trans-Diaquabis(isoquinoline-1-carboxylato-κ2N,O)cobalt(II) dihydrate, [Co(C10H6NO2)2(H2O)2]·2H2O, and trans-diaquabis(isoquinoline-1-carboxylato-κ2N,O)nickel(II) dihydrate, [Ni(C10H6NO2)2(H2O)2]·2H2O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.
Supporting information
CCDC references: 201255; 201256
Orange plate-like crystals of (I) were obtained by slow evaporation of a
solution in methanol-water [90:10 (v/v)] of a mixture of
isoquinoline-1-carboxylic acid and CoCl4·6H2O (molar ratio 4:1). Blue
needle-like crystals of (II) were obtained by slow evaporation of a solution
in methanol-water [70:30 (v/v)] of a mixture of
isoquinoline-1-carboxylic acid and NiCl2·6H2O (molar ratio 4:1).
All H atoms of (I) and (II) were treated as riding, with C—H distances of 0.93 Å and O—H distances in the range 0.86–0.91 Å. Is this added text OK?
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
(I)
trans-Bisaquabis(isoquinoline-1-carboxylato-N,
O)cobalt(II)
dihydrate
top
Crystal data top
[Co(C10H6NO2)2(H2O)2]·2H2O | F(000) = 490 |
Mr = 475.31 | Dx = 1.610 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 12.271 (2) Å | θ = 14.3–15.0° |
b = 5.324 (2) Å | µ = 0.93 mm−1 |
c = 15.150 (1) Å | T = 296 K |
β = 97.85 (1)° | Plate, orange |
V = 980.5 (4) Å3 | 0.40 × 0.15 × 0.10 mm |
Z = 2 | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.016 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→15 |
Tmin = 0.846, Tmax = 0.911 | k = 0→6 |
2594 measured reflections | l = −19→19 |
2241 independent reflections | 3 standard reflections every 150 reflections |
1675 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.116 | (Δ/σ)max < 0.001 |
S = 0.84 | Δρmax = 0.32 e Å−3 |
2241 reflections | Δρmin = −0.22 e Å−3 |
142 parameters | |
Crystal data top
[Co(C10H6NO2)2(H2O)2]·2H2O | V = 980.5 (4) Å3 |
Mr = 475.31 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.271 (2) Å | µ = 0.93 mm−1 |
b = 5.324 (2) Å | T = 296 K |
c = 15.150 (1) Å | 0.40 × 0.15 × 0.10 mm |
β = 97.85 (1)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1675 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.846, Tmax = 0.911 | 3 standard reflections every 150 reflections |
2594 measured reflections | intensity decay: none |
2241 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 142 parameters |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.32 e Å−3 |
2241 reflections | Δρmin = −0.22 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The
weighted R-factor (wR), goodness of fit (S) and
R-factor (gt) are based on F, with F set to zero for
negative F. The threshold expression of F2 > 2.0
σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.0242 (1) | |
O1 | 0.1067 (1) | −0.2763 (3) | 0.0523 (1) | 0.0304 (4) | |
O1W | 0.0545 (1) | 0.2412 (3) | 0.1126 (1) | 0.0340 (4) | |
O2 | 0.2816 (1) | −0.3942 (4) | 0.0688 (1) | 0.0437 (5) | |
O2W | 0.1988 (2) | 0.0196 (4) | 0.2526 (1) | 0.0524 (5) | |
N1 | 0.1408 (1) | 0.0834 (4) | −0.0587 (1) | 0.0255 (4) | |
