A pseudo­tetra­hedral nickel(II) complex with a tridentate oxazoline-based scorpionate ligand: chlorido­[tris­(4,4-di­methyl­oxazolin-2-yl)phenyl­borato]nickel(II)

Poly(pyrazol-1-yl)borates have been utilized extensively in coordination compounds due to their high affinity toward cationic metal ions on the basis of electrostatic inter­actions derived from the mononegatively charged boron centre. The original poly(pyrazol-1-yl)borates, christened `scorpionates', were pioneered by the late Professor Swiatoslaw Trofimenko and have expanded to include various borate ligands with N-, P-, O-, S-, Se- and C-donors. Scorpionate ligands with boron–carbon bonds, rather than the normal boron–nitro­gen bonds, have been developed and in these new types of scorpionate ligands, amines and azoles, such as pyridines, imidazoles and oxazolines, have been employed as N-donors instead of pyrazoles. Furthermore, a variety of bis- and tris­(oxazolin­yl)borate ligands, including chiral ones, have been developed. Tris(oxazolin-2-yl)borates work as facially capping tridentate chelating ligands in the same way as tris­(pyrazol-1-yl)borates. In the title compound, [Ni(C₂₁H₂₉BN₃O₃)Cl], the Ni^II ion is coordinated by three N atoms from the facially capping tridentate chelating tris­(4,4-di­methyl­oxazolin-2-yl)phenyl­borate ligand and a chloride ligand in a highly distorted tetra­hedral geometry. The Ni—Cl bond length [2.1851 (5) Å] is comparable to those found in a previously reported tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate derivative [2.1955 (18) and 2.150 (2) Å]. The mol­ecular structure deviates from C_3v symmetry due to the structural flexibility of the tris­(4,4-di­methyl­oxazolin-2-yl)phenyl­borate ligand.

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007), SORTAV (Blessing, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

Ni(Ph-To)Cl

Crystal data

C21H29BClN3NiO3	F(000) = 1000
Mr = 476.44	Dx = 1.388 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8792 (17) Å	Cell parameters from 6816 reflections
b = 13.221 (2) Å	θ = 1.9–27.5°
c = 15.972 (3) Å	µ = 1.00 mm^−1
β = 96.899 (2)°	T = 113 K
V = 2280.7 (7) Å^3	Block, red
