) | 165 |
Symmetry code: (i) −x+2, −y, −z+1. |
As part of our studies of new therapeutic drugs, we have reported the structures of ternary Cu(II) complexes with the heterocyclic ligand 2,2'-bipyridylamine (bpa) and various carboxylate ligands, such as p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005), cyclobutane-1,1-dicarboxylate (Yodoshi, Mototsuji & Okabe, 2007), benzenecarboxylate (BA) (Okabe et al., 2007), and glycinate (Yodoshi, Odoko & Okabe, 2007). In this study, we describe the structure of the title Cu(II) complex, (I), containing bpa and 4-nitrobenzoate (p-NBA) and chloride anions.
The overall structure of (I) is similar to those of the ternary Cu(II) complexes with bpa and p-HB (Wang & Okabe, 2005) and BA (Okabe et al., 2007). The central Cu atom in (I) (Fig. 1) has a square pyramidal CuN2O2Cl geometry (Table 1), resulting from its coordination by two N atoms from the bpa molecule, two O atoms from the p-NBA anion and one Cl atom. The four basal atoms (N1, N2, O1 and O2) are neary coplanar and the Cu atom deviates from their least-squares plane towards the apical Cl atom by 0.3274 (1) Å. The O1—Cu1—O2 and N1—Cu1—N2 bite angles of 64.25 (7) and 94.71 (8) Å, respectively, are in the ranges normally observed for these complexes (Wang & Okabe, 2005; Okabe et al., 2007; Yodoshi, Mototsuji & Okabe, 2007; Yodoshi, Odoko & Okabe, 2007; Youngme et al., 2004). The Cu—Cl distance of 2.468 (3)Å is intermediate between the known values from 2.336 (2) to 2.733 (2) Å (Mao et al., 2004; Brophy et al., 1999). Such long Cu—Cl bonds are explained by the well known Jahn-Teller effect.
As shown in Fig. 2, the crystal structure is stabilized by N3—H9···Cl1i hydrogen bonds [i: 2 - x, -y, 1 - z] as well as by three kinds of π-π stacking interactions with the distances between the centroids of the aromatic rings being 3.531 (4) Å for Cg1(N1/C1—C5) and Cg3(N2/C6—C10) at (1 - x, -y, -z), 3.754 (4) Å for Cg2(N1/C5/N3/C6/N2/Cu1) and Cg2 at (1 - x, -y, -z), and 3.549 (4) Å for Cg4(C12—C17) and Cg2 at (-x, -y, -1 - z).