Bis(3-aminopyridine-N)(4,4'-dimethyl-2,2'-bipyridine-2N,N')(perchlorato-O)copper(II) perchlorate
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106021160/sf3007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106021160/sf3007Isup2.hkl |
CCDC reference: 618604
All solvents and chemicals were of analytical grade, purchased as commercial chemicals from Aldrich or ACROS, and were used without further purification. Compound (I) was synthesized by in situ partial ligand substitution at room temperature. A colorless methanol solution (20 ml) of sixfold 3-aminopyridine (0.282 g, 3.0 mmol) was added to a blue methanol solution (10 ml) of [Cu(ClO4)2]·6H2O (0.186 g, 0.5 mmol) at room temperature, and then a methanol solution (20 ml) of 4,4'-dimethyl-2,2'-bipyridine (0.092 g, 0.5 mmol) was added to the resulting green mixture. The color of the solution turned quickly from green to brown, which demonstrated the exchange between the monodentate and bidentate ligands. Finally, the mixture was slowly evaporated in air at room temperature to near 10 ml, and then the micro-crystals were collected, washed with acetone and dried in vacuo (yield 77%, 0.244 g). FT–IR (KBr pellets, cm−1): 3459 (s), 3381 (s), 3222 (w), 3087 (m), 2924 (m), 1620 (s), 1582 (s), 1560 (m), 1496 (s), 1450 (s), 1107 (vs), 1088 (vs), 803 (s), 699 (m), 625 (s). Elemental analysis calculated for CuC22H24N6O8Cl2: C, 48.99; H, 3.74; N, 10.39%. Found: C, 49.03; H, 3.79; N, 10.42%. UV-vis (δmax) in methanol: 263, 254, 250, 220 nm. ESI-MS (m/z): 534 [M-ClO4]+. Brown single-crystals of (I) suitable for X-ray diffraction determination were grown from methanol by slow evaporation in air at room temperature.
H atoms were placed in geometrically idealized positions (C—H = 0.93–0.96 Å and N—H = 0.86 Å) and refined as riding atoms [Uiso(H) = 1.5Ueq(N and methyl C) or Uiso(H) = 1.2Ueq(other C atoms)].
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku Corporation, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu(ClO4)(C5H6N2)2(C12H12N2)]ClO4 | F(000) = 1300 |
Mr = 634.91 | Dx = 1.630 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 10557 reflections |
a = 16.112 (3) Å | θ = 3.1–27.5° |
b = 10.442 (2) Å | µ = 1.11 mm−1 |
c = 17.058 (3) Å | T = 120 K |
β = 115.67 (3)° | Block, brown |
V = 2586.6 (11) Å3 | 0.20 × 0.15 × 0.10 mm |
Z = 4 |
Rigaku Mercury CCD area-detector diffractometer | 4949 independent reflections |
Radiation source: Rigaku rotating anode | 4665 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 14.6199 pixels mm-1 | θmax = 26.0°, θmin = 3.1° |
ϕ and ω scans | h = −19→17 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −12→12 |
Tmin = 0.808, Tmax = 0.897 | l = −19→21 |