C1 | 0.2252 (2) | −0.0722 (4) | −0.0380 (1) | 0.0243 (4) | |
C2 | 0.3238 (2) | −0.0547 (4) | −0.0773 (1) | 0.0247 (4) | |
C3 | 0.4125 (2) | −0.2262 (5) | −0.0628 (2) | 0.0337 (5) | |
C4 | 0.5028 (2) | −0.1954 (5) | −0.1061 (2) | 0.0407 (6) | |
C5 | 0.5099 (2) | 0.0056 (5) | −0.1649 (2) | 0.0397 (6) | |
C6 | 0.4262 (2) | 0.1736 (5) | −0.1808 (2) | 0.0366 (5) | |
C7 | 0.3308 (2) | 0.1473 (4) | −0.1383 (1) | 0.0277 (4) | |
C8 | 0.2404 (2) | 0.3109 (5) | −0.1566 (2) | 0.0335 (5) | |
C9 | 0.1484 (2) | 0.2736 (4) | −0.1178 (2) | 0.0313 (5) | |
C10 | 0.2054 (2) | −0.2642 (4) | 0.0332 (1) | 0.0269 (4) | |
H1A | 0.1015 | 0.1846 | 0.1557 | 0.0478* | |
H1B | 0.0850 | 0.3756 | 0.1014 | 0.0478* | |
H2A | 0.2134 | −0.1478 | 0.2485 | 0.0478* | |
H2B | 0.1988 | 0.0403 | 0.3093 | 0.0478* | |
H3 | 0.4096 | −0.3602 | −0.0238 | 0.0404* | |
H4 | 0.5604 | −0.3100 | −0.0963 | 0.0488* | |
H5 | 0.5721 | 0.0239 | −0.1931 | 0.0476* | |
H6 | 0.4315 | 0.3066 | −0.2198 | 0.0439* | |
H8 | 0.2438 | 0.4451 | −0.1954 | 0.0402* | |
H9 | 0.0887 | 0.3808 | −0.1320 | 0.0376* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0194 (2) | 0.0257 (2) | 0.0279 (2) | 0.0031 (2) | 0.0049 (1) | 0.0032 (2) |
O1 | 0.0242 (8) | 0.0304 (8) | 0.0375 (8) | 0.0040 (6) | 0.0078 (6) | 0.0105 (7) |
O1W | 0.0345 (9) | 0.0322 (9) | 0.0344 (8) | −0.0033 (7) | 0.0016 (6) | 0.0002 (7) |
O2 | 0.0293 (9) | 0.057 (1) | 0.0463 (10) | 0.0151 (9) | 0.0105 (7) | 0.0229 (9) |
O2W | 0.075 (2) | 0.043 (1) | 0.0373 (9) | 0.0058 (9) | 0.0034 (10) | 0.0011 (8) |
N1 | 0.0221 (8) | 0.0278 (9) | 0.0268 (8) | 0.0027 (7) | 0.0046 (7) | 0.0037 (7) |
C1 | 0.0227 (10) | 0.0245 (10) | 0.0256 (9) | 0.0009 (8) | 0.0023 (8) | 0.0005 (8) |
C2 | 0.0205 (10) | 0.028 (1) | 0.0259 (10) | 0.0000 (8) | 0.0029 (7) | −0.0036 (8) |
C3 | 0.029 (1) | 0.032 (1) | 0.041 (1) | 0.0055 (10) | 0.0087 (9) | 0.0028 (10) |
C4 | 0.026 (1) | 0.049 (2) | 0.049 (1) | 0.007 (1) | 0.010 (1) | −0.002 (1) |
C5 | 0.030 (1) | 0.049 (2) | 0.043 (1) | −0.005 (1) | 0.0150 (10) | −0.006 (1) |
C6 | 0.034 (1) | 0.040 (1) | 0.038 (1) | −0.007 (1) | 0.0113 (10) | 0.001 (1) |
C7 | 0.028 (1) | 0.028 (1) | 0.027 (1) | −0.0031 (9) | 0.0062 (8) | −0.0014 (8) |
C8 | 0.038 (1) | 0.031 (1) | 0.032 (1) | 0.0016 (10) | 0.0058 (9) | 0.0084 (9) |
C9 | 0.030 (1) | 0.030 (1) | 0.033 (1) | 0.0058 (9) | 0.0039 (9) | 0.0067 (9) |
C10 | 0.027 (1) | 0.028 (1) | 0.0257 (9) | 0.0026 (8) | 0.0036 (8) | 0.0029 (8) |
Geometric parameters (Å, º) top
Co1—O1 | 2.055 (2) | C2—C7 | 1.428 (3) |
Co1—O1W | 2.167 (2) | C3—C4 | 1.373 (4) |
Co1—N1 | 2.096 (2) | C3—H3 | 0.930 |
O1—C10 | 1.284 (3) | C4—C5 | 1.402 (4) |
O1W—H1A | 0.864 | C4—H4 | 0.930 |
O1W—H1B | 0.835 | C5—C6 | 1.359 (4) |
O2—C10 | 1.227 (3) | C5—H5 | 0.930 |
O2W—H2A | 0.913 | C6—C7 | 1.418 (3) |
O2W—H2B | 0.866 | C6—H6 | 0.930 |
N1—C1 | 1.329 (3) | C7—C8 | 1.408 (3) |
N1—C9 | 1.364 (3) | C8—C9 | 1.356 (4) |
C1—C2 | 1.422 (3) | C8—H8 | 0.930 |
C1—C10 | 1.530 (3) | C9—H9 | 0.930 |
C2—C3 | 1.415 (3) | | |
| | | |
O1···O1Wi | 2.829 (2) | O2W···O2Wiv | 2.949 (2) |
