Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032837/hb2471sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032837/hb2471Isup2.hkl |
CCDC reference: 657558
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.002 Å
- R factor = 0.021
- wR factor = 0.062
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT148_ALERT_3_B su on the a - Axis is Too Large (x 1000) . 10 Ang. PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cu1 - Cl1 .. 11.98 su
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.728 0.851 Tmin and Tmax expected: 0.654 0.864 RR = 1.130 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.13 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.02 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 1000 Ang. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1 .. 6.18 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O2 .. 5.04 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - C11 .. 7.03 su
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.30
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 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 p-aminobenzoic acid (4.0 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.
The water H atoms were located in a difference map and refined as riding in their as-found relative postions with Uiso(H) = 1.5Ueq(O). The C– and N-bound H atoms were located in difference maps, relocated in idealized positions and treated as riding, with C—H = 0.93 Å, N—H = 0.86Å and Uiso(H) = 1.2Ueq(C,N).
As part of our studies of new therapeutic drugs, we have reported the structures of the ternary Cu(II) complexes with the heterocyclic ligand, 2,2'-bipyridylamine (bpa) and various carboxylate-containing compounds, such as bpa and p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005), cyclobutane-1,1-dicarboxylate (Yodoshi, Mototsuji & Okabe, 2007), benzenecarboxylate (BA) (Okabe et al., 2007), and glycine (Yodoshi, Odoko & Okabe, 2007). In this study, we report the structure of the title Cu(II) complex, (I), with bpa and the p-aminobenzenecarboxylate (p-ABA) and chloride anions. An uncoordinated water molecule completes the structure.
The overall structure of (I) is similar to those of the 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 one bpa and two O atoms from one p-ABA and one chloride anion. The four basal ligand atoms (N1, N2,O1 and O2) are neary coplanar, and the Cu atom deviates from the mean square plane towards the apical Cl atom by 0.2591 (1) Å. The bite angles N1—Cu1—N2 and O1—Cu1—O2 are in the range 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 2.597 (1)%A in (I) is slightly longer than the median of 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 of (I) is stabilized by N—H···Cl, O—H···Cl, N—H···O, and O—H···O hydrogen bonds (Table 2), and no π-π stacking interactions are present.
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).
For related literature, see: Altomare et al. (1999); Farrugia (1997); Kelland (2005); Li et al. (2005); Ranford et al. (1993); Selvakumar et al. (2006); Spek (2003).
