The molecules of 8-hydroxyquinolinium-2-carboxylate, C
10H
7NO
3, have a planar structure, in which the carboxyl group is ionized and the ring N atom is protonated. The derived nickel(II) complex, bis(8-hydroxyquinoline-2-carboxylato-
3O2,
N,
O8)nickel(II) trihydrate, [Ni(C
10H
6NO
3)
2]·3H
2O, contains an octahedral central Ni
II ion coordinated by the hydroxyl O atom, the ring N atom and the carboxylate O atom of each of the two tridentate ligands, with a perpendicular orientation of the quinoline rings.
Supporting information
CCDC references: 195606; 195607
Yellow plate crystals of (I) and light-yellow prismatic crystals of (II) were
obtained by, respectively, slow evaporation of an ethanol-water solution
(ca 70% does this mean 70:30 v/v?), and of an
ethanol-water solution (ca 70% does this mean 70:30 v/v?)
of a mixture of 8-hydroxyquinaldinic acid and nickel(II) acetate tetrahydrate
(molar ratio 4:1).
For compound (I), all H atoms were initially located from the difference Fourier
maps, and then they were refined at their ideal positions by a riding model,
using the SHELXL97 HFIX instruction (Sheldrick, 1997) with C—H =
0.93, O—H = 0.82 and N—H = 0.86 Å. Is this added text OK? For complex
(II), all H atoms were also initially located from the difference Fourier
maps, and then all except those of the 8-hydroxyl groups were refined at their
ideal positions by riding models using the SHELXL97 HFIX instruction,
with C—H = 0.93 Å. Is this added text OK? The H atoms of the 8-hydroxyl
groups were fixed in the positions located from the Fourier maps. The water H
atoms were idealized using the SHELXL97 SADI restriction.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation & Rigaku Corporation, 1999); 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) 8-hydroxyquinolinium-2-carboxylate
top
Crystal data top
C10H7NO3 | F(000) = 784.0 |
Mr = 189.17 | Dx = 1.583 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -C 2yc | Cell parameters from 16 reflections |
a = 12.748 (2) Å | θ = 10.2–12.9° |
b = 7.476 (3) Å | µ = 0.12 mm−1 |
c = 16.657 (2) Å | T = 296 K |
β = 90.68 (1)° | Plate, yellow |
V = 1587.3 (7) Å3 | 0.20 × 0.10 × 0.05 mm |
Z = 8 | |
Data collection top
Rigaku AFC-5R diffractometer | θmax = 27.5° |
ω/2θ scans | h = 12→16 |
2068 measured reflections | k = 0→9 |
1838 independent reflections | l = −21→21 |
691 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.066 | intensity decay: 0.8% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.197 | (Δ/σ)max < 0.001 |
S = 0.87 | Δρmax = 0.28 e Å−3 |
1838 reflections | Δρmin = −0.27 e Å−3 |
128 parameters | |
Crystal data top
C10H7NO3 | V = 1587.3 (7) Å3 |
Mr = 189.17 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.748 (2) Å | µ = 0.12 mm−1 |
b = 7.476 (3) Å | T = 296 K |
c = 16.657 (2) Å | 0.20 × 0.10 × 0.05 mm |
β = 90.68 (1)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.066 |
2068 measured reflections | 3 standard reflections every 150 reflections |
1838 independent reflections | intensity decay: 0.8% |
691 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 128 parameters |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.28 e Å−3 |
1838 reflections | Δρmin = −0.27 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 | |
O1 | 0.3802 (2) | 0.1005 (4) | 0.7905 (2) | 0.0381 (8) | |
O2 | 0.3821 (3) | −0.1027 (4) | 0.6906 (2) | 0.0443 (9) | |
O3E | 0.4069 (3) | 0.0399 (4) | 0.4296 (2) | 0.0347 (8) | |
N1 | 0.3840 (3) | 0.1568 (4) | 0.5812 (2) | 0.0248 (8) | |
C1 | 0.3718 (3) | 0.2025 (5) | 0.6578 (2) | 0.0268 (9) | |
C2 | 0.3518 (4) | 0.3799 (5) | 0.6771 (2) | 0.033 (1) | |
C3 | 0.3478 (4) | 0.5061 (5) | 0.6176 (2) | 0.035 (1) | |
C4 | 0.3621 (3) | 0.4587 (5) | 0.5368 (2) | 0.0263 (9) | |
C5 | 0.3606 (3) | 0.5821 (6) | 0.4732 (2) | 0.034 (1) | |
C6 | 0.3749 (4) | 0.5240 (6) | 0.3965 (3) | 0.038 (1) | |
C7 | 0.3908 (4) | 0.3418 (6) | 0.3786 (2) | 0.035 (1) | |
