Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001915/cf6147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001915/cf6147Isup2.hkl |
CCDC reference: 182570
The synthesis and growth of crystals of (I) have been described by Kuksa et al. (2000).
A more complete account of the data collection process is given by Darr et al. (1993). H atoms attached to C (methylene groups) were placed in calculated positions, with C—H = 0.99 Å and refined as riding atoms with Uiso = 1.2Ueq(C). H atoms attached to N and O were located in a difference map and refined isotropically.
Data collection: MADNES (Pflugrath & Messerschmidt, 1989); cell refinement: MADNES; data reduction: ABSMAD (Karaulov, 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Ni(C12H28N4O4)(H2O)2]Cl2 | F(000) = 484 |
Mr = 458.03 | Dx = 1.555 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4288 (3) Å | Cell parameters from 15576 reflections |
b = 13.1426 (5) Å | θ = 2.0–26.4° |
c = 10.2527 (3) Å | µ = 1.30 mm−1 |
β = 102.2480 (18)° | T = 150 K |
V = 978.22 (6) Å3 | Block, light violet |
Z = 2 | 0.60 × 0.15 × 0.15 mm |
Delft Instruments FAST area-detector diffractometer | 2090 independent reflections |
Radiation source: fine-focus sealed tube | 1892 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ϕ scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) | h = −9→9 |
Tmin = 0.710, Tmax = 0.823 | k = −16→16 |
15576 measured reflections | l = −12→12 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: geom and difmap |
wR(F2) = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0267P)2 + 0.4373P] where P = (Fo2 + 2Fc2)/3 |
2090 reflections | (Δ/σ)max < 0.001 |
152 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Ni(C12H28N4O4)(H2O)2]Cl2 | V = 978.22 (6) Å3 |
Mr = 458.03 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 7.4288 (3) Å | µ = 1.30 mm−1 |
b = 13.1426 (5) Å | T = 150 K |
c = 10.2527 (3) Å | 0.60 × 0.15 × 0.15 mm |
β = 102.2480 (18)° |
Delft Instruments FAST area-detector diffractometer | 2090 independent reflections |
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) | 1892 reflections with I > 2σ(I) |
Tmin = 0.710, Tmax = 0.823 | Rint = 0.051 |
15576 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
2090 reflections | Δρmin = −0.64 e Å−3 |
152 parameters |
Experimental. General cell determination and refinement and data collection strategy given by Darr et al., (1993). [Darr, J·A, Drake, S·R., Hursthouse, M·B. & Malik, K·M·A. (1993). Inorg. Chem. 32, 5704–5708.] |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.1501 (0.0011) x - 0.0000 (0.0000) y - 4.8119 (0.0047) z = 0.5695 (0.0015) * 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) O1_$1 * 0.0000 (0.0000) O2_$1 - 0.0656 (0.0006) Ni1 Rms deviation of fitted atoms = 0.0000 6.4812 (0.0022) x - 0.0000 (0.0000) y + 2.9991 (0.0059) z = 2.2657 (0.0012) Angle to previous plane (with approximate e.s.d.) = 45.00 (0.03) * 0.0000 (0.0000) N1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) N1_$1 * 0.0000 (0.0000) N2_$1 - 0.0214 (0.0008) Ni1 Rms deviation of fitted atoms = 0.0000 'Linear' torsion angles excluded as per PLATON element of checkcif N2 Ni1 N1 O1 154 (2) 4_565.. . ? N2 Ni1 N1 C2 - 82 (2) 4_565.. . ? N1 Ni1 N2 O2 - 20 (2) 4_565.. . ? N1 Ni1 N2 C6 104 (2) 4_565.. . ? |
