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The nickel chloride complex of the Schiff base N2,N2′-propanediylbis(2,3-butanedione-2-imine-3-oxime), namely, chlorido(3,9-dimethylundeca-3,8-diene-2,10-dione 10-oxime 2-oximato-κ4N,N′,N′′,N′′′)nickel(II), [NiCl(C11H19N4O2)], at 100 K crystallizes in the orthorhombic space group Cmce. The structure exhibits mirror disorder of the main molecule that is not present in the bromide analogue. The relatively small number of unique reflections in the data set and the disorder imposed by the crystallographic mirror plane present a challenging educational case study.
Supporting information
CCDC reference: 2122259
Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: Mercury (Macrae et al., 2020).
Chlorido(3,9-dimethylundeca-3,8-diene-2,10-dione 10-oxime 2-oximato-
κ4N,
N',
N'',
N''')nickel(II)
top
Crystal data top
[NiCl(C11H19N4O2)] | Dx = 1.644 Mg m−3 |
Mr = 333.46 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmce | Cell parameters from 7235 reflections |
a = 14.3402 (14) Å | θ = 2.5–27.2° |
b = 14.2577 (12) Å | µ = 1.64 mm−1 |
c = 13.1777 (13) Å | T = 100 K |
V = 2694.3 (4) Å3 | Plate, brown |
Z = 8 | 0.10 × 0.08 × 0.03 mm |
F(000) = 1392 | |
Data collection top
Bruker APEXII CCD diffractometer | 1256 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.104 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 27.2°, θmin = 2.5° |
Tmin = 0.623, Tmax = 0.746 | h = −18→18 |
56076 measured reflections | k = −18→18 |
1558 independent reflections | l = −16→16 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.021P)2 + 11.8731P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1558 reflections | Δρmax = 0.61 e Å−3 |
115 parameters | Δρmin = −0.45 e Å−3 |
12 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. 1. Fixed Uiso
At 1.2 times of:
All C(H,H) groups
At 1.5 times of:
All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
N1 ~ O1 ~ C5: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
N2 ~ O2 ~ C7: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
3. Others
Fixed Sof: O1(0.5) O2(0.5) H2(0.5) C5(0.5) H5A(0.5) H5B(0.5) C6(0.5) H6A(0.5)
H6B(0.5) C7(0.5) H7A(0.5) H7B(0.5)
4.a Secondary CH2 refined with riding coordinates:
C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B)
4.b Idealised Me refined as rotating group:
C2(H2A,H2B,H2C), C4(H4A,H4B,H4C)
4.c Idealised tetrahedral OH refined as rotating group:
O2(H2) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ni1 | 0.500000 | 0.62249 (3) | 0.63581 (3) | 0.01318 (14) | |
Cl1 | 0.500000 | 0.62131 (7) | 0.82563 (7) | 0.0291 (2) | |
N1 | 0.41391 (14) | 0.52300 (14) | 0.62930 (17) | 0.0158 (4) | |
N2 | 0.41383 (15) | 0.72035 (15) | 0.61322 (17) | 0.0173 (5) | |
