2-(Diphenyl­phosphinoylmeth­yl)pyrrole–2-(diphenyl­phosphinometh­yl)pyrrole (0.43/0.57) and tetra­chlorido­(5-diphenyl­phosphinometh­yl-2H-pyrrole-κ²N,P)titanium(IV)

The title phosphine oxide–phosphine, 0.43C₁₇H₁₆NOP·0.57C₁₇H₁₆NP, (I)/(II), was obtained as a 0.861 (6):1.139 (6) cocrystallized mixture. Hydrogen bonding between the two constituents leads to the formation of 2:2 solid-state assemblies. Instead of forming the expected simple N,P-chelated system via loss of the N-bound H atom, reaction of 2-(diphenyl­phosphinometh­yl)pyrrole, (II), with TiCl₄ leads to the formation of the title titanium(IV) complex, [TiCl₄(C₁₇H₁₆NP)], (IV), containing a rearranged neutral ligand in which the N-bound H atom moves to one of the pyrrole C atoms, giving a partially unsaturated ring.

S1. Comment

The desire to improve on existing catalytic processes, and to find new catalytic systems, continues to drive synthetic chemists to create novel ligand systems. For example, ongoing efforts to find post-metallocene polymerization catalysts for alkenes (Gibson & Spitzmesser, 2003) have led to the introduction of a large class of salicylaldiminato and pyrrolaldiminato ligands (see, for example, Yoshida et al., 2001; Tsurugi & Mashima, 2006; Cui et al., 2003; Yang et al., 2007). The combination of an anionic pyrrolate moiety with other donors is, however, less common. In an effort to explore routes to new N—P and N—O chelate ligands based on pyrrolates, we have recently introduced the families of pyrrole–phosphine oxide and pyrrole–phosphine ligands, (I) and (II) (see Scheme) (Broomfield, Boschert et al., 2009; Broomfield, Wright et al., 2009). These ligands are attractive as the nature of the R group can be varied at a late stage of the synthesis by appropriate choice of phosphine starting material. Introduction of other groups onto the pyrrole ring is another potential method to tune the properties of the ligand system. Exploring the reactivity of (I) (R = Ph) with early transition metals has shown that coordination demonstrates that the phosphine oxide acts as well behaved ligand with these metals. Here, we report on efforts to use the pyrrole–phosphine, (II) (R = Ph) with early transition metals.

Reaction of (II) (R = Ph) with ZrCl₄ in thf [tetrahyrdrofuran] was carried out with the intention of forming the bis-ligand complex (III) (see Scheme). However, crystallization of the reaction mixture led to the isolation of crystals with an approximately stoichiometric mixture of co-crystallized (I) and (II) (Fig. 1). Synthesis of (II) from (I) is complicated by the reactivity of the phosphine with oxygen, and it is possible that the metal complex is not involved in formation of the co-crystals. The occupancy of O1 was refined freely, establishing that the site is largely occupied [occupancy of 0.861 (6)].

The molecular geometry of (I) here (Table 1) is very similar to that observed when the same molecule crystallizes in the absence of (II) (Broomfield, Wright et al., 2009). The geometric data observed for (I) are also in the range anticipated for this molecule. More interesting are the inter-molecular interactions between (I) and (II) (Fig. 2, Table 2). Hydrogen bonding between two molecules of (I) leads to solid-state dimer formation. This is in contrast to the supramolecular arrangement seen in crystals of (I) alone, where infinite one-dimensional chains are formed by hydrogen bonding between adjacent molecules (Broomfield, Wright et al., 2009). The O1···N1 separation observed here [2.821 (4) Å] is slightly shorter than that seen in the infinite chain arrangement [2.868 (3) Å]. In addition to this pairing hydrogen-bond interaction, each molecule of (I) also hydrogen bonds to one molecule of (II), with an O1···N2 distance of 2.792 (3) Å. The result of this hydrogen-bond framework is the formation of an overall 0D 2:2 supramolecular structure.