O1W···C10ii | 3.524 (3) | O2W···C10vii | 3.492 (3) |
O1W···O2ii | 3.533 (3) | C2···C4vi | 3.522 (3) |
O1W···C9iii | 3.595 (3) | C3···C8i | 3.425 (3) |
O2···O2Wiv | 2.723 (3) | C3···C4vi | 3.455 (4) |
O2···C4v | 3.417 (3) | C3···C3vi | 3.594 (5) |
O2···C5vi | 3.454 (3) | C6···C8viii | 3.550 (3) |
O2···C9i | 3.540 (3) | C7···C8viii | 3.591 (3) |
O2W···O2Wvii | 2.949 (2) | C9···C10ii | 3.368 (3) |
| | | |
O1—Co1—O1ix | 180.0 | C3—C2—C7 | 118.2 (2) |
O1—Co1—O1W | 90.52 (6) | C2—C3—C4 | 120.2 (2) |
O1—Co1—O1Wix | 89.48 (6) | C2—C3—H3 | 119.9 |
O1—Co1—N1 | 78.25 (7) | C4—C3—H3 | 119.9 |
O1—Co1—N1ix | 101.75 (7) | C3—C4—C5 | 121.2 (2) |
O1ix—Co1—O1W | 89.48 (6) | C3—C4—H4 | 119.4 |
O1ix—Co1—N1 | 101.75 (7) | C5—C4—H4 | 119.4 |
O1W—Co1—O1Wix | 180.0 | C4—C5—C6 | 120.3 (2) |
O1W—Co1—N1 | 91.42 (7) | C4—C5—H5 | 119.8 |
O1W—Co1—N1ix | 88.58 (7) | C6—C5—H5 | 119.8 |
O1Wix—Co1—N1 | 88.58 (7) | C5—C6—C7 | 120.3 (2) |
N1—Co1—N1ix | 180.0 | C5—C6—H6 | 119.8 |
Co1—O1—C10 | 116.6 (1) | C7—C6—H6 | 119.9 |
Co1—O1W—H1A | 119.4 | C2—C7—C6 | 119.7 (2) |
Co1—O1W—H1B | 116.5 | C2—C7—C8 | 118.5 (2) |
H1A—O1W—H1B | 100.4 | C6—C7—C8 | 121.8 (2) |
H2A—O2W—H2B | 102.6 | C7—C8—C9 | 120.3 (2) |
Co1—N1—C1 | 115.4 (1) | C7—C8—H8 | 119.8 |
Co1—N1—C9 | 124.8 (1) | C9—C8—H8 | 119.8 |
C1—N1—C9 | 119.8 (2) | N1—C9—C8 | 121.9 (2) |
N1—C1—C2 | 122.7 (2) | N1—C9—H9 | 119.0 |
N1—C1—C10 | 112.9 (2) | C8—C9—H9 | 119.1 |
C2—C1—C10 | 124.4 (2) | O1—C10—O2 | 123.9 (2) |
C1—C2—C3 | 125.0 (2) | O1—C10—C1 | 116.0 (2) |
C1—C2—C7 | 116.8 (2) | O2—C10—C1 | 120.1 (2) |
| | | |
Co1—O1—C10—O2 | 169.8 (2) | C1—C2—C3—C4 | 178.2 (2) |
Co1—O1—C10—C1 | −9.8 (2) | C1—C2—C7—C6 | −179.1 (2) |
Co1—N1—C1—C2 | 175.0 (2) | C1—C2—C7—C8 | −1.1 (3) |
Co1—N1—C1—C10 | −6.5 (2) | C2—C1—N1—C9 | −1.9 (3) |
Co1—N1—C9—C8 | −177.0 (2) | C2—C3—C4—C5 | 0.4 (4) |
O1—Co1—N1—C1 | 1.5 (1) | C2—C7—C6—C5 | 1.1 (3) |
O1—Co1—N1—C9 | 178.2 (2) | C2—C7—C8—C9 | −1.0 (3) |
O1—C10—C1—N1 | 10.8 (3) | C3—C2—C1—C10 | 6.6 (3) |
O1—C10—C1—C2 | −170.7 (2) | C3—C2—C7—C6 | −1.3 (3) |
O1W—Co1—O1—C10 | −86.4 (1) | C3—C2—C7—C8 | 176.7 (2) |
O1W—Co1—N1—C1 | 91.7 (2) | C3—C4—C5—C6 | −0.6 (4) |
O1W—Co1—N1—C9 | −91.5 (2) | C4—C3—C2—C7 | 0.5 (3) |
O2—C10—C1—N1 | −168.8 (2) | C4—C5—C6—C7 | −0.1 (4) |
O2—C10—C1—C2 | 9.7 (3) | C5—C6—C7—C8 | −176.9 (2) |
N1—Co1—O1—C10 | 4.9 (1) | C6—C7—C8—C9 | 176.9 (2) |
N1—C1—C2—C3 | −175.0 (2) | C7—C2—C1—C10 | −175.7 (2) |
N1—C1—C2—C7 | 2.6 (3) | C9—N1—C1—C10 | 176.6 (2) |
N1—C9—C8—C7 | 1.8 (3) | C9—N1—C1—C10 | 176.6 (2) |
C1—N1—C9—C8 | −0.4 (3) | | |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x, −y+1, −z; (iv) −x+1/2, y−1/2, −z+1/2; (v) −x+1, −y−1, −z; (vi) −x+1, −y, −z; (vii) −x+1/2, y+1/2, −z+1/2; (viii) −x+1/2, y−1/2, −z−1/2; (ix) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.86 | 1.97 | 2.829 (3) | 173 |
O1W—H1B···O1ii | 0.84 | 2.03 | 2.829 (2) | 160 |
O2W—H2A···O2Wiv | 0.91 | 2.07 | 2.949 (2) | 160 |
O2W—H2B···O2vii | 0.87 | 1.86 | 2.723 (3) | 172 |