22276 measured reflections |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0336P)2 + 5.1887P] where P = (Fo2 + 2Fc2)/3 |
4949 reflections | (Δ/σ)max = 0.001 |
354 parameters | Δρmax = 1.30 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
[Cu(ClO4)(C5H6N2)2(C12H12N2)]ClO4 | V = 2586.6 (11) Å3 |
Mr = 634.91 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.112 (3) Å | µ = 1.11 mm−1 |
b = 10.442 (2) Å | T = 120 K |
c = 17.058 (3) Å | 0.20 × 0.15 × 0.10 mm |
β = 115.67 (3)° |
Rigaku Mercury CCD area-detector diffractometer | 4949 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 4665 reflections with I > 2σ(I) |
Tmin = 0.808, Tmax = 0.897 | Rint = 0.041 |
22276 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.13 | Δρmax = 1.30 e Å−3 |
4949 reflections | Δρmin = −0.44 e Å−3 |
354 parameters |
Experimental. Elemental analyses for carbon, hydrogen and nitrogen were performed on a Perkin-Elmer 1400 C analyzer. Infrared (IR) spectra (4000–400 cm−1) were recorded on a Nicolet FTIR 170X spectrophotometer at 298 K using KBr plates. UV-visible (UV-vis) spectra were recorded on a Shimadzu UV-3150 double-beam spectrophotometer using a Pyrex cell with a 10 mm path length. Electrospray ionization mass spectra (ESI-MS) were recorded on a Finnigan MAT SSQ 710 mass spectrometer over a scan range of 100–1200 amu. |
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. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. 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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.76970 (2) | 0.61379 (3) | 0.06151 (2) | 0.01943 (12) | |
C1 | 0.73518 (18) | 0.6107 (3) | −0.12456 (17) | 0.0199 (5) | |
H1 | 0.6891 | 0.6704 | −0.1335 | 0.024* | |
C2 | 0.74854 (19) | 0.5696 (3) | −0.19525 (17) | 0.0213 (6) | |
H2 | 0.7114 | 0.6004 | −0.2506 | 0.026* | |
C3 | 0.81776 (19) | 0.4820 (3) | −0.18282 (17) | 0.0206 (6) | |
C4 | 0.86963 (19) | 0.4375 (3) | −0.09892 (18) | 0.0207 (6) | |
H4 | 0.9168 | 0.3790 | −0.0882 | 0.025* | |
C5 | 0.85146 (17) | 0.4799 (2) | −0.03163 (17) | 0.0166 (5) | |
C6 | 0.89808 (18) | 0.4296 (3) | 0.05848 (17) | 0.0171 (5) | |
C7 | 0.96820 (18) | 0.3393 (3) | 0.08422 (17) | 0.0191 (5) | |
H7 | 0.9891 | 0.3094 | 0.0446 | 0.023* | |
C8 | 1.00716 (18) | 0.2935 (3) | 0.16917 (18) | 0.0202 (6) | |
C9 | 0.9709 (2) | 0.3400 (3) | 0.22450 (18) | 0.0231 (6) | |
H9 | 0.9937 | 0.3104 | 0.2814 | 0.028* | |
C10 | 0.9013 (2) | 0.4300 (3) | 0.19497 (18) | 0.0240 (6) | |
H10 | 0.8782 | 0.4599 | 0.2330 | 0.029* | |
C11 | 0.8347 (2) | 0.4352 (3) | −0.25811 (19) | 0.0297 (7) | |
H11A | 0.7784 | 0.4019 | −0.3025 | 0.045* | |
H11B | 0.8804 | 0.3689 | −0.2386 | 0.045* | |
H11C | 0.8559 | 0.5050 | −0.2812 | 0.045* | |
C12 | 1.0853 (2) | 0.1998 (3) | 0.20023 (19) | 0.0250 (6) | |
H12A | 1.0701 | 0.1274 | 0.2262 | 0.038* | |