A search of the Cambridge Structural Database (CSD; Allen, 2002) reveals five structures which consist of independent molecules of a phosphine and its oxide: AZUDII (Atikinson et al., 2004), EXUDAC (Mohamed et al., 2004), QEMFAP (Chekhlov, 2000), SIXJEO (Carriedo et al., 1990) and UJAPEA (Hitchcock et al., 2003). All show statistical interspersion of the phosphine oxide in the structure, in marked contrast to the pattern seen here. The presence of the strongly hydrogen-bonding amine group and the resulting hydrogen-bond network may account for the greater order seen in the present structure.

In contrast to the lack of reaction between (II) and ZrCl₄, reaction of (II) with TiCl₄ did lead to the formation of a metal-containing species (see Scheme). However, analysis of the Fourier difference map following data collection revealed that C3 carries two H atoms, and that the ligand is overall neutral, giving complex (IV) (Fig. 3). The C—C distances in the nitrogen-containing ring are fully in agreement with the locations of the H atoms (Table 3). The geometry of the metal is approximately octahedral, with the N1—Ti1—P1 bite angle significantly smaller than 90°, presumably due to the constraint imposed by the ligand backbone. The mechanism for the reaction is likely to involve initial coordination of (II) to the metal, yielding (V), followed by an acid-mediated rearragement (see Scheme). This type of rearrangement has previously been reported when pyrroles are reacted in the precence of the strong Lewis base B(C₆F₅)₃ (Guidotti et al., 2003; Focante et al., 2004; Kehr et al., 2001).

There are two structures in the CSD which contain a rearranged pyrrole ligand without the presence of a porphyrin ring or secondary bonding interactions: WELTIQ (DuBois et al., 1999) and XITLES (Kreickmann et al., 2007). WELTIQ contains rhenium, and has a Re—N bond distance of 2.171 (6) Å, while XITLES is a tungsten complex with a W—N distance of 2.136 (3) Å. The Ti—N distance obtained in the current work, 2.174 (5) Å, is therefore somewhat longer than might be initially anticipated on the basis of the smaller size of the Ti centre compared to Re and W. In the case of Ti—P bonds, a search of the CSD gives a range of 2.254–2.904 Å for 226 database entries, with a mean value of 2.584 (4) Å. The value observed for (IV) is above the average, at 2.6428 (17) Å, but is not atypical. Presumably the chelating nature of the ligand in (IV) is responsible for the length of the bonds observed here.

In summary, whilst ligand (II) shows good promise in forming complexes with later transition metals, early metals reveal additional ligand reactivity which may have to be modulated in order to successfully obtain the desired complexes. Efforts to control this reactivity are ongoing, for example by blocking the 2-position on the pyrrole ring with a bulky alkyl to prevent ligand rearrangement.

Related literature

For related literature, see: Allen (2002); Atikinson et al. (2004); Broomfield, Boschert, Wright, Highes & Bochmann (2009); Broomfield, Wright & Bochmann (2009); Carriedo et al. (1990); Chekhlov (2000); Cui et al. (2003); DuBois, Vasquez, Peslherbe & Noll (1999); Focante et al. (2004); Gibson & Spitzmesser (2003); Guidotti et al. (2003); Hitchcock et al. (2003); Kehr et al. (2001); Kreickmann et al. (2007); Sheldrick (2008); Tsurugi & Mashima (2006); Yang et al. (2007); Yoshida et al. (2001).

S2. Experimental

Ligand (II) was obtained as described elsewhere (Broomfield, Wright et al., 2009). Reaction of the free ligand with ZrCl₄ in thf, followed by addition of an equal amount of hexane and cooling to 243 K led to the formation of crystals of (I)/(II) [0.861:1.139 (6)]. Reaction of TiCl₄ with the free ligand in dichloromethane, followed by dilution with hexane and cooling to 243 K gave crystals of (IV) after storage for some days.

