Two atropisomers of tri­carbonyl­[η6-7-chloro-3-(3-chloro-2-methyl­phenyl)-2,4,8-tri­methyl-1,2,3,4-tetra­hydro-2,4-dibora-1,3-di­aza­naphthalene]­chromium(0)

Abouhamza, B.; Ait Ali, M.; Allaoud, S.; Blacque, O.; Frange, B.; Karim, A.

doi:10.1107/S0108270101006187

Two atropisomers of tricarbonyl[η⁶-7-chloro-3-(3-chloro-2-methylphenyl)-2,4,8-trimethyl-1,2,3,4-tetrahydro-2,4-dibora-1,3-diazanaphthalene]chromium(0)

B. Abouhamza, M. Ait Ali, S. Allaoud, O. Blacque, B. Frange and A. Karim

The structures of two atropisomers of the title compound, [Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃], are reported. For both compounds, the Cr(CO)₃ moiety is bound to the C₆ aromatic ring of the molecule; the existence of atropisomers resulting from the non-equivalence of both faces of the C₆ aromatic ring is a consequence of the 3-chloro-2-methylphenyl ring being nearly perpendicular to the mean plane of the 2,4-dibora-1,3-diazanaphthalene ring. The orientation of the Cr(CO)₃ tripod relative to the C₆ aromatic ring is such that it is nearly eclipsed in one isomer (2.4° rotation from being eclipsed with C—N, C—Cl and C—H) and slightly twisted (16.2°) from an eclipsed conformation in the other.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101006187/fg1625sup1.cif Contains datablocks global, I, II
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006187/fg1625Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006187/fg1625IIsup3.hkl Contains datablock II

CCDC references: 169924; 169925

Comment top

A large number of polycyclic-arenetricarbonylchromium complexes have been reported to date (Bruce 1982; Solladié-Cavallo 1989; Blake et al.. 1995). These compounds have been greatly studied in part because the Cr(CO)₃ unit alters the reactivity of substituted arenes in ways that depend on the stereochemistry of the complexes. Complexes of a natural sesquiterpene series occur with high regio- and stereoselectivity (El Firdoussi et al., 1997; Abouhamza et al.. 1999). The present work follows related research by our group on organometallic compounds of aromatic terpene hydrocarbons (Ait Ali et al., 2000). The title compounds are members of this series of complexes and the crystal structures of both isomers, (I) and (II), were determined to obtain the ligand arrangement around the metal center and to ascertain the stereochemistry. \sch

Views of the two molecules are shown in Figs. 1 and 2. A first comparison of these structures with the parent ligand, i.e. 7-chloro-3-(3'chloro-2'methylphenyl)-2,4,8-trimethyl-1,2,3,4-tetrahydro- 2,4-dibora-1,3-diazanaphthalene whose structure was previously reported (Allaoud et al., 1994) is of interest. Thus, the two expected atropisomers were indeed observed: compound (I) where the Cr(CO)₃ moiety together with the chlorine and methyl substituents on the phenyl ring are on the same side of the diboradiazanaphthalene mean plane (cis compound) and compound (II) where they are on the opposite side of the same plane (trans compound). The angles measured between the planes of the diboradiazanaphthalene and phenyl ring planes are 77.22 (5)° for compound (I) and 84.33 (6)° for compound (II); the corresponding value in the parent uncomplexed compound is 84.2°.

The presence of the Cr(CO)₃ group mainly induces a systematic lengthening of the C—C bonds of the attached C₆ aromatic ring compared with the parent ligand: mean values of +0.026 Å and +0.024 Å are observed for compounds (I) and (I), respectively. For comparison dimensions of the adjacent heteroatomic ring C8,C9,N1,B2,N2,B1 only differs by +0.007 Å for (I) and +0.011 Å for (II) from those of the parent molecule. For both isomers, the Cr—C(ring) bond lengths fall in the range 2.178 (2) to 2.308 (2) Å. For compound 1, the C1—Cr—Cg—C9, C2—Cr—Cg—C7 and C3—Cr—Cg—C5 torsion angles are 16.0, 17.0 and 15.6°, respectively (Cg is the aromatic C₆ ring centroid), while for compound (II), the corresponding values (1.5, 1.8 and 3.9°) are indicative of a nearly eclipsed conformation as already observed with disubstituted benzene containing electron-donating substituents (Mutterties et al., 1982).

Few structural data are found where B—N heterocyclic arenes are bound to Cr(CO)₃ with the exception of the parent borazine ring. Thus in the hexaethylborazine-Cr(CO)₃, the B₃N₃ borazine ring is puckered in a chair form such that all three Cr—N distances are shorter than the three Cr—B bonds (Huttner & Kreig, 1972). Every time a 6π-electron boron nitrogen heterocycle is fused to a benzene ring, the Cr(CO)₃ moiety prefers attachment to the benzene part of the molecule.

Experimental top

All reactions were carried out under dry argon using Schlenk techniques. The reaction of Cr(CO)₆ (2.18 mmol) with the relevant ligand (1.51 mmol) produced a mixture of both isomers in 29% yield (Allaoud et al., 1994) which was chromatographed on a silica column with a diethyl ether-hexane mixture (25/75) to yield a first fraction of pure compound (I) (m.p. 453–455 K) and a second fraction of compound 2 (m.p. 449–451 K). Each isomer was characterized by its ¹H and ¹³C NMR spectrum; the attribution of the correct configuration was in complete agreement with those deduced from solvent effects in our previous study. Crystals were grown from a diethyl ether-hexane mixture (1:1).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.
	Fig. 2. The molecular structure of (II) showing 50% probability displacement ellipsoids.

