Bis-BBN (9-borabi­cyclo­[3.3.1]­nonane) adduct of bis­(diethyl­glyoximato)­nickel(II)

Krivokapić, A.; Faiz, J.A.; Anderson, H.L.

doi:10.1107/S1600536803017288

Bis-BBN (9-borabicyclo[3.3.1]nonane) adduct of bis(diethylglyoximato)nickel(II)

A. Krivokapić, J. A. Faiz and H. L. Anderson

The bis-BBN adduct of bis(diethylglyoximato)nickel(II), [2,9-bis(cyclooctane-1,5-diyl)-4,6,11,13-tetraethyl-1,3,8,10-tetraoxa-4,7,11,14-tetraaza-2,9-diboracyclotetradecane-4,6,11,13-tetraene-κ⁴N]nickel(II), [Ni(C₂₈H₄₈B₂N₄O₄)], crystallizes as a monomer, with no short Ni

Ni contacts. The asymmetric unit contains only half a molecule and the Ni atom lies on an inversion centre.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017288/ci6244sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017288/ci6244Isup2.hkl Contains datablock I

CCDC reference: 222807

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.002 Å
R factor = 0.025
wR factor = 0.031
Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .....       0.99
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N1     =       8.92 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N2     =       9.15 su
PLAT410_ALERT_2_C Short Intra H...H Contact:H91     .. H132    =       1.93 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

In the previous paper in this journal, we reported the structure of a mono-9-borabicyclo[3.3.1]nonane (BBN) adduct of bis(diethylglyoxato)nickel(II) (Krivokapic et al., 2003). We report here the structure of the bis-adduct, (I). This compound was prepared in good yield by treating bis(diethylglyoximato)nickel(II) with methoxy-BBN in toluene at reflux for 2 d.

The geometry of (I) (Fig.1 and Table 1) is similar to those of previously reported complexes of this type (Chakavorty, 1974; Krivokapic et al., 2003). Compound (I) adopts a C_i conformation, with virtual C_{2 h} symmetry, with the BBN units shifted towards opposite faces of the macrocycle; this conformation evidently prevents stacking and making it monomeric, whereas the analogous mono-adduct is dimeric in the crystal (Krivokapic et al., 2003). The geometry of the 9BBN unit leads to short contact between H91···H132 (1.91 Å).

Experimental top

Methoxy-9-BBN (1.50 ml, 1.0 M in hexanes; 1.50 mmol) was added to a solution of bis(diethylglyoximato)nickel(II) (0.10 g, 0.29 mmol) in toluene (5 ml). After heating to reflux for 2 d, the product was chromatographed (SiO₂, toluene) to yield (I) (0.114 g, 67%) as orange crystals. M.p. 532–534 K; δ_H (400 MHz, CDCl₃): 2.61 (8H, q), 1.88–1.80 (4H, m), 1.75–1.60 (20H, m), 1.50–1.43 (4H, m), 1.20, (6H, t); δ_C (100 MHz, CDCl₃) 160.4, 31.6, 24.8, 19.7, 10.2; m/z (APCI⁺) 585.56 [M+H]⁺. Crystals of (I) were grown from acetone by evaporation.

Computing details top

Data collection: COLLECT (Nonius, 1997-2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top

Fig. 1. Plot showing the atomic numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. Only the contents of the asymmetric unit are numbered. The Ni atom lies on an inversion centre.

[2,9-bis(cyclooctane-1,5-diyl)-4,6,11,13-tetraethyl-1,3,8,10-tetraoxa- 4,7,11,14-tetraaza-2,9-diboracyclotetradecane-4,6,11,13-tetraene- κ⁴N]nickel(II) top

Crystal data top

[Ni(C₂₈H₄₈B₂N₄O₄)]	F(000) = 628.000
M_r = 585.05	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 532-534 K K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4047 (1) Å	Cell parameters from 3483 reflections
b = 19.2467 (2) Å	θ = 5–27°
c = 10.5508 (2) Å	µ = 0.69 mm⁻¹
β = 94.7398 (5)°	T = 150 K
V = 1498.52 (4) Å³	Block, orange
Z = 2	0.20 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius KappaCCD diffractometer	2934 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.03
ω scans	θ_max = 27.4°, θ_min = 5.3°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = 0→9
T_min = 0.87, T_max = 0.87	k = 0→24
3497 measured reflections	l = −13→13
3386 independent reflections