Symmetry codes: (ii) x, y+1, z; (iv) −x+1/2, y−1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+1/2. |
(II)
trans-Bisaquabis(isoquinoline-1-carboxylato-N,
O)nickel(II)
dihydrate
top
Crystal data top
[Ni(C10H6NO2)2(H2O)2]·2H2O | F(000) = 492 |
Mr = 475.07 | Dx = 1.619 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 12.171 (2) Å | θ = 14.0–14.6° |
b = 5.351 (4) Å | µ = 1.05 mm−1 |
c = 15.107 (2) Å | T = 296 K |
β = 97.91 (1)° | Needle, blue |
V = 974.5 (8) Å3 | 0.50 × 0.10 × 0.05 mm |
Z = 2 | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.018 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 12→15 |
Tmin = 0.882, Tmax = 0.949 | k = 0→6 |
2573 measured reflections | l = −19→19 |
2225 independent reflections | 3 standard reflections every 150 reflections |
1620 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.143 | (Δ/σ)max < 0.001 |
S = 0.99 | Δρmax = 0.66 e Å−3 |
2225 reflections | Δρmin = −0.48 e Å−3 |
142 parameters | |
Crystal data top
[Ni(C10H6NO2)2(H2O)2]·2H2O | V = 974.5 (8) Å3 |
Mr = 475.07 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.171 (2) Å | µ = 1.05 mm−1 |
b = 5.351 (4) Å | T = 296 K |
c = 15.107 (2) Å | 0.50 × 0.10 × 0.05 mm |
β = 97.91 (1)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1620 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.018 |
Tmin = 0.882, Tmax = 0.949 | 3 standard reflections every 150 reflections |
2573 measured reflections | intensity decay: none |
2225 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 142 parameters |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.66 e Å−3 |
2225 reflections | Δρmin = −0.48 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > -10.0 σ(F2). 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). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.0247 (2) | |
O1 | −0.1028 (2) | 0.2786 (4) | −0.0526 (1) | 0.0326 (5) | |
O1W | 0.0552 (2) | 0.2349 (4) | 0.1108 (1) | 0.0357 (5) | |
O2 | −0.2785 (2) | 0.4003 (5) | −0.0681 (2) | 0.0458 (6) | |
O2W | 0.1974 (3) | 0.0143 (6) | 0.2515 (2) | 0.0637 (9) | |
N1 | −0.1374 (2) | −0.0804 (5) | 0.0581 (2) | 0.0257 (5) | |
C1 | −0.2225 (2) | 0.0763 (6) | 0.0376 (2) | 0.0254 (6) | |
C2 | −0.3216 (2) | 0.0582 (6) | 0.0772 (2) | 0.0258 (6) | |
C3 | −0.4114 (3) | 0.2285 (6) | 0.0630 (2) | 0.0338 (7) | |
C4 | −0.5022 (3) | 0.1966 (7) | 0.1057 (2) | 0.0405 (8) | |
C5 | −0.5099 (3) | −0.0047 (7) | 0.1643 (2) | 0.0408 (8) | |
C6 | −0.4256 (3) | −0.1751 (7) | 0.1795 (2) | 0.0362 (7) | |
C7 | −0.3292 (2) | −0.1455 (6) | 0.1376 (2) | 0.0278 (6) | |
C8 | −0.2379 (3) | −0.3072 (6) | 0.1558 (2) | 0.0324 (6) | |
C9 | −0.1451 (3) | −0.2697 (6) | 0.1168 (2) | 0.0326 (6) | |
C10 | −0.2023 (2) | 0.2695 (6) | −0.0334 (2) | 0.0279 (6) | |
H1A | 0.1010 | 0.1598 | 0.1583 | 0.0474* | |
H1B | 0.0810 | 0.3937 | 0.1041 | 0.0474* | |
H2A | 0.2079 | −0.1609 | 0.2525 | 0.0474* | |
H2B | 0.1987 | 0.0461 | 0.3136 | 0.0474* | |
H3 | −0.4084 | 0.3630 | 0.0244 | 0.0405* | |
H4 | −0.5602 | 0.3106 | 0.0957 | 0.0487* | |
H5 | −0.5725 | −0.0221 | 0.1927 | 0.0490* | |