(I) η⁶-benzo-{2,4-Dimethyl-3-phenyl-[2'-methyl-3'-chloro]-7-chloro- 8-methyl-2,4-dibora-1,3-diazaronaphthalene}chromium Tricarbonyl top

Crystal data top

[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]	Z = 2
M_r = 466.87	F(000) = 476
Triclinic, P1	D_x = 1.509 Mg m⁻³
a = 6.750 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.839 (1) Å	Cell parameters from 12140 reflections
c = 14.858 (1) Å	θ = 1.0–27.5°
α = 80.537 (2)°	µ = 0.84 mm⁻¹
β = 88.717 (1)°	T = 110 K
γ = 73.409 (2)°	Prism, yellow
V = 1027.3 (1) Å³	0.20 × 0.10 × 0.07 mm

Data collection top

Nonius KappaCCD diffractometer	1834 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.100
Graphite monochromator	θ_max = 27.5°, θ_min = 2.2°
ω scans	h = 0→8
12140 measured reflections	k = −12→14
4611 independent reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.010P)²] where P = (F_o² + 2F_c²)/3
3590 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]	γ = 73.409 (2)°
M_r = 466.87	V = 1027.3 (1) Å³
Triclinic, P1	Z = 2
a = 6.750 (1) Å	Mo Kα radiation
b = 10.839 (1) Å	µ = 0.84 mm⁻¹
c = 14.858 (1) Å	T = 110 K
α = 80.537 (2)°	0.20 × 0.10 × 0.07 mm
β = 88.717 (1)°

Data collection top

Nonius KappaCCD diffractometer	1834 reflections with I > 2σ(I)
12140 measured reflections	R_int = 0.100
4611 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 0.82	Δρ_max = 0.26 e Å⁻³
3590 reflections	Δρ_min = −0.28 e Å⁻³
266 parameters

Special details top

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.

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.