Refinement top

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters not refined
wR(F²) = 0.031	Method = Prince modified Chebychev polynomial, (Watkin, 1994) W = [weight][1-(δF/6σF)²]², with 2.03, 0.469E-1 and 1.40
S = 1.04	(Δ/σ)_max < 0.001
2934 reflections	Δρ_max = 0.31 e Å⁻³
178 parameters	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Ni(C₂₈H₄₈B₂N₄O₄)]	V = 1498.52 (4) Å³
M_r = 585.05	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4047 (1) Å	µ = 0.69 mm⁻¹
b = 19.2467 (2) Å	T = 150 K
c = 10.5508 (2) Å	0.20 × 0.20 × 0.20 mm
β = 94.7398 (5)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	3386 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	2934 reflections with I > 3σ(I)
T_min = 0.87, T_max = 0.87	R_int = 0.03
3497 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	178 parameters
wR(F²) = 0.031	H-atom parameters not refined
S = 1.04	Δρ_max = 0.31 e Å⁻³
2934 reflections	Δρ_min = −0.28 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	1.0000	0.0000	1.0000	0.0138
O2	0.88490 (11)	0.13345 (4)	0.90774 (7)	0.0176
O1	1.14610 (11)	−0.03759 (4)	1.24972 (7)	0.0189
N2	0.94948 (13)	0.09437 (5)	1.00776 (9)	0.0164
N1	1.08510 (13)	0.01367 (5)	1.16935 (9)	0.0167
C11	1.32556 (15)	−0.14890 (6)	1.29107 (11)	0.0192
C7	1.41922 (15)	−0.06462 (6)	1.11578 (11)	0.0199
C3	1.11726 (17)	0.09517 (6)	1.34941 (11)	0.0227
C5	0.96163 (16)	0.20048 (6)	1.13804 (11)	0.0207
C10	1.41059 (16)	−0.21003 (6)	1.22263 (12)	0.0242
C2	0.98932 (14)	0.12451 (5)	1.11628 (11)	0.0170
C1	1.06963 (15)	0.07616 (6)	1.21357 (11)	0.0176
C12	1.45707 (17)	−0.11135 (7)	1.38923 (12)	0.0266
C14	1.54724 (17)	−0.02626 (7)	1.21519 (12)	0.0259
C6	1.11434 (19)	0.24364 (7)	1.08963 (16)	0.0341
C13	1.60934 (18)	−0.06996 (7)	1.33320 (13)	0.0314
B1	1.25066 (17)	−0.09465 (6)	1.18507 (12)	0.0168
C8	1.50944 (17)	−0.12539 (7)	1.04918 (13)	0.0257
C4	0.9517 (2)	0.08936 (8)	1.42620 (13)	0.0350
C9	1.55602 (18)	−0.18953 (7)	1.13361 (14)	0.0301
H111	1.2265	−0.1682	1.3403	0.0238*
H71	1.3799	−0.0296	1.0479	0.0250*
H31	1.2146	0.0629	1.3870	0.0277*
H32	1.1649	0.1440	1.3544	0.0277*
H51	0.9570	0.2093	1.2315	0.0260*
H52	0.8433	0.2154	1.0926	0.0260*
H101	1.4670	−0.2427	1.2890	0.0301*
H102	1.3113	−0.2354	1.1708	0.0301*
H121	1.5135	−0.1472	1.4497	0.0329*
H122	1.3847	−0.0782	1.4390	0.0329*
H141	1.6565	−0.0107	1.1732	0.0320*
H142	1.4820	0.0159	1.2448	0.0320*
H61	1.0937	0.2941	1.1046	0.0408*
H62	1.2332	0.2294	1.1346	0.0408*
H63	1.1195	0.2355	0.9957	0.0408*
H131	1.6666	−0.0381	1.4003	0.0388*
H132	1.7039	−0.1038	1.3080	0.0388*
H81	1.6246	−0.1077	1.0161	0.0317*
H82	1.4255	−0.1408	0.9746	0.0317*
H41	0.9832	0.1022	1.5166	0.0427*
H42	0.9033	0.0406	1.4214	0.0427*
H43	0.8535	0.1217	1.3888	0.0427*
H91	1.6713	−0.1792	1.1874	0.0374*
H92	1.5774	−0.2300	1.0768	0.0374*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01705 (11)	0.0112 (1)	0.01274 (11)	0.00116 (7)	−0.00152 (7)	−0.00176 (7)
O2	0.0196 (4)	0.0143 (3)	0.0182 (4)	0.0004 (3)	−0.0027 (3)	0.0026 (3)
O1	0.0244 (4)	0.0174 (4)	0.0143 (4)	0.0021 (3)	−0.0012 (3)	0.0023 (3)
N2	0.0166 (4)	0.0146 (4)	0.0177 (4)	0.0008 (3)	−0.0009 (3)	0.0006 (3)
N1	0.0181 (4)	0.0160 (4)	0.0156 (4)	0.0008 (3)	−0.0005 (3)	−0.0001 (3)
C11	0.0192 (5)	0.0190 (5)	0.0196 (5)	−0.0007 (4)	0.0022 (4)	0.0056 (4)
C7	0.0201 (5)	0.0208 (5)	0.0187 (5)	−0.0022 (4)	0.0004 (4)	0.0057 (4)
C3	0.0290 (6)	0.0218 (5)	0.0168 (5)	−0.0017 (4)	−0.0011 (4)	−0.0048 (4)
C5	0.0231 (5)	0.0147 (5)	0.0242 (6)	0.0024 (4)	0.0021 (4)	−0.0053 (4)
C10	0.0229 (6)	0.0200 (5)	0.0298 (6)	0.0041 (4)	0.0040 (5)	0.0074 (5)
C2	0.0161 (5)	0.0156 (5)	0.0194 (5)	0.0003 (4)	0.0023 (4)	−0.0022 (4)
C1	0.0174 (5)	0.0183 (5)	0.0171 (5)	−0.0000 (4)	0.0011 (4)	−0.0028 (4)
C12	0.0280 (6)	0.0291 (6)	0.0216 (6)	−0.0037 (5)	−0.0048 (5)	0.0092 (5)
C14	0.0235 (6)	0.0282 (6)	0.0252 (6)	−0.0097 (5)	−0.0025 (5)	0.0076 (5)
C6	0.0279 (6)	0.0202 (6)	0.0547 (9)	−0.0049 (5)	0.0059 (6)	−0.0039 (6)
C13	0.0271 (6)	0.0356 (7)	0.0297 (7)	−0.0095 (5)	−0.0093 (5)	0.0095 (5)
B1	0.0171 (5)	0.0159 (5)	0.0169 (5)	−0.0007 (4)	−0.0007 (4)	0.0006 (4)
C8	0.0224 (5)	0.0298 (6)	0.0260 (6)	−0.0003 (5)	0.0086 (5)	0.0035 (5)
C4	0.0428 (8)	0.0413 (8)	0.0221 (6)	−0.0070 (6)	0.0098 (6)	−0.0042 (5)
C9	0.0240 (6)	0.0296 (6)	0.0380 (7)	0.0049 (5)	0.0097 (5)	0.0059 (5)