C8 | 0.3927 (3) | 0.2162 (5) | 0.4383 (2) | 0.0257 (9) | |
C9 | 0.3799 (3) | 0.2773 (5) | 0.5195 (2) | 0.0230 (9) | |
C10 | 0.3792 (3) | 0.0492 (6) | 0.7188 (2) | 0.0288 (10) | |
H1 | 0.3950 | 0.0461 | 0.5700 | 0.0297* | |
H2 | 0.3412 | 0.4128 | 0.7302 | 0.0396* | |
H3 | 0.3355 | 0.6250 | 0.6308 | 0.0419* | |
H3E | 0.4021 | 0.0136 | 0.3819 | 0.0521* | |
H5 | 0.3499 | 0.7030 | 0.4833 | 0.0409* | |
H6 | 0.3742 | 0.6069 | 0.3548 | 0.0454* | |
H7 | 0.4002 | 0.3066 | 0.3256 | 0.0416* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.061 (2) | 0.035 (2) | 0.018 (1) | 0.006 (2) | 0.002 (1) | 0.004 (1) |
O2 | 0.075 (3) | 0.027 (2) | 0.031 (2) | −0.002 (2) | −0.003 (2) | −0.001 (1) |
O3E | 0.056 (2) | 0.030 (2) | 0.018 (1) | 0.012 (2) | −0.002 (1) | −0.003 (1) |
N1 | 0.034 (2) | 0.020 (2) | 0.020 (1) | 0.000 (1) | −0.002 (1) | −0.005 (1) |
C1 | 0.032 (2) | 0.027 (2) | 0.022 (2) | 0.000 (2) | −0.002 (2) | 0.001 (2) |
C2 | 0.056 (3) | 0.024 (2) | 0.020 (2) | 0.002 (2) | −0.001 (2) | −0.002 (2) |
C3 | 0.050 (3) | 0.025 (2) | 0.030 (2) | 0.003 (2) | −0.002 (2) | −0.006 (2) |
C4 | 0.030 (2) | 0.025 (2) | 0.025 (2) | −0.001 (2) | −0.002 (2) | −0.004 (2) |
C5 | 0.046 (3) | 0.026 (2) | 0.030 (2) | 0.002 (2) | −0.003 (2) | 0.003 (2) |
C6 | 0.061 (3) | 0.032 (3) | 0.020 (2) | −0.002 (2) | −0.007 (2) | 0.006 (2) |
C7 | 0.050 (3) | 0.038 (3) | 0.016 (2) | 0.001 (2) | −0.002 (2) | −0.001 (2) |
C8 | 0.030 (2) | 0.026 (2) | 0.021 (2) | 0.004 (2) | −0.002 (2) | 0.000 (2) |
C9 | 0.026 (2) | 0.026 (2) | 0.016 (2) | −0.003 (2) | −0.003 (2) | 0.000 (2) |
C10 | 0.032 (2) | 0.033 (3) | 0.021 (2) | −0.002 (2) | 0.003 (2) | 0.004 (2) |
Geometric parameters (Å, º) top
O1—C10 | 1.255 (4) | C3—C4 | 1.405 (6) |
O2—C10 | 1.230 (5) | C3—H3 | 0.930 |
O3E—C8 | 1.338 (5) | C4—C5 | 1.405 (6) |
O3E—H3E | 0.820 | C4—C9 | 1.406 (6) |
N1—C1 | 1.332 (4) | C5—C6 | 1.364 (6) |
N1—C9 | 1.367 (5) | C5—H5 | 0.930 |
N1—H1 | 0.860 | C6—C7 | 1.409 (6) |
C1—C2 | 1.388 (6) | C6—H6 | 0.930 |
C1—C10 | 1.533 (5) | C7—C8 | 1.368 (6) |
C2—C3 | 1.369 (6) | C7—H7 | 0.930 |
C2—H2 | 0.930 | C8—C9 | 1.438 (5) |
| | | |
O1···O3Ei | 2.562 (4) | O3E···C4vii | 3.480 (5) |
O1···C10ii | 3.098 (5) | O3E···C5v | 3.549 (5) |
O1···C6iii | 3.317 (5) | O3E···C10viii | 3.587 (4) |
O1···O1ii | 3.354 (6) | N1···C7vii | 3.574 (6) |
O1···C1ii | 3.355 (5) | N1···C6vii | 3.590 (6) |
O1···C3iv | 3.375 (5) | C1···C7vii | 3.411 (6) |
O1···O2ii | 3.401 (5) | C3···C7ix | 3.520 (6) |
O1···C8i | 3.418 (5) | C3···C6ix | 3.552 (7) |
O1···C2iv | 3.435 (5) | C4···C6ix | 3.522 (6) |
O2···C3v | 3.195 (5) | C4···C8vii | 3.530 (6) |
O2···O3Evi | 3.404 (4) | C4···C5ix | 3.554 (6) |
O2···C10ii | 3.567 (5) | C5···C9ix | 3.472 (6) |
O2···O2ii | 3.580 (7) | C8···C9vii | 3.553 (5) |
O3E···N1vi | 3.052 (4) | C9···C9vii | 3.391 (7) |
O3E···C3vii | 3.349 (5) | C10···C10ii | 3.240 (8) |
O3E···O3Evi | 3.371 (6) | | |
| | | |
C8—O3E—H3E | 109.5 | C4—C5—H5 | 120.1 |
C1—N1—C9 | 123.2 (3) | C6—C5—H5 | 120.1 |
C1—N1—H1 | 118.4 | C5—C6—C7 | 121.8 (4) |
C9—N1—H1 | 118.4 | C5—C6—H6 | 119.1 |
N1—C1—C2 | 119.3 (3) | C7—C6—H6 | 119.1 |
N1—C1—C10 | 115.8 (3) | C6—C7—C8 | 120.8 (4) |
C2—C1—C10 | 124.8 (3) | C6—C7—H7 | 119.6 |
C1—C2—C3 | 119.8 (4) | C8—C7—H7 | 119.6 |
C1—C2—H2 | 120.1 | O3E—C8—C7 | 126.7 (3) |
C3—C2—H2 | 120.1 | O3E—C8—C9 | 115.6 (3) |
C2—C3—C4 | 121.0 (4) | C7—C8—C9 | 117.7 (4) |
C2—C3—H3 | 119.5 | N1—C9—C4 | 119.1 (3) |
C4—C3—H3 | 119.5 | N1—C9—C8 | 119.6 (3) |
C3—C4—C5 | 123.8 (4) | C4—C9—C8 | 121.3 (3) |
C3—C4—C9 | 117.6 (3) | O1—C10—O2 | 130.2 (4) |
C5—C4—C9 | 118.6 (3) | O1—C10—C1 | 113.7 (3) |
C4—C5—C6 | 119.8 (4) | O2—C10—C1 | 116.0 (3) |
| | | |
O1—C10—C1—N1 | 171.7 (4) | C2—C1—N1—C9 | 1.3 (6) |
O1—C10—C1—C2 | −9.5 (6) | C2—C3—C4—C5 | −178.9 (4) |
O2—C10—C1—N1 | −9.0 (5) | C2—C3—C4—C9 | 0.4 (6) |
O2—C10—C1—C2 | 169.8 (4) | C3—C2—C1—C10 | 179.5 (4) |
O3E—C8—C7—C6 | 179.9 (4) | C3—C4—C5—C6 | −179.9 (4) |
O3E—C8—C9—N1 | 0.8 (5) | C3—C4—C9—C8 | 178.4 (4) |
O3E—C8—C9—C4 | −178.6 (3) | C4—C5—C6—C7 | 0.4 (7) |