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: SHELXS97 (Sheldrick, 1997); 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(C7H6NO2)Cl(C10H9N3)]·H2O | F(000) = 868.00 |
Mr = 424.35 | Dx = 1.646 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 14678 reflections |
a = 9.86 (1) Å | θ = 3.2–27.5° |
b = 12.10 (1) Å | µ = 1.46 mm−1 |
c = 14.60 (1) Å | T = 123 K |
β = 100.63 (3)° | Prism, green |
V = 1712 (3) Å3 | 0.30 × 0.30 × 0.10 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 3424 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.017 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −12→12 |
Tmin = 0.728, Tmax = 0.851 | k = −14→15 |
16167 measured reflections | l = −18→18 |
3922 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.021 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.6204P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.36 e Å−3 |
3922 reflections | Δρmin = −0.42 e Å−3 |
242 parameters |
[Cu(C7H6NO2)Cl(C10H9N3)]·H2O | V = 1712 (3) Å3 |
Mr = 424.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.86 (1) Å | µ = 1.46 mm−1 |
b = 12.10 (1) Å | T = 123 K |
c = 14.60 (1) Å | 0.30 × 0.30 × 0.10 mm |
β = 100.63 (3)° |
Rigaku R-AXIS RAPID diffractometer | 3922 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3424 reflections with F2 > 2.0σ(F2) |
Tmin = 0.728, Tmax = 0.851 | Rint = 0.017 |
16167 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 242 parameters |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.36 e Å−3 |
3922 reflections | Δρmin = −0.42 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 | 0.93181 (2) | 0.23066 (1) | 0.48560 (1) | 0.01293 (6) | |
Cl1 | 0.70895 (4) | 0.33281 (3) | 0.40723 (2) | 0.01702 (8) | |
O1 | 0.9042 (1) | 0.08460 (8) | 0.40938 (7) | 0.0156 (2) | |
O2 | 0.8285 (1) | 0.11464 (8) | 0.53813 (7) | 0.0177 (2) | |
O3 | 0.5317 (1) | 0.51357 (9) | 0.26822 (8) | 0.0225 (2) | |
N1 | 1.0627 (1) | 0.3078 (1) | 0.42339 (8) | 0.0131 (2) | |
N2 | 0.9776 (1) | 0.32012 (9) | 0.60007 (8) | 0.0137 (2) | |
N3 | 1.1401 (1) | 0.43479 (9) | 0.54583 (8) | 0.0140 (2) | |
N4 | 0.4964 (1) | −0.3283 (1) | 0.41741 (9) | 0.0212 (3) | |
C1 | 1.0691 (1) | 0.2727 (1) | 0.3360 (1) | 0.0160 (3) | |
C2 | 1.1551 (1) | 0.3188 (1) | 0.2827 (1) | 0.0178 (3) | |
C3 | 1.2434 (1) | 0.4038 (1) | 0.3211 (1) | 0.0185 (3) | |
C4 | 1.2391 (1) | 0.4396 (1) | 0.4095 (1) | 0.0169 (3) | |
C5 | 1.1449 (1) | 0.3914 (1) | 0.45928 (9) | 0.0129 (2) | |
C6 | 1.0676 (1) | 0.4034 (1) | 0.61365 (9) | 0.0128 (2) | |
C7 | 1.0937 (1) | 0.4632 (1) | 0.69802 (9) | 0.0162 (3) | |
C8 | 1.0244 (2) | 0.4345 (1) | 0.7678 (1) | 0.0196 (3) | |
C9 | 0.9302 (2) | 0.3477 (1) | 0.7538 (1) | 0.0221 (3) | |
C10 | 0.9100 (2) | 0.2933 (1) | 0.6701 (1) | 0.0189 (3) | |
C11 | 0.8334 (1) | 0.0513 (1) | 0.46906 (9) | 0.0137 (3) | |
C12 | 0.7553 (1) | −0.0525 (1) | 0.45855 (9) | 0.0131 (3) | |
C13 | 0.6597 (1) | −0.0730 (1) | 0.51656 (9) | 0.0159 (3) | |
C14 | 0.5743 (1) | −0.1639 (1) | 0.50303 (9) | 0.0170 (3) | |
C15 | 0.5830 (1) | −0.2395 (1) | 0.4310 (1) | 0.0151 (3) | |
C16 | 0.6805 (1) | −0.2201 (1) | 0.37370 (9) | 0.0141 (3) | |