Geometric parameters (Å, º) top

Ni1—N2	1.8576 (9)	C5—H51	1.004
Ni1—N2ⁱ	1.8576 (9)	C5—H52	1.005
Ni1—N1	1.864 (1)	C10—C9	1.5377 (17)
Ni1—N1ⁱ	1.864 (1)	C10—H101	1.006
O1—N1	1.3540 (12)	C10—H102	1.005
O1—B1	1.5357 (14)	C12—C13	1.5380 (18)
O2—N2	1.3508 (12)	C12—H121	1.006
O2—B1ⁱ	1.5367 (14)	C12—H122	1.008
N1—C1	1.2984 (15)	C14—C13	1.5408 (18)
N2—C2	1.2956 (15)	C14—H141	1.000
C1—C2	1.4740 (15)	C14—H142	1.007
C11—C10	1.5418 (16)	C6—H61	0.999
C11—C12	1.5417 (17)	C6—H62	1.003
C11—B1	1.5957 (16)	C6—H63	1.007
C11—H111	1.004	C13—H131	1.004
C7—C14	1.5426 (17)	C13—H132	1.007
C7—B1	1.6053 (16)	C8—C9	1.5445 (18)
C7—C8	1.5445 (17)	C8—H81	1.007
C7—H71	1.008	C8—H82	1.007
C3—C1	1.4929 (15)	C4—H41	0.995
C3—C4	1.5282 (18)	C4—H42	1.004
C3—H31	1.007	C4—H43	1.012
C3—H32	1.003	C9—H91	1.005
C5—C2	1.4968 (15)	C9—H92	1.004
C5—C6	1.5247 (17)