N1—C1—C2—C3 | −1.8 (6) | C4—C9—C8—C7 | 2.4 (6) |
N1—C9—C4—C3 | −0.9 (5) | C5—C4—C9—C8 | −2.2 (6) |
N1—C9—C4—C5 | 178.4 (4) | C5—C6—C7—C8 | −0.2 (7) |
N1—C9—C8—C7 | −178.3 (4) | C6—C5—C4—C9 | 0.9 (6) |
C1—N1—C9—C4 | 0.1 (5) | C6—C7—C8—C9 | −1.1 (6) |
C1—N1—C9—C8 | −179.3 (4) | C9—N1—C1—C10 | −179.8 (3) |
C1—C2—C3—C4 | 1.0 (7) | C9—N1—C1—C10 | −179.8 (3) |
Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1, y, −z+3/2; (iii) x, −y+1, z+1/2; (iv) −x+1/2, y−1/2, −z+3/2; (v) x, y−1, z; (vi) −x+1, −y, −z+1; (vii) −x+1/2, −y+1/2, −z+1; (viii) x, −y, z−1/2; (ix) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.30 | 2.662 (4) | 105 |
N1—H1···O3E | 0.86 | 2.35 | 2.692 (4) | 104 |
O3E—H3E···O1viii | 0.82 | 1.76 | 2.562 (4) | 164 |
Symmetry code: (viii) x, −y, z−1/2. |
(II) bis(8-hydroxyquinoline-2-carboxylato-
κ3O2,
N,
O8)nickel(II) trihydrate
top
Crystal data top
[Ni(C10H6NO3)2](H2O)3 | Z = 2 |
Mr = 489.05 | F(000) = 504.0 |
Triclinic, P1 | Dx = 1.681 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 9.237 (1) Å | Cell parameters from 25 reflections |
b = 15.865 (3) Å | θ = 14.5–15.0° |
c = 7.200 (1) Å | µ = 1.06 mm−1 |
α = 97.63 (1)° | T = 296 K |
β = 106.95 (1)° | Prismatic, yellow |
γ = 101.90 (1)° | 0.25 × 0.10 × 0.10 mm |
V = 966.4 (3) Å3 | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.024 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→11 |
Tmin = 0.880, Tmax = 0.899 | k = −20→20 |
4703 measured reflections | l = −9→8 |
4434 independent reflections | 3 standard reflections every 150 reflections |
3202 reflections with I > 2σ(I) | intensity decay: 0.3% |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.134 | (Δ/σ)max < 0.001 |
S = 0.90 | Δρmax = 0.64 e Å−3 |
4434 reflections | Δρmin = −0.32 e Å−3 |
307 parameters | |
Crystal data top
[Ni(C10H6NO3)2](H2O)3 | γ = 101.90 (1)° |
Mr = 489.05 | V = 966.4 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.237 (1) Å | Mo Kα radiation |
b = 15.865 (3) Å | µ = 1.06 mm−1 |
c = 7.200 (1) Å | T = 296 K |
α = 97.63 (1)° | 0.25 × 0.10 × 0.10 mm |
β = 106.95 (1)° | |
Data collection top
Rigaku AFC-5R diffractometer | 3202 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.880, Tmax = 0.899 | 3 standard reflections every 150 reflections |
4703 measured reflections | intensity decay: 0.3% |
4434 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 307 parameters |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | Δρmax = 0.64 e Å−3 |
4434 reflections | Δρmin = −0.32 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 | 0.35159 (4) | 0.24765 (2) | 0.51613 (5) | 0.0330 (1) | |
O1 | 0.5238 (3) | 0.1381 (2) | 0.1118 (3) | 0.0476 (5) | |
O2 | 0.4618 (3) | 0.2384 (1) | 0.3029 (3) | 0.0419 (5) | |
O3E | 0.2416 (3) | 0.1921 (2) | 0.7356 (3) | 0.0445 (5) | |
O4 | −0.0255 (3) | 0.3462 (2) | 0.2899 (4) | 0.0510 (6) | |
O5 | 0.1311 (2) | 0.2542 (1) | 0.3279 (3) | 0.0405 (5) | |
O6E | 0.5855 (2) | 0.3045 (1) | 0.7478 (3) | 0.0381 (4) | |
O7 | 0.7305 (3) | 0.2340 (2) | 0.9998 (3) | 0.0458 (5) | |
O8 | 0.8476 (5) | 0.3037 (3) | 0.6064 (6) | 0.098 (1) | |
O9 | 1.0476 (4) | 0.2373 (3) | 0.8940 (5) | 0.082 (1) | |
N1 | 0.3338 (3) | 0.1197 (2) | 0.4607 (3) | 0.0316 (5) | |
N2 | 0.3606 (3) | 0.3735 (1) | 0.5880 (3) | 0.0288 (4) | |
C1 | 0.3830 (3) | 0.0892 (2) | 0.3185 (4) | 0.0331 (6) | |
C2 | 0.3643 (4) | −0.0018 (2) | 0.2550 (5) | 0.0396 (6) | |
C3 | 0.2938 (4) | −0.0592 (2) | 0.3487 (5) | 0.0435 (7) | |
C4 | 0.2408 (3) | −0.0275 (2) | 0.5046 (5) | 0.0392 (7) | |
C5 | 0.1645 (4) | −0.0811 (2) | 0.6087 (5) | 0.0489 (8) | |
C6 | 0.1160 (4) | −0.0429 (2) | 0.7510 (6) | 0.0531 (9) | |
C7 | 0.1387 (4) | 0.0485 (2) | 0.8018 (5) | 0.0472 (8) | |
C8 | 0.2131 (3) | 0.1029 (2) | 0.7056 (4) | 0.0381 (6) | |
C9 | 0.2641 (3) | 0.0642 (2) | 0.5559 (4) | 0.0340 (6) | |
C10 | 0.4623 (3) | 0.1605 (2) | 0.2346 (4) | 0.0352 (6) | |
C11 | 0.2379 (3) | 0.4020 (2) | 0.5028 (4) | 0.0300 (5) | |