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

	x	y	z	U_iso*/U_eq
Cr	0.19443 (5)	0.77226 (3)	0.80295 (2)	0.01325 (12)
Cl1	0.25571 (8)	1.03245 (5)	0.90972 (4)	0.02377 (15)
Cl2	0.69033 (10)	0.04950 (5)	0.61866 (4)	0.03138 (16)
O1	0.1681 (2)	0.53207 (14)	0.92740 (10)	0.0266 (4)
O2	−0.0511 (2)	0.71298 (15)	0.65823 (9)	0.0243 (4)
O3	−0.2007 (3)	0.93433 (17)	0.87190 (10)	0.0314 (4)
N1	0.6726 (3)	0.56855 (16)	0.86375 (10)	0.0157 (4)
H1	0.7022	0.5544	0.9212	0.020*
N2	0.6974 (2)	0.48464 (15)	0.71954 (10)	0.0148 (4)
B1	0.5712 (3)	0.6061 (2)	0.67439 (14)	0.0147 (5)
B2	0.7581 (4)	0.4640 (2)	0.81548 (16)	0.0164 (5)
C1	0.1744 (3)	0.62473 (19)	0.87814 (13)	0.0171 (4)
C2	0.0410 (3)	0.7362 (2)	0.71372 (13)	0.0186 (4)
C3	−0.0476 (3)	0.8697 (2)	0.84611 (13)	0.0180 (4)
C4	0.4611 (3)	0.78523 (18)	0.88672 (13)	0.0137 (4)
C5	0.3478 (3)	0.90996 (19)	0.84507 (12)	0.0157 (4)
C6	0.3046 (3)	0.94381 (18)	0.74964 (13)	0.0167 (4)
H6	0.2309	1.0281	0.7236	0.022*
C7	0.3776 (3)	0.84505 (19)	0.69576 (13)	0.0161 (4)
H7	0.3448	0.8646	0.6336	0.021*
C8	0.4983 (3)	0.71770 (18)	0.73241 (13)	0.0142 (4)
C9	0.5473 (3)	0.69042 (19)	0.82821 (14)	0.0172 (4)
C10	0.5095 (3)	0.74995 (19)	0.98767 (13)	0.0209 (5)
H10A	0.4146	0.8120	1.0189	0.027*
H10B	0.6483	0.7512	0.9992	0.027*
H10C	0.4966	0.6642	1.0093	0.027*
C11	0.4991 (3)	0.6315 (2)	0.57045 (12)	0.0212 (5)
H11A	0.3614	0.6239	0.5666	0.028*
H11B	0.5914	0.5684	0.5391	0.028*
H11C	0.5008	0.7177	0.5427	0.028*
C12	0.9143 (3)	0.33451 (19)	0.86375 (14)	0.0215 (5)
H12A	0.9272	0.3382	0.9274	0.028*
H12B	1.0469	0.3242	0.8363	0.028*
H12C	0.8647	0.2618	0.8571	0.028*
C13	0.7847 (3)	0.38031 (19)	0.66941 (13)	0.0190 (5)
C14	0.6992 (3)	0.27649 (19)	0.67270 (13)	0.0172 (4)
C15	0.7943 (3)	0.18019 (19)	0.62130 (14)	0.0193 (4)
C16	0.9638 (3)	0.18359 (19)	0.56824 (12)	0.0215 (5)
H16	1.0212	0.1177	0.5343	0.028*
C17	1.0468 (4)	0.2876 (2)	0.56650 (14)	0.0253 (5)
H17	1.1616	0.2913	0.5316	0.033*
C18	0.9595 (3)	0.3844 (2)	0.61616 (14)	0.0197 (4)
H18	1.0159	0.4535	0.6148	0.026*
C19	0.5130 (3)	0.2695 (2)	0.72888 (14)	0.0254 (5)
H19A	0.5535	0.2000	0.7799	0.033*
H19B	0.4111	0.2533	0.6919	0.033*
H19C	0.4556	0.3507	0.7506	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr	0.01176 (19)	0.01269 (19)	0.01488 (19)	−0.00304 (13)	−0.00139 (13)	−0.00167 (13)
Cl1	0.0246 (3)	0.0154 (3)	0.0307 (3)	−0.0003 (2)	−0.0029 (2)	−0.0111 (2)
Cl2	0.0426 (4)	0.0196 (3)	0.0359 (3)	−0.0131 (3)	−0.0026 (3)	−0.0080 (2)
O1	0.0304 (10)	0.0231 (8)	0.0257 (8)	−0.0133 (7)	−0.0036 (6)	0.0082 (7)
O2	0.0222 (9)	0.0361 (10)	0.0192 (8)	−0.0128 (7)	−0.0024 (6)	−0.0089 (7)
O3	0.0217 (9)	0.0430 (10)	0.0335 (9)	−0.0084 (8)	0.0070 (7)	−0.0203 (8)
N1	0.0192 (10)	0.0124 (8)	0.0118 (8)	0.0034 (7)	−0.0039 (6)	−0.0047 (6)
N2	0.0136 (9)	0.0147 (8)	0.0191 (9)	−0.0065 (6)	0.0069 (7)	−0.0075 (7)
B1	0.0067 (12)	0.0247 (13)	0.0138 (11)	−0.0081 (10)	−0.0010 (9)	0.0003 (9)
B2	0.0124 (12)	0.0166 (12)	0.0194 (12)	−0.0028 (9)	−0.0009 (9)	−0.0030 (8)
C1	0.0111 (10)	0.0217 (11)	0.0186 (10)	−0.0039 (8)	−0.0029 (7)	−0.0049 (9)
C2	0.0158 (11)	0.0183 (12)	0.0205 (12)	−0.0063 (8)	0.0036 (9)	0.0024 (9)
C3	0.0177 (12)	0.0271 (11)	0.0129 (10)	−0.0123 (9)	0.0003 (8)	−0.0034 (8)
C4	0.0130 (10)	0.0134 (10)	0.0156 (10)	−0.0065 (8)	−0.0004 (7)	−0.0003 (8)
C5	0.0176 (11)	0.0153 (10)	0.0177 (10)	−0.0088 (8)	−0.0010 (8)	−0.0049 (8)
C6	0.0123 (10)	0.0092 (9)	0.0260 (11)	−0.0023 (8)	−0.0028 (8)	0.0036 (8)
C7	0.0164 (11)	0.0161 (10)	0.0153 (10)	−0.0071 (8)	0.0008 (8)	0.0031 (8)
C8	0.0108 (11)	0.0157 (10)	0.0166 (10)	−0.0049 (8)	0.0013 (7)	−0.0019 (7)
C9	0.0140 (11)	0.0112 (9)	0.0260 (11)	−0.0043 (8)	−0.0027 (8)	−0.0001 (8)
C10	0.0184 (12)	0.0180 (11)	0.0257 (11)	−0.0012 (9)	−0.0034 (9)	−0.0082 (8)
C11	0.0174 (11)	0.0269 (12)	0.0195 (11)	−0.0054 (9)	0.0030 (8)	−0.0063 (8)
C12	0.0185 (12)	0.0191 (11)	0.0254 (11)	−0.0021 (9)	0.0006 (8)	−0.0052 (8)
C13	0.0179 (12)	0.0167 (11)	0.0191 (11)	0.0005 (9)	−0.0051 (8)	−0.0019 (8)
C14	0.0168 (11)	0.0188 (10)	0.0159 (10)	−0.0044 (8)	−0.0002 (7)	−0.0042 (8)
C15	0.0203 (12)	0.0118 (9)	0.0256 (11)	−0.0042 (9)	−0.0063 (8)	−0.0025 (8)
C16	0.0206 (12)	0.0188 (11)	0.0211 (11)	0.0012 (9)	−0.0012 (9)	−0.0035 (8)
C17	0.0226 (12)	0.0262 (13)	0.0264 (11)	−0.0056 (9)	0.0025 (9)	−0.0050 (9)
C18	0.0129 (11)	0.0221 (11)	0.0253 (11)	−0.0082 (9)	0.0044 (8)	−0.0020 (9)
C19	0.0258 (12)	0.0281 (12)	0.0259 (11)	−0.0100 (10)	0.0078 (9)	−0.0122 (9)