Refinement. 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. Anisotropic displacement parameters refined for all non-H atoms. H atoms of water and N—H groups from difference maps and refined isotropically in the usual manner. All other H (methylene groups) placed in calculated positions with C—H 0.99 A and refined riding with Uiso 1.2 times Uequ of C. C4 and C7 disordered in pairs as C4/C4A and C7/C7A with sof's for major components determined prior to final refinement as 0.744 (3) and 0.810 (5) resp. applied to the pairs and to H attached both to them and neighbouring C (C3, C5 and C6). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.23391 (3) | 0.2500 | 0.24285 (2) | 0.01320 (10) | |
Cl1 | 0.73803 (4) | 0.07626 (3) | 0.24487 (3) | 0.01941 (11) | |
O1W | 0.51256 (19) | 0.2500 | 0.35069 (15) | 0.0182 (3) | |
H1W | 0.568 (3) | 0.2013 (14) | 0.3345 (18) | 0.036 (5)* | |
O2W | −0.04151 (19) | 0.2500 | 0.13598 (14) | 0.0180 (3) | |
H2W | −0.096 (3) | 0.2002 (14) | 0.1564 (18) | 0.034 (5)* | |
O1 | 0.15440 (12) | 0.05709 (8) | 0.11108 (10) | 0.0204 (2) | |
O2 | 0.33653 (13) | 0.06625 (8) | 0.38171 (10) | 0.0206 (2) | |
N1 | 0.29493 (16) | 0.13413 (9) | 0.11811 (12) | 0.0170 (2) | |
H1N | 0.396 (2) | 0.1059 (13) | 0.1653 (16) | 0.022 (4)* | |
N2 | 0.17873 (16) | 0.13271 (9) | 0.36923 (12) | 0.0170 (3) | |
H2N | 0.085 (2) | 0.0976 (13) | 0.3214 (15) | 0.017 (4)* | |
C1 | 0.4252 (3) | 0.2500 | −0.0275 (2) | 0.0249 (5) | |
H1A | 0.5352 | 0.2500 | 0.0465 | 0.030* | |
H1B | 0.4685 | 0.2500 | −0.1124 | 0.030* | |
C2 | 0.3158 (2) | 0.15393 (13) | −0.01978 (14) | 0.0263 (3) | |
H2A | 0.1924 | 0.1606 | −0.0790 | 0.032* | |
H2B | 0.3790 | 0.0956 | −0.0515 | 0.032* | |
C3 | 0.2234 (2) | −0.04547 (11) | 0.12978 (15) | 0.0230 (3) | |
H3A | 0.3583 | −0.0467 | 0.1363 | 0.028* | 0.74 |
H3B | 0.1639 | −0.0892 | 0.0542 | 0.028* | 0.74 |
H3C | 0.2953 | −0.0576 | 0.0603 | 0.028* | 0.26 |
H3D | 0.1149 | −0.0909 | 0.1087 | 0.028* | 0.26 |
C4 | 0.1765 (3) | −0.08232 (16) | 0.2592 (2) | 0.0232 (4) | 0.74 |
H4A | 0.0463 | −0.0650 | 0.2575 | 0.028* | 0.74 |
H4B | 0.1871 | −0.1574 | 0.2625 | 0.028* | 0.74 |
C4A | 0.3383 (8) | −0.0822 (4) | 0.2574 (6) | 0.0224 (12) | 0.26 |
H4C | 0.4685 | −0.0656 | 0.2580 | 0.027* | 0.26 |
H4D | 0.3282 | −0.1573 | 0.2596 | 0.027* | 0.26 |
C5 | 0.2923 (2) | −0.04018 (12) | 0.38390 (15) | 0.0248 (3) | |
H5A | 0.2279 | −0.0520 | 0.4577 | 0.030* | 0.74 |
H5B | 0.4091 | −0.0791 | 0.4047 | 0.030* | 0.74 |
H5C | 0.1602 | −0.0500 | 0.3839 | 0.030* | 0.26 |
H5D | 0.3671 | −0.0738 | 0.4637 | 0.030* | 0.26 |
