(η2,η2-Cyclo­octa-1,5-diene)[2-(di­phenyl­phos­phanyl­meth­yl)pyridine-κ2N,P]rhodium(I) tetra­fluorido­borate 1,2-di­chloro­ethane monosolvate

Wei, S.; Möller, S.; Heller, D.; Drexler, H.-J.

doi:10.1107/S2414314616013183

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161318

doi:10.1107/S2414314616013183

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(η²,η²-Cycloocta-1,5-diene)[2-(diphenylphosphanylmethyl)pyridine-κ²N,P]rhodium(I) tetrafluoridoborate 1,2-dichloroethane monosolvate

Siping Wei,^a Saskia Möller,^a Detlef Heller ^a and Hans-Joachim Drexler ^a ^*

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
^*Correspondence e-mail: hans-joachim.drexler@catalysis.de

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 12 August 2016; accepted 16 August 2016; online 26 August 2016)

The title compound, [Rh(C₈H₁₂)(C₁₈H₁₆NP)]BF₄ has been prepared as a precatalyst for applications in rhodium-catalysed additions of carbocyclic acids to terminal alkynes leading to anti-Markovnikov Z-enol esters. Here the triclinic pseudopolymorph of the title compound is presented. In contrast to the earlier reported pseudopolymorph (orthorhombic space group) [Wei et al. (2013). Chem. Eur. J. 19, 12067–12076], the triclinic polymorph contains half a molecule of dichloromethane as solvent in the asymmetric unit. The rhodium(I) atom exhibits a square-planar coordination. The estimated diffraction contribution of the disordered solvent (a half molecule of dichloroethane per asymmetric unit) was subtracted from the observed diffraction data using the SQUEEZE [Spek (2015 ). Acta Cryst. C71, 9–16] routine in PLATON. The given chemical formula and other crystal data do not take the solvent into account.

Keywords: crystal structure; polymorph; rhodium complex.

CCDC reference: 1499364

Structure description

The title compound was formed by the exchange of aectylacetonate (acac) by dppmp in presence of HBF₄ starting from the precursor [Rh(acac)(COD)] (Fennis et al., 1990 ; Wei et al., 2013 ). Two pseudo-polymorphs (triclinic, space group P $[\overline{1}]$ with dichloromethane as solvent; orthorhombic, space group Pbca, no solvent) of the title compound were observed, of which the triclinic one is presented here (Fig. 1).

Figure 1
The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity.

The main difference to the earlier reported pseudo polymorph (Wei et al., 2013; CCDC 914750) is the half molecule of a disordered 1,2-dichloroethane solvate. On the other hand, there are only minor differences in the conformation of the complex cations (Figs. 2 and 3) and the bond lengths and angles are nearly equal (Table 1). An important structural feature is the square-planar coordination of the rhodium(I) atom. The dihedral angles between the P/Rh/N and X/Rh/X (X = centroid of the double bond) planes are 4.7° (triclinic polymorph) and 2.8° (pseudo polymorph). The r.m.s. deviation of P/N/X/X to this plane is in both cases very small (0.0333 and 0.0474 Å, respectively).

Table 1
Selected distances and angles (Å, °) of the two polymorphs of [Rh(COD)(dppmp)]BF₄

C_M are the centroids of the COD double bonds.

	Triclinic polymorph	Orthorhombic pseudopolymorph
Rh—P	2.2371 (4)	2.2491 (5)
Rh—N	2.1295 (14)	2.1333 (17)
Rh—C_M	2.019 (2), 2.140 (2)	2.119 (2), 2.140 (2)
P—Rh—N	80.58 (4)	80.81 (5)
C_M—Rh—C_M	86.48 (7)	86.47 (8)

Figure 2
Front view (left) and side view (right) of triclinic polymorph of [Rh(COD)(dppmp)]⁺ (ellipsoids drawn at the 50% probability level).

Figure 3
Front view (left) and side view (right) of pseudopolymorph of [Rh(COD)(dppmp)]⁺ (ellipsoids drawn at the 50% probability level).