Geometric parameters (Å, º) top

Cr—Cg	1.732	C6—C7	1.412 (3)
Cr—C1	1.831 (1)	C6—H6	0.9300
Cr—C2	1.856 (2)	C7—C8	1.413 (3)
Cr—C3	1.840 (2)	C7—H7	0.9300
Cr—C4	2.261 (2)	C8—C9	1.432 (3)
Cr—C5	2.216 (2)	C10—H10A	0.9600
Cr—C6	2.218 (2)	C10—H10B	0.9600
Cr—C7	2.178 (2)	C10—H10C	0.9600
Cr—C8	2.252 (2)	C11—H11A	0.9600
Cr—C9	2.308 (2)	C11—H11B	0.9600
Cl1—C5	1.730 (2)	C11—H11C	0.9600
Cl2—C15	1.757 (2)	C12—H12A	0.9600
O1—C1	1.152 (2)	C12—H12B	0.9600
O2—C2	1.145 (2)	C12—H12C	0.9600
O3—C3	1.168 (3)	C13—C14	1.398 (3)
N1—C9	1.375 (3)	C13—C18	1.413 (3)
N1—B2	1.417 (3)	C14—C15	1.394 (3)
N1—H1	0.8600	C14—C19	1.506 (3)
N2—B1	1.416 (3)	C15—C16	1.380 (3)
N2—B2	1.456 (3)	C16—C17	1.391 (3)
N2—C13	1.434 (2)	C16—H16	0.9300
B1—C8	1.559 (3)	C17—C18	1.369 (3)
B1—C11	1.586 (3)	C17—H17	0.9300
B2—C12	1.566 (3)	C18—H18	0.9300
C4—C5	1.397 (3)	C19—H19A	0.9600
C4—C9	1.442 (3)	C19—H19B	0.9600
C4—C10	1.505 (3)	C19—H19C	0.9600
C5—C6	1.420 (3)

Cg—Cr—C1	122.9	C7—C6—C5	117.66 (17)
Cg—Cr—C2	127.5	C7—C6—Cr	69.75 (10)
Cg—Cr—C3	125.7	C5—C6—Cr	71.25 (10)
C1—Cr—C2	89.55 (8)	C7—C6—H6	121.2
C1—Cr—C3	91.09 (9)	C5—C6—H6	121.2
C2—Cr—C3	88.97 (9)	Cr—C6—H6	130.2
C1—Cr—C7	143.45 (9)	C6—C7—C8	122.68 (17)
C3—Cr—C7	125.38 (9)	C6—C7—Cr	72.80 (12)
C2—Cr—C7	88.83 (7)	C8—C7—Cr	74.27 (10)
C1—Cr—C5	123.25 (7)	C6—C7—H7	118.7
C3—Cr—C5	87.74 (8)	C8—C7—H7	118.7
C2—Cr—C5	147.08 (8)	Cr—C7—H7	126.2
C7—Cr—C5	66.93 (7)	C7—C8—C9	117.51 (18)
C1—Cr—C6	159.35 (7)	C7—C8—B1	123.08 (17)
C3—Cr—C6	94.27 (8)	C9—C8—B1	119.36 (17)
C2—Cr—C6	110.44 (7)	C7—C8—Cr	68.58 (11)
C7—Cr—C6	37.45 (7)	C9—C8—Cr	73.84 (12)
C5—Cr—C6	37.36 (7)	B1—C8—Cr	126.26 (13)
C1—Cr—C8	106.85 (8)	N1—C9—C8	117.92 (18)
C3—Cr—C8	161.51 (8)	N1—C9—C4	120.71 (18)
C2—Cr—C8	95.47 (8)	C8—C9—C4	121.32 (18)
C7—Cr—C8	37.15 (7)	N1—C9—Cr	132.61 (14)
C5—Cr—C8	78.78 (7)	C8—C9—Cr	69.59 (12)
C6—Cr—C8	67.35 (7)	C4—C9—Cr	69.83 (11)
C1—Cr—C4	92.29 (7)	C4—C10—H10A	109.5
C3—Cr—C4	108.28 (8)	C4—C10—H10B	109.5
C2—Cr—C4	162.60 (8)	H10A—C10—H10B	109.5
C7—Cr—C4	79.43 (7)	C4—C10—H10C	109.5
C5—Cr—C4	36.35 (7)	H10A—C10—H10C	109.5
C6—Cr—C4	67.10 (7)	H10B—C10—H10C	109.5
C8—Cr—C4	67.45 (7)	B1—C11—H11A	109.5
C1—Cr—C9	86.49 (8)	B1—C11—H11B	109.5
C3—Cr—C9	144.64 (8)	H11A—C11—H11B	109.5
C2—Cr—C9	126.23 (8)	B1—C11—H11C	109.5
C7—Cr—C9	65.59 (7)	H11A—C11—H11C	109.5
C5—Cr—C9	64.86 (7)	H11B—C11—H11C	109.5
C6—Cr—C9	77.64 (7)	B2—C12—H12A	109.5
C8—Cr—C9	36.57 (7)	B2—C12—H12B	109.5
C4—Cr—C9	36.79 (8)	H12A—C12—H12B	109.5
C9—N1—B2	126.75 (17)	B2—C12—H12C	109.5
C9—N1—H1	116.6	H12A—C12—H12C	109.5
B2—N1—H1	116.6	H12B—C12—H12C	109.5
B1—N2—C13	120.35 (15)	C14—C13—C18	120.33 (19)
B1—N2—B2	122.00 (16)	C14—C13—N2	120.98 (18)
C13—N2—B2	117.44 (16)	C18—C13—N2	118.69 (16)
N2—B1—C8	116.88 (16)	C15—C14—C13	116.72 (19)
N2—B1—C11	123.38 (19)	C15—C14—C19	121.76 (18)
C8—B1—C11	119.73 (18)	C13—C14—C19	121.52 (19)
N1—B2—N2	116.76 (18)	C16—C15—C14	123.57 (18)
N1—B2—C12	120.80 (18)	C16—C15—Cl2	116.95 (16)
N2—B2—C12	122.42 (18)	C14—C15—Cl2	119.43 (16)
O1—C1—Cr	177.37 (16)	C15—C16—C17	118.63 (19)
O2—C2—Cr	179.0 (2)	C15—C16—H16	120.7
O3—C3—Cr	178.2 (2)	C17—C16—H16	120.7
C5—C4—C9	117.47 (17)	C18—C17—C16	120.0 (2)
C5—C4—C10	122.95 (17)	C18—C17—H17	120.0
C9—C4—C10	119.40 (17)	C16—C17—H17	120.0
C5—C4—Cr	70.07 (10)	C17—C18—C13	120.71 (19)
C9—C4—Cr	73.38 (11)	C17—C18—H18	119.6
C10—C4—Cr	131.27 (13)	C13—C18—H18	119.6
C4—C5—C6	122.97 (18)	C14—C19—H19A	109.5
C4—C5—Cl1	120.23 (14)	C14—C19—H19B	109.5
C6—C5—Cl1	116.79 (15)	H19A—C19—H19B	109.5
C4—C5—Cr	73.58 (10)	C14—C19—H19C	109.5
C6—C5—Cr	71.39 (10)	H19A—C19—H19C	109.5
Cl1—C5—Cr	129.78 (11)	H19B—C19—H19C	109.5