C17 | 0.7645 (1) | −0.1280 (1) | 0.38739 (9) | 0.0138 (3) | |
H1 | 1.0125 | 0.2146 | 0.3110 | 0.019* | |
H2 | 1.1545 | 0.2941 | 0.2223 | 0.021* | |
H3 | 1.3044 | 0.4356 | 0.2871 | 0.022* | |
H4 | 1.2981 | 0.4954 | 0.4364 | 0.020* | |
H5 | 1.1568 | 0.5211 | 0.7062 | 0.019* | |
H6 | 1.0402 | 0.4728 | 0.8239 | 0.024* | |
H7 | 0.8822 | 0.3271 | 0.8002 | 0.027* | |
H8 | 0.8471 | 0.2353 | 0.6607 | 0.023* | |
H9 | 1.1917 | 0.4918 | 0.5601 | 0.017* | |
H10 | 0.6539 | −0.0245 | 0.5650 | 0.019* | |
H11 | 0.5105 | −0.1754 | 0.5417 | 0.020* | |
H12 | 0.6884 | −0.2696 | 0.3263 | 0.017* | |
H13 | 0.8282 | −0.1159 | 0.3487 | 0.017* | |
H14 | 0.5007 | −0.3740 | 0.3729 | 0.025* | |
H15 | 0.4376 | −0.3386 | 0.4533 | 0.025* | |
H16 | 0.5769 | 0.4615 | 0.2935 | 0.034* | |
H17 | 0.5563 | 0.5234 | 0.2197 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0154 (1) | 0.0118 (1) | 0.0125 (1) | −0.00460 (6) | 0.00479 (6) | −0.00184 (5) |
Cl1 | 0.0150 (2) | 0.0150 (2) | 0.0205 (2) | −0.0028 (1) | 0.0018 (1) | 0.0013 (1) |
O1 | 0.0181 (5) | 0.0133 (5) | 0.0165 (5) | −0.0038 (4) | 0.0061 (4) | −0.0009 (3) |
O2 | 0.0236 (6) | 0.0142 (5) | 0.0165 (5) | −0.0071 (4) | 0.0071 (4) | −0.0031 (4) |
O3 | 0.0275 (6) | 0.0224 (6) | 0.0199 (6) | 0.0061 (5) | 0.0103 (4) | 0.0033 (4) |
N1 | 0.0128 (6) | 0.0132 (6) | 0.0135 (5) | −0.0009 (4) | 0.0033 (4) | 0.0000 (4) |
N2 | 0.0147 (6) | 0.0139 (6) | 0.0126 (5) | −0.0023 (4) | 0.0029 (4) | −0.0006 (4) |
N3 | 0.0149 (6) | 0.0122 (6) | 0.0151 (6) | −0.0055 (4) | 0.0034 (4) | −0.0019 (4) |
N4 | 0.0250 (7) | 0.0188 (6) | 0.0210 (6) | −0.0108 (5) | 0.0078 (5) | −0.0044 (5) |
C1 | 0.0156 (7) | 0.0163 (7) | 0.0163 (7) | −0.0020 (5) | 0.0032 (5) | −0.0028 (5) |
C2 | 0.0184 (7) | 0.0213 (7) | 0.0150 (7) | −0.0001 (6) | 0.0063 (5) | −0.0019 (5) |
C3 | 0.0158 (7) | 0.0218 (7) | 0.0198 (7) | −0.0023 (6) | 0.0079 (5) | 0.0018 (5) |
C4 | 0.0141 (7) | 0.0171 (7) | 0.0198 (7) | −0.0045 (5) | 0.0039 (5) | −0.0001 (5) |
C5 | 0.0121 (6) | 0.0136 (6) | 0.0131 (6) | 0.0006 (5) | 0.0022 (5) | 0.0010 (5) |
C6 | 0.0116 (6) | 0.0126 (6) | 0.0137 (6) | 0.0010 (5) | 0.0011 (5) | 0.0006 (5) |
C7 | 0.0150 (7) | 0.0169 (7) | 0.0163 (7) | −0.0038 (5) | 0.0012 (5) | −0.0031 (5) |
C8 | 0.0212 (8) | 0.0243 (8) | 0.0128 (7) | −0.0043 (6) | 0.0021 (5) | −0.0049 (5) |
C9 | 0.0258 (8) | 0.0279 (8) | 0.0141 (7) | −0.0094 (6) | 0.0077 (6) | −0.0025 (6) |
C10 | 0.0213 (8) | 0.0198 (7) | 0.0168 (7) | −0.0073 (6) | 0.0066 (5) | −0.0022 (5) |
C11 | 0.0132 (7) | 0.0130 (6) | 0.0142 (6) | 0.0002 (5) | 0.0008 (5) | 0.0013 (5) |
C12 | 0.0139 (7) | 0.0111 (6) | 0.0137 (6) | −0.0012 (5) | 0.0008 (5) | 0.0015 (4) |
C13 | 0.0199 (7) | 0.0149 (7) | 0.0133 (6) | −0.0020 (5) | 0.0041 (5) | −0.0012 (5) |
C14 | 0.0192 (7) | 0.0180 (7) | 0.0150 (7) | −0.0041 (5) | 0.0061 (5) | 0.0001 (5) |
C15 | 0.0159 (7) | 0.0133 (6) | 0.0149 (7) | −0.0019 (5) | −0.0003 (5) | 0.0019 (5) |
C16 | 0.0157 (7) | 0.0133 (7) | 0.0127 (6) | 0.0005 (5) | 0.0011 (5) | −0.0007 (4) |
C17 | 0.0136 (7) | 0.0144 (6) | 0.0134 (6) | 0.0020 (5) | 0.0025 (5) | 0.0027 (5) |
Cu1—Cl1 | 2.596 (3) | C3—C4 | 1.370 (2) |
Cu1—O1 | 2.080 (1) | C3—H3 | 0.9300 |
