Mirror-plane disorder in a nickel chloride Schiff base com­plex: a suitable case study for crystallographic instruction

The nickel chloride com­plex of the Schiff base N²,N^2′-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.

Computing details

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)

Crystal data

[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) Å^3	Plate, brown
Z = 8	0.10 × 0.08 × 0.03 mm
F(000) = 1392

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.021P)^2 + 11.8731P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ni1—N1	1.882 (2)	C2—H2C	0.9800
Ni1—N1^i	1.882 (2)	C3—C3^i	1.473 (5)
Ni1—N2^i	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—C1^i	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—N1^i	81.97 (13)	N2—C3—C3^i	112.80 (15)
N1—Ni1—N2^i	168.30 (10)	N2—C3—C4	125.7 (2)
N1^i—Ni1—N2^i	96.92 (9)	C3^i—C3—C4	121.51 (15)
N1—Ni1—N2	96.92 (9)	C3—C4—H4A	109.5
N1^i—Ni1—N2	168.30 (10)	C3—C4—H4B	109.5
N2^i—Ni1—N2	81.79 (13)	H4A—C4—H4B	109.5
N1—Ni1—Cl1	92.32 (7)	C3—C4—H4C	109.5
N1^i—Ni1—Cl1	92.32 (7)	H4A—C4—H4C	109.5
N2^i—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—C1^i	112.94 (14)	C7—C6—H6B	108.6
N1—C1—C2	123.0 (2)	H6A—C6—H6B	107.6
C1^i—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
N1^i—Ni1—N1—C1	5.8 (2)	N1^i—Ni1—N2—C7	105.3 (10)
N2^i—Ni1—N1—C1	91.1 (5)	N2^i—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—C1^i	175.3 (7)
N1^i—Ni1—N1—O1	−174.2 (8)	C5—N1—C1—C1^i	−173.5 (11)
N2^i—Ni1—N1—O1	−88.9 (9)	Ni1—N1—C1—C1^i	−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)
N1^i—Ni1—N1—C5	174.7 (11)	Ni1—N1—C1—C2	174.06 (19)
N2^i—Ni1—N1—C5	−100.0 (12)	O2—N2—C3—C3^i	−173.6 (5)
N2—Ni1—N1—C5	−17.1 (12)	C7—N2—C3—C3^i	171.1 (8)
Cl1—Ni1—N1—C5	82.7 (12)	Ni1—N2—C3—C3^i	0.5 (2)
N1—Ni1—N2—C3	−168.9 (2)	O2—N2—C3—C4	5.3 (7)
N1^i—Ni1—N2—C3	−85.1 (5)	C7—N2—C3—C4	−10.0 (9)
N2^i—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)
N1^i—Ni1—N2—O2	89.0 (7)	N1—C5—C6—C7	66 (2)
N2^i—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.