H6 | −0.4316 | −0.3100 | 0.2174 | 0.0434* | |
H8 | −0.2411 | −0.4408 | 0.1947 | 0.0388* | |
H9 | −0.0851 | −0.3769 | 0.1308 | 0.0391* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0202 (3) | 0.0241 (3) | 0.0301 (3) | 0.0031 (2) | 0.0050 (2) | 0.0039 (2) |
O1 | 0.028 (1) | 0.029 (1) | 0.041 (1) | 0.0053 (9) | 0.0100 (9) | 0.0129 (9) |
O1W | 0.039 (1) | 0.029 (1) | 0.038 (1) | −0.0018 (10) | 0.0008 (9) | −0.0001 (9) |
O2 | 0.032 (1) | 0.056 (2) | 0.052 (1) | 0.017 (1) | 0.012 (1) | 0.026 (1) |
O2W | 0.089 (3) | 0.052 (2) | 0.049 (2) | 0.008 (1) | 0.003 (2) | 0.002 (1) |
N1 | 0.023 (1) | 0.025 (1) | 0.029 (1) | 0.0030 (10) | 0.0033 (9) | 0.0045 (10) |
C1 | 0.023 (1) | 0.024 (1) | 0.029 (1) | 0.000 (1) | 0.004 (1) | 0.000 (1) |
C2 | 0.021 (1) | 0.029 (2) | 0.027 (1) | 0.000 (1) | 0.0020 (10) | −0.002 (1) |
C3 | 0.031 (2) | 0.030 (2) | 0.042 (2) | 0.005 (1) | 0.008 (1) | 0.002 (1) |
C4 | 0.028 (2) | 0.041 (2) | 0.053 (2) | 0.009 (1) | 0.008 (1) | 0.000 (2) |
C5 | 0.029 (2) | 0.051 (2) | 0.044 (2) | 0.000 (2) | 0.014 (1) | −0.006 (2) |
C6 | 0.036 (2) | 0.038 (2) | 0.036 (2) | −0.005 (1) | 0.011 (1) | 0.000 (1) |
C7 | 0.027 (1) | 0.030 (2) | 0.027 (1) | −0.004 (1) | 0.005 (1) | −0.001 (1) |
C8 | 0.037 (2) | 0.029 (2) | 0.032 (1) | 0.002 (1) | 0.008 (1) | 0.006 (1) |
C9 | 0.032 (2) | 0.030 (2) | 0.037 (1) | 0.007 (1) | 0.007 (1) | 0.008 (1) |
C10 | 0.026 (1) | 0.028 (1) | 0.030 (1) | 0.003 (1) | 0.005 (1) | 0.004 (1) |
Geometric parameters (Å, º) top
Ni1—O1 | 2.036 (2) | C2—C7 | 1.433 (4) |
Ni1—O1W | 2.127 (2) | C3—C4 | 1.365 (5) |
Ni1—N1 | 2.039 (3) | C3—H3 | 0.930 |
O1—C10 | 1.285 (4) | C4—C5 | 1.406 (5) |
O1W—H1A | 0.936 | C4—H4 | 0.930 |
O1W—H1B | 0.916 | C5—C6 | 1.368 (5) |
O2—C10 | 1.221 (4) | C5—H5 | 0.930 |
O2W—H2A | 0.946 | C6—C7 | 1.418 (5) |
O2W—H2B | 0.951 | C6—H6 | 0.930 |
N1—C1 | 1.335 (4) | C7—C8 | 1.405 (4) |
N1—C9 | 1.358 (4) | C8—C9 | 1.358 (5) |
C1—C2 | 1.421 (4) | C8—H8 | 0.930 |
C1—C10 | 1.533 (4) | C9—H9 | 0.930 |
C2—C3 | 1.416 (4) | | |
| | | |
O1···O1Wi | 2.833 (3) | O2W···O2Wvii | 2.969 (3) |
O1W···O2i | 3.478 (4) | O2W···C10viii | 3.506 (4) |
O1W···C10i | 3.490 (4) | C2···C4iv | 3.529 (4) |
O2···O2Wii | 2.739 (4) | C3···C8v | 3.432 (4) |
O2···C4iii | 3.418 (4) | C3···C4iv | 3.469 (5) |
O2···C5iv | 3.492 (4) | C6···C8ix | 3.559 (4) |
O2···C9v | 3.508 (4) | C9···C10x | 3.359 (4) |
O2W···O2Wvi | 2.969 (3) | | |
| | | |
O1—Ni1—O1xi | 180.0 | C2—C3—H3 | 119.8 |
O1—Ni1—O1W | 89.14 (8) | C4—C3—H3 | 119.8 |
O1—Ni1—O1Wxi | 90.86 (8) | C3—C4—C5 | 121.5 (3) |
O1—Ni1—N1 | 80.00 (9) | C3—C4—H4 | 119.3 |
O1—Ni1—N1xi | 100.00 (9) | C5—C4—H4 | 119.3 |
O1W—Ni1—O1Wxi | 180.0 | C4—C5—C6 | 120.2 (3) |
O1W—Ni1—N1 | 88.56 (9) | C4—C5—H5 | 119.9 |
O1W—Ni1—N1xi | 91.44 (9) | C6—C5—H5 | 119.9 |
N1—Ni1—N1xi | 180.0 | C5—C6—C7 | 119.9 (3) |
Ni1—O1—C10 | 115.6 (2) | C5—C6—H6 | 120.1 |
Ni1—O1W—H1A | 116.1 | C7—C6—H6 | 120.1 |
Ni1—O1W—H1B | 122.5 | C2—C7—C6 | 120.0 (3) |
H1A—O1W—H1B | 107.9 | C2—C7—C8 | 118.3 (3) |
H2A—O2W—H2B | 100.2 | C6—C7—C8 | 121.7 (3) |