C1 | 0.44918 (17) | 0.43926 (17) | 0.63273 (19) | 0.0155 (5) | |
C2 | 0.39092 (18) | 0.35273 (17) | 0.6383 (2) | 0.0200 (6) | |
H2A | 0.431498 | 0.297431 | 0.639172 | 0.030* | |
H2B | 0.349725 | 0.349825 | 0.579038 | 0.030* | |
H2C | 0.353252 | 0.354084 | 0.700333 | 0.030* | |
C3 | 0.44866 (18) | 0.80203 (18) | 0.59531 (19) | 0.0166 (5) | |
C4 | 0.3943 (2) | 0.88915 (19) | 0.5744 (2) | 0.0279 (7) | |
H4A | 0.415144 | 0.939212 | 0.620013 | 0.042* | |
H4B | 0.327801 | 0.876996 | 0.585622 | 0.042* | |
H4C | 0.404144 | 0.908442 | 0.503838 | 0.042* | |
O1 | 0.3218 (7) | 0.5321 (10) | 0.6216 (11) | 0.0166 (18) | 0.5 |
O2 | 0.3204 (8) | 0.7038 (9) | 0.6068 (9) | 0.019 (2) | 0.5 |
H2 | 0.310498 | 0.645796 | 0.610017 | 0.029* | 0.5 |
C5 | 0.3120 (11) | 0.5400 (18) | 0.6394 (19) | 0.028 (4) | 0.5 |
H5A | 0.283806 | 0.539140 | 0.570793 | 0.033* | 0.5 |
H5B | 0.284291 | 0.487639 | 0.678419 | 0.033* | 0.5 |
C6 | 0.2869 (4) | 0.6285 (4) | 0.6891 (4) | 0.0232 (11) | 0.5 |
H6A | 0.317844 | 0.631006 | 0.756180 | 0.028* | 0.5 |
H6B | 0.218703 | 0.629051 | 0.700928 | 0.028* | 0.5 |
C7 | 0.3130 (12) | 0.7157 (15) | 0.6300 (15) | 0.021 (3) | 0.5 |
H7A | 0.280482 | 0.715311 | 0.563689 | 0.026* | 0.5 |
H7B | 0.292500 | 0.772015 | 0.667838 | 0.026* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0099 (2) | 0.0108 (2) | 0.0189 (2) | 0.000 | 0.000 | −0.00033 (19) |
Cl1 | 0.0557 (7) | 0.0154 (5) | 0.0162 (4) | 0.000 | 0.000 | 0.0001 (4) |
N1 | 0.0098 (10) | 0.0149 (10) | 0.0226 (11) | −0.0010 (8) | −0.0003 (9) | −0.0024 (8) |
N2 | 0.0102 (10) | 0.0172 (11) | 0.0246 (12) | 0.0016 (8) | 0.0023 (8) | 0.0025 (9) |
C1 | 0.0157 (13) | 0.0145 (12) | 0.0162 (12) | −0.0019 (10) | −0.0005 (11) | 0.0005 (10) |
C2 | 0.0192 (13) | 0.0166 (13) | 0.0243 (13) | −0.0031 (10) | 0.0013 (11) | −0.0009 (10) |
C3 | 0.0191 (14) | 0.0134 (12) | 0.0173 (12) | 0.0000 (10) | 0.0010 (11) | 0.0008 (10) |
C4 | 0.0386 (17) | 0.0175 (15) | 0.0276 (15) | 0.0072 (13) | 0.0024 (13) | 0.0042 (11) |
O1 | 0.011 (3) | 0.009 (3) | 0.030 (5) | 0.001 (2) | −0.001 (2) | 0.000 (3) |
O2 | 0.011 (3) | 0.011 (4) | 0.036 (5) | 0.003 (2) | 0.002 (3) | 0.006 (4) |
C5 | 0.007 (3) | 0.034 (7) | 0.042 (9) | 0.000 (3) | −0.003 (4) | −0.010 (5) |
C6 | 0.011 (2) | 0.030 (3) | 0.028 (3) | 0.000 (2) | 0.006 (2) | 0.002 (3) |
C7 | 0.008 (3) | 0.021 (5) | 0.036 (7) | 0.002 (3) | 0.002 (4) | −0.008 (4) |
Geometric parameters (Å, º) top
Ni1—N1 | 1.882 (2) | C2—H2C | 0.9800 |
Ni1—N1i | 1.882 (2) | C3—C3i | 1.473 (5) |
Ni1—N2i | 1.887 (2) | C3—C4 | 1.492 (4) |
Ni1—N2 | 1.887 (2) | C4—H4A | 0.9800 |
Ni1—Cl1 | 2.5014 (11) | C4—H4B | 0.9800 |
N1—C1 | 1.297 (3) | C4—H4C | 0.9800 |
N1—O1 | 1.332 (10) | O2—H2 | 0.8400 |
N1—C5 | 1.487 (15) | C5—C6 | 1.47 (2) |
N2—C3 | 1.289 (3) | C5—H5A | 0.9900 |