Z = 4	0.35 × 0.35 × 0.20 mm

Data collection

Saturn70 (4x4 bin mode) diffractometer	5168 independent reflections
Radiation source: Rotating Anode	4140 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.029
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: numerical [CrystalClear (Rigaku , 2007) and ABSCOR (Higashi, 1995)]	h = −10→14
Tmin = 0.761, Tmax = 0.861	k = −16→16
16162 measured reflections	l = −20→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.0354P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
5168 reflections	Δρmax = 0.37 e Å^−3
277 parameters	Δρmin = −0.25 e Å^−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.81347 (2)	0.22126 (2)	0.46290 (2)	0.01215 (6)
Cl1	0.99249 (3)	0.25093 (3)	0.53634 (2)	0.02534 (9)
O1	0.58962 (8)	0.07426 (6)	0.28034 (6)	0.01325 (19)
O2	0.47256 (9)	0.13747 (7)	0.52167 (6)	0.0182 (2)
O3	0.54481 (8)	0.41357 (7)	0.36278 (6)	0.0176 (2)
N3	0.72065 (10)	0.34364 (8)	0.42058 (7)	0.0128 (2)
N1	0.75107 (10)	0.14194 (8)	0.35986 (7)	0.0124 (2)
N2	0.67335 (10)	0.16895 (8)	0.52071 (7)	0.0140 (2)
C8	0.66903 (13)	0.12461 (10)	0.60568 (8)	0.0159 (3)
C11	0.60804 (12)	0.32907 (10)	0.38978 (8)	0.0119 (3)
C7	0.53129 (14)	0.09517 (11)	0.60120 (9)	0.0218 (3)
H7A	0.5217	0.0207	0.6018	0.026*
H7B	0.4941	0.1240	0.6495	0.026*
C6	0.56418 (12)	0.17442 (9)	0.47998 (8)	0.0123 (3)
C4	0.83302 (14)	−0.02671 (10)	0.39302 (9)	0.0203 (3)
H4A	0.8900	0.0028	0.4387	0.030*
H4B	0.8712	−0.0866	0.3708	0.030*
H4C	0.7559	−0.0463	0.4147	0.030*
C3	0.80490 (12)	0.05100 (10)	0.32263 (8)	0.0136 (3)
C2	0.69696 (12)	0.01915 (10)	0.25686 (9)	0.0159 (3)
H2A	0.7137	0.0379	0.1993	0.019*
H2B	0.6832	−0.0548	0.2589	0.019*
C12	0.63387 (13)	0.49687 (10)	0.37142 (10)	0.0204 (3)
H12A	0.6008	0.5548	0.4010	0.024*
H12B	0.6528	0.5198	0.3154	0.024*
C10	0.75462 (15)	0.03299 (11)	0.61774 (9)	0.0249 (3)
H10A	0.7318	−0.0159	0.5724	0.037*
H10B	0.7466	0.0013	0.6723	0.037*
H10C	0.8405	0.0547	0.6163	0.037*
C21	0.30135 (13)	0.24998 (10)	0.38473 (9)	0.0187 (3)
H21	0.3166	0.2558	0.4444	0.022*
C13	0.75064 (13)	0.45344 (10)	0.42343 (9)	0.0158 (3)
C18	0.25241 (13)	0.23450 (10)	0.21099 (9)	0.0184 (3)
H18	0.2366	0.2286	0.1514	0.022*
C5	0.92108 (13)	0.07726 (11)	0.28313 (10)	0.0237 (3)