Ni1—N1—C1 | 115.0 (2) | C7—C8—C9 | 120.4 (3) |
Ni1—N1—C9 | 125.0 (2) | C7—C8—H8 | 119.8 |
C1—N1—C9 | 119.9 (3) | C9—C8—H8 | 119.8 |
N1—C1—C2 | 122.4 (3) | N1—C9—C8 | 122.0 (3) |
N1—C1—C10 | 113.1 (3) | N1—C9—H9 | 119.0 |
C2—C1—C10 | 124.5 (3) | C8—C9—H9 | 119.0 |
C1—C2—C3 | 125.0 (3) | O1—C10—O2 | 124.5 (3) |
C1—C2—C7 | 116.9 (3) | O1—C10—C1 | 115.5 (2) |
C3—C2—C7 | 118.0 (3) | O2—C10—C1 | 120.1 (3) |
C2—C3—C4 | 120.4 (3) | | |
| | | |
Ni1—O1—C10—O2 | −170.0 (3) | C1—C2—C3—C4 | −178.8 (3) |
Ni1—O1—C10—C1 | 9.4 (3) | C1—C2—C7—C6 | 180.0 (3) |
Ni1—N1—C1—C2 | −175.4 (2) | C1—C2—C7—C8 | 2.0 (4) |
Ni1—N1—C1—C10 | 5.8 (3) | C2—C1—N1—C9 | 2.0 (4) |
Ni1—N1—C9—C8 | 177.4 (2) | C2—C3—C4—C5 | −0.2 (5) |
O1—Ni1—N1—C1 | −1.0 (2) | C2—C7—C6—C5 | −1.9 (5) |
O1—Ni1—N1—C9 | −178.3 (2) | C2—C7—C8—C9 | 0.1 (4) |
O1—C10—C1—N1 | −10.1 (4) | C3—C2—C1—C10 | −6.0 (5) |
O1—C10—C1—C2 | 171.1 (3) | C3—C2—C7—C6 | 1.4 (4) |
O1W—Ni1—O1—C10 | −93.6 (2) | C3—C2—C7—C8 | −176.5 (3) |
O1W—Ni1—N1—C1 | 88.3 (2) | C3—C4—C5—C6 | −0.3 (5) |
O1W—Ni1—N1—C9 | −88.9 (2) | C4—C3—C2—C7 | −0.4 (4) |
O2—C10—C1—N1 | 169.3 (3) | C4—C5—C6—C7 | 1.3 (5) |
O2—C10—C1—C2 | −9.5 (4) | C5—C6—C7—C8 | 176.0 (3) |
N1—Ni1—O1—C10 | −5.0 (2) | C6—C7—C8—C9 | −177.8 (3) |
N1—C1—C2—C3 | 175.3 (3) | C7—C2—C1—C10 | 175.5 (3) |
N1—C1—C2—C7 | −3.1 (4) | C9—N1—C1—C10 | −176.8 (2) |
N1—C9—C8—C7 | −1.4 (5) | C9—N1—C1—C10 | −176.8 (2) |
C1—N1—C9—C8 | 0.3 (4) | | |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x−1, −y+1, −z; (iv) −x−1, −y, −z; (v) x, y+1, z; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+1/2, y−1/2, −z+1/2; (viii) x+1/2, −y+1/2, z+1/2; (ix) −x−1/2, y+1/2, −z+1/2; (x) x, y−1, z; (xi) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.94 | 1.87 | 2.810 (4) | 178 |
O1W—H1B···O1i | 0.92 | 1.95 | 2.833 (3) | 161 |
O2W—H2B···O2viii | 0.95 | 1.79 | 2.739 (4) | 172 |
O2W—H2A···O2Wvii | 0.95 | 2.09 | 2.969 (4) | 154 |
Symmetry codes: (i) −x, −y+1, −z; (vii) −x+1/2, y−1/2, −z+1/2; (viii) x+1/2, −y+1/2, z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C10H6NO2)2(H2O)2]·2H2O | [Ni(C10H6NO2)2(H2O)2]·2H2O |
Mr | 475.31 | 475.07 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 12.271 (2), 5.324 (2), 15.150 (1) | 12.171 (2), 5.351 (4), 15.107 (2) |
β (°) | 97.85 (1) | 97.91 (1) |
V (Å3) | 980.5 (4) | 974.5 (8) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.93 | 1.05 |
Crystal size (mm) | 0.40 × 0.15 × 0.10 | 0.50 × 0.10 × 0.05 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.846, 0.911 | 0.882, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2594, 2241, 1675 | 2573, 2225, 1620 |
Rint | 0.016 | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.116, 0.84 | 0.040, 0.143, 0.99 |
No. of reflections | 2241 | 2225 |
No. of parameters | 142 | 142 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.22 | 0.66, −0.48 |
Selected geometric parameters (Å, º) for (I) topCo1—O1 | 2.055 (2) | Co1—N1 | 2.096 (2) |
Co1—O1W | 2.167 (2) | | |
| | | |
O1—Co1—O1i | 180.0 | O1W—Co1—N1 | 91.42 (7) |