(II) η⁶-benzo-{2,4-Dimethyl-3-phenyl-[2'-methyl-3'-chloro]-7-chloro- 8-methyl-2,4-dibora-1,3-diazaronaphthalene}chromium Tricarbonyl top

Crystal data top

[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]	F(000) = 1904
M_r = 466.87	D_x = 1.471 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.666 (1) Å	Cell parameters from 19870 reflections
b = 7.0290 (3) Å	θ = 1.0–27.5°
c = 25.366 (1) Å	µ = 0.82 mm⁻¹
β = 112.907 (2)°	T = 110 K
V = 4215.3 (3) Å³	Prism, yellow
Z = 8	0.20 × 0.15 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	4105 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.140
Graphite monochromator	θ_max = 27.5°, θ_min = 1.7°
ω–scans	h = 0→33
19870 measured reflections	k = 0→9
4824 independent reflections	l = −32→30

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0306P)² + 8.1507P] where P = (F_o² + 2F_c²)/3
4824 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]	V = 4215.3 (3) Å³
M_r = 466.87	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.666 (1) Å	µ = 0.82 mm⁻¹
b = 7.0290 (3) Å	T = 110 K
c = 25.366 (1) Å	0.20 × 0.15 × 0.05 mm
β = 112.907 (2)°

Data collection top

Nonius KappaCCD diffractometer	4105 reflections with I > 2σ(I)
19870 measured reflections	R_int = 0.140
4824 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.05	Δρ_max = 0.67 e Å⁻³
4824 reflections	Δρ_min = −0.54 e Å⁻³
266 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Cr	0.15971 (1)	0.61763 (4)	0.54569 (1)	0.01566 (9)
Cl1	0.18305 (2)	0.49397 (7)	0.42016 (2)	0.02542 (12)
Cl2	0.12059 (3)	−0.13299 (9)	0.82257 (2)	0.04168 (16)
O1	0.05435 (6)	0.7359 (2)	0.56081 (6)	0.0273 (3)
O2	0.23077 (6)	0.8791 (2)	0.64016 (6)	0.0324 (4)
O3	0.14402 (6)	0.9424 (2)	0.46444 (6)	0.0274 (3)
N1	0.07183 (6)	0.2525 (2)	0.53916 (7)	0.0190 (3)
H1	0.0440	0.2309	0.5072	0.025*
N2	0.10905 (7)	0.2546 (2)	0.64409 (7)	0.0203 (3)
B1	0.16408 (9)	0.3097 (3)	0.64727 (10)	0.0221 (4)
B2	0.06273 (9)	0.2176 (3)	0.59043 (9)	0.0196 (4)
C1	0.09554 (8)	0.6936 (3)	0.55508 (8)	0.0201 (4)
C2	0.20347 (8)	0.7779 (3)	0.60418 (8)	0.0228 (4)
C3	0.15051 (8)	0.8173 (3)	0.49589 (8)	0.0198 (4)
C4	0.12308 (8)	0.3752 (2)	0.48286 (8)	0.0172 (4)
C5	0.17631 (8)	0.4314 (3)	0.48353 (8)	0.0198 (4)
C6	0.22573 (8)	0.4365 (3)	0.53374 (9)	0.0222 (4)
H6	0.2603	0.4688	0.5324	0.029*
C7	0.22181 (8)	0.3920 (3)	0.58578 (9)	0.0214 (4)
H7	0.2541	0.4000	0.6193	0.028*
C8	0.16988 (8)	0.3347 (3)	0.58902 (8)	0.0192 (4)
C9	0.12162 (8)	0.3179 (3)	0.53634 (8)	0.0171 (4)
C10	0.07113 (8)	0.3631 (3)	0.42835 (8)	0.0213 (4)
H10A	0.0758	0.4432	0.3998	0.028*
H10B	0.0388	0.4044	0.4354	0.028*
H10C	0.0657	0.2339	0.4150	0.028*
C11	0.21547 (9)	0.3445 (3)	0.70527 (9)	0.0323 (5)
H11A	0.2033	0.3323	0.7364	0.042*
H11B	0.2302	0.4701	0.7054	0.042*
H11C	0.2445	0.2524	0.7096	0.042*
C12	0.00362 (8)	0.1457 (3)	0.58697 (9)	0.0227 (4)