C6 | 0.1419 (2) | 0.15349 (13) | 0.50294 (15) | 0.0268 (3) | |
H6A | 0.1880 | 0.0957 | 0.5627 | 0.032* | 0.81 |
H6B | 0.0071 | 0.1581 | 0.4957 | 0.032* | 0.81 |
H6C | 0.0613 | 0.0988 | 0.5244 | 0.032* | 0.19 |
H6D | 0.2601 | 0.1492 | 0.5689 | 0.032* | 0.19 |
C7 | 0.2304 (4) | 0.2500 | 0.5643 (2) | 0.0237 (6) | 0.81 |
H7A | 0.3612 | 0.2500 | 0.5570 | 0.028* | 0.81 |
H7B | 0.2279 | 0.2500 | 0.6604 | 0.028* | 0.81 |
C7A | 0.0573 (15) | 0.2500 | 0.5204 (10) | 0.022 (2) | 0.19 |
H7C | 0.0343 | 0.2500 | 0.6121 | 0.026* | 0.19 |
H7D | −0.0649 | 0.2500 | 0.4589 | 0.026* | 0.19 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01242 (14) | 0.01446 (15) | 0.01340 (15) | 0.000 | 0.00427 (9) | 0.000 |
Cl1 | 0.01442 (18) | 0.0204 (2) | 0.0240 (2) | 0.00084 (12) | 0.00530 (14) | −0.00023 (13) |
O1W | 0.0153 (7) | 0.0164 (8) | 0.0234 (8) | 0.000 | 0.0051 (6) | 0.000 |
O2W | 0.0149 (7) | 0.0172 (8) | 0.0218 (8) | 0.000 | 0.0033 (6) | 0.000 |
O1 | 0.0132 (5) | 0.0175 (5) | 0.0294 (6) | −0.0017 (4) | 0.0021 (4) | −0.0033 (4) |
O2 | 0.0135 (5) | 0.0183 (5) | 0.0275 (6) | 0.0021 (4) | −0.0012 (4) | 0.0022 (4) |
N1 | 0.0125 (5) | 0.0202 (6) | 0.0185 (6) | −0.0022 (5) | 0.0035 (4) | −0.0031 (5) |
N2 | 0.0129 (6) | 0.0197 (6) | 0.0182 (6) | 0.0013 (5) | 0.0030 (4) | 0.0018 (5) |
C1 | 0.0225 (11) | 0.0354 (13) | 0.0189 (10) | 0.000 | 0.0092 (8) | 0.000 |
C2 | 0.0304 (8) | 0.0322 (9) | 0.0184 (7) | −0.0031 (7) | 0.0096 (6) | −0.0063 (6) |
C3 | 0.0238 (7) | 0.0179 (7) | 0.0272 (8) | 0.0018 (6) | 0.0047 (6) | −0.0045 (6) |
C4 | 0.0225 (10) | 0.0163 (10) | 0.0294 (11) | −0.0009 (8) | 0.0026 (8) | −0.0002 (8) |
C4A | 0.019 (3) | 0.015 (3) | 0.035 (3) | −0.002 (2) | 0.007 (2) | −0.001 (2) |
C5 | 0.0288 (8) | 0.0175 (8) | 0.0277 (8) | 0.0018 (6) | 0.0048 (6) | 0.0051 (6) |
C6 | 0.0319 (8) | 0.0308 (9) | 0.0205 (7) | −0.0014 (7) | 0.0120 (6) | 0.0048 (7) |
C7 | 0.0254 (13) | 0.0318 (15) | 0.0129 (12) | 0.000 | 0.0021 (10) | 0.000 |
C7A | 0.024 (6) | 0.031 (6) | 0.013 (5) | 0.000 | 0.013 (4) | 0.000 |
Ni1—N1 | 2.0990 (12) | C3—H3B | 0.990 |
Ni1—O2W | 2.1061 (14) | C3—H3C | 0.990 |
Ni1—N2 | 2.1091 (12) | C3—H3D | 0.990 |
Ni1—O1W | 2.1299 (14) | C4—C5 | 1.488 (2) |
O1W—H1Wi | 0.796 (18) | C4—H4A | 0.990 |
O1W—H1W | 0.796 (18) | C4—H4B | 0.990 |
O2W—H2Wi | 0.820 (18) | C4A—C5 | 1.514 (6) |
O2W—H2W | 0.820 (18) | C4A—H4C | 0.990 |
O1—C3 | 1.4404 (17) | C4A—H4D | 0.990 |
O1—N1 | 1.4451 (14) | C5—H5A | 0.990 |
O2—C5 | 1.4381 (18) | C5—H5B | 0.990 |
O2—N2 | 1.4457 (14) | C5—H5C | 0.990 |
N1—C2 | 1.4776 (18) | C5—H5D | 0.990 |
N1—H1N | 0.883 (18) | C6—C7A | 1.443 (5) |
N2—C6 | 1.4792 (18) | C6—C7 | 1.504 (2) |
N2—H2N | 0.890 (17) | C6—H6A | 0.990 |
C1—C2 | 1.5130 (19) | C6—H6B | 0.990 |
C1—H1A | 0.990 | C6—H6C | 0.990 |
C1—H1B | 0.990 | C6—H6D | 0.990 |
C2—H2A | 0.990 | C7—H7A | 0.990 |
C2—H2B | 0.990 | C7—H7B | 0.990 |
C3—C4A | 1.484 (6) | C7A—H7C | 0.990 |
C3—C4 | 1.521 (2) | C7A—H7D | 0.990 |