Synthesis and crystallization

A dry argon-flushed Schlenk tube was charged with dppmp (110 mg), Rh(COD)(acac) (124 mg) and THF (40 ml). The HBF₄ in water (40%) (50 µL) was added directly. After stirring for 16 h under room temperature, the solvent was removed under vacuum. Orange-coloured rystals suitable for X-ray crystallography were obtained by slow diffusion of diethyl ether into a dichloroethane solution. The reaction scheme is shown in Fig. 4.

Figure 4
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The estimated diffraction contribution of the disordered solvent (a half molecule of dichloroethane per asymmetric unit) was subtracted from the observed diffraction data using SQUEEZE (Spek, 2015) in PLATON (Spek, 2009 ).

Table 2
Experimental details

Crystal data
Chemical formula	[Rh(C₈H₁₂)(C₁₈H₁₆NP)]BF₄
M_r	575.18
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	8.7638 (2), 9.2286 (2), 16.7192 (3)
α, β, γ (°)	89.402 (1), 88.904 (1), 76.121 (1)
V (Å³)	1312.47 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.75
Crystal size (mm)	0.46 × 0.40 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.639, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	17088, 5176, 4973
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.054, 1.05
No. of reflections	5176
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.46
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010 ) and PLATON (Spek, 2009).

Structural data

CCDC reference: 1499364

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616013183/bt4024sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616013183/bt4024Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

(η²,η²-cycloocta-1,5-diene)[2-(diphenylphosphanylmethyl)pyridine-κ²N,P]rhodium(I) tetrafluoridoborate 1,2-dichloroethane monosolvate top