H12B | 1.1398 | 0.2403 | 0.2425 | 0.038* | |
H12C | 1.0961 | 0.1716 | 0.1519 | 0.038* | |
C13 | 0.7038 (2) | 0.6053 (3) | 0.19703 (18) | 0.0215 (6) | |
H13 | 0.6567 | 0.5558 | 0.1567 | 0.026* | |
C14 | 0.7061 (2) | 0.6256 (3) | 0.27922 (18) | 0.0224 (6) | |
C15 | 0.7768 (2) | 0.7029 (3) | 0.33750 (18) | 0.0255 (6) | |
H15 | 0.7805 | 0.7196 | 0.3925 | 0.031* | |
C16 | 0.8411 (2) | 0.7543 (3) | 0.31317 (19) | 0.0265 (6) | |
H16 | 0.8880 | 0.8063 | 0.3515 | 0.032* | |
C17 | 0.8355 (2) | 0.7282 (3) | 0.2317 (2) | 0.0252 (6) | |
H17 | 0.8794 | 0.7619 | 0.2158 | 0.030* | |
C18 | 0.74752 (19) | 0.8751 (3) | 0.00201 (18) | 0.0205 (5) | |
H18 | 0.8091 | 0.8636 | 0.0140 | 0.025* | |
C19 | 0.70920 (19) | 0.9964 (3) | −0.02269 (17) | 0.0197 (5) | |
C20 | 0.6155 (2) | 1.0098 (3) | −0.04325 (19) | 0.0243 (6) | |
H20 | 0.5866 | 1.0888 | −0.0602 | 0.029* | |
C21 | 0.5668 (2) | 0.9039 (3) | −0.0381 (2) | 0.0309 (7) | |
H21 | 0.5043 | 0.9112 | −0.0528 | 0.037* | |
C22 | 0.6105 (2) | 0.7871 (3) | −0.0111 (2) | 0.0267 (6) | |
H22 | 0.5771 | 0.7167 | −0.0071 | 0.032* | |
Cl1 | 0.58934 (4) | 0.40621 (6) | −0.06222 (4) | 0.01987 (16) | |
Cl2 | 1.00511 (4) | 0.86590 (7) | 0.11695 (5) | 0.02500 (17) | |
N1 | 0.78562 (15) | 0.5683 (2) | −0.04404 (14) | 0.0170 (4) | |
N2 | 0.86556 (16) | 0.4761 (2) | 0.11348 (14) | 0.0188 (5) | |
N3 | 0.76732 (17) | 0.6546 (2) | 0.17463 (15) | 0.0223 (5) | |
N4 | 0.6425 (2) | 0.5678 (3) | 0.30053 (19) | 0.0400 (7) | |
H4A | 0.6451 | 0.5783 | 0.3515 | 0.060* | |
H4B | 0.6000 | 0.5210 | 0.2630 | 0.060* | |
N5 | 0.70014 (16) | 0.7741 (2) | 0.00931 (15) | 0.0204 (5) | |
N6 | 0.76277 (18) | 1.0983 (2) | −0.02401 (18) | 0.0295 (6) | |
H6A | 0.8205 | 1.0874 | −0.0095 | 0.044* | |
H6B | 0.7385 | 1.1729 | −0.0394 | 0.044* | |
O1 | 0.64103 (14) | 0.4714 (2) | 0.01998 (12) | 0.0261 (4) | |
O2 | 0.53652 (17) | 0.4989 (2) | −0.12619 (15) | 0.0414 (6) | |
O3 | 0.53009 (16) | 0.3130 (2) | −0.05082 (16) | 0.0341 (5) | |
O4 | 0.65200 (16) | 0.3430 (2) | −0.08884 (16) | 0.0342 (5) | |
O5 | 1.02635 (16) | 0.8604 (3) | 0.20756 (15) | 0.0391 (6) | |
O6 | 1.08891 (14) | 0.8670 (2) | 0.10619 (14) | 0.0317 (5) | |
O7 | 0.95115 (14) | 0.7536 (2) | 0.07386 (16) | 0.0364 (6) | |
O8 | 0.95279 (15) | 0.9795 (2) | 0.07913 (16) | 0.0369 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02401 (19) | 0.01909 (19) | 0.01972 (18) | 0.00660 (13) | 0.01372 (14) | 0.00474 (13) |
C1 | 0.0181 (13) | 0.0212 (13) | 0.0199 (13) | 0.0012 (10) | 0.0078 (11) | 0.0053 (11) |
C2 | 0.0207 (13) | 0.0245 (14) | 0.0166 (12) | −0.0019 (11) | 0.0062 (11) | 0.0025 (11) |
C3 | 0.0213 (13) | 0.0229 (14) | 0.0193 (13) | −0.0051 (11) | 0.0104 (11) | −0.0023 (11) |
C4 | 0.0196 (13) | 0.0191 (13) | 0.0242 (14) | 0.0017 (11) | 0.0104 (11) | −0.0016 (11) |