S3. Refinement

All C-bound H atoms were refined using a riding model (Sheldrick, 2008) and with isotropic thermal parameters 1.2 times that of the parent C atom for CH and CH₂ and 1.5 times for methyl H. Methyl groups were allowed additional rotational freedom. In (I)/(II), protons H1 and H2 (bound to N) were located in the Fourier difference map and both coordinates and U_iso values were freely refined. The site occupancy of the O atom in (I)/(II) (O1) was freely refined to a value of 0.861 (6).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Figures

	Fig. 1. ORTEP representation of the structure of co-crystallized (I) and (II) with 50% probability ellipsoids; H atoms except H1 and H2 have been omitted for clarity.
	Fig. 2. ORTEP representation of the hydrogen-bond arrangement in co-crystallized (I) and (II) with 50% ellipsoids; symmetry operations to generate equivalent positions: (i) = - x, 1 - y, -z.
	Fig. 3. ORTEP representation of the structure of (IV) with 50% probability ellipsoids.

(I_II) 2-(Diphenylphosphinoylmethyl)pyrrole–2-(diphenylphosphinomethyl)pyrrole (0.43/0.57)

Crystal data

0.43C17H16NOP·0.57C17H16NP	F(000) = 1147.2
Mr = 272.18	Dx = 1.229 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5193 reflections
a = 9.6282 (9) Å	θ = 3.3–27.5°
b = 15.2848 (14) Å	µ = 0.18 mm^−1
c = 20.391 (2) Å	T = 140 K
β = 101.376 (8)°	Needle, colourless
V = 2941.9 (5) Å^3	0.32 × 0.08 × 0.08 mm
Z = 8