Crystal data top

[Rh(C₈H₁₂)(C₁₈H₁₆NP)]BF₄	Z = 2
M_r = 575.18	F(000) = 584
Triclinic, P1	D_x = 1.455 Mg m⁻³
a = 8.7638 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2286 (2) Å	Cell parameters from 9922 reflections
c = 16.7192 (3) Å	θ = 2.3–27.5°
α = 89.402 (1)°	µ = 0.75 mm⁻¹
β = 88.904 (1)°	T = 150 K
γ = 76.121 (1)°	Part of block, orange
V = 1312.47 (5) Å³	0.46 × 0.40 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	5176 independent reflections
Radiation source: fine-focus sealed tube	4973 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.017
φ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −10→10
T_min = 0.639, T_max = 0.746	k = −10→11
17088 measured reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0262P)² + 0.9042P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5176 reflections	Δρ_max = 0.41 e Å⁻³
307 parameters	Δρ_min = −0.46 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
Rh1	0.06970 (2)	0.24000 (2)	0.32462 (2)	0.01711 (5)
P1	−0.00629 (5)	0.06162 (5)	0.25753 (2)	0.01705 (9)
N1	−0.09923 (16)	0.19334 (16)	0.40800 (8)	0.0195 (3)
C1	−0.0567 (2)	−0.04882 (18)	0.34135 (10)	0.0204 (3)
H1A	−0.1288	−0.1094	0.3235	0.025*
H1B	0.0395	−0.1171	0.3622	0.025*
C2	−0.13519 (19)	0.05816 (18)	0.40573 (10)	0.0187 (3)
C3	−0.2401 (2)	0.0188 (2)	0.46045 (10)	0.0237 (4)
H3	−0.2632	−0.0765	0.4578	0.028*
C4	−0.3105 (2)	0.1194 (2)	0.51872 (11)	0.0264 (4)
H4	−0.3804	0.0934	0.5573	0.032*
C5	−0.2774 (2)	0.2587 (2)	0.51993 (11)	0.0262 (4)
H5	−0.3264	0.3305	0.5585	0.031*
C6	−0.1723 (2)	0.2917 (2)	0.46427 (11)	0.0246 (4)
H6	−0.1502	0.3875	0.4655	0.030*
C7	−0.18679 (19)	0.12701 (19)	0.20282 (10)	0.0210 (3)
C8	−0.2745 (2)	0.0289 (2)	0.17701 (11)	0.0270 (4)
H8	−0.2407	−0.0748	0.1884	0.032*
C9	−0.4113 (2)	0.0836 (3)	0.13474 (12)	0.0353 (5)
H9	−0.4709	0.0171	0.1169	0.042*
C10	−0.4612 (2)	0.2350 (3)	0.11839 (12)	0.0378 (5)
H10	−0.5548	0.2717	0.0893	0.045*
C11	−0.3758 (2)	0.3324 (2)	0.14405 (12)	0.0364 (5)
H11	−0.4109	0.4361	0.1327	0.044*
C12	−0.2384 (2)	0.2795 (2)	0.18655 (11)	0.0274 (4)
H12	−0.1799	0.3470	0.2044	0.033*
C13	0.12691 (19)	−0.06447 (18)	0.19045 (10)	0.0191 (3)
C14	0.2673 (2)	−0.15094 (19)	0.22032 (10)	0.0217 (3)
H14	0.2877	−0.1494	0.2759	0.026*
C15	0.3777 (2)	−0.2394 (2)	0.16938 (11)	0.0255 (4)
H15	0.4725	−0.2989	0.1903	0.031*
C16	0.3497 (2)	−0.2407 (2)	0.08854 (12)	0.0303 (4)
H16	0.4253	−0.3013	0.0538	0.036*
C17	0.2122 (2)	−0.1543 (3)	0.05804 (12)	0.0379 (5)
H17	0.1935	−0.1550	0.0023	0.045*
C18	0.1007 (2)	−0.0661 (2)	0.10865 (11)	0.0312 (4)
H18	0.0063	−0.0066	0.0873	0.037*
C19	0.0899 (2)	0.46505 (19)	0.36720 (11)	0.0233 (4)
H19	−0.0080	0.5251	0.3936	0.028*
C20	0.1787 (2)	0.35865 (19)	0.41578 (10)	0.0223 (3)
H20	0.1353	0.3556	0.4714	0.027*
C21	0.3542 (2)	0.2977 (2)	0.40802 (11)	0.0263 (4)
H21A	0.3842	0.2037	0.4392	0.032*
H21B	0.4075	0.3699	0.4316	0.032*
C22	0.4131 (2)	0.2669 (2)	0.32124 (11)	0.0266 (4)
H22A	0.4344	0.3592	0.2978	0.032*
H22B	0.5133	0.1896	0.3212	0.032*
C23	0.2964 (2)	0.21490 (19)	0.26906 (11)	0.0229 (4)
H23	0.3392	0.1138	0.2456	0.027*
C24	0.1833 (2)	0.3075 (2)	0.22174 (10)	0.0239 (4)