Ni1—N1—O1	124.50 (7)	N1—C1—C3	123.4 (1)
Ni1—N1—C1	116.26 (8)	C3—C1—C2	124.3 (1)
Ni1—N2—O2	124.72 (7)	C11—C12—C13	115.3 (1)
Ni1—N2—C2	116.41 (8)	C11—C12—H121	108.098
O1—N1—C1	118.99 (9)	C13—C12—H121	108.607
O2—N2—C2	118.76 (9)	C11—C12—H122	108.252
O2ⁱ—B1—O1	107.68 (9)	C13—C12—H122	108.126
N1—Ni1—N1ⁱ	179.994	H121—C12—H122	108.292
N1—O1—B1	113.41 (8)	C7—C14—C13	114.4 (1)
N1—C1—C2	112.1 (1)	C7—C14—H141	108.417
N2—Ni1—N2ⁱ	179.994	C13—C14—H141	108.845
N2—Ni1—N1	82.71 (4)	C7—C14—H142	108.249
N2ⁱ—Ni1—N1	97.29 (4)	C13—C14—H142	107.911
N2—Ni1—N1ⁱ	97.29 (4)	H141—C14—H142	108.862
N2ⁱ—Ni1—N1ⁱ	82.71 (4)	C5—C6—H61	110.495
N2—O2—B1ⁱ	113.43 (8)	C5—C6—H62	109.762
N2—C2—C1	112.46 (9)	H61—C6—H62	109.357
C10—C11—C12	114.4 (1)	C5—C6—H63	109.531
C10—C11—B1	107.63 (9)	H61—C6—H63	109.004
C12—C11—B1	109.13 (9)	H62—C6—H63	108.660
C10—C11—H111	107.734	C12—C13—C14	114.5 (1)
C12—C11—H111	105.851	C12—C13—H131	108.980
B1—C11—H111	112.211	C14—C13—H131	108.497
C14—C7—B1	108.66 (9)	C12—C13—H132	108.306
C14—C7—C8	114.0 (1)	C14—C13—H132	107.887
B1—C7—C8	108.45 (9)	H131—C13—H132	108.575
C14—C7—H71	106.767	O2ⁱ—B1—C11	107.43 (9)
B1—C7—H71	111.955	O1—B1—C11	108.39 (9)
C8—C7—H71	107.048	O2ⁱ—B1—C7	112.11 (9)
C1—C3—C4	110.8 (1)	O1—B1—C7	112.60 (9)
C1—C3—H31	109.364	C11—B1—C7	108.45 (9)
C4—C3—H31	108.999	C7—C8—C9	115.3 (1)
C1—C3—H32	109.494	C7—C8—H81	108.159
C4—C3—H32	109.543	C9—C8—H81	108.374
H31—C3—H32	108.623	C7—C8—H82	108.425
C2—C5—C6	111.5 (1)	C9—C8—H82	108.055
C2—C5—H51	109.337	H81—C8—H82	108.355
C6—C5—H51	108.920	C3—C4—H41	110.841
C2—C5—H52	109.322	C3—C4—H42	109.913
C6—C5—H52	109.045	H41—C4—H42	109.608
H51—C5—H52	108.705	C3—C4—H43	109.277
C11—C10—C9	115.1 (1)	H41—C4—H43	108.945
C11—C10—H101	108.254	H42—C4—H43	108.206
C9—C10—H101	108.312	C10—C9—C8	115.0 (1)
C11—C10—H102	108.423	C10—C9—H91	108.109
C9—C10—H102	108.063	C8—C9—H91	107.878
H101—C10—H102	108.552	C10—C9—H92	108.568
N2—C2—C5	123.3 (1)	C8—C9—H92	108.372
C5—C2—C1	124.2 (1)	H91—C9—H92	108.743

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Ni(C₂₈H₄₈B₂N₄O₄)]
M_r	585.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.4047 (1), 19.2467 (2), 10.5508 (2)
β (°)	94.7398 (5)
V (Å³)	1498.52 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.87, 0.87
No. of measured, independent and observed [I > 3σ(I)] reflections	3497, 3386, 2934
R_int	0.03
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.031, 1.04
No. of reflections	2934
No. of parameters	178
No. of restraints	?
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28

Computer programs: COLLECT (Nonius, 1997-2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 2001), CAMERON (Watkin et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top

Ni1—N2	1.8576 (9)	O2—N2	1.3508 (12)
Ni1—N2ⁱ	1.8576 (9)	O2—B1ⁱ	1.5367 (14)
Ni1—N1	1.864 (1)	N1—C1	1.2984 (15)
Ni1—N1ⁱ	1.864 (1)	N2—C2	1.2956 (15)
O1—N1	1.3540 (12)	C1—C2	1.4740 (15)
O1—B1	1.5357 (14)

Ni1—N1—O1	124.50 (7)	N1—C1—C2	112.1 (1)
Ni1—N1—C1	116.26 (8)	N2—Ni1—N2ⁱ	179.994
Ni1—N2—O2	124.72 (7)	N2—Ni1—N1	82.71 (4)
Ni1—N2—C2	116.41 (8)	N2ⁱ—Ni1—N1	97.29 (4)
O1—N1—C1	118.99 (9)	N2—Ni1—N1ⁱ	97.29 (4)
O2—N2—C2	118.76 (9)	N2ⁱ—Ni1—N1ⁱ	82.71 (4)
O2ⁱ—B1—O1	107.68 (9)	N2—O2—B1ⁱ	113.43 (8)
N1—Ni1—N1ⁱ	179.994	N2—C2—C1	112.46 (9)
N1—O1—B1	113.41 (8)