Data collection

Oxford Diffraction Xcalibur 3/CCD diffractometer	5167 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.110
Detector resolution: 16.0050 pixels mm^-1	θmax = 25.0°, θmin = 3.3°
Thin slice ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006)	k = −18→18
Tmin = 0.822, Tmax = 0.986	l = −24→24
30196 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0309P)^2] where P = (Fo^2 + 2Fc^2)/3
5167 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
H1	−0.056 (3)	0.5599 (19)	0.0613 (15)	0.042 (10)*
N1	−0.0998 (3)	0.55652 (17)	0.09407 (14)	0.0313 (7)
O1	−0.0511 (2)	0.39822 (15)	0.00634 (11)	0.0352 (10)	0.861 (6)
P1	−0.19363 (8)	0.37050 (5)	0.01121 (4)	0.0284 (2)
C1	−0.2987 (3)	0.46179 (18)	0.03278 (14)	0.0282 (7)
H1A	−0.3200	0.5025	−0.0057	0.034*
H1B	−0.3898	0.4392	0.0413	0.034*
C2	−0.2238 (3)	0.51095 (19)	0.09337 (15)	0.0268 (7)
C3	−0.0572 (3)	0.5970 (2)	0.15504 (15)	0.0334 (8)
H3	0.0241	0.6330	0.1679	0.040*
C4	−0.1534 (3)	0.5760 (2)	0.19380 (16)	0.0383 (8)
H4	−0.1508	0.5945	0.2385	0.046*
C5	−0.2575 (3)	0.5214 (2)	0.15505 (16)	0.0375 (8)
H5	−0.3368	0.4965	0.1694	0.045*
C6	−0.2895 (3)	0.32452 (19)	−0.06648 (14)	0.0270 (7)
C7	−0.2174 (3)	0.2669 (2)	−0.10100 (15)	0.0341 (8)
H7	−0.1215	0.2526	−0.0829	0.041*
C8	−0.2829 (4)	0.2303 (2)	−0.16111 (16)	0.0422 (9)
H8	−0.2325	0.1908	−0.1838	0.051*
C9	−0.4226 (4)	0.2514 (2)	−0.18815 (16)	0.0413 (9)
H9	−0.4676	0.2271	−0.2298	0.050*
C10	−0.4962 (3)	0.3075 (2)	−0.15463 (16)	0.0392 (9)
H10	−0.5923	0.3211	−0.1729	0.047*
C11	−0.4301 (3)	0.3445 (2)	−0.09385 (15)	0.0347 (8)
H11	−0.4812	0.3835	−0.0711	0.042*
C12	−0.1943 (3)	0.28782 (18)	0.07457 (13)	0.0231 (7)
C13	−0.2745 (3)	0.2114 (2)	0.06199 (15)	0.0326 (8)
H13	−0.3307	0.2014	0.0188	0.039*
C14	−0.2724 (3)	0.1496 (2)	0.11254 (16)	0.0430 (9)
H14	−0.3275	0.0979	0.1038	0.052*
C15	−0.1907 (4)	0.1637 (2)	0.17498 (16)	0.0477 (10)
H15	−0.1895	0.1215	0.2093	0.057*
C16	−0.1106 (3)	0.2387 (2)	0.18801 (16)	0.0432 (9)
H16	−0.0542	0.2480	0.2312	0.052*
C17	−0.1120 (3)	0.3007 (2)	0.13826 (15)	0.0324 (8)
H17	−0.0566	0.3523	0.1476	0.039*
N2	0.2147 (3)	0.38732 (17)	0.09038 (13)	0.0334 (7)
H2	0.128 (3)	0.3884 (19)	0.0656 (14)	0.038 (9)*