C12 | 0.2383 (4) | 0.4909 (2) | 0.5395 (4) | 0.0364 (6) | |
C13 | 0.3726 (4) | 0.5507 (2) | 0.6685 (4) | 0.0357 (6) | |
C14 | 0.5050 (3) | 0.5216 (2) | 0.7618 (4) | 0.0313 (5) | |
C15 | 0.6481 (4) | 0.5766 (2) | 0.8961 (4) | 0.0385 (6) | |
C16 | 0.7667 (4) | 0.5399 (2) | 0.9789 (4) | 0.0400 (7) | |
C17 | 0.7528 (3) | 0.4483 (2) | 0.9352 (4) | 0.0372 (6) | |
C18 | 0.6158 (3) | 0.3931 (2) | 0.8057 (4) | 0.0311 (5) | |
C19 | 0.4924 (3) | 0.4307 (2) | 0.7181 (4) | 0.0285 (5) | |
C20 | 0.1018 (3) | 0.3284 (2) | 0.3616 (4) | 0.0340 (6) | |
H2 | 0.3989 | −0.0222 | 0.1528 | 0.0475* | |
H3 | 0.2805 | −0.1194 | 0.3099 | 0.0522* | |
H3E | 0.1891 | 0.2136 | 0.7843 | 0.0609* | |
H5 | 0.1479 | −0.1419 | 0.5795 | 0.0586* | |
H6 | 0.0655 | −0.0786 | 0.8178 | 0.0637* | |
H6E | 0.6261 | 0.2801 | 0.8322 | 0.0609* | |
H7 | 0.1036 | 0.0722 | 0.9004 | 0.0566* | |
H7A | 0.672 (4) | 0.202 (2) | 1.050 (6) | 0.0687* | |
H7B | 0.798 (4) | 0.271 (2) | 1.099 (5) | 0.0687* | |
H8A | 0.756 (5) | 0.304 (5) | 0.532 (8) | 0.1463* | |
H8B | 0.893 (7) | 0.293 (5) | 0.519 (8) | 0.1463* | |
H9A | 0.982 (6) | 0.257 (4) | 0.814 (7) | 0.1233* | |
H9B | 1.018 (7) | 0.236 (4) | 0.994 (6) | 0.1233* | |
H12 | 0.1502 | 0.5094 | 0.4785 | 0.0436* | |
H13 | 0.3758 | 0.6102 | 0.6939 | 0.0428* | |
H15 | 0.6613 | 0.6370 | 0.9279 | 0.0462* | |
H16 | 0.8603 | 0.5766 | 1.0673 | 0.0480* | |
H17 | 0.8361 | 0.4257 | 0.9942 | 0.0447* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0366 (2) | 0.0275 (2) | 0.0335 (2) | 0.0076 (1) | 0.0102 (1) | 0.0060 (1) |
O1 | 0.052 (1) | 0.048 (1) | 0.046 (1) | 0.009 (1) | 0.026 (1) | 0.0056 (10) |
O2 | 0.054 (1) | 0.030 (1) | 0.045 (1) | 0.0055 (9) | 0.024 (1) | 0.0081 (9) |
O3E | 0.053 (1) | 0.043 (1) | 0.045 (1) | 0.014 (1) | 0.024 (1) | 0.0122 (10) |
O4 | 0.034 (1) | 0.056 (1) | 0.053 (1) | 0.012 (1) | 0.0004 (10) | 0.011 (1) |
O5 | 0.037 (1) | 0.033 (1) | 0.042 (1) | 0.0043 (9) | 0.0029 (9) | 0.0048 (9) |
O6E | 0.036 (1) | 0.034 (1) | 0.036 (1) | 0.0102 (8) | 0.0013 (8) | 0.0051 (8) |
O7 | 0.050 (1) | 0.047 (1) | 0.035 (1) | 0.006 (1) | 0.0074 (9) | 0.0126 (9) |
O8 | 0.093 (3) | 0.121 (3) | 0.120 (3) | 0.055 (3) | 0.069 (3) | 0.041 (3) |
O9 | 0.064 (2) | 0.096 (2) | 0.081 (2) | 0.012 (2) | 0.037 (2) | −0.020 (2) |
N1 | 0.030 (1) | 0.029 (1) | 0.033 (1) | 0.0055 (9) | 0.0063 (9) | 0.0083 (9) |
N2 | 0.030 (1) | 0.029 (1) | 0.025 (1) | 0.0053 (9) | 0.0077 (9) | 0.0061 (8) |
C1 | 0.031 (1) | 0.032 (1) | 0.031 (1) | 0.006 (1) | 0.005 (1) | 0.007 (1) |
C2 | 0.042 (2) | 0.033 (1) | 0.037 (1) | 0.008 (1) | 0.007 (1) | 0.001 (1) |
C3 | 0.043 (2) | 0.029 (1) | 0.050 (2) | 0.008 (1) | 0.004 (1) | 0.007 (1) |
C4 | 0.032 (1) | 0.031 (1) | 0.044 (2) | 0.003 (1) | −0.001 (1) | 0.011 (1) |
C5 | 0.043 (2) | 0.040 (2) | 0.055 (2) | 0.001 (1) | 0.005 (1) | 0.023 (1) |
C6 | 0.045 (2) | 0.052 (2) | 0.058 (2) | 0.000 (2) | 0.011 (2) | 0.034 (2) |
C7 | 0.040 (2) | 0.063 (2) | 0.042 (2) | 0.010 (1) | 0.015 (1) | 0.024 (2) |
C8 | 0.034 (1) | 0.042 (2) | 0.038 (1) | 0.009 (1) | 0.009 (1) | 0.016 (1) |
C9 | 0.027 (1) | 0.033 (1) | 0.038 (1) | 0.005 (1) | 0.003 (1) | 0.013 (1) |
C10 | 0.037 (1) | 0.035 (1) | 0.029 (1) | 0.005 (1) | 0.007 (1) | 0.006 (1) |
C11 | 0.030 (1) | 0.031 (1) | 0.028 (1) | 0.005 (1) | 0.011 (1) | 0.005 (1) |
C12 | 0.038 (1) | 0.038 (1) | 0.040 (1) | 0.015 (1) | 0.016 (1) | 0.014 (1) |
C13 | 0.047 (2) | 0.027 (1) | 0.037 (1) | 0.011 (1) | 0.018 (1) | 0.007 (1) |
C14 | 0.038 (1) | 0.029 (1) | 0.028 (1) | 0.005 (1) | 0.016 (1) | 0.0057 (10) |
C15 | 0.048 (2) | 0.028 (1) | 0.035 (1) | −0.001 (1) | 0.017 (1) | 0.002 (1) |
C16 | 0.037 (2) | 0.041 (2) | 0.031 (1) | −0.006 (1) | 0.008 (1) | 0.001 (1) |
C17 | 0.031 (1) | 0.043 (2) | 0.032 (1) | 0.004 (1) | 0.007 (1) | 0.006 (1) |
C18 | 0.034 (1) | 0.032 (1) | 0.026 (1) | 0.006 (1) | 0.009 (1) | 0.005 (1) |
C19 | 0.032 (1) | 0.031 (1) | 0.023 (1) | 0.006 (1) | 0.011 (1) | 0.0051 (10) |
C20 | 0.031 (1) | 0.038 (1) | 0.030 (1) | 0.006 (1) | 0.006 (1) | 0.008 (1) |