H12A	−0.0159	0.2479	0.5967	0.029*
H12B	0.0089	0.0425	0.6133	0.029*
H12C	−0.0184	0.1028	0.5488	0.029*
C13	0.09947 (8)	0.2404 (3)	0.69667 (8)	0.0229 (4)
C14	0.11202 (8)	0.0696 (3)	0.72774 (8)	0.0229 (4)
C15	0.10410 (9)	0.0701 (3)	0.77931 (9)	0.0293 (5)
C16	0.08446 (11)	0.2264 (4)	0.79902 (10)	0.0379 (6)
H16	0.0799	0.2211	0.8336	0.049*
C17	0.07171 (12)	0.3900 (4)	0.76680 (11)	0.0427 (6)
H17	0.0582	0.4959	0.7794	0.056*
C18	0.07903 (11)	0.3972 (3)	0.71539 (10)	0.0342 (5)
H18	0.0702	0.5078	0.6935	0.045*
C19	0.13296 (9)	−0.0997 (3)	0.70590 (9)	0.0277 (4)
H19A	0.1050	−0.1372	0.6695	0.036*
H19B	0.1398	−0.2029	0.7326	0.036*
H19C	0.1675	−0.0674	0.7017	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr	0.01483 (15)	0.01615 (15)	0.01782 (16)	−0.00094 (11)	0.00833 (12)	0.00003 (11)
Cl1	0.0307 (3)	0.0275 (2)	0.0261 (3)	−0.0019 (2)	0.0198 (2)	−0.0009 (2)
Cl2	0.0513 (4)	0.0483 (4)	0.0257 (3)	−0.0093 (3)	0.0153 (3)	0.0114 (2)
O1	0.0197 (7)	0.0348 (8)	0.0307 (8)	0.0015 (6)	0.0135 (6)	−0.0044 (6)
O2	0.0321 (8)	0.0402 (9)	0.0258 (8)	−0.0135 (7)	0.0124 (7)	−0.0116 (7)
O3	0.0299 (8)	0.0223 (7)	0.0333 (8)	0.0020 (6)	0.0160 (7)	0.0080 (6)
N1	0.0167 (7)	0.0207 (8)	0.0187 (8)	−0.0033 (6)	0.0059 (6)	0.0013 (6)
N2	0.0229 (8)	0.0204 (8)	0.0187 (8)	−0.0035 (6)	0.0093 (7)	0.0015 (6)
B1	0.0235 (11)	0.0188 (10)	0.0228 (11)	−0.0011 (8)	0.0077 (9)	0.0036 (9)
B2	0.0210 (10)	0.0158 (10)	0.0228 (11)	−0.0002 (8)	0.0095 (9)	0.0016 (8)
C1	0.0225 (9)	0.0190 (9)	0.0180 (9)	−0.0039 (7)	0.0068 (7)	−0.0015 (7)
C2	0.0213 (9)	0.0276 (10)	0.0240 (10)	−0.0005 (8)	0.0136 (8)	0.0037 (9)
C3	0.0179 (9)	0.0208 (9)	0.0243 (10)	−0.0018 (7)	0.0121 (8)	−0.0043 (8)
C4	0.0194 (9)	0.0129 (8)	0.0209 (9)	0.0015 (7)	0.0097 (7)	0.0008 (7)
C5	0.0246 (9)	0.0160 (9)	0.0241 (10)	0.0015 (7)	0.0153 (8)	−0.0011 (7)
C6	0.0184 (9)	0.0199 (9)	0.0315 (11)	0.0022 (7)	0.0132 (8)	0.0005 (8)
C7	0.0161 (9)	0.0206 (9)	0.0258 (10)	0.0028 (7)	0.0062 (8)	0.0037 (8)
C8	0.0179 (9)	0.0164 (9)	0.0223 (10)	0.0004 (7)	0.0068 (7)	0.0035 (7)
C9	0.0179 (9)	0.0131 (8)	0.0218 (9)	−0.0001 (7)	0.0094 (7)	0.0000 (7)
C10	0.0233 (9)	0.0221 (10)	0.0190 (10)	−0.0024 (8)	0.0087 (8)	−0.0005 (8)
C11	0.0296 (11)	0.0396 (13)	0.0239 (11)	−0.0098 (10)	0.0061 (9)	0.0038 (9)
C12	0.0219 (9)	0.0230 (10)	0.0245 (10)	−0.0012 (8)	0.0106 (8)	0.0020 (8)
C13	0.0247 (9)	0.0255 (10)	0.0194 (10)	−0.0073 (8)	0.0095 (8)	−0.0027 (8)
C14	0.0217 (9)	0.0273 (10)	0.0187 (9)	−0.0074 (8)	0.0069 (8)	−0.0004 (8)
C15	0.0324 (11)	0.0346 (12)	0.0209 (10)	−0.0124 (9)	0.0104 (9)	0.0008 (9)
C16	0.0502 (14)	0.0446 (14)	0.0272 (12)	−0.0153 (12)	0.0242 (11)	−0.0103 (10)
C17	0.0613 (17)	0.0345 (13)	0.0454 (15)	−0.0078 (12)	0.0351 (13)	−0.0138 (11)
C18	0.0475 (14)	0.0248 (11)	0.0358 (13)	−0.0042 (10)	0.0221 (11)	−0.0013 (9)
C19	0.0317 (11)	0.0286 (11)	0.0226 (10)	0.0026 (9)	0.0105 (9)	0.0051 (8)