C5 | 0.0141 (12) | 0.0161 (12) | 0.0198 (13) | −0.0013 (10) | 0.0076 (10) | 0.0011 (10) |
C6 | 0.0177 (13) | 0.0161 (12) | 0.0177 (12) | −0.0018 (10) | 0.0079 (10) | −0.0012 (10) |
C7 | 0.0190 (13) | 0.0188 (13) | 0.0195 (13) | 0.0009 (10) | 0.0084 (11) | −0.0004 (11) |
C8 | 0.0179 (13) | 0.0168 (13) | 0.0212 (13) | −0.0009 (10) | 0.0040 (11) | −0.0004 (11) |
C9 | 0.0283 (15) | 0.0201 (14) | 0.0176 (13) | 0.0017 (11) | 0.0068 (11) | 0.0046 (11) |
C10 | 0.0297 (15) | 0.0230 (14) | 0.0202 (13) | 0.0025 (12) | 0.0117 (12) | 0.0028 (11) |
C11 | 0.0373 (17) | 0.0317 (16) | 0.0229 (14) | 0.0013 (14) | 0.0156 (13) | −0.0027 (13) |
C12 | 0.0210 (14) | 0.0225 (14) | 0.0257 (14) | 0.0057 (11) | 0.0046 (12) | 0.0029 (12) |
C13 | 0.0259 (14) | 0.0189 (13) | 0.0217 (13) | 0.0012 (11) | 0.0122 (11) | −0.0002 (11) |
C14 | 0.0275 (14) | 0.0202 (14) | 0.0230 (13) | 0.0024 (11) | 0.0144 (12) | −0.0010 (11) |
C15 | 0.0322 (16) | 0.0243 (15) | 0.0194 (14) | 0.0036 (12) | 0.0106 (12) | −0.0010 (11) |
C16 | 0.0267 (15) | 0.0219 (14) | 0.0268 (15) | 0.0001 (12) | 0.0078 (12) | 0.0000 (12) |
C17 | 0.0238 (14) | 0.0228 (14) | 0.0323 (15) | 0.0023 (11) | 0.0152 (13) | 0.0050 (12) |
C18 | 0.0165 (13) | 0.0238 (14) | 0.0216 (13) | 0.0026 (11) | 0.0087 (11) | 0.0019 (11) |
C19 | 0.0237 (14) | 0.0203 (13) | 0.0163 (12) | −0.0001 (11) | 0.0097 (11) | 0.0002 (11) |
C20 | 0.0242 (14) | 0.0197 (14) | 0.0290 (15) | 0.0061 (11) | 0.0114 (12) | 0.0023 (12) |
C21 | 0.0204 (14) | 0.0271 (16) | 0.0481 (19) | 0.0035 (12) | 0.0176 (14) | −0.0009 (14) |
C22 | 0.0250 (15) | 0.0204 (14) | 0.0426 (17) | 0.0002 (12) | 0.0219 (14) | 0.0015 (13) |
Cl1 | 0.0232 (3) | 0.0169 (3) | 0.0209 (3) | −0.0019 (2) | 0.0109 (3) | −0.0006 (2) |
Cl2 | 0.0165 (3) | 0.0270 (4) | 0.0279 (4) | −0.0001 (3) | 0.0061 (3) | −0.0083 (3) |
N1 | 0.0177 (11) | 0.0162 (11) | 0.0178 (10) | −0.0002 (9) | 0.0084 (9) | 0.0017 (9) |
N2 | 0.0218 (11) | 0.0179 (11) | 0.0181 (11) | 0.0023 (9) | 0.0099 (9) | 0.0019 (9) |
N3 | 0.0279 (13) | 0.0193 (12) | 0.0242 (12) | 0.0062 (10) | 0.0156 (10) | 0.0027 (10) |
N4 | 0.0453 (17) | 0.0467 (17) | 0.0349 (15) | −0.0056 (14) | 0.0240 (14) | −0.0037 (14) |
N5 | 0.0220 (12) | 0.0204 (11) | 0.0227 (11) | 0.0046 (9) | 0.0131 (10) | 0.0035 (10) |
N6 | 0.0271 (13) | 0.0219 (13) | 0.0428 (15) | −0.0004 (10) | 0.0182 (12) | 0.0053 (11) |
O1 | 0.0302 (11) | 0.0295 (11) | 0.0195 (10) | −0.0062 (9) | 0.0117 (9) | −0.0049 (9) |
O2 | 0.0418 (14) | 0.0384 (13) | 0.0294 (12) | 0.0032 (11) | 0.0018 (10) | 0.0109 (11) |
O3 | 0.0362 (12) | 0.0267 (11) | 0.0492 (14) | −0.0135 (10) | 0.0279 (11) | −0.0065 (10) |
O4 | 0.0442 (13) | 0.0259 (11) | 0.0479 (14) | −0.0026 (10) | 0.0344 (12) | −0.0074 (10) |
O5 | 0.0331 (12) | 0.0552 (15) | 0.0302 (12) | −0.0054 (11) | 0.0148 (10) | −0.0047 (11) |