Geometric parameters (Å, º) top
Ni1—O2 | 2.080 (3) | C2—H2 | 0.930 |
Ni1—O3E | 2.290 (3) | C3—C4 | 1.423 (5) |
Ni1—O5 | 2.124 (2) | C3—H3 | 0.930 |
Ni1—O6E | 2.227 (2) | C4—C5 | 1.418 (5) |
Ni1—N1 | 1.979 (2) | C4—C9 | 1.408 (4) |
Ni1—N2 | 1.972 (2) | C5—C6 | 1.354 (6) |
O1—C10 | 1.234 (4) | C5—H5 | 0.930 |
O2—C10 | 1.269 (4) | C6—C7 | 1.403 (5) |
O3E—C8 | 1.360 (4) | C6—H6 | 0.930 |
O3E—H3E | 0.781 | C7—C8 | 1.374 (5) |
O4—C20 | 1.245 (4) | C7—H7 | 0.930 |
O5—C20 | 1.270 (4) | C8—C9 | 1.415 (5) |
O6E—C18 | 1.358 (3) | C11—C12 | 1.401 (4) |
O6E—H6E | 0.806 | C11—C20 | 1.520 (3) |
O7—H7A | 0.85 (4) | C12—C13 | 1.382 (3) |
O7—H7B | 0.85 (3) | C12—H12 | 0.930 |
O8—H8A | 0.86 (6) | C13—C14 | 1.413 (4) |
O8—H8B | 0.87 (6) | C13—H13 | 0.930 |
O9—H9A | 0.85 (6) | C14—C15 | 1.413 (3) |
O9—H9B | 0.84 (5) | C14—C19 | 1.407 (4) |
N1—C1 | 1.311 (4) | C15—C16 | 1.367 (5) |
N1—C9 | 1.358 (4) | C15—H15 | 0.930 |
N2—C11 | 1.321 (4) | C16—C17 | 1.417 (4) |
N2—C19 | 1.356 (3) | C16—H16 | 0.930 |
C1—C2 | 1.414 (4) | C17—C18 | 1.370 (3) |
C1—C10 | 1.510 (4) | C17—H17 | 0.930 |
C2—C3 | 1.372 (5) | C18—C19 | 1.419 (4) |
| | | |
O1···O7i | 2.576 (4) | O9···C3ii | 3.576 (4) |
O1···C8i | 3.334 (3) | N2···C14iii | 3.569 (4) |
O1···C5ii | 3.368 (4) | N2···C13iii | 3.599 (4) |
O1···C7i | 3.478 (4) | C1···C3ii | 3.406 (4) |
O1···O3Ei | 3.505 (3) | C2···C3ii | 3.435 (4) |
O2···C13iii | 3.332 (3) | C2···C4ii | 3.453 (4) |
O3E···O9iv | 2.556 (5) | C2···C6i | 3.572 (4) |
O4···O7v | 2.689 (3) | C4···C7vi | 3.476 (4) |
O4···O8iv | 2.943 (6) | C5···C8vi | 3.478 (4) |
O4···O9v | 3.444 (5) | C6···C9vi | 3.481 (4) |
O4···C17v | 3.572 (4) | C7···C10vii | 3.565 (4) |
O5···O9v | 2.952 (4) | C11···C15iii | 3.369 (5) |
O5···C6vi | 3.515 (4) | C11···C14iii | 3.578 (4) |
O7···C3ii | 3.406 (4) | C12···C16xi | 3.578 (5) |
O7···C10vii | 3.482 (4) | C13···C17xi | 3.377 (5) |
O7···C20viii | 3.526 (3) | C13···C19iii | 3.388 (5) |
O8···C20ix | 3.315 (6) | C13···C16xi | 3.505 (5) |
O9···C8ix | 3.242 (6) | C14···C15xi | 3.554 (5) |
O9···C7ix | 3.311 (6) | C14···C16xi | 3.598 (5) |
O9···C20viii | 3.332 (5) | C15···C19xi | 3.397 (5) |
O9···C15x | 3.438 (4) | C15···C20iii | 3.586 (5) |
O9···C16x | 3.463 (5) | | |
| | | |
O2—Ni1—O3E | 153.13 (9) | C6—C5—H5 | 120.3 |
O2—Ni1—O5 | 97.86 (9) | C5—C6—C7 | 122.7 (4) |
O2—Ni1—O6E | 89.13 (8) | C5—C6—H6 | 118.7 |
O2—Ni1—N1 | 78.96 (10) | C7—C6—H6 | 118.7 |
O2—Ni1—N2 | 105.83 (9) | C6—C7—C8 | 119.9 (4) |
O3E—Ni1—O5 | 91.84 (9) | C6—C7—H7 | 120.1 |
O3E—Ni1—O6E | 93.02 (8) | C8—C7—H7 | 120.1 |
O3E—Ni1—N1 | 74.6 (1) | O3E—C8—C7 | 126.8 (3) |
O3E—Ni1—N2 | 100.67 (10) | O3E—C8—C9 | 114.9 (3) |
O5—Ni1—O6E | 154.03 (8) | C7—C8—C9 | 118.3 (3) |
O5—Ni1—N1 | 101.60 (8) | N1—C9—C4 | 121.5 (3) |
O5—Ni1—N2 | 78.10 (8) | N1—C9—C8 | 116.7 (3) |
O6E—Ni1—N1 | 104.29 (8) | C4—C9—C8 | 121.8 (3) |
O6E—Ni1—N2 | 75.93 (8) | O1—C10—O2 | 126.7 (3) |
N1—Ni1—N2 | 175.2 (1) | O1—C10—C1 | 117.6 (3) |
Ni1—O2—C10 | 114.3 (2) | O2—C10—C1 | 115.7 (3) |
Ni1—O3E—C8 | 111.8 (2) | N2—C11—C12 | 122.3 (2) |
Ni1—O3E—H3E | 125.0 | N2—C11—C20 | 112.6 (2) |
C8—O3E—H3E | 117.0 | C12—C11—C20 | 125.1 (3) |
Ni1—O5—C20 | 113.9 (1) | C11—C12—C13 | 118.5 (3) |
Ni1—O6E—C18 | 111.9 (2) | C11—C12—H12 | 120.8 |
Ni1—O6E—H6E | 124.9 | C13—C12—H12 | 120.8 |
C18—O6E—H6E | 114.8 | C12—C13—C14 | 120.1 (3) |
H7A—O7—H7B | 104 (3) | C12—C13—H13 | 119.9 |
H8A—O8—H8B | 102 (5) | C14—C13—H13 | 119.9 |
H9A—O9—H9B | 105 (6) | C13—C14—C15 | 125.1 (3) |
Ni1—N1—C1 | 117.3 (2) | C13—C14—C19 | 117.2 (2) |
Ni1—N1—C9 | 121.8 (2) | C15—C14—C19 | 117.7 (3) |
C1—N1—C9 | 120.7 (3) | C14—C15—C16 | 119.4 (3) |
Ni1—N2—C11 | 119.1 (1) | C14—C15—H15 | 120.3 |
Ni1—N2—C19 | 120.7 (2) | C16—C15—H15 | 120.3 |
C11—N2—C19 | 120.1 (2) | C15—C16—C17 | 122.6 (2) |
N1—C1—C2 | 122.2 (3) | C15—C16—H16 | 118.7 |
N1—C1—C10 | 113.4 (2) | C17—C16—H16 | 118.7 |
C2—C1—C10 | 124.4 (3) | C16—C17—C18 | 119.6 (3) |
C1—C2—C3 | 118.1 (3) | C16—C17—H17 | 120.2 |
C1—C2—H2 | 121.0 | C18—C17—H17 | 120.2 |