H24	0.1619	0.2602	0.1709	0.029*
C25	0.1473 (2)	0.4753 (2)	0.21814 (11)	0.0289 (4)
H25A	0.0411	0.5134	0.1959	0.035*
H25B	0.2237	0.5060	0.1813	0.035*
C26	0.1537 (2)	0.5468 (2)	0.30030 (11)	0.0276 (4)
H26A	0.2640	0.5474	0.3116	0.033*
H26B	0.0919	0.6518	0.2987	0.033*
B1	0.6485 (2)	0.6941 (3)	0.33427 (13)	0.0267 (4)
F1	0.74911 (15)	0.65862 (16)	0.26872 (7)	0.0450 (3)
F2	0.73545 (15)	0.67145 (14)	0.40401 (7)	0.0402 (3)
F3	0.53948 (16)	0.60835 (16)	0.33567 (8)	0.0483 (3)
F4	0.57017 (14)	0.84420 (14)	0.32976 (8)	0.0403 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01708 (7)	0.01760 (7)	0.01754 (8)	−0.00597 (5)	0.00292 (5)	−0.00431 (5)
P1	0.0170 (2)	0.0176 (2)	0.0168 (2)	−0.00476 (15)	0.00187 (15)	−0.00293 (16)
N1	0.0178 (7)	0.0226 (7)	0.0184 (7)	−0.0051 (5)	0.0011 (5)	−0.0036 (6)
C1	0.0221 (8)	0.0196 (8)	0.0202 (8)	−0.0063 (6)	0.0022 (6)	−0.0014 (6)
C2	0.0165 (7)	0.0219 (8)	0.0170 (8)	−0.0031 (6)	−0.0020 (6)	−0.0009 (6)
C3	0.0241 (9)	0.0269 (9)	0.0214 (9)	−0.0085 (7)	0.0000 (7)	0.0014 (7)
C4	0.0223 (8)	0.0374 (10)	0.0200 (9)	−0.0086 (7)	0.0030 (7)	−0.0006 (7)
C5	0.0235 (9)	0.0330 (10)	0.0207 (9)	−0.0043 (7)	0.0037 (7)	−0.0094 (7)
C6	0.0238 (9)	0.0252 (9)	0.0250 (9)	−0.0061 (7)	0.0025 (7)	−0.0079 (7)
C7	0.0170 (8)	0.0270 (9)	0.0178 (8)	−0.0032 (7)	0.0032 (6)	−0.0029 (7)
C8	0.0230 (9)	0.0354 (10)	0.0235 (9)	−0.0091 (7)	0.0027 (7)	−0.0049 (7)
C9	0.0217 (9)	0.0618 (14)	0.0253 (10)	−0.0154 (9)	0.0023 (7)	−0.0063 (9)
C10	0.0193 (9)	0.0660 (15)	0.0219 (10)	0.0015 (9)	0.0026 (7)	0.0023 (9)
C11	0.0301 (10)	0.0407 (11)	0.0302 (11)	0.0067 (9)	0.0049 (8)	0.0058 (9)
C12	0.0255 (9)	0.0283 (9)	0.0256 (9)	−0.0016 (7)	0.0044 (7)	−0.0009 (7)
C13	0.0197 (8)	0.0186 (8)	0.0194 (8)	−0.0059 (6)	0.0042 (6)	−0.0047 (6)
C14	0.0253 (8)	0.0206 (8)	0.0197 (8)	−0.0066 (7)	0.0004 (7)	−0.0023 (6)
C15	0.0234 (9)	0.0228 (9)	0.0279 (9)	−0.0012 (7)	0.0007 (7)	−0.0016 (7)
C16	0.0279 (9)	0.0327 (10)	0.0261 (10)	0.0006 (8)	0.0066 (7)	−0.0077 (8)
C17	0.0328 (10)	0.0549 (13)	0.0189 (9)	0.0033 (9)	0.0010 (8)	−0.0062 (9)
C18	0.0246 (9)	0.0419 (11)	0.0215 (9)	0.0029 (8)	−0.0006 (7)	−0.0021 (8)
C19	0.0248 (9)	0.0198 (8)	0.0258 (9)	−0.0061 (7)	0.0031 (7)	−0.0094 (7)
C20	0.0236 (8)	0.0257 (9)	0.0203 (8)	−0.0106 (7)	0.0008 (7)	−0.0088 (7)
C21	0.0217 (9)	0.0311 (9)	0.0272 (9)	−0.0084 (7)	−0.0032 (7)	0.0001 (7)
C22	0.0197 (8)	0.0290 (9)	0.0317 (10)	−0.0070 (7)	0.0033 (7)	−0.0043 (8)
C23	0.0207 (8)	0.0235 (8)	0.0257 (9)	−0.0083 (7)	0.0091 (7)	−0.0062 (7)
C24	0.0283 (9)	0.0283 (9)	0.0187 (8)	−0.0140 (7)	0.0067 (7)	−0.0048 (7)
C25	0.0350 (10)	0.0283 (9)	0.0260 (10)	−0.0129 (8)	−0.0008 (8)	0.0034 (7)
C26	0.0319 (10)	0.0193 (8)	0.0326 (10)	−0.0078 (7)	0.0005 (8)	−0.0023 (7)
B1	0.0223 (10)	0.0352 (11)	0.0237 (10)	−0.0086 (8)	0.0005 (8)	−0.0040 (8)
F1	0.0380 (7)	0.0615 (8)	0.0326 (7)	−0.0071 (6)	0.0122 (5)	−0.0084 (6)
F2	0.0400 (7)	0.0453 (7)	0.0307 (6)	−0.0002 (5)	−0.0116 (5)	−0.0063 (5)
F3	0.0461 (8)	0.0579 (8)	0.0510 (8)	−0.0323 (7)	0.0007 (6)	−0.0018 (7)
F4	0.0370 (7)	0.0390 (7)	0.0408 (7)	−0.0011 (5)	−0.0031 (5)	−0.0002 (5)