C3—H3A | 0.990 | ||
N1—Ni1—N1i | 93.02 (7) | C4A—C3—H3C | 106.6 |
N1—Ni1—O2W | 89.69 (4) | O1—C3—H3D | 106.6 |
N1—Ni1—N2i | 178.75 (4) | C4A—C3—H3D | 106.6 |
N1—Ni1—N2 | 86.52 (5) | H3C—C3—H3D | 106.6 |
O2W—Ni1—N2 | 91.47 (4) | C5—C4—C3 | 115.67 (16) |
N2i—Ni1—N2 | 93.92 (7) | C5—C4—H4A | 108.4 |
N1—Ni1—O1W | 90.26 (4) | C3—C4—H4A | 108.4 |
O2W—Ni1—O1W | 179.93 (5) | C5—C4—H4B | 108.4 |
N2i—Ni1—O1W | 88.58 (4) | C3—C4—H4B | 108.4 |
H1Wi—O1W—Ni1 | 112.2 (14) | H4A—C4—H4B | 107.4 |
H1Wi—O1W—H1W | 107 (3) | C3—C4A—C5 | 116.4 (4) |
Ni1—O1W—H1W | 112.2 (14) | C3—C4A—H4C | 108.2 |
H2Wi—O2W—Ni1 | 110.1 (13) | C5—C4A—H4C | 108.2 |
H2Wi—O2W—H2W | 106 (3) | C3—C4A—H4D | 108.2 |
Ni1—O2W—H2W | 110.1 (13) | C5—C4A—H4D | 108.2 |
C3—O1—N1 | 114.59 (10) | H4C—C4A—H4D | 107.3 |
C5—O2—N2 | 113.93 (10) | O2—C5—C4 | 116.16 (13) |
O1—N1—C2 | 107.27 (10) | O2—C5—C4A | 104.3 (2) |
O1—N1—Ni1 | 106.96 (7) | O2—C5—H5A | 108.2 |
C2—N1—Ni1 | 122.35 (10) | C4—C5—H5A | 108.2 |
O1—N1—H1N | 104.7 (11) | O2—C5—H5B | 108.2 |
C2—N1—H1N | 110.4 (11) | C4—C5—H5B | 108.2 |
Ni1—N1—H1N | 103.8 (11) | H5A—C5—H5B | 107.4 |
O2—N2—C6 | 109.60 (11) | O2—C5—H5C | 110.9 |
O2—N2—Ni1 | 103.67 (7) | C4A—C5—H5C | 110.9 |
C6—N2—Ni1 | 122.19 (10) | O2—C5—H5D | 110.9 |
O2—N2—H2N | 105.0 (10) | C4A—C5—H5D | 110.9 |
C6—N2—H2N | 109.2 (10) | H5C—C5—H5D | 108.9 |
Ni1—N2—H2N | 105.8 (10) | C7A—C6—N2 | 116.6 (4) |
C2i—C1—C2 | 113.13 (18) | N2—C6—C7 | 113.13 (15) |
C2i—C1—H1A | 109.0 | N2—C6—H6A | 109.0 |
C2—C1—H1A | 109.0 | C7—C6—H6A | 109.0 |
C2i—C1—H1B | 109.0 | N2—C6—H6B | 109.0 |
C2—C1—H1B | 109.0 | C7—C6—H6B | 109.0 |
H1A—C1—H1B | 107.8 | H6A—C6—H6B | 107.8 |
N1—C2—C1 | 111.34 (13) | C7A—C6—H6C | 108.1 |
N1—C2—H2A | 109.4 | N2—C6—H6C | 108.1 |
C1—C2—H2A | 109.4 | C7A—C6—H6D | 108.1 |
N1—C2—H2B | 109.4 | N2—C6—H6D | 108.1 |
C1—C2—H2B | 109.4 | H6C—C6—H6D | 107.3 |
H2A—C2—H2B | 108.0 | C6—C7—C6i | 115.0 (2) |
O1—C3—C4A | 123.0 (2) | C6—C7—H7A | 108.5 |
O1—C3—C4 | 105.85 (13) | C6—C7—H7B | 108.5 |
O1—C3—H3A | 110.6 | H7A—C7—H7B | 107.5 |
C4—C3—H3A | 110.6 | C6—C7A—C6i | 123.0 (7) |
O1—C3—H3B | 110.6 | C6—C7A—H7C | 106.6 |
C4—C3—H3B | 110.6 | C6—C7A—H7D | 106.6 |
H3A—C3—H3B | 108.7 | H7C—C7A—H7D | 106.5 |
O1—C3—H3C | 106.6 | ||
C3—O1—N1—C2 | 94.10 (13) | C2i—C1—C2—N1 | −75.6 (2) |
C3—O1—N1—Ni1 | −133.00 (9) | N1—O1—C3—C4A | 65.5 (3) |
N1i—Ni1—N1—O1 | −137.98 (6) | N1—O1—C3—C4 | 114.49 (13) |
O2W—Ni1—N1—O1 | −48.31 (8) | O1—C3—C4—C5 | −74.79 (17) |
N2—Ni1—N1—O1 | 43.18 (8) | C4A—C3—C4—C5 | 45.7 (3) |
O1W—Ni1—N1—O1 | 131.74 (8) | O1—C3—C4A—C5 | 36.0 (5) |
N1i—Ni1—N1—C2 | −13.89 (13) | C4—C3—C4A—C5 | −45.1 (3) |
O2W—Ni1—N1—C2 | 75.78 (11) | N2—O2—C5—C4 | 65.48 (18) |
N2—Ni1—N1—C2 | 167.28 (11) | N2—O2—C5—C4A | 114.7 (2) |
O1W—Ni1—N1—C2 | −104.16 (11) | C3—C4—C5—O2 | 41.1 (2) |
C5—O2—N2—C6 | 86.09 (14) | C3—C4—C5—C4A | −44.5 (3) |
C5—O2—N2—Ni1 | −141.95 (9) | C3—C4A—C5—O2 | −66.2 (4) |
N1—Ni1—N2—O2 | 48.24 (8) | C3—C4A—C5—C4 | 46.3 (3) |