O6 | 0.0208 (10) | 0.0425 (13) | 0.0315 (11) | −0.0013 (9) | 0.0111 (9) | −0.0071 (10) |
O7 | 0.0195 (11) | 0.0283 (12) | 0.0521 (14) | −0.0020 (9) | 0.0067 (10) | −0.0174 (11) |
O8 | 0.0254 (11) | 0.0283 (12) | 0.0465 (14) | 0.0028 (9) | 0.0057 (10) | −0.0061 (10) |
Cu1—N1 | 1.983 (2) | C13—C14 | 1.403 (4) |
Cu1—N3 | 1.993 (2) | C13—H13 | 0.9300 |
Cu1—N5 | 1.997 (2) | C14—N4 | 1.366 (4) |
Cu1—N2 | 2.013 (2) | C14—C15 | 1.399 (4) |
Cu1—O1 | 2.396 (2) | C15—C16 | 1.381 (4) |
C1—N1 | 1.333 (3) | C15—H15 | 0.9300 |
C1—C2 | 1.382 (4) | C16—C17 | 1.381 (4) |
C1—H1 | 0.9300 | C16—H16 | 0.9300 |
C2—C3 | 1.386 (4) | C17—N3 | 1.348 (4) |
C2—H2 | 0.9300 | C17—H17 | 0.9300 |
C3—C4 | 1.388 (4) | C18—N5 | 1.339 (4) |
C3—C11 | 1.505 (4) | C18—C19 | 1.393 (4) |
C4—C5 | 1.375 (4) | C18—H18 | 0.9300 |
C4—H4 | 0.9300 | C19—N6 | 1.376 (4) |
C5—N1 | 1.352 (3) | C19—C20 | 1.400 (4) |
C5—C6 | 1.484 (4) | C20—C21 | 1.381 (4) |
C6—N2 | 1.347 (3) | C20—H20 | 0.9300 |
C6—C7 | 1.389 (4) | C21—C22 | 1.384 (4) |
C7—C8 | 1.391 (4) | C21—H21 | 0.9300 |
C7—H7 | 0.9300 | C22—N5 | 1.339 (4) |
C8—C9 | 1.395 (4) | C22—H22 | 0.9300 |
C8—C12 | 1.499 (4) | Cl1—O2 | 1.431 (2) |
C9—C10 | 1.381 (4) | Cl1—O3 | 1.434 (2) |
C9—H9 | 0.9300 | Cl1—O4 | 1.435 (2) |
C10—N2 | 1.342 (4) | Cl1—O1 | 1.453 (2) |
C10—H10 | 0.9300 | Cl2—O5 | 1.432 (2) |
C11—H11A | 0.9600 | Cl2—O8 | 1.436 (2) |
C11—H11B | 0.9600 | Cl2—O6 | 1.439 (2) |
C11—H11C | 0.9600 | Cl2—O7 | 1.455 (2) |
C12—H12A | 0.9600 | N4—H4A | 0.8600 |
C12—H12B | 0.9600 | N4—H4B | 0.8600 |
C12—H12C | 0.9600 | N6—H6A | 0.8600 |
C13—N3 | 1.340 (4) | N6—H6B | 0.8600 |
N1—Cu1—N3 | 174.07 (9) | C15—C14—C13 | 117.3 (3) |
N1—Cu1—N5 | 93.69 (9) | C16—C15—C14 | 119.8 (3) |
N3—Cu1—N5 | 90.58 (9) | C16—C15—H15 | 120.1 |
N1—Cu1—N2 | 81.51 (9) | C14—C15—H15 | 120.1 |
N3—Cu1—N2 | 93.39 (9) | C17—C16—C15 | 119.7 (3) |
N5—Cu1—N2 | 166.06 (9) | C17—C16—H16 | 120.2 |
N1—Cu1—O1 | 91.06 (8) | C15—C16—H16 | 120.2 |
N3—Cu1—O1 | 92.40 (9) | N3—C17—C16 | 121.2 (3) |
N5—Cu1—O1 | 98.15 (9) | N3—C17—H17 | 119.4 |
N2—Cu1—O1 | 95.02 (9) | C16—C17—H17 | 119.4 |
N1—C1—C2 | 122.7 (3) | N5—C18—C19 | 123.3 (2) |
N1—C1—H1 | 118.6 | N5—C18—H18 | 118.4 |
C2—C1—H1 | 118.6 | C19—C18—H18 | 118.4 |
C1—C2—C3 | 119.4 (3) | N6—C19—C18 | 120.6 (3) |
C1—C2—H2 | 120.3 | N6—C19—C20 | 122.3 (3) |
C3—C2—H2 | 120.3 | C18—C19—C20 | 117.0 (3) |
C2—C3—C4 | 117.6 (2) | C21—C20—C19 | 119.0 (3) |
C2—C3—C11 | 121.0 (3) | C21—C20—H20 | 120.5 |
C4—C3—C11 | 121.4 (3) | C19—C20—H20 | 120.5 |
C5—C4—C3 | 120.2 (3) | C20—C21—C22 | 120.4 (3) |
C5—C4—H4 | 119.9 | C20—C21—H21 | 119.8 |
C3—C4—H4 | 119.9 | C22—C21—H21 | 119.8 |
N1—C5—C4 | 121.7 (2) | N5—C22—C21 | 120.7 (3) |
N1—C5—C6 | 114.5 (2) | N5—C22—H22 | 119.6 |