P2	0.16415 (8)	0.18713 (5)	0.02148 (4)	0.0323 (2)
C18	0.2944 (3)	0.27617 (19)	0.01553 (14)	0.0306 (8)
H18A	0.3852	0.2496	0.0100	0.037*
H18B	0.2584	0.3121	−0.0246	0.037*
C19	0.3203 (3)	0.33382 (19)	0.07588 (14)	0.0262 (7)
C20	0.2644 (4)	0.4336 (2)	0.14746 (16)	0.0406 (9)
H20	0.2120	0.4746	0.1678	0.049*
C21	0.4027 (3)	0.4107 (2)	0.17018 (16)	0.0431 (9)
H21	0.4638	0.4327	0.2090	0.052*
C22	0.4380 (3)	0.3478 (2)	0.12503 (15)	0.0344 (8)
H22	0.5274	0.3201	0.1282	0.041*
C23	0.1336 (3)	0.14105 (19)	−0.06363 (14)	0.0299 (8)
C24	0.2087 (3)	0.1642 (2)	−0.11299 (16)	0.0394 (9)
H24	0.2861	0.2037	−0.1024	0.047*
C25	0.1719 (3)	0.1305 (2)	−0.17742 (15)	0.0417 (9)
H25	0.2228	0.1481	−0.2107	0.050*
C26	0.0624 (4)	0.0719 (2)	−0.19321 (17)	0.0454 (9)
H26	0.0384	0.0483	−0.2371	0.055*
C27	−0.0136 (4)	0.0470 (2)	−0.14471 (18)	0.0489 (10)
H27	−0.0890	0.0061	−0.1554	0.059*
C28	0.0210 (3)	0.0821 (2)	−0.08079 (16)	0.0391 (9)
H28	−0.0324	0.0658	−0.0482	0.047*
C29	0.2838 (3)	0.10498 (19)	0.06945 (14)	0.0282 (7)
C30	0.3283 (3)	0.1189 (2)	0.13835 (15)	0.0368 (8)
H30	0.2959	0.1691	0.1584	0.044*
C31	0.4186 (3)	0.0606 (2)	0.17753 (15)	0.0418 (9)
H31	0.4493	0.0716	0.2240	0.050*
C32	0.4647 (3)	−0.0141 (2)	0.14909 (16)	0.0401 (9)
H32	0.5260	−0.0544	0.1761	0.048*
C33	0.4211 (3)	−0.0293 (2)	0.08175 (15)	0.0382 (8)
H33	0.4523	−0.0803	0.0623	0.046*
C34	0.3317 (3)	0.0295 (2)	0.04204 (15)	0.0339 (8)
H34	0.3025	0.0183	−0.0045	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0308 (17)	0.0312 (17)	0.0334 (18)	−0.0002 (13)	0.0098 (14)	0.0022 (14)
O1	0.0308 (16)	0.0387 (18)	0.0363 (17)	−0.0021 (12)	0.0068 (11)	0.0031 (12)
P1	0.0321 (5)	0.0243 (5)	0.0296 (5)	0.0024 (4)	0.0077 (4)	0.0025 (4)
C1	0.0273 (17)	0.0231 (18)	0.0344 (19)	0.0006 (15)	0.0062 (14)	0.0059 (15)
C2	0.0242 (18)	0.0205 (18)	0.0366 (19)	0.0043 (15)	0.0080 (14)	0.0053 (15)
C3	0.0311 (19)	0.028 (2)	0.038 (2)	−0.0005 (15)	−0.0002 (15)	0.0007 (16)
C4	0.043 (2)	0.041 (2)	0.033 (2)	0.0058 (18)	0.0118 (16)	−0.0036 (16)
C5	0.0345 (19)	0.036 (2)	0.048 (2)	−0.0004 (17)	0.0218 (16)	−0.0009 (17)
C6	0.0287 (17)	0.0225 (18)	0.0301 (18)	0.0029 (15)	0.0065 (14)	0.0064 (15)