H5A	0.9020	0.1301	0.2405	0.036*
H5B	0.9513	0.0169	0.2564	0.036*
H5C	0.9850	0.1017	0.3269	0.036*
C16	0.39976 (12)	0.22645 (9)	0.33932 (8)	0.0129 (3)
C1	0.63387 (12)	0.14514 (9)	0.33751 (8)	0.0114 (3)
C19	0.15687 (13)	0.25763 (10)	0.25776 (10)	0.0212 (3)
H19	0.0754	0.2683	0.2305	0.025*
C9	0.70621 (15)	0.20563 (11)	0.67177 (9)	0.0255 (3)
H9A	0.7910	0.2280	0.6671	0.038*
H9B	0.7019	0.1777	0.7282	0.038*
H9C	0.6497	0.2633	0.6625	0.038*
C17	0.37173 (12)	0.21982 (9)	0.25145 (8)	0.0147 (3)
H17	0.4364	0.2048	0.2184	0.018*
C14	0.86871 (14)	0.47303 (11)	0.38378 (11)	0.0255 (3)
H14A	0.9381	0.4381	0.4164	0.038*
H14B	0.8854	0.5459	0.3837	0.038*
H14C	0.8588	0.4477	0.3257	0.038*
C20	0.18157 (13)	0.26514 (11)	0.34502 (10)	0.0223 (3)
H20	0.1166	0.2806	0.3777	0.027*
C15	0.76375 (16)	0.48866 (12)	0.51477 (10)	0.0298 (4)
H15A	0.6853	0.4783	0.5379	0.045*
H15B	0.7852	0.5607	0.5174	0.045*
H15C	0.8292	0.4497	0.5478	0.045*
B1	0.54017 (13)	0.21873 (11)	0.38307 (9)	0.0116 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01108 (9)	0.01108 (9)	0.01357 (9)	−0.00066 (7)	−0.00151 (6)	0.00106 (7)
Cl1	0.01819 (18)	0.0260 (2)	0.0285 (2)	−0.00325 (14)	−0.01106 (15)	0.00344 (15)
O1	0.0131 (5)	0.0119 (5)	0.0145 (5)	0.0008 (4)	0.0004 (4)	−0.0035 (4)
O2	0.0176 (5)	0.0204 (5)	0.0175 (5)	−0.0041 (4)	0.0057 (4)	0.0032 (4)
O3	0.0143 (5)	0.0094 (5)	0.0277 (6)	0.0000 (4)	−0.0035 (4)	0.0030 (4)
N3	0.0139 (6)	0.0103 (6)	0.0138 (6)	−0.0020 (4)	0.0004 (4)	0.0006 (4)
N1	0.0125 (5)	0.0100 (5)	0.0148 (6)	0.0006 (4)	0.0016 (4)	−0.0007 (4)
N2	0.0174 (6)	0.0130 (6)	0.0114 (6)	−0.0013 (5)	0.0014 (4)	0.0018 (4)
C8	0.0243 (8)	0.0138 (7)	0.0099 (6)	−0.0017 (6)	0.0030 (6)	0.0018 (5)
C11	0.0147 (7)	0.0116 (6)	0.0095 (6)	0.0019 (5)	0.0020 (5)	0.0010 (5)
C7	0.0275 (8)	0.0225 (8)	0.0159 (7)	−0.0054 (6)	0.0049 (6)	0.0039 (6)
C6	0.0156 (6)	0.0075 (6)	0.0143 (6)	−0.0024 (5)	0.0042 (5)	−0.0025 (5)
C4	0.0241 (8)	0.0145 (7)	0.0209 (8)	0.0037 (6)	−0.0029 (6)	0.0000 (6)
C3	0.0137 (7)	0.0119 (6)	0.0153 (6)	0.0024 (5)	0.0024 (5)	−0.0009 (5)
C2	0.0162 (7)	0.0156 (7)	0.0159 (7)	0.0044 (5)	0.0024 (5)	−0.0026 (5)
C12	0.0191 (7)	0.0093 (7)	0.0314 (8)	−0.0023 (5)	−0.0028 (6)	0.0026 (6)