O2W—Ni1—N2—O2 | 137.84 (8) | O2—N2—C6—C7A | 150.9 (5) |
N2i—Ni1—N2—O2 | −130.59 (6) | Ni1—N2—C6—C7A | 29.5 (5) |
O1W—Ni1—N2—O2 | −42.11 (8) | O2—N2—C6—C7 | 94.40 (16) |
N1—Ni1—N2—C6 | 172.37 (11) | Ni1—N2—C6—C7 | −26.97 (18) |
O2W—Ni1—N2—C6 | −98.03 (11) | C7A—C6—C7—C6i | −33.6 (5) |
N2i—Ni1—N2—C6 | −6.46 (13) | N2—C6—C7—C6i | 72.7 (2) |
O1W—Ni1—N2—C6 | 82.02 (11) | N2—C6—C7A—C6i | −60.6 (10) |
O1—N1—C2—C1 | 166.45 (12) | C7—C6—C7A—C6i | 38.5 (6) |
Ni1—N1—C2—C1 | 42.49 (17) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···Cl1 | 0.796 (18) | 2.375 (18) | 3.1571 (11) | 167.7 (18) |
O2W—H2W···Cl1ii | 0.820 (18) | 2.339 (18) | 3.1493 (11) | 169.9 (17) |
N1—H1N···Cl1 | 0.883 (18) | 2.529 (18) | 3.3597 (12) | 156.9 (14) |
N2—H2N···Cl1ii | 0.890 (17) | 2.546 (17) | 3.3351 (12) | 148.0 (13) |
Symmetry code: (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C12H28N4O4)(H2O)2]Cl2 |
Mr | 458.03 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 150 |
a, b, c (Å) | 7.4288 (3), 13.1426 (5), 10.2527 (3) |
β (°) | 102.2480 (18) |
V (Å3) | 978.22 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.60 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Delft Instruments FAST area-detector diffractometer |
Absorption correction | Part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) |
Tmin, Tmax | 0.710, 0.823 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15576, 2090, 1892 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.063, 1.05 |
No. of reflections | 2090 |
No. of parameters | 152 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.64 |
Computer programs: MADNES (Pflugrath & Messerschmidt, 1989), MADNES, ABSMAD (Karaulov, 1992), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Ni1—N1 | 2.0990 (12) | N2—C6 | 1.4792 (18) |
Ni1—O2W | 2.1061 (14) | C1—C2 | 1.5130 (19) |
Ni1—N2 | 2.1091 (12) | C3—C4A | 1.484 (6) |
Ni1—O1W | 2.1299 (14) | C3—C4 | 1.521 (2) |
O1—C3 | 1.4404 (17) | C4—C5 | 1.488 (2) |
O1—N1 | 1.4451 (14) | C4A—C5 | 1.514 (6) |
O2—C5 | 1.4381 (18) | C6—C7A | 1.443 (5) |
O2—N2 | 1.4457 (14) | C6—C7 | 1.504 (2) |
N1—C2 | 1.4776 (18) | ||
N1—Ni1—N1i | 93.02 (7) | O2—N2—C6 | 109.60 (11) |
N1—Ni1—O2W | 89.69 (4) | C2i—C1—C2 | 113.13 (18) |
N1—Ni1—N2i | 178.75 (4) | N1—C2—C1 | 111.34 (13) |
N1—Ni1—N2 | 86.52 (5) | O1—C3—C4A | 123.0 (2) |
O2W—Ni1—N2 | 91.47 (4) | O1—C3—C4 | 105.85 (13) |
N2i—Ni1—N2 | 93.92 (7) | C5—C4—C3 | 115.67 (16) |
N1—Ni1—O1W | 90.26 (4) | C3—C4A—C5 | 116.4 (4) |
O2W—Ni1—O1W | 179.93 (5) | O2—C5—C4 | 116.16 (13) |
N2i—Ni1—O1W | 88.58 (4) | O2—C5—C4A | 104.3 (2) |
C3—O1—N1 | 114.59 (10) | C7A—C6—N2 | 116.6 (4) |
C5—O2—N2 | 113.93 (10) | N2—C6—C7 | 113.13 (15) |
O1—N1—C2 | 107.27 (10) | C6—C7—C6i | 115.0 (2) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···Cl1 | 0.796 (18) | 2.375 (18) | 3.1571 (11) | 167.7 (18) |
O2W—H2W···Cl1ii | 0.820 (18) | 2.339 (18) | 3.1493 (11) | 169.9 (17) |