C7	0.0296 (18)	0.033 (2)	0.039 (2)	0.0022 (16)	0.0041 (15)	0.0025 (16)
C8	0.050 (2)	0.039 (2)	0.040 (2)	−0.0020 (19)	0.0128 (17)	−0.0078 (17)
C9	0.053 (2)	0.036 (2)	0.032 (2)	−0.0048 (19)	−0.0006 (17)	0.0014 (17)
C10	0.035 (2)	0.038 (2)	0.041 (2)	0.0008 (18)	−0.0024 (16)	0.0070 (18)
C11	0.039 (2)	0.029 (2)	0.036 (2)	0.0046 (16)	0.0079 (15)	0.0036 (16)
C12	0.0194 (16)	0.0243 (19)	0.0266 (18)	0.0059 (14)	0.0071 (13)	0.0012 (14)
C13	0.0362 (19)	0.033 (2)	0.0275 (18)	−0.0050 (16)	0.0040 (14)	−0.0017 (16)
C14	0.056 (2)	0.030 (2)	0.043 (2)	−0.0124 (17)	0.0106 (17)	0.0004 (17)
C15	0.074 (3)	0.035 (2)	0.035 (2)	0.000 (2)	0.0146 (18)	0.0123 (17)
C16	0.057 (2)	0.042 (2)	0.028 (2)	0.0006 (19)	0.0013 (16)	0.0048 (17)
C17	0.0367 (19)	0.029 (2)	0.0326 (19)	−0.0039 (16)	0.0083 (15)	0.0025 (16)
N2	0.0279 (16)	0.0347 (18)	0.0374 (17)	0.0004 (14)	0.0060 (13)	0.0002 (14)
P2	0.0293 (5)	0.0286 (5)	0.0397 (5)	−0.0013 (4)	0.0086 (4)	−0.0028 (4)
C18	0.0313 (18)	0.0279 (19)	0.0323 (18)	0.0019 (16)	0.0055 (14)	0.0020 (15)
C19	0.0266 (18)	0.0232 (18)	0.0297 (18)	−0.0005 (15)	0.0074 (14)	0.0042 (14)
C20	0.048 (2)	0.038 (2)	0.041 (2)	−0.0051 (18)	0.0202 (17)	−0.0091 (18)
C21	0.041 (2)	0.055 (3)	0.034 (2)	−0.0196 (19)	0.0091 (17)	−0.0103 (18)
C22	0.0282 (18)	0.039 (2)	0.037 (2)	−0.0047 (16)	0.0070 (15)	0.0027 (16)
C23	0.0271 (18)	0.0247 (19)	0.0364 (19)	0.0054 (15)	0.0027 (14)	0.0023 (15)
C24	0.0322 (19)	0.041 (2)	0.043 (2)	−0.0071 (17)	0.0033 (16)	−0.0046 (18)
C25	0.044 (2)	0.046 (2)	0.035 (2)	−0.0012 (19)	0.0045 (16)	0.0005 (18)
C26	0.053 (2)	0.040 (2)	0.039 (2)	0.0031 (19)	−0.0010 (18)	−0.0042 (18)
C27	0.047 (2)	0.038 (2)	0.056 (3)	−0.0118 (18)	−0.0009 (19)	−0.007 (2)
C28	0.039 (2)	0.033 (2)	0.045 (2)	−0.0008 (17)	0.0080 (16)	0.0010 (17)
C29	0.0308 (18)	0.0252 (19)	0.0305 (19)	−0.0083 (15)	0.0103 (14)	0.0024 (15)
C30	0.052 (2)	0.028 (2)	0.035 (2)	−0.0047 (17)	0.0172 (16)	0.0003 (17)
C31	0.062 (2)	0.036 (2)	0.0262 (19)	−0.006 (2)	0.0056 (17)	0.0055 (17)
C32	0.047 (2)	0.033 (2)	0.040 (2)	0.0023 (18)	0.0079 (16)	0.0111 (17)
C33	0.049 (2)	0.029 (2)	0.037 (2)	0.0017 (17)	0.0081 (16)	0.0008 (16)
C34	0.040 (2)	0.034 (2)	0.0284 (18)	0.0003 (17)	0.0068 (15)	−0.0030 (16)