Geometric parameters (Å, º) top

Rh1—N1	2.1295 (14)	C13—C14	1.394 (2)
Rh1—C24	2.1323 (17)	C14—C15	1.390 (2)
Rh1—C23	2.1395 (16)	C14—H14	0.9500
Rh1—P1	2.2371 (4)	C15—C16	1.379 (3)
Rh1—C20	2.2423 (16)	C15—H15	0.9500
Rh1—C19	2.2503 (17)	C16—C17	1.380 (3)
P1—C7	1.8135 (17)	C16—H16	0.9500
P1—C13	1.8166 (16)	C17—C18	1.391 (3)
P1—C1	1.8331 (17)	C17—H17	0.9500
N1—C6	1.354 (2)	C18—H18	0.9500
N1—C2	1.359 (2)	C19—C20	1.368 (3)
C1—C2	1.508 (2)	C19—C26	1.515 (3)
C1—H1A	0.9900	C19—H19	1.0000
C1—H1B	0.9900	C20—C21	1.509 (2)
C2—C3	1.391 (2)	C20—H20	1.0000
C3—C4	1.383 (3)	C21—C22	1.537 (3)
C3—H3	0.9500	C21—H21A	0.9900
C4—C5	1.384 (3)	C21—H21B	0.9900
C4—H4	0.9500	C22—C23	1.521 (2)
C5—C6	1.380 (3)	C22—H22A	0.9900
C5—H5	0.9500	C22—H22B	0.9900
C6—H6	0.9500	C23—C24	1.396 (3)
C7—C8	1.397 (3)	C23—H23	1.0000
C7—C12	1.397 (3)	C24—C25	1.506 (3)
C8—C9	1.388 (3)	C24—H24	1.0000
C8—H8	0.9500	C25—C26	1.538 (3)
C9—C10	1.386 (3)	C25—H25A	0.9900
C9—H9	0.9500	C25—H25B	0.9900
C10—C11	1.376 (3)	C26—H26A	0.9900
C10—H10	0.9500	C26—H26B	0.9900
C11—C12	1.392 (3)	B1—F3	1.379 (2)
C11—H11	0.9500	B1—F1	1.385 (2)
C12—H12	0.9500	B1—F2	1.392 (2)
C13—C18	1.392 (3)	B1—F4	1.393 (3)