Geometric parameters (Å, º) top

Cr—Cg	1.738	C6—C7	1.398 (3)
Cr—C1	1.833 (2)	C6—H6	0.9300
Cr—C2	1.853 (2)	C7—C8	1.425 (3)
Cr—C3	1.841 (2)	C7—H7	0.9300
Cr—C4	2.272 (2)	C8—C9	1.430 (3)
Cr—C5	2.214 (2)	C10—H10A	0.9600
Cr—C6	2.232 (2)	C10—H10B	0.9600
Cr—C7	2.197 (2)	C10—H10C	0.9600
Cr—C8	2.238 (2)	C11—H11A	0.9600
Cr—C9	2.296 (2)	C11—H11B	0.9600
Cl1—C5	1.739 (2)	C11—H11C	0.9600
Cl2—C15	1.749 (2)	C12—H12A	0.9600
O1—C1	1.161 (2)	C12—H12B	0.9600
O2—C2	1.154 (2)	C12—H12C	0.9600
O3—C3	1.155 (2)	C13—C18	1.382 (3)
N1—C9	1.386 (2)	C13—C14	1.403 (3)
N1—B2	1.429 (3)	C14—C15	1.400 (3)
N1—H1	0.8600	C14—C19	1.498 (3)
N2—B1	1.436 (3)	C15—C16	1.381 (3)
N2—B2	1.440 (3)	C16—C17	1.374 (4)
N2—C13	1.451 (2)	C16—H16	0.9300
B1—C8	1.552 (3)	C17—C18	1.389 (3)
B1—C11	1.566 (3)	C17—H17	0.9300
B2—C12	1.569 (3)	C18—H18	0.9300
C4—C5	1.416 (3)	C19—H19A	0.9600
C4—C9	1.429 (2)	C19—H19B	0.9600
C4—C10	1.504 (3)	C19—H19C	0.9600
C5—C6	1.405 (3)

Cg—Cr—C1	122.6	C7—C6—C5	118.61 (17)
Cg—Cr—C2	127.6	C7—C6—Cr	70.25 (10)
Cg—Cr—C3	127.2	C5—C6—Cr	70.88 (10)
C1—Cr—C2	90.81 (8)	C7—C6—H6	120.7
C1—Cr—C3	89.16 (8)	C5—C6—H6	120.7
C2—Cr—C3	87.81 (8)	Cr—C6—H6	130.7
C1—Cr—C7	132.58 (8)	C6—C7—C8	122.04 (18)
C3—Cr—C7	138.08 (7)	C6—C7—Cr	72.98 (11)
C2—Cr—C7	87.94 (8)	C8—C7—Cr	72.81 (11)
C1—Cr—C5	134.13 (8)	C6—C7—H7	119.0
C3—Cr—C5	88.33 (8)	C8—C7—H7	119.0
C2—Cr—C5	134.82 (8)	Cr—C7—H7	127.4
C7—Cr—C5	66.23 (7)	C7—C8—C9	117.31 (17)
C1—Cr—C6	162.10 (8)	C7—C8—B1	121.71 (17)
C3—Cr—C6	104.07 (8)	C9—C8—B1	120.74 (16)
C2—Cr—C6	101.54 (8)	C7—C8—Cr	69.72 (10)
C7—Cr—C6	36.77 (7)	C9—C8—Cr	73.82 (10)
C5—Cr—C6	36.85 (7)	B1—C8—Cr	122.13 (13)
C1—Cr—C8	97.69 (8)	N1—C9—C4	120.53 (16)
C3—Cr—C8	166.86 (8)	N1—C9—C8	117.37 (16)
C2—Cr—C8	103.21 (8)	C4—C9—C8	122.02 (16)
C7—Cr—C8	37.46 (7)	N1—C9—Cr	131.56 (13)
C5—Cr—C8	78.84 (7)	C4—C9—Cr	70.85 (10)
C6—Cr—C8	67.06 (7)	C8—C9—Cr	69.43 (10)
C1—Cr—C4	99.33 (7)	C4—C10—H10A	109.5
C3—Cr—C4	100.54 (8)	C4—C10—H10B	109.5
C2—Cr—C4	166.89 (8)	H10A—C10—H10B	109.5
C7—Cr—C4	79.09 (7)	C4—C10—H10C	109.5
C5—Cr—C4	36.77 (7)	H10A—C10—H10C	109.5
C6—Cr—C4	66.78 (7)	H10B—C10—H10C	109.5
C8—Cr—C4	67.37 (7)	B1—C11—H11A	109.5
C1—Cr—C9	84.98 (7)	B1—C11—H11B	109.5
C3—Cr—C9	133.87 (8)	H11A—C11—H11B	109.5
C2—Cr—C9	137.86 (8)	B1—C11—H11C	109.5
C7—Cr—C9	65.69 (7)	H11A—C11—H11C	109.5
C5—Cr—C9	64.93 (6)	H11B—C11—H11C	109.5
C6—Cr—C9	77.16 (7)	B2—C12—H12A	109.5
C8—Cr—C9	36.75 (7)	B2—C12—H12B	109.5
C4—Cr—C9	36.47 (6)	H12A—C12—H12B	109.5
C9—N1—B2	125.77 (16)	B2—C12—H12C	109.5
C9—N1—H1	117.1	H12A—C12—H12C	109.5
B2—N1—H1	117.1	H12B—C12—H12C	109.5
B1—N2—B2	122.26 (16)	C18—C13—C14	121.62 (18)
B1—N2—C13	118.79 (16)	C18—C13—N2	118.94 (18)
B2—N2—C13	118.93 (15)	C14—C13—N2	119.43 (17)
N2—B1—C8	115.71 (18)	C15—C14—C13	115.98 (19)
N2—B1—C11	123.03 (18)	C15—C14—C19	123.43 (19)
C8—B1—C11	121.26 (18)	C13—C14—C19	120.58 (17)
N1—B2—N2	117.52 (17)	C16—C15—C14	123.1 (2)
N1—B2—C12	120.09 (18)	C16—C15—Cl2	117.08 (16)
N2—B2—C12	122.38 (17)	C14—C15—Cl2	119.79 (18)
O1—C1—Cr	177.92 (17)	C17—C16—C15	119.1 (2)
O2—C2—Cr	179.23 (17)	C17—C16—H16	120.5
O3—C3—Cr	179.16 (18)	C15—C16—H16	120.5
C5—C4—C9	116.68 (17)	C16—C17—C18	120.1 (2)
C5—C4—C10	122.20 (17)	C16—C17—H17	120.0
C9—C4—C10	121.00 (16)	C18—C17—H17	120.0
C5—C4—Cr	69.42 (10)	C13—C18—C17	120.1 (2)
C9—C4—Cr	72.68 (10)	C13—C18—H18	120.0
C10—C4—Cr	131.63 (13)	C17—C18—H18	120.0
C6—C5—C4	122.97 (17)	C14—C19—H19A	109.5
C6—C5—Cl1	116.87 (14)	C14—C19—H19B	109.5
C4—C5—Cl1	120.15 (15)	H19A—C19—H19B	109.5
C6—C5—Cr	72.28 (11)	C14—C19—H19C	109.5
C4—C5—Cr	73.81 (10)	H19A—C19—H19C	109.5
Cl1—C5—Cr	128.66 (10)	H19B—C19—H19C	109.5