C4—C5—C6 | 123.8 (2) | C21—C22—H22 | 119.6 |
N2—C6—C7 | 122.2 (2) | O2—Cl1—O3 | 110.59 (15) |
N2—C6—C5 | 114.8 (2) | O2—Cl1—O4 | 109.72 (15) |
C7—C6—C5 | 123.0 (2) | O3—Cl1—O4 | 109.37 (13) |
C6—C7—C8 | 120.1 (2) | O2—Cl1—O1 | 108.78 (14) |
C6—C7—H7 | 120.0 | O3—Cl1—O1 | 108.90 (13) |
C8—C7—H7 | 120.0 | O4—Cl1—O1 | 109.46 (14) |
C7—C8—C9 | 116.9 (2) | O5—Cl2—O8 | 109.73 (15) |
C7—C8—C12 | 121.6 (3) | O5—Cl2—O6 | 109.81 (14) |
C9—C8—C12 | 121.5 (2) | O8—Cl2—O6 | 109.66 (15) |
C10—C9—C8 | 120.2 (3) | O5—Cl2—O7 | 108.90 (15) |
C10—C9—H9 | 119.9 | O8—Cl2—O7 | 109.42 (13) |
C8—C9—H9 | 119.9 | O6—Cl2—O7 | 109.30 (13) |
N2—C10—C9 | 122.5 (3) | C1—N1—C5 | 118.4 (2) |
N2—C10—H10 | 118.7 | C1—N1—Cu1 | 126.52 (19) |
C9—C10—H10 | 118.7 | C5—N1—Cu1 | 115.00 (17) |
C3—C11—H11A | 109.5 | C10—N2—C6 | 118.1 (2) |
C3—C11—H11B | 109.5 | C10—N2—Cu1 | 127.95 (19) |
H11A—C11—H11B | 109.5 | C6—N2—Cu1 | 113.96 (18) |
C3—C11—H11C | 109.5 | C13—N3—C17 | 119.8 (2) |
H11A—C11—H11C | 109.5 | C13—N3—Cu1 | 122.1 (2) |
H11B—C11—H11C | 109.5 | C17—N3—Cu1 | 118.00 (19) |
C8—C12—H12A | 109.5 | C14—N4—H4A | 120.0 |
C8—C12—H12B | 109.5 | C14—N4—H4B | 120.0 |
H12A—C12—H12B | 109.5 | H4A—N4—H4B | 120.0 |
C8—C12—H12C | 109.5 | C18—N5—C22 | 119.4 (2) |
H12A—C12—H12C | 109.5 | C18—N5—Cu1 | 117.98 (18) |
H12B—C12—H12C | 109.5 | C22—N5—Cu1 | 122.3 (2) |
N3—C13—C14 | 122.3 (3) | C19—N6—H6A | 120.0 |
N3—C13—H13 | 118.9 | C19—N6—H6B | 120.0 |
C14—C13—H13 | 118.9 | H6A—N6—H6B | 120.0 |
N4—C14—C15 | 122.6 (3) | Cl1—O1—Cu1 | 129.57 (12) |
N4—C14—C13 | 120.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O3i | 0.93 | 2.35 | 3.067 (4) | 134 |
C20—H20···O3ii | 0.93 | 2.54 | 3.432 (4) | 161 |
C18—H18···O8 | 0.93 | 2.41 | 3.176 (4) | 139 |
C18—H18···O7 | 0.93 | 2.36 | 3.224 (3) | 154 |
C13—H13···O1 | 0.93 | 2.40 | 3.074 (3) | 129 |
C10—H10···N3 | 0.93 | 2.60 | 3.103 (4) | 114 |
C4—H4···O7iii | 0.93 | 2.46 | 3.382 (4) | 171 |
C4—H4···O6iii | 0.93 | 2.58 | 3.263 (4) | 130 |
C2—H2···O6iv | 0.93 | 2.41 | 3.313 (4) | 164 |
C1—H1···N5 | 0.93 | 2.60 | 3.093 (4) | 114 |
N6—H6B···O4ii | 0.86 | 2.19 | 3.037 (4) | 169 |
N6—H6A···O8 | 0.86 | 2.30 | 3.057 (4) | 146 |
N4—H4B···O2i | 0.86 | 2.42 | 3.197 (4) | 150 |
N4—H4A···O8v | 0.86 | 2.56 | 3.187 (4) | 130 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+2, −y+1, −z; (iv) x−1/2, −y+3/2, z−1/2; (v) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(ClO4)(C5H6N2)2(C12H12N2)]ClO4 |
Mr | 634.91 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 16.112 (3), 10.442 (2), 17.058 (3) |
β (°) | 115.67 (3) |
V (Å3) | 2586.6 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.808, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22276, 4949, 4665 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.103, 1.13 |