N1—H1N···Cl1 | 0.883 (18) | 2.529 (18) | 3.3597 (12) | 156.9 (14) |
N2—H2N···Cl1ii | 0.890 (17) | 2.546 (17) | 3.3351 (12) | 148.0 (13) |
Symmetry code: (ii) x−1, y, z. |
A feature of the structure of the title comound, (I) (Fig. 1), as reported previously by Kuksa et al. (2000) was comparatively high residual electron density in the vicinity of C4. Modelling this and a similar but somewhat smaller feature in the vicinity of C7 in terms of disorder of the atoms concerned brought about a significant improvement in the structure determination with the reduction of R[F2 > 2σ(F2)] and wR2 (all F2 data) from 0.050 and 0.136, respectively, to the corresponding values given below. The introduction of disorder into the model, whereby C4 and C7 are both distributed over pairs of sites as C4/C4A and C7/C7A with occupancies of 0.744 (3) and 0.810 (5) for the major (C4 and C7) components, respectively, and with H attached to these and neighbouring atoms treated appropriately, has little effect upon the structural features of the major component such as the coordination of Ni and the internal geometry of the macrocyclic ligand (Table 1) or the hydrogen-bond parameters (Table 2).
The coordination of Ni is octahedral with equatorial N, with Ni1—N1 and Ni1—N2 2.0990 (12) and 2.1091 (12) Å, respectively, and water molecules in the axial positions, with Ni1—O1W and Ni1—O2W at 2.1299 (14) and 2.1061 (14) Å, respectively. The angles at Ni involving cis-donor atoms lie in the range 86.52 (5)–93.92 (7)°, while trans angles of 178.75 (4) and 179.93 (5)° are observed. The chloride anion does not participate in the coordination of Ni, but is heavily involved as an H-bond acceptor (see below).
A notable feature of the major component form of the macrocyclic ligand (Fig. 1) is the two-up two-down arrangement of the methylene groups at the points of the envelope flaps of the six- (C1 and C7) and eight-membered [C4 and C4i; symmetry code: (i) x, 1/2 - y, z] chelate rings relative to the plane defined by Ni and its attached N, with C4 and C4i above the plane and C1 and C7 below it. In the minor component form with C4A and C7A replacing C4 and C7, the arrangement is now three-up, one-down, with only C1 below the reference plane, and is clearly not simply a total inversion of the original two-up two-down arrangement. This further justifies the use, adopted initially on the basis of the magnitudes of the difference map peaks, of two distinct occupancy factors in modelling the disorder. As shown in Table 1, the major and minor forms of the macrocyclic ligand differ appreciably in terms of the C3—C4, C4—C5 and C6–C7 bond lengths (or their equivalent for the minor component) and also in the angles subtended by non-H atoms at C3, C5 and C6, as well as those at C4, C4A, C7 and C7A.
The hydrogen bonds listed in Table 2, all of which have Cl as acceptor, create infinite chains propagated in the direction of the a axis (Fig. 2).