Cu1—O2 | 1.972 (1) | C4—C5 | 1.408 (2) |
Cu1—N1 | 1.948 (1) | C4—H4 | 0.9300 |
Cu1—N2 | 1.973 (1) | C6—C7 | 1.411 (2) |
O1—C11 | 1.278 (2) | C7—C8 | 1.371 (2) |
O2—C11 | 1.275 (2) | C7—H5 | 0.9299 |
O3—H16 | 0.8189 | C8—C9 | 1.393 (2) |
O3—H17 | 0.7997 | C8—H6 | 0.9300 |
N1—C1 | 1.358 (2) | C9—C10 | 1.370 (2) |
N1—C5 | 1.341 (2) | C9—H7 | 0.9299 |
N2—C6 | 1.334 (2) | C10—H8 | 0.9300 |
N2—C10 | 1.359 (2) | C11—C12 | 1.468 (2) |
N3—C5 | 1.378 (2) | C12—C13 | 1.401 (2) |
N3—C6 | 1.378 (2) | C12—C17 | 1.399 (2) |
N3—H9 | 0.8601 | C13—C14 | 1.378 (2) |
N4—C15 | 1.364 (2) | C13—H10 | 0.9299 |
N4—H14 | 0.8600 | C14—C15 | 1.408 (2) |
N4—H15 | 0.8600 | C14—H11 | 0.9299 |
C1—C2 | 1.371 (2) | C15—C16 | 1.406 (2) |
C1—H1 | 0.9300 | C16—C17 | 1.382 (2) |
C2—C3 | 1.397 (2) | C16—H12 | 0.9299 |
C2—H2 | 0.9301 | C17—H13 | 0.9300 |
O1—Cu1—O2 | 64.96 (4) | H4—C4—C3 | 120.1972 |
O1—Cu1—N1 | 100.99 (5) | C7—C6—N2 | 121.8 (1) |
O1—Cu1—N2 | 155.07 (4) | C7—C6—N3 | 116.8 (1) |
O2—Cu1—N1 | 163.19 (5) | C8—C7—C6 | 118.9 (1) |
O2—Cu1—N2 | 96.61 (5) | C8—C7—H5 | 120.5419 |
N1—Cu1—N2 | 93.69 (5) | H5—C7—C6 | 120.5617 |
C11—O1—Cu1 | 86.39 (8) | C9—C8—C7 | 119.5 (1) |
C11—O2—Cu1 | 91.27 (9) | C9—C8—H6 | 120.2575 |
H16—O3—H17 | 106.5428 | H6—C8—C7 | 120.2656 |
C1—N1—Cu1 | 116.01 (9) | C10—C9—C8 | 118.5 (2) |
C1—N1—C5 | 118.2 (1) | C10—C9—H7 | 120.7387 |
C5—N1—Cu1 | 125.8 (1) | H7—C9—C8 | 120.7571 |
C6—N2—Cu1 | 125.6 (1) | H8—C10—N2 | 118.4789 |
C6—N2—C10 | 118.3 (1) | H8—C10—C9 | 118.4777 |
C10—N2—Cu1 | 116.05 (9) | C12—C11—O1 | 122.7 (1) |
C5—N3—C6 | 131.6 (1) | C12—C11—O2 | 120.1 (1) |
C5—N3—H9 | 114.1757 | C13—C12—C11 | 119.2 (1) |
C6—N3—H9 | 114.1759 | C13—C12—C17 | 118.5 (1) |
C15—N4—H14 | 120.0009 | C17—C12—C11 | 122.1 (1) |
C15—N4—H15 | 119.9993 | C14—C13—C12 | 121.1 (1) |
H14—N4—H15 | 119.9998 | C14—C13—H10 | 119.4483 |
C2—C1—N1 | 123.2 (1) | H10—C13—C12 | 119.4502 |
C2—C1—H1 | 118.3955 | C15—C14—C13 | 120.4 (1) |
H1—C1—N1 | 118.3871 | C15—C14—H11 | 119.8033 |
C3—C2—C1 | 118.5 (1) | H11—C14—C13 | 119.8016 |
C3—C2—H2 | 120.7520 | C16—C15—N4 | 121.5 (1) |
H2—C2—C1 | 120.7608 | C16—C15—C14 | 118.6 (1) |
C4—C3—C2 | 119.1 (1) | C17—C16—C15 | 120.4 (1) |
C4—C3—H3 | 120.4688 | C17—C16—H12 | 119.7788 |
H3—C3—C2 | 120.4693 | H12—C16—C15 | 119.7821 |
C5—C4—C3 | 119.6 (1) | H13—C17—C12 | 119.5207 |
C5—C4—H4 | 120.2014 | H13—C17—C16 | 119.5239 |
O2—Cu1—O1—C11 | 3.07 (6) | C1—C2—C3—C4 | −1.4 (2) |
O1—Cu1—O2—C11 | −3.07 (7) | C2—C3—C4—C5 | −0.8 (2) |
O1—Cu1—N1—C1 | 20.2 (1) | C3—C4—C5—N1 | 2.7 (2) |
O1—Cu1—N2—C6 | 128.1 (1) | C3—C4—C5—N3 | −176.6 (1) |
Cu1—O1—C11—O2 | −4.8 (1) | N2—C6—C7—C8 | 0.1 (2) |
Cu1—O2—C11—O1 | 5.1 (1) | C6—C7—C8—C9 | −0.1 (2) |
Cu1—N1—C1—C2 | 179.5 (1) | C7—C8—C9—C10 | 0.1 (2) |
Cu1—N1—C5—N3 | −2.7 (2) | C8—C9—C10—N2 | −0.0 (2) |
Cu1—N1—C5—C4 | 178.1 (1) | O1—C11—C12—C13 | −167.7 (1) |
Cu1—N2—C6—N3 | −0.4 (2) | C11—C12—C13—C14 | 173.4 (1) |
Cu1—N2—C10—C9 | −179.9 (1) | C11—C12—C17—C16 | −173.9 (1) |
C6—N3—C5—N1 | 5.3 (2) | C12—C13—C14—C15 | 1.0 (2) |
C6—N3—C5—C4 | −175.5 (1) | C13—C14—C15—N4 | −179.0 (1) |
C5—N3—C6—N2 | −3.6 (2) | N4—C15—C16—C17 | 178.3 (1) |