No. of reflections | 4949 |
No. of parameters | 354 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −0.44 |
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku Corporation, 2001), CrystalClear, TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000), SHELXTL (Bruker, 2000), SHELXTL.
Cu1—N1 | 1.983 (2) | Cu1—N2 | 2.013 (2) |
Cu1—N3 | 1.993 (2) | Cu1—O1 | 2.396 (2) |
Cu1—N5 | 1.997 (2) | ||
N1—Cu1—N3 | 174.07 (9) | N5—Cu1—N2 | 166.06 (9) |
N1—Cu1—N5 | 93.69 (9) | N1—Cu1—O1 | 91.06 (8) |
N3—Cu1—N5 | 90.58 (9) | N3—Cu1—O1 | 92.40 (9) |
N1—Cu1—N2 | 81.51 (9) | N5—Cu1—O1 | 98.15 (9) |
N3—Cu1—N2 | 93.39 (9) | N2—Cu1—O1 | 95.02 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O3i | 0.93 | 2.35 | 3.067 (4) | 133.5 |
C20—H20···O3ii | 0.93 | 2.54 | 3.432 (4) | 160.5 |
C18—H18···O8 | 0.93 | 2.41 | 3.176 (4) | 139.1 |
C18—H18···O7 | 0.93 | 2.36 | 3.224 (3) | 154.2 |
C13—H13···O1 | 0.93 | 2.40 | 3.074 (3) | 129.1 |
C10—H10···N3 | 0.93 | 2.60 | 3.103 (4) | 114.2 |
C4—H4···O7iii | 0.93 | 2.46 | 3.382 (4) | 171.0 |
C4—H4···O6iii | 0.93 | 2.58 | 3.263 (4) | 130.3 |
C2—H2···O6iv | 0.93 | 2.41 | 3.313 (4) | 164.4 |
C1—H1···N5 | 0.93 | 2.60 | 3.093 (4) | 113.5 |
N6—H6B···O4ii | 0.86 | 2.19 | 3.037 (4) | 169.1 |
N6—H6A···O8 | 0.86 | 2.30 | 3.057 (4) | 146.3 |
N4—H4B···O2i | 0.86 | 2.42 | 3.197 (4) | 149.8 |
N4—H4A···O8v | 0.86 | 2.56 | 3.187 (4) | 130.3 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+2, −y+1, −z; (iv) x−1/2, −y+3/2, z−1/2; (v) −x+3/2, y−1/2, −z+1/2. |
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The rational design and synthesis of coordination complexes are of continuing interest for developing new functional molecular-based materials (Robson et al., 1992). A commonly used strategy is preparing the metal complexes with mixed functional ligands in order to tune precisely their chemical and physical properties. Some weakly coordinated ligands can cap or preoccupy certain coordination sites of the central metal ions, and they can be replaced by a variety of bridging groups capable of stronger coordination ability in the subsequent synthesis (Huang et al., 2003, 2006). However, owing to the different coordination ability of the ligands, it is difficult to obtain the desired complexes in many cases (Huang & Ogawa, 2006b). We report here the title CuII complex, (I), having monodentate and bidentate ligands in the molecular structure simultaneously, which can be synthesized in a very facile way, namely, in situ partial ligand substitution between 3-aminopyridine and 4,4'-dimethyl-2,2'-bipyridine at room temperature. The Cambridge Structural Database (Version 5.26; Allen, 2002) contains no structural reports of compounds in which 4,4'-dimethyl-2,2'-bipyridine and 3-aminopyridine molecules are coordinated simultaneously to one metal center.