N2—O2 | 1.363 (11) | C5—H5B | 0.9900 |
N2—C7 | 1.464 (17) | C6—C7 | 1.51 (2) |
C1—C1i | 1.458 (5) | C6—H6A | 0.9900 |
C1—C2 | 1.492 (3) | C6—H6B | 0.9900 |
C2—H2A | 0.9800 | C7—H7A | 0.9900 |
C2—H2B | 0.9800 | C7—H7B | 0.9900 |
| | | |
N1—Ni1—N1i | 81.97 (13) | N2—C3—C3i | 112.80 (15) |
N1—Ni1—N2i | 168.30 (10) | N2—C3—C4 | 125.7 (2) |
N1i—Ni1—N2i | 96.92 (9) | C3i—C3—C4 | 121.51 (15) |
N1—Ni1—N2 | 96.92 (9) | C3—C4—H4A | 109.5 |
N1i—Ni1—N2 | 168.30 (10) | C3—C4—H4B | 109.5 |
N2i—Ni1—N2 | 81.79 (13) | H4A—C4—H4B | 109.5 |
N1—Ni1—Cl1 | 92.32 (7) | C3—C4—H4C | 109.5 |
N1i—Ni1—Cl1 | 92.32 (7) | H4A—C4—H4C | 109.5 |
N2i—Ni1—Cl1 | 99.36 (7) | H4B—C4—H4C | 109.5 |
N2—Ni1—Cl1 | 99.36 (7) | N2—O2—H2 | 109.5 |
C1—N1—O1 | 118.6 (6) | C6—C5—N1 | 114.9 (15) |
C1—N1—C5 | 122.0 (10) | C6—C5—H5A | 108.5 |
C1—N1—Ni1 | 115.86 (17) | N1—C5—H5A | 108.5 |
O1—N1—Ni1 | 125.5 (6) | C6—C5—H5B | 108.5 |
C5—N1—Ni1 | 121.2 (10) | N1—C5—H5B | 108.5 |
C3—N2—O2 | 121.7 (6) | H5A—C5—H5B | 107.5 |
C3—N2—C7 | 116.8 (9) | C5—C6—C7 | 114.6 (12) |
C3—N2—Ni1 | 116.30 (18) | C5—C6—H6A | 108.6 |
O2—N2—Ni1 | 121.7 (6) | C7—C6—H6A | 108.6 |
C7—N2—Ni1 | 126.1 (9) | C5—C6—H6B | 108.6 |
N1—C1—C1i | 112.94 (14) | C7—C6—H6B | 108.6 |
N1—C1—C2 | 123.0 (2) | H6A—C6—H6B | 107.6 |
C1i—C1—C2 | 124.06 (14) | N2—C7—C6 | 111.0 (14) |
C1—C2—H2A | 109.5 | N2—C7—H7A | 109.4 |
C1—C2—H2B | 109.5 | C6—C7—H7A | 109.4 |
H2A—C2—H2B | 109.5 | N2—C7—H7B | 109.4 |
C1—C2—H2C | 109.5 | C6—C7—H7B | 109.4 |
H2A—C2—H2C | 109.5 | H7A—C7—H7B | 108.0 |
H2B—C2—H2C | 109.5 | | |
| | | |
N1i—Ni1—N1—C1 | 5.8 (2) | N1i—Ni1—N2—C7 | 105.3 (10) |
N2i—Ni1—N1—C1 | 91.1 (5) | N2i—Ni1—N2—C7 | −170.2 (9) |
N2—Ni1—N1—C1 | 174.0 (2) | Cl1—Ni1—N2—C7 | −72.0 (9) |
Cl1—Ni1—N1—C1 | −86.25 (19) | O1—N1—C1—C1i | 175.3 (7) |
N1i—Ni1—N1—O1 | −174.2 (8) | C5—N1—C1—C1i | −173.5 (11) |
N2i—Ni1—N1—O1 | −88.9 (9) | Ni1—N1—C1—C1i | −4.7 (2) |
N2—Ni1—N1—O1 | −6.0 (8) | O1—N1—C1—C2 | −5.9 (8) |
Cl1—Ni1—N1—O1 | 93.7 (8) | C5—N1—C1—C2 | 5.2 (12) |
N1i—Ni1—N1—C5 | 174.7 (11) | Ni1—N1—C1—C2 | 174.06 (19) |
N2i—Ni1—N1—C5 | −100.0 (12) | O2—N2—C3—C3i | −173.6 (5) |
N2—Ni1—N1—C5 | −17.1 (12) | C7—N2—C3—C3i | 171.1 (8) |
Cl1—Ni1—N1—C5 | 82.7 (12) | Ni1—N2—C3—C3i | 0.5 (2) |
N1—Ni1—N2—C3 | −168.9 (2) | O2—N2—C3—C4 | 5.3 (7) |
N1i—Ni1—N2—C3 | −85.1 (5) | C7—N2—C3—C4 | −10.0 (9) |
N2i—Ni1—N2—C3 | −0.6 (2) | Ni1—N2—C3—C4 | 179.4 (2) |
Cl1—Ni1—N2—C3 | 97.60 (19) | C1—N1—C5—C6 | 147.5 (12) |
N1—Ni1—N2—O2 | 5.2 (6) | Ni1—N1—C5—C6 | −21 (2) |
N1i—Ni1—N2—O2 | 89.0 (7) | N1—C5—C6—C7 | 66 (2) |
N2i—Ni1—N2—O2 | 173.4 (6) | C3—N2—C7—C6 | −157.6 (7) |
Cl1—Ni1—N2—O2 | −88.3 (6) | Ni1—N2—C7—C6 | 12.0 (15) |
N1—Ni1—N2—C7 | 21.6 (9) | C5—C6—C7—N2 | −60.3 (15) |
Symmetry code: (i) −x+1, y, z. |
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