C10	0.0344 (9)	0.0212 (8)	0.0193 (8)	0.0055 (7)	0.0038 (7)	0.0055 (6)
C21	0.0170 (7)	0.0193 (7)	0.0201 (7)	0.0009 (6)	0.0035 (6)	−0.0015 (6)
C13	0.0177 (7)	0.0088 (6)	0.0198 (7)	−0.0020 (5)	−0.0015 (6)	0.0005 (5)
C18	0.0196 (7)	0.0132 (7)	0.0208 (7)	−0.0025 (6)	−0.0042 (6)	0.0010 (6)
C5	0.0160 (7)	0.0251 (8)	0.0313 (8)	0.0020 (6)	0.0083 (6)	−0.0002 (7)
C16	0.0130 (6)	0.0063 (6)	0.0192 (7)	−0.0014 (5)	0.0013 (5)	−0.0002 (5)
C1	0.0157 (7)	0.0090 (6)	0.0097 (6)	−0.0026 (5)	0.0019 (5)	0.0027 (5)
C19	0.0123 (7)	0.0162 (7)	0.0335 (9)	−0.0020 (5)	−0.0044 (6)	0.0036 (6)
C9	0.0350 (9)	0.0252 (8)	0.0163 (7)	−0.0053 (7)	0.0027 (6)	−0.0043 (6)
C17	0.0143 (6)	0.0109 (6)	0.0185 (7)	0.0003 (5)	0.0008 (5)	−0.0007 (5)
C14	0.0199 (8)	0.0197 (8)	0.0364 (9)	−0.0050 (6)	0.0016 (7)	0.0081 (7)
C20	0.0132 (7)	0.0231 (8)	0.0314 (8)	0.0011 (6)	0.0054 (6)	0.0019 (6)
C15	0.0358 (10)	0.0242 (8)	0.0275 (9)	0.0036 (7)	−0.0041 (7)	−0.0111 (7)
B1	0.0115 (7)	0.0100 (7)	0.0131 (7)	−0.0005 (6)	0.0011 (6)	0.0001 (6)

Geometric parameters (Å, º)

Ni1—N3	1.9825 (11)	C12—H12A	0.9900
Ni1—N2	1.9982 (11)	C12—H12B	0.9900
Ni1—N1	2.0002 (11)	C10—H10A	0.9800
Ni1—Cl1	2.1851 (5)	C10—H10B	0.9800
O1—C1	1.3559 (15)	C10—H10C	0.9800
O1—C2	1.4631 (15)	C21—C20	1.394 (2)
O2—C6	1.3546 (15)	C21—C16	1.3984 (19)
O2—C7	1.4627 (16)	C21—H21	0.9500
O3—C11	1.3550 (15)	C13—C14	1.521 (2)
O3—C12	1.4624 (16)	C13—C15	1.522 (2)
N3—C11	1.2788 (16)	C18—C19	1.385 (2)
N3—C13	1.4875 (16)	C18—C17	1.3923 (19)
N1—C1	1.2827 (16)	C18—H18	0.9500
N1—C3	1.4919 (17)	C5—H5A	0.9800
N2—C6	1.2859 (17)	C5—H5B	0.9800
N2—C8	1.4842 (16)	C5—H5C	0.9800
C8—C9	1.5241 (19)	C16—C17	1.4027 (18)
C8—C10	1.5259 (19)	C16—B1	1.6049 (19)
C8—C7	1.542 (2)	C1—B1	1.6412 (19)
C11—B1	1.6327 (19)	C19—C20	1.391 (2)
C7—H7A	0.9900	C19—H19	0.9500
C7—H7B	0.9900	C9—H9A	0.9800
C6—B1	1.6462 (19)	C9—H9B	0.9800
C4—C3	1.5267 (19)	C9—H9C	0.9800
C4—H4A	0.9800	C17—H17	0.9500
C4—H4B	0.9800	C14—H14A	0.9800
C4—H4C	0.9800	C14—H14B	0.9800
C3—C5	1.5191 (19)	C14—H14C	0.9800
C3—C2	1.5373 (18)	C20—H20	0.9500
C2—H2A	0.9900	C15—H15A	0.9800
C2—H2B	0.9900	C15—H15B	0.9800
C12—C13	1.5427 (19)	C15—H15C	0.9800
N3—Ni1—N2	93.12 (5)	H10A—C10—H10B	109.5
N3—Ni1—N1	92.22 (4)	C8—C10—H10C	109.5