The atom-numbering scheme of (I) at 120 (2) K is shown in Fig. 1, while bond distances and bond angles related to the copper(II) center are given in Table 1. The coordination configuration of the CuII center is a slightly distorted five-coordinate square pyramid, which has a τ value of 0.134 (Addison et al., 1984). Two N atoms from one bidentate 4,4'-dimethyl-2,2'-bipyridine molecule and two monodentate pyridine-coordinated 3-aminopyridine molecules constitute the basal plane, with the Cu—N bond lengths in the range 1.983 (2)–2.013 (2) Å. Atom O1 from one perchlorate counter-ion occupies the apical position, the Cu—O bond length being 2.396 (2) Å. The other perchlorate anion is believed to be uncoordinated since the shortest distance between the O atom and the central copper ion is 3.192 (3) Å (Cu1···O7). Neither of the perchlorate anions in (I) is disordered at 120 (2) K. Compared with the related data for the same complex at 291 (2) K [Cu—N = 1.980 (3)–2.012 (3) Å, Cu—O = 2.433 (3) Å for the coordinated perchlorate anion, and the shortest Cu···O separation between the uncoordinated perchlorate anion and the CuII center being 3.179 (5) Å for Cu1···O7], one can easily find that the square pyramid around the copper(II) center in (I) is slightly compressed, when the temperature is decreased, but the geometries of the basal N4 plane are almost unchanged.
The two pyridine rings of the 4,4'-dimethyl-2,2'-bipyridine molecule are essentially coplanar, with a torsion angle of 7.2 (2)°, which is analogous to those in our previous reports (Huang & Ogawa, 2006a; Qian & Huang, 2006). The dihedral angles between the 4,4'-dimethyl-2,2'-bipyridine least-squares plane and the two 3-aminopyridine molecular planes in (I) are 77.5 (2) and 76.2 (2)°, respectively, while the two 3-aminopyridine molecular planes are nearly perpendicular, with a dihedral angle of 93.6 (2)° in order to minimize the steric hindrance.
Versatile hydrogen-bonding interactions are another remarkable structural feature of the title compound. In the crystal structure, every molecule is connected to six adjacent perchlorate groups besides the coordinated one by means of intermolecular N—H···O and C—H···O hydrogen-bonding contacts (Fig. 2 and Table 2). The donors come from the H atoms of the amine groups in the 3-aminopyridine ligands as well as the pyridyl H atoms of 4,4'-dimethyl-2,2'-bipyridine and 3-aminopyridine, while the acceptors are the O atoms of the perchlorate anions. As a result, two kinds of neighbouring eight-membered ClO2H2C2N hydrogen-bond rings are formed. Furthermore, all the molecules in (I) pack along the crystallographic b axis, forming a hydrogen-bond-sustained supramolecular framework.