O1—Co1—O1W | 90.52 (6) | O1W—Co1—N1i | 88.58 (7) |
O1—Co1—O1Wi | 89.48 (6) | O1Wi—Co1—N1 | 88.58 (7) |
O1—Co1—N1 | 78.25 (7) | N1—Co1—N1i | 180.0 |
O1—Co1—N1i | 101.75 (7) | Co1—O1—C10 | 116.6 (1) |
O1i—Co1—O1W | 89.48 (6) | Co1—N1—C1 | 115.4 (1) |
O1i—Co1—N1 | 101.75 (7) | Co1—N1—C9 | 124.8 (1) |
O1W—Co1—O1Wi | 180.0 | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.86 | 1.97 | 2.829 (3) | 173 |
O1W—H1B···O1ii | 0.84 | 2.03 | 2.829 (2) | 160 |
O2W—H2A···O2Wiii | 0.91 | 2.07 | 2.949 (2) | 160 |
O2W—H2B···O2iv | 0.87 | 1.86 | 2.723 (3) | 172 |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topNi1—O1 | 2.036 (2) | Ni1—N1 | 2.039 (3) |
Ni1—O1W | 2.127 (2) | | |
| | | |
O1—Ni1—O1i | 180.0 | O1W—Ni1—N1 | 88.56 (9) |
O1—Ni1—O1W | 89.14 (8) | O1W—Ni1—N1i | 91.44 (9) |
O1—Ni1—O1Wi | 90.86 (8) | N1—Ni1—N1i | 180.0 |
O1—Ni1—N1 | 80.00 (9) | Ni1—O1—C10 | 115.6 (2) |
O1—Ni1—N1i | 100.00 (9) | Ni1—N1—C1 | 115.0 (2) |
O1W—Ni1—O1Wi | 180.0 | Ni1—N1—C9 | 125.0 (2) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.94 | 1.87 | 2.810 (4) | 178 |
O1W—H1B···O1ii | 0.92 | 1.95 | 2.833 (3) | 161 |
O2W—H2B···O2iii | 0.95 | 1.79 | 2.739 (4) | 172 |
O2W—H2A···O2Wiv | 0.95 | 2.09 | 2.969 (4) | 154 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1/2, y−1/2, −z+1/2. |
Isoquinoline-1-carboxylic acid (IQCA) is a potent inhibitor of the Cu enzyme dopamine β-hydroxylase, which catalyses the biosynthesis of norepinephrine and lowers endogeneous levels of norepinephrine and epinephrine in the brain, heart, spleen and adrenal glands (Townes et al., 1990). These authors reported the strong binding affinity of IQCA to dopamine β-hydroxylase as compared with the analogous compound, quinoline-2-carboxylic acid (QCA), which also inhibits the same enzyme. Their explanation for the large difference (a factor of over 100) in the apparent affinities of these two inhibitors is that the hydrophobic portions of these molecules would be oriented very differently with regard to the enzyme surface if the coordination of the ligand atoms to the CuII centre(s) in the oxidized enzyme was the same for both compounds. To date, the crystal structure of the CuII (Tomas et al., 1999) and SnIV (Smith et al., 1995) complexes with IQCA have been reported. Based on these findings, we aimed to clarify the interaction mode between IQCA and transition metal ions, and have determined the crystal structures of the CoII complex, (I), and the NiII complex, (II). \sch
The molecular structure of (I) is shown in Fig. 1. The Co atom has a distorted octahedral coordination in the trans form, defined by two N atoms and two O atoms of the bidentate ligands in the equatorial plane, and two axial O atoms of the water molecules. The coordination bond length in the axial direction [Co1—O1W 2.167 (2) Å] is longer than those in the equatorial plane (Table 1). In the crystal packing of (I), the isoquinoline rings are stacked in relation to each other at a mean distance of 3.403 (4) Å, and hydrogen bonds are formed between the coordinated water, the carboxylate group and the hydrated water (Table 2).