C3—C2—H2 | 121.0 | O6E—C18—C17 | 126.4 (3) |
C2—C3—C4 | 120.6 (3) | O6E—C18—C19 | 115.5 (2) |
C2—C3—H3 | 119.7 | C17—C18—C19 | 118.1 (3) |
C4—C3—H3 | 119.7 | N2—C19—C14 | 121.7 (2) |
C3—C4—C5 | 125.2 (3) | N2—C19—C18 | 115.7 (2) |
C3—C4—C9 | 116.9 (3) | C14—C19—C18 | 122.6 (2) |
C5—C4—C9 | 118.0 (3) | O4—C20—O5 | 126.5 (2) |
C4—C5—C6 | 119.4 (3) | O4—C20—C11 | 117.9 (3) |
C4—C5—H5 | 120.3 | O5—C20—C11 | 115.6 (2) |
| | | |
Ni1—O2—C10—O1 | −177.8 (2) | O6E—Ni1—N2—C19 | 4.3 (2) |
Ni1—O2—C10—C1 | 0.3 (3) | O6E—C18—C17—C16 | 179.2 (3) |
Ni1—O3E—C8—C7 | −175.3 (2) | O6E—C18—C19—N2 | −0.1 (4) |
Ni1—O3E—C8—C9 | 3.3 (3) | O6E—C18—C19—C14 | −179.9 (3) |
Ni1—O5—C20—O4 | −170.6 (3) | N1—Ni1—O2—C10 | 2.2 (2) |
Ni1—O5—C20—C11 | 9.9 (3) | N1—Ni1—O3E—C8 | −3.9 (2) |
Ni1—O6E—C18—C17 | −175.4 (3) | N1—Ni1—O5—C20 | 168.2 (2) |
Ni1—O6E—C18—C19 | 3.3 (3) | N1—Ni1—O6E—C18 | −179.1 (2) |
Ni1—N1—C1—C2 | −174.7 (2) | N1—C1—C2—C3 | −0.9 (4) |
Ni1—N1—C1—C10 | 6.2 (3) | N1—C9—C4—C3 | 0.1 (4) |
Ni1—N1—C9—C4 | 174.9 (2) | N1—C9—C4—C5 | −178.8 (3) |
Ni1—N1—C9—C8 | −3.7 (3) | N1—C9—C8—C7 | 178.5 (3) |
Ni1—N2—C11—C12 | −177.0 (2) | N2—Ni1—O2—C10 | −177.9 (2) |
Ni1—N2—C11—C20 | 2.0 (3) | N2—Ni1—O3E—C8 | 175.9 (2) |
Ni1—N2—C19—C14 | 175.9 (2) | N2—Ni1—O5—C20 | −7.0 (2) |
Ni1—N2—C19—C18 | −3.9 (4) | N2—Ni1—O6E—C18 | −4.0 (2) |
O1—C10—C1—N1 | 174.1 (2) | N2—C11—C12—C13 | 0.5 (5) |
O1—C10—C1—C2 | −5.0 (4) | N2—C19—C14—C13 | 1.7 (5) |
O2—Ni1—O3E—C8 | −13.9 (3) | N2—C19—C14—C15 | −178.7 (3) |
O2—Ni1—O5—C20 | −111.6 (2) | N2—C19—C18—C17 | 178.7 (3) |
O2—Ni1—O6E—C18 | 102.5 (2) | C1—N1—C9—C4 | −0.7 (4) |
O2—Ni1—N1—C1 | −4.8 (2) | C1—N1—C9—C8 | −179.3 (2) |
O2—Ni1—N1—C9 | 179.5 (2) | C1—C2—C3—C4 | 0.2 (4) |
O2—Ni1—N2—C11 | 97.2 (2) | C2—C1—N1—C9 | 1.1 (4) |
O2—Ni1—N2—C19 | −80.7 (2) | C2—C3—C4—C5 | 179.0 (3) |
O2—C10—C1—N1 | −4.2 (3) | C2—C3—C4—C9 | 0.1 (4) |
O2—C10—C1—C2 | 176.7 (3) | C3—C2—C1—C10 | 178.1 (3) |
O3E—Ni1—O2—C10 | 12.0 (3) | C3—C4—C5—C6 | −178.3 (3) |
O3E—Ni1—O5—C20 | 93.6 (2) | C3—C4—C9—C8 | 178.6 (3) |
O3E—Ni1—O6E—C18 | −104.3 (2) | C4—C5—C6—C7 | −0.4 (5) |
O3E—Ni1—N1—C1 | 179.8 (2) | C4—C9—C8—C7 | −0.1 (4) |
O3E—Ni1—N1—C9 | 4.0 (2) | C5—C4—C9—C8 | −0.3 (4) |
O3E—Ni1—N2—C11 | −87.4 (2) | C5—C6—C7—C8 | −0.1 (5) |
O3E—Ni1—N2—C19 | 94.8 (2) | C6—C5—C4—C9 | 0.5 (4) |
O3E—C8—C7—C6 | 178.9 (3) | C6—C7—C8—C9 | 0.3 (4) |
O3E—C8—C9—N1 | −0.3 (4) | C9—N1—C1—C10 | −178.0 (2) |
O3E—C8—C9—C4 | −178.9 (2) | C11—N2—C19—C14 | −2.0 (4) |
O4—C20—C11—N2 | 172.3 (3) | C11—N2—C19—C18 | 178.2 (3) |
O4—C20—C11—C12 | −8.7 (5) | C11—C12—C13—C14 | −0.7 (5) |
O5—Ni1—O2—C10 | −98.1 (2) | C12—C11—N2—C19 | 0.9 (5) |
O5—Ni1—O3E—C8 | 97.6 (2) | C12—C13—C14—C15 | −179.9 (3) |
O5—Ni1—O6E—C18 | −3.8 (3) | C12—C13—C14—C19 | −0.3 (5) |
O5—Ni1—N1—C1 | 91.1 (2) | C13—C12—C11—C20 | −178.4 (3) |
O5—Ni1—N1—C9 | −84.7 (2) | C13—C14—C15—C16 | 179.0 (3) |
O5—Ni1—N2—C11 | 2.3 (2) | C13—C14—C19—C18 | −178.5 (3) |
O5—Ni1—N2—C19 | −175.6 (2) | C14—C15—C16—C17 | 0.1 (5) |
O5—C20—C11—N2 | −8.2 (4) | C14—C19—C18—C17 | −1.1 (5) |
O5—C20—C11—C12 | 170.8 (3) | C15—C14—C19—C18 | 1.1 (5) |
O6E—Ni1—O2—C10 | 107.0 (2) | C15—C16—C17—C18 | −0.1 (5) |
O6E—Ni1—O3E—C8 | −107.9 (2) | C16—C15—C14—C19 | −0.6 (5) |
O6E—Ni1—O5—C20 | −7.2 (4) | C16—C17—C18—C19 | 0.5 (5) |
O6E—Ni1—N1—C1 | −91.0 (2) | C19—N2—C11—C20 | 179.8 (3) |
O6E—Ni1—N1—C9 | 93.2 (2) | C19—N2—C11—C20 | 179.8 (3) |
O6E—Ni1—N2—C11 | −177.8 (2) | | |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) x−1, y, z−1; (vi) −x, −y, −z+1; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x+1, y, z; (x) −x+2, −y+1, −z+2; (xi) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3E—H3E···O9iv | 0.78 | 1.79 | 2.556 (4) | 167 |
O6E—H6E···O7 | 0.81 | 1.66 | 2.465 (3) | 173 |
O7—H7A···O1vii | 0.85 (2) | 1.73 (2) | 2.576 (3) | 169 (4) |
O7—H7A···O2vii | 0.85 (2) | 3.10 (3) | 3.757 (3) | 135 (3) |
O7—H7B···O4viii | 0.85 (2) | 1.85 (2) | 2.689 (3) | 168 (4) |