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]	[Cr(C₁₆H₁₈B₂Cl₂N₂)(CO)₃]
M_r	466.87	466.87
Crystal system, space group	Triclinic, P1	Monoclinic, C2/c
Temperature (K)	110	110
a, b, c (Å)	6.750 (1), 10.839 (1), 14.858 (1)	25.666 (1), 7.0290 (3), 25.366 (1)
α, β, γ (°)	80.537 (2), 88.717 (1), 73.409 (2)	90, 112.907 (2), 90
V (Å³)	1027.3 (1)	4215.3 (3)
Z	2	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.84	0.82
Crystal size (mm)	0.20 × 0.10 × 0.07	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12140, 4611, 1834	19870, 4824, 4105
R_int	0.100	0.140
(sin θ/λ)_max (Å⁻¹)	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.076, 0.82	0.034, 0.087, 1.05
No. of reflections	3590	4824
No. of parameters	266	266
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28	0.67, −0.54

Computer programs: COLLECT (Nonius, 1998), COLLECT, DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) for (I) top

Cr—Cg	1.732	Cr—C7	2.178 (2)
Cr—C1	1.831 (1)	Cr—C8	2.252 (2)
Cr—C2	1.856 (2)	Cr—C9	2.308 (2)
Cr—C3	1.840 (2)	O1—C1	1.152 (2)
Cr—C4	2.261 (2)	O2—C2	1.145 (2)
Cr—C5	2.216 (2)	O3—C3	1.168 (3)
Cr—C6	2.218 (2)

Cg—Cr—C1	122.9	C1—Cr—C2	89.55 (8)
Cg—Cr—C2	127.5	C1—Cr—C3	91.09 (9)
Cg—Cr—C3	125.7	C2—Cr—C3	88.97 (9)

Selected geometric parameters (Å, º) for (II) top

Cr—Cg	1.738	Cr—C5	2.214 (2)
Cr—C1	1.833 (2)	Cr—C6	2.232 (2)
Cr—C2	1.853 (2)	Cr—C7	2.197 (2)
Cr—C3	1.841 (2)	Cr—C8	2.238 (2)
Cr—C4	2.272 (2)	Cr—C9	2.296 (2)

Cg—Cr—C1	122.6	C1—Cr—C2	90.81 (8)
Cg—Cr—C2	127.6	C1—Cr—C3	89.16 (8)
Cg—Cr—C3	127.2	C2—Cr—C3	87.81 (8)

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Two atropisomers of tri­carbonyl­[η6-7-chloro-3-(3-chloro-2-methyl­phenyl)-2,4,8-tri­methyl-1,2,3,4-tetra­hydro-2,4-dibora-1,3-di­aza­naphthalene]­chromium(0)

Supporting information

Two atropisomers of tricarbonyl[η⁶-7-chloro-3-(3-chloro-2-methylphenyl)-2,4,8-trimethyl-1,2,3,4-tetrahydro-2,4-dibora-1,3-diazanaphthalene]chromium(0)