H14—N4—C15—C14 | 179.0 | C15—C16—C17—C12 | 0.4 (2) |
N1—C1—C2—C3 | 2.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···Cl1i | 0.86 | 2.35 | 3.196 (3) | 169 |
N4—H14···O3ii | 0.86 | 2.11 | 2.968 (2) | 174 |
N4—H15···Cl1iii | 0.86 | 2.71 | 3.547 (2) | 166 |
O3—H16···Cl1 | 0.82 | 2.47 | 3.263 (4) | 164 |
O3—H17···O1iv | 0.80 | 2.13 | 2.911 (2) | 166 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+1, −y, −z+1; (iv) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H6NO2)Cl(C10H9N3)]·H2O |
Mr | 424.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 123 |
a, b, c (Å) | 9.86 (1), 12.10 (1), 14.60 (1) |
β (°) | 100.63 (3) |
V (Å3) | 1712 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.46 |
Crystal size (mm) | 0.30 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.728, 0.851 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 16167, 3922, 3424 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.062, 1.07 |
No. of reflections | 3922 |
No. of parameters | 242 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.42 |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Betteridge et al., 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), and PLATON (Spek, 2003), CrystalStructure.
Cu1—Cl1 | 2.596 (3) | Cu1—N1 | 1.948 (1) |
Cu1—O1 | 2.080 (1) | Cu1—N2 | 1.973 (1) |
Cu1—O2 | 1.972 (1) | ||
O1—Cu1—O2 | 64.96 (4) | N1—Cu1—N2 | 93.69 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···Cl1i | 0.86 | 2.35 | 3.196 (3) | 169 |
N4—H14···O3ii | 0.86 | 2.11 | 2.968 (2) | 174 |
N4—H15···Cl1iii | 0.86 | 2.71 | 3.547 (2) | 166 |
O3—H16···Cl1 | 0.82 | 2.47 | 3.263 (4) | 164 |
O3—H17···O1iv | 0.80 | 2.13 | 2.911 (2) | 166 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+1, −y, −z+1; (iv) −x+3/2, y+1/2, −z+1/2. |
As part of our studies of new therapeutic drugs, we have reported the structures of the ternary Cu(II) complexes with the heterocyclic ligand, 2,2'-bipyridylamine (bpa) and various carboxylate-containing compounds, such as bpa and p-hydroxybenzenecarboxylate (p-HB) (Wang & Okabe, 2005), cyclobutane-1,1-dicarboxylate (Yodoshi, Mototsuji & Okabe, 2007), benzenecarboxylate (BA) (Okabe et al., 2007), and glycine (Yodoshi, Odoko & Okabe, 2007). In this study, we report the structure of the title Cu(II) complex, (I), with bpa and the p-aminobenzenecarboxylate (p-ABA) and chloride anions. An uncoordinated water molecule completes the structure.
The overall structure of (I) is similar to those of the 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 one bpa and two O atoms from one p-ABA and one chloride anion. The four basal ligand atoms (N1, N2,O1 and O2) are neary coplanar, and the Cu atom deviates from the mean square plane towards the apical Cl atom by 0.2591 (1) Å. The bite angles N1—Cu1—N2 and O1—Cu1—O2 are in the range 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 2.597 (1)%A in (I) is slightly longer than the median of 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 of (I) is stabilized by N—H···Cl, O—H···Cl, N—H···O, and O—H···O hydrogen bonds (Table 2), and no π-π stacking interactions are present.