N2—Ni1—N1	89.79 (5)	H10A—C10—H10C	109.5
N3—Ni1—Cl1	114.91 (3)	H10B—C10—H10C	109.5
N2—Ni1—Cl1	119.62 (4)	C20—C21—C16	121.89 (14)
N1—Ni1—Cl1	136.75 (3)	C20—C21—H21	119.1
C1—O1—C2	106.68 (10)	C16—C21—H21	119.1
C6—O2—C7	107.12 (10)	N3—C13—C14	110.27 (11)
C11—O3—C12	106.60 (10)	N3—C13—C15	108.84 (11)
C11—N3—C13	110.81 (11)	C14—C13—C15	111.13 (12)
C11—N3—Ni1	115.69 (9)	N3—C13—C12	100.57 (10)
C13—N3—Ni1	133.26 (8)	C14—C13—C12	113.23 (12)
C1—N1—C3	109.90 (11)	C15—C13—C12	112.25 (12)
C1—N1—Ni1	116.07 (9)	C19—C18—C17	119.91 (13)
C3—N1—Ni1	129.78 (8)	C19—C18—H18	120.0
C6—N2—C8	110.86 (11)	C17—C18—H18	120.0
C6—N2—Ni1	117.14 (9)	C3—C5—H5A	109.5
C8—N2—Ni1	131.99 (9)	C3—C5—H5B	109.5
N2—C8—C9	108.71 (11)	H5A—C5—H5B	109.5
N2—C8—C10	110.07 (11)	C3—C5—H5C	109.5
C9—C8—C10	111.30 (12)	H5A—C5—H5C	109.5
N2—C8—C7	101.23 (10)	H5B—C5—H5C	109.5
C9—C8—C7	112.66 (12)	C21—C16—C17	116.42 (12)
C10—C8—C7	112.37 (12)	C21—C16—B1	122.43 (12)
N3—C11—O3	115.12 (11)	C17—C16—B1	120.85 (12)
N3—C11—B1	124.38 (12)	N1—C1—O1	115.17 (11)
O3—C11—B1	120.50 (11)	N1—C1—B1	123.08 (11)
O2—C7—C8	105.34 (10)	O1—C1—B1	121.27 (11)
O2—C7—H7A	110.7	C18—C19—C20	119.28 (13)
C8—C7—H7A	110.7	C18—C19—H19	120.4
O2—C7—H7B	110.7	C20—C19—H19	120.4
C8—C7—H7B	110.7	C8—C9—H9A	109.5
H7A—C7—H7B	108.8	C8—C9—H9B	109.5
N2—C6—O2	114.86 (12)	H9A—C9—H9B	109.5
N2—C6—B1	121.89 (11)	C8—C9—H9C	109.5
O2—C6—B1	123.19 (11)	H9A—C9—H9C	109.5
C3—C4—H4A	109.5	H9B—C9—H9C	109.5
C3—C4—H4B	109.5	C18—C17—C16	122.29 (13)
H4A—C4—H4B	109.5	C18—C17—H17	118.9
C3—C4—H4C	109.5	C16—C17—H17	118.9
H4A—C4—H4C	109.5	C13—C14—H14A	109.5
H4B—C4—H4C	109.5	C13—C14—H14B	109.5
N1—C3—C5	111.55 (11)	H14A—C14—H14B	109.5
N1—C3—C4	107.60 (11)	C13—C14—H14C	109.5
C5—C3—C4	110.88 (11)	H14A—C14—H14C	109.5
N1—C3—C2	100.89 (10)	H14B—C14—H14C	109.5
C5—C3—C2	112.60 (12)	C19—C20—C21	120.22 (14)
C4—C3—C2	112.82 (11)	C19—C20—H20	119.9
O1—C2—C3	104.85 (10)	C21—C20—H20	119.9
O1—C2—H2A	110.8	C13—C15—H15A	109.5
C3—C2—H2A	110.8	C13—C15—H15B	109.5
O1—C2—H2B	110.8	H15A—C15—H15B	109.5
C3—C2—H2B	110.8	C13—C15—H15C	109.5
H2A—C2—H2B	108.9	H15A—C15—H15C	109.5
O3—C12—C13	105.30 (10)	H15B—C15—H15C	109.5
O3—C12—H12A	110.7	C16—B1—C11	111.78 (11)
C13—C12—H12A	110.7	C16—B1—C1	117.01 (11)