O7—H7B···O5viii | 0.85 (2) | 3.12 (4) | 3.687 (3) | 126 (3) |
O8—H8B···O4ix | 0.87 (3) | 2.20 (5) | 2.943 (4) | 144 (7) |
O8—H8B···O5ix | 0.87 (3) | 3.03 (7) | 3.872 (4) | 162 (5) |
O8—H8A···O6E | 0.87 (3) | 2.51 (6) | 2.888 (4) | 107 (5) |
O8—H8A···O2 | 0.87 (3) | 2.63 (4) | 3.447 (5) | 157 (7) |
O9—H9A···O8 | 0.85 (6) | 1.98 (5) | 2.821 (6) | 172 (6) |
O9—H9B···O5viii | 0.84 (5) | 2.27 (4) | 2.952 (4) | 138 (5) |
Symmetry codes: (iv) x−1, y, z; (vii) x, y, z+1; (viii) x+1, y, z+1; (ix) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C10H7NO3 | [Ni(C10H6NO3)2](H2O)3 |
Mr | 189.17 | 489.05 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 12.748 (2), 7.476 (3), 16.657 (2) | 9.237 (1), 15.865 (3), 7.200 (1) |
α, β, γ (°) | 90, 90.68 (1), 90 | 97.63 (1), 106.95 (1), 101.90 (1) |
V (Å3) | 1587.3 (7) | 966.4 (3) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 1.06 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 | 0.25 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – | ψ scan (North et al., 1968) |
Tmin, Tmax | – | 0.880, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2068, 1838, 691 | 4703, 4434, 3202 |
Rint | 0.066 | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.197, 0.87 | 0.040, 0.134, 0.90 |
No. of reflections | 1838 | 4434 |
No. of parameters | 128 | 307 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.27 | 0.64, −0.32 |
Selected geometric parameters (Å, º) for (I) topO1—C10 | 1.255 (4) | C3—C4 | 1.405 (6) |
O2—C10 | 1.230 (5) | C4—C5 | 1.405 (6) |
O3E—C8 | 1.338 (5) | C4—C9 | 1.406 (6) |
N1—C1 | 1.332 (4) | C5—C6 | 1.364 (6) |
N1—C9 | 1.367 (5) | C6—C7 | 1.409 (6) |
C1—C2 | 1.388 (6) | C7—C8 | 1.368 (6) |
C1—C10 | 1.533 (5) | C8—C9 | 1.438 (5) |
C2—C3 | 1.369 (6) | | |
| | | |
N1—C1—C10 | 115.8 (3) | O1—C10—O2 | 130.2 (4) |
C2—C1—C10 | 124.8 (3) | O1—C10—C1 | 113.7 (3) |
O3E—C8—C7 | 126.7 (3) | O2—C10—C1 | 116.0 (3) |
O3E—C8—C9 | 115.6 (3) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.30 | 2.662 (4) | 105 |
N1—H1···O3E | 0.86 | 2.35 | 2.692 (4) | 104 |
O3E—H3E···O1i | 0.82 | 1.76 | 2.562 (4) | 164 |
Symmetry code: (i) x, −y, z−1/2. |
Selected geometric parameters (Å, º) for (II) topNi1—O2 | 2.080 (3) | Ni1—O6E | 2.227 (2) |
Ni1—O3E | 2.290 (3) | Ni1—N1 | 1.979 (2) |
Ni1—O5 | 2.124 (2) | Ni1—N2 | 1.972 (2) |
| | | |
O2—Ni1—O3E | 153.13 (9) | O6E—Ni1—N1 | 104.29 (8) |
O2—Ni1—O5 | 97.86 (9) | O6E—Ni1—N2 | 75.93 (8) |
O2—Ni1—O6E | 89.13 (8) | N1—Ni1—N2 | 175.2 (1) |
O2—Ni1—N1 | 78.96 (10) | Ni1—O2—C10 | 114.3 (2) |
O2—Ni1—N2 | 105.83 (9) | Ni1—O3E—C8 | 111.8 (2) |
O3E—Ni1—O5 | 91.84 (9) | Ni1—O5—C20 | 113.9 (1) |
O3E—Ni1—O6E | 93.02 (8) | Ni1—O6E—C18 | 111.9 (2) |
O3E—Ni1—N1 | 74.6 (1) | Ni1—N1—C1 | 117.3 (2) |
O3E—Ni1—N2 | 100.67 (10) | Ni1—N1—C9 | 121.8 (2) |
O5—Ni1—O6E | 154.03 (8) | Ni1—N2—C11 | 119.1 (1) |
O5—Ni1—N1 | 101.60 (8) | Ni1—N2—C19 | 120.7 (2) |
O5—Ni1—N2 | 78.10 (8) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3E—H3E···O9i | 0.78 | 1.79 | 2.556 (4) | 167 |
O6E—H6E···O7 | 0.81 | 1.66 | 2.465 (3) | 173 |
O7—H7A···O1ii | 0.85 (2) | 1.73 (2) | 2.576 (3) | 169 (4) |
O7—H7A···O2ii | 0.85 (2) | 3.10 (3) | 3.757 (3) | 135 (3) |
O7—H7B···O4iii | 0.85 (2) | 1.85 (2) | 2.689 (3) | 168 (4) |
O7—H7B···O5iii | 0.85 (2) | 3.12 (4) | 3.687 (3) | 126 (3) |
O8—H8B···O4iv | 0.87 (3) | 2.20 (5) | 2.943 (4) | 144 (7) |
O8—H8B···O5iv | 0.87 (3) | 3.03 (7) | 3.872 (4) | 162 (5) |
O8—H8A···O6E | 0.87 (3) | 2.51 (6) | 2.888 (4) | 107 (5) |
O8—H8A···O2 | 0.87 (3) | 2.63 (4) | 3.447 (5) | 157 (7) |
O9—H9A···O8 | 0.85 (6) | 1.98 (5) | 2.821 (6) | 172 (6) |
O9—H9B···O5iii | 0.84 (5) | 2.27 (4) | 2.952 (4) | 138 (5) |
Symmetry codes: (i) x−1, y, z; (ii) x, y, z+1; (iii) x+1, y, z+1; (iv) x+1, y, z. |