The molecular structure of (II) is shown in Fig. 2. In this complex, the Ni atom has the same distorted octahedral coordination geometry bonded by the same ligand atoms as seen for the Co atom in (I). The bond length in the axial direction [Ni1—O1W 2.127 (2) Å] is also longer than the other coordination bond lengths (Table 2). These long bond lengths in the axial direction as compared with the equatorial plane, which are observed in the octahedral coordination geometry, may be explained by a Jahn-Teller effect. In the crystal packing of (II), the isoquinoline rings are stacked in relation to each other at a mean distance of 3.681 (12) Å.
The distorted octahedral coordination mode observed in this study has also been observed in the transition metal complexes of QCA [CoII (Okabe & Makino, 1999), NiII (Odoko et al., 2001), MnII (Haendler, 1996; Okabe & Koizumi, 1997), FeII (Okabe & Makino, 1998), VIV (Okabe & Muranishi, 2002)], with an exception being the pentacoordination of the CuII complex (Haendler, 1986).
In complexes (I) and (II), the central metal atom forms a five-membered ring with the O and N atoms of the bidentate ligand, as observed in the QCA complexes, as well as in the CuII complex with IQCA. The O—Co—N angle in (I) [101.75 (7)°] is larger than that in the CoII complex with QCA [77.23 (7)°; Okabe & Makino, 1999]. Similarly, the O—Ni—N angle in (II) [100.00 (9)°] is larger than that in the NiII complex with QCA [78.53 (6)°; Odoko et al., 2001). The O—Cu—N angles of the CuII complex with IQCA [82.96 (12)–97.04 (12)°; Tomas et al., 1999] are somewhat larger than those of the complex with QCA [82.1 (1)–82.5 (1)°; Haendler, 1986]. Thus, the included angle, O-metal-N, in the five-membered ring of the IQCA complex is larger than that in the QCA complex.
The Cu atom in the CuII complex of IQCA, trans-bis(isoquinoline-1-carboxylato)copper(II), has also octahedral coordination to two axial O atoms from the adjacent carboxylate groups (Tomas et al., 1999). It is noted that the water is not coordinated to the central Cu atom, although the crystal was prepared in the presence of water (Tomas et al., 1999).
The results of the present study indicate that the coordination geometry of (I) and (II) is the same as that in the CuII complex with IQCA, but the ligand atoms of (I) and (II) are different from those of the CuII complex. In all the crystal structures of the complexes of QCA with transition metal ions, CoII, NiII, MnII and FeII, as well as those of compounds (I) and (II), the central metal atom is coordinated to two water molecules, although the CuII and VIV complexes of QCA contain only one coordinated water molecule. The absence of coordinated water in the CuII complex of IQCA may have some role in the potent inhibitory activity of IQCA against dopamine β-hydroxylase, although this must be further confirmed by solution studies in a biological environment.