N1—Rh1—C24	164.31 (6)	C13—C14—H14	119.8
N1—Rh1—C23	156.54 (6)	C16—C15—C14	120.08 (17)
C24—Rh1—C23	38.15 (7)	C16—C15—H15	120.0
N1—Rh1—P1	80.58 (4)	C14—C15—H15	120.0
C24—Rh1—P1	92.74 (5)	C15—C16—C17	120.07 (17)
C23—Rh1—P1	97.92 (5)	C15—C16—H16	120.0
N1—Rh1—C20	93.09 (6)	C17—C16—H16	120.0
C24—Rh1—C20	97.17 (7)	C16—C17—C18	120.23 (18)
C23—Rh1—C20	81.31 (7)	C16—C17—H17	119.9
P1—Rh1—C20	162.34 (5)	C18—C17—H17	119.9
N1—Rh1—C19	100.93 (6)	C17—C18—C13	120.29 (17)
C24—Rh1—C19	81.10 (7)	C17—C18—H18	119.9
C23—Rh1—C19	87.72 (6)	C13—C18—H18	119.9
P1—Rh1—C19	161.96 (5)	C20—C19—C26	125.25 (16)
C20—Rh1—C19	35.45 (7)	C20—C19—Rh1	71.96 (10)
C7—P1—C13	105.76 (8)	C26—C19—Rh1	110.01 (11)
C7—P1—C1	105.55 (8)	C20—C19—H19	113.9
C13—P1—C1	107.98 (8)	C26—C19—H19	113.9
C7—P1—Rh1	114.28 (6)	Rh1—C19—H19	113.9
C13—P1—Rh1	121.83 (5)	C19—C20—C21	125.40 (16)
C1—P1—Rh1	100.07 (6)	C19—C20—Rh1	72.60 (10)
C6—N1—C2	117.88 (14)	C21—C20—Rh1	106.52 (11)
C6—N1—Rh1	123.16 (12)	C19—C20—H20	114.5
C2—N1—Rh1	118.96 (11)	C21—C20—H20	114.5
C2—C1—P1	107.80 (11)	Rh1—C20—H20	114.5
C2—C1—H1A	110.1	C20—C21—C22	113.70 (15)
P1—C1—H1A	110.1	C20—C21—H21A	108.8
C2—C1—H1B	110.1	C22—C21—H21A	108.8
P1—C1—H1B	110.1	C20—C21—H21B	108.8
H1A—C1—H1B	108.5	C22—C21—H21B	108.8
N1—C2—C3	121.73 (15)	H21A—C21—H21B	107.7
N1—C2—C1	117.45 (14)	C23—C22—C21	113.02 (14)
C3—C2—C1	120.82 (15)	C23—C22—H22A	109.0
C4—C3—C2	119.49 (17)	C21—C22—H22A	109.0
C4—C3—H3	120.3	C23—C22—H22B	109.0
C2—C3—H3	120.3	C21—C22—H22B	109.0
C5—C4—C3	118.97 (16)	H22A—C22—H22B	107.8
C5—C4—H4	120.5	C24—C23—C22	125.30 (16)
C3—C4—H4	120.5	C24—C23—Rh1	70.65 (10)
C6—C5—C4	119.06 (16)	C22—C23—Rh1	113.35 (11)
C6—C5—H5	120.5	C24—C23—H23	113.4
C4—C5—H5	120.5	C22—C23—H23	113.4
N1—C6—C5	122.84 (17)	Rh1—C23—H23	113.4
N1—C6—H6	118.6	C23—C24—C25	126.26 (16)
C5—C6—H6	118.6	C23—C24—Rh1	71.21 (10)
C8—C7—C12	119.70 (17)	C25—C24—Rh1	109.23 (12)
C8—C7—P1	121.64 (14)	C23—C24—H24	113.9
C12—C7—P1	118.66 (14)	C25—C24—H24	113.9
C9—C8—C7	119.72 (19)	Rh1—C24—H24	113.9
C9—C8—H8	120.1	C24—C25—C26	113.05 (15)
C7—C8—H8	120.1	C24—C25—H25A	109.0
C10—C9—C8	120.2 (2)	C26—C25—H25A	109.0
C10—C9—H9	119.9	C24—C25—H25B	109.0
C8—C9—H9	119.9	C26—C25—H25B	109.0
C11—C10—C9	120.35 (18)	H25A—C25—H25B	107.8
C11—C10—H10	119.8	C19—C26—C25	112.51 (15)
C9—C10—H10	119.8	C19—C26—H26A	109.1
C10—C11—C12	120.2 (2)	C25—C26—H26A	109.1
C10—C11—H11	119.9	C19—C26—H26B	109.1
C12—C11—H11	119.9	C25—C26—H26B	109.1
C11—C12—C7	119.78 (19)	H26A—C26—H26B	107.8
C11—C12—H12	120.1	F3—B1—F1	110.61 (17)
C7—C12—H12	120.1	F3—B1—F2	110.21 (17)
C18—C13—C14	118.88 (15)	F1—B1—F2	109.38 (16)
C18—C13—P1	121.84 (13)	F3—B1—F4	109.06 (16)
C14—C13—P1	118.95 (13)	F1—B1—F4	109.12 (17)
C15—C14—C13	120.44 (16)	F2—B1—F4	108.41 (16)
C15—C14—H14	119.8

Selected distances and angles (Å, °) of the two polymorphs of [Rh(COD)(dppmp)]BF₄ top

C_M are the centroids of the COD double bonds.

	Triclinic polymorph	Orthorhombic pseudopolymorph
Rh—P	2.2371 (4)	2.2491 (5)
Rh—N	2.1295 (14)	2.1333 (17)
Rh—C_M	2.019 (2), 2.140 (2)	2.119 (2), 2.140 (2)
P—Rh—N	80.58 (4)	80.81 (5)
C_M—Rh—C_M	86.48 (7)	86.47 (8)

Acknowledgements

We thank our technical staff for assistance. This work was supported by the Deutsche Forschungsgemeinschaft (HE2890/7–1). The publication of this article was funded by the Open Access Fund of the Leibniz Association.

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