O3—C12—H12B	110.7	C11—B1—C1	104.99 (10)
C13—C12—H12B	110.7	C16—B1—C6	117.86 (11)
H12A—C12—H12B	108.8	C11—B1—C6	103.70 (10)
C8—C10—H10A	109.5	C1—B1—C6	99.73 (10)
C8—C10—H10B	109.5
C6—N2—C8—C9	−113.21 (13)	O3—C12—C13—C14	129.85 (12)
Ni1—N2—C8—C9	65.54 (15)	O3—C12—C13—C15	−103.32 (13)
C6—N2—C8—C10	124.64 (13)	C20—C21—C16—C17	0.6 (2)
Ni1—N2—C8—C10	−56.60 (15)	C20—C21—C16—B1	174.30 (12)
C6—N2—C8—C7	5.59 (14)	C3—N1—C1—O1	−6.50 (15)
Ni1—N2—C8—C7	−175.65 (9)	Ni1—N1—C1—O1	−165.66 (8)
C13—N3—C11—O3	3.59 (16)	C3—N1—C1—B1	165.61 (11)
Ni1—N3—C11—O3	178.61 (8)	Ni1—N1—C1—B1	6.46 (16)
C13—N3—C11—B1	−175.62 (11)	C2—O1—C1—N1	−4.34 (14)
Ni1—N3—C11—B1	−0.61 (16)	C2—O1—C1—B1	−176.61 (11)
C12—O3—C11—N3	5.09 (15)	C17—C18—C19—C20	−0.5 (2)
C12—O3—C11—B1	−175.66 (11)	C19—C18—C17—C16	0.7 (2)
C6—O2—C7—C8	7.07 (14)	C21—C16—C17—C18	−0.76 (19)
N2—C8—C7—O2	−7.40 (13)	B1—C16—C17—C18	−174.60 (12)
C9—C8—C7—O2	108.52 (13)	C18—C19—C20—C21	0.3 (2)
C10—C8—C7—O2	−124.79 (12)	C16—C21—C20—C19	−0.4 (2)
C8—N2—C6—O2	−1.40 (15)	C21—C16—B1—C11	−85.36 (15)
Ni1—N2—C6—O2	179.64 (8)	C17—C16—B1—C11	88.09 (14)
C8—N2—C6—B1	−178.93 (11)	C21—C16—B1—C1	153.55 (12)
Ni1—N2—C6—B1	2.11 (16)	C17—C16—B1—C1	−32.99 (17)
C7—O2—C6—N2	−3.84 (15)	C21—C16—B1—C6	34.61 (18)
C7—O2—C6—B1	173.66 (11)	C17—C16—B1—C6	−151.93 (12)
C1—N1—C3—C5	133.38 (12)	N3—C11—B1—C16	−178.65 (12)
Ni1—N1—C3—C5	−71.20 (14)	O3—C11—B1—C16	2.18 (16)
C1—N1—C3—C4	−104.79 (13)	N3—C11—B1—C1	−50.82 (16)
Ni1—N1—C3—C4	50.63 (15)	O3—C11—B1—C1	130.00 (12)
C1—N1—C3—C2	13.59 (14)	N3—C11—B1—C6	53.38 (16)
Ni1—N1—C3—C2	169.01 (9)	O3—C11—B1—C6	−125.79 (12)
C1—O1—C2—C3	12.67 (13)	N1—C1—B1—C16	171.15 (12)
N1—C3—C2—O1	−15.31 (12)	O1—C1—B1—C16	−17.21 (17)
C5—C3—C2—O1	−134.34 (11)	N1—C1—B1—C11	46.57 (16)
C4—C3—C2—O1	99.21 (12)	O1—C1—B1—C11	−141.79 (11)
C11—O3—C12—C13	−11.02 (14)	N1—C1—B1—C6	−60.57 (15)
C11—N3—C13—C14	−129.72 (12)	O1—C1—B1—C6	111.08 (12)
Ni1—N3—C13—C14	56.45 (16)	N2—C6—B1—C16	−177.58 (12)
C11—N3—C13—C15	108.13 (13)	O2—C6—B1—C16	5.10 (18)
Ni1—N3—C13—C15	−65.69 (15)	N2—C6—B1—C11	−53.47 (15)
C11—N3—C13—C12	−9.95 (14)	O2—C6—B1—C11	129.21 (12)
Ni1—N3—C13—C12	176.23 (10)	N2—C6—B1—C1	54.71 (15)
O3—C12—C13—N3	12.23 (14)	O2—C6—B1—C1	−122.62 (12)