8-Hydroxyquinaldic acid (8-hydroxyquinoline-2-carboxylic acid), (I), is one of the tryptophan metabolites formed through the kynurenine metabolic pathway (Rodwell, 1983). This compound is known as a tridentate chelating agent with three ligand atoms, the hydroxyl O atom, the quinoline ring N atom, and the carboxyl O atom (Irving & Pinnington, 1954; Moberg & Weber, 1984). The physiological role of this compound or of its metal complexes are as yet unclear, but the analogous compound 8-hydroxyquinoline and its metal complexes have various biological properties, such as antimicrobial or fungicidal activity (Okide et al., 2000; Patel et al., 1999) or antitumour activity (Smith et al., 1998). These findings drive structural research of various quinoline derivatives because of their therapeutic value.
Until now, the solid-state structures of 8-hydroxyquinaldinic acid and its metal complexes have not been determined, apart from the structure of the cobalt(II) complex which we reported recently (Okabe & Muranishi; 2002). Therefore, it is of interest to clarify the detailed structure of this compound and the coordinating behaviour of its metal complexes in connection with their physiological role, as well as their use as selective chelating reagents for metal ions (Högberg et al. 1985). In this study, the structure of (I) and of its nickel(II) complex, (II), have been determined and the results are presented here. \sch
The structure of (I) is shown in Fig. 1. It is planar, with a slight torsion of the carboxylate group [O2—C10—C1—N1 - 4.2 (3)°]. The carboxyl group is ionized, the ring N atom is protonated, and the hydroxyl group remains unchanged. The net charge of the molecule is kept neutral by this H-atom transfer. Bifurcated hydrogen bonds are formed intramolecularly between the protonated NH+ group and the carboxyl O atom, and between NH+ and the hydroxyl O atoms (Table 2). Neighbouring molecules are linked together by intermolecular hydrogen bonds between the carboxylate and hydroxyl groups along the c axis (Fig. 2). The quinoline rings are stacked together along the a axis, with a mean distance between the rings of 3.380 (5) Å.
The molecular structure of complex (II) is shown in Fig. 3. In this complex, two tridentate ligand molecules coordinate to the central NiII ion in a bisected octahedral coordination geometry, in which two quinoline rings are oriented perpendicularly. The two carboxyl groups of the two ligand molecules are ionized and are essentially coplanar with the quinoline ring planes, as shown by the relevant torsion angles [O2—C10—C1—N1 - 4.2 (3)° and O5—C20—C11—N2 - 8.2 (4)°].
The overall structure of (II) is the same as the cobalt(II) complex (Okabe & Muranishi, 2002). Three ligand atoms (the hydroxyl O, the quinoline N and the carboxyl O atoms) and the central NiII ion form five-membered rings. The distances between NiII and the carboxylato O atoms, [2.080 (3)–2.124 (2) Å] are shorter than those between NiII and the hydroxyl O atoms [2.227 (2)–2.290 (3) Å]. The Ni—N distance is the shortest of those involving the three coordinated ligand atoms.
In an NMR study of the manganese(II) complex of quinaldinic acid derivatives (Moberg & Weber, 1984), a bisected octahedral structure with a perpendicular orientation of the quinoline rings was postulated as one of the possible coordination modes around the central metal ion. However, the manganese(II) complex of 8-hydroxyquinaldinic acid could not be clearly deduced as a bisected octahedral structure from the NMR study. The bisected octahedral coordination mode of the cobalt(II) complex (Okabe & Muranishi, 2002) and the nickel(II) complex, (II), may be a common feature of the metal complexes of 8-hydroxyquinaldinic acid, although further structural studies are needed for confirmation.
In the crystal packing of (II), stacking interactions are present between the C1—C9/N1 quinoline rings and between the C11—C19/N2 rings. The mean distances are 3.454 (4) Å for the C1—C9/N1 rings and 3.378 (4) Å for the C11—C19/N2 rings. Neighbouring nickel(II) complex molecules are also connected together by a hydrogen-bonding network through the water molecules (Table 4).