Geometric parameters (Å, º)

N1—C3	1.377 (4)	N2—C20	1.365 (4)
N1—C2	1.379 (4)	N2—C19	1.381 (3)
N1—H1	0.86 (3)	N2—H2	0.88 (3)
O1—P1	1.458 (2)	P2—C23	1.842 (3)
P1—C12	1.808 (3)	P2—C29	1.848 (3)
P1—C6	1.811 (3)	P2—C18	1.871 (3)
P1—C1	1.827 (3)	C18—C19	1.494 (4)
C1—C2	1.503 (4)	C18—H18A	0.9900
C1—H1A	0.9900	C18—H18B	0.9900
C1—H1B	0.9900	C19—C22	1.374 (4)
C2—C5	1.369 (4)	C20—C21	1.366 (4)
C3—C4	1.369 (4)	C20—H20	0.9500
C3—H3	0.9500	C21—C22	1.418 (4)
C4—C5	1.418 (4)	C21—H21	0.9500
C4—H4	0.9500	C22—H22	0.9500
C5—H5	0.9500	C23—C24	1.396 (4)
C6—C11	1.393 (4)	C23—C28	1.400 (4)
C6—C7	1.394 (4)	C24—C25	1.391 (4)
C7—C8	1.382 (4)	C24—H24	0.9500
C7—H7	0.9500	C25—C26	1.373 (4)
C8—C9	1.387 (4)	C25—H25	0.9500
C8—H8	0.9500	C26—C27	1.394 (4)
C9—C10	1.377 (4)	C26—H26	0.9500
C9—H9	0.9500	C27—C28	1.388 (4)
C10—C11	1.396 (4)	C27—H27	0.9500
C10—H10	0.9500	C28—H28	0.9500
C11—H11	0.9500	C29—C34	1.399 (4)
C12—C13	1.395 (4)	C29—C30	1.402 (4)
C12—C17	1.396 (4)	C30—C31	1.384 (4)
C13—C14	1.395 (4)	C30—H30	0.9500
C13—H13	0.9500	C31—C32	1.393 (4)
C14—C15	1.375 (4)	C31—H31	0.9500
C14—H14	0.9500	C32—C33	1.374 (4)
C15—C16	1.378 (4)	C32—H32	0.9500
C15—H15	0.9500	C33—C34	1.390 (4)
C16—C17	1.387 (4)	C33—H33	0.9500
C16—H16	0.9500	C34—H34	0.9500
C17—H17	0.9500
C3—N1—C2	109.9 (3)	C12—C17—H17	119.8
C3—N1—H1	125 (2)	C20—N2—C19	109.9 (3)
C2—N1—H1	125 (2)	C20—N2—H2	127.6 (19)
O1—P1—C12	112.83 (12)	C19—N2—H2	122.5 (19)
O1—P1—C6	112.16 (13)	C23—P2—C29	101.88 (13)
C12—P1—C6	106.31 (13)	C23—P2—C18	101.63 (13)
O1—P1—C1	111.55 (13)	C29—P2—C18	99.95 (13)
C12—P1—C1	106.36 (13)	C19—C18—P2	112.4 (2)
C6—P1—C1	107.23 (13)	C19—C18—H18A	109.1
C2—C1—P1	112.40 (18)	P2—C18—H18A	109.1
C2—C1—H1A	109.1	C19—C18—H18B	109.1
P1—C1—H1A	109.1	P2—C18—H18B	109.1
C2—C1—H1B	109.1	H18A—C18—H18B	107.9
P1—C1—H1B	109.1	C22—C19—N2	106.8 (3)
H1A—C1—H1B	107.9	C22—C19—C18	132.2 (3)
C5—C2—N1	107.0 (3)	N2—C19—C18	121.0 (2)
C5—C2—C1	130.7 (3)	N2—C20—C21	108.1 (3)
N1—C2—C1	122.3 (3)	N2—C20—H20	126.0
C4—C3—N1	107.5 (3)	C21—C20—H20	126.0
C4—C3—H3	126.3	C20—C21—C22	107.2 (3)
N1—C3—H3	126.3	C20—C21—H21	126.4
C3—C4—C5	107.5 (3)	C22—C21—H21	126.4
C3—C4—H4	126.2	C19—C22—C21	108.1 (3)
C5—C4—H4	126.2	C19—C22—H22	126.0
C2—C5—C4	108.1 (3)	C21—C22—H22	126.0
C2—C5—H5	125.9	C24—C23—C28	118.0 (3)
C4—C5—H5	125.9	C24—C23—P2	125.0 (2)
C11—C6—C7	118.5 (3)	C28—C23—P2	117.0 (2)
C11—C6—P1	123.6 (2)	C25—C24—C23	121.0 (3)
C7—C6—P1	117.9 (2)	C25—C24—H24	119.5
C8—C7—C6	121.2 (3)	C23—C24—H24	119.5
C8—C7—H7	119.4	C26—C25—C24	120.3 (3)
C6—C7—H7	119.4	C26—C25—H25	119.8
C7—C8—C9	119.7 (3)	C24—C25—H25	119.8
C7—C8—H8	120.1	C25—C26—C27	119.8 (3)
C9—C8—H8	120.1	C25—C26—H26	120.1
C10—C9—C8	120.0 (3)	C27—C26—H26	120.1
C10—C9—H9	120.0	C28—C27—C26	119.9 (3)
C8—C9—H9	120.0	C28—C27—H27	120.0
C9—C10—C11	120.3 (3)	C26—C27—H27	120.0
C9—C10—H10	119.9	C27—C28—C23	120.9 (3)
C11—C10—H10	119.9	C27—C28—H28	119.5
C6—C11—C10	120.2 (3)	C23—C28—H28	119.5
C6—C11—H11	119.9	C34—C29—C30	117.8 (3)
C10—C11—H11	119.9	C34—C29—P2	124.7 (2)
C13—C12—C17	118.8 (3)	C30—C29—P2	117.5 (2)
C13—C12—P1	122.2 (2)	C31—C30—C29	120.9 (3)
C17—C12—P1	119.0 (2)	C31—C30—H30	119.6
C14—C13—C12	120.3 (3)	C29—C30—H30	119.6
C14—C13—H13	119.9	C30—C31—C32	120.2 (3)
C12—C13—H13	119.9	C30—C31—H31	119.9
C15—C14—C13	120.0 (3)	C32—C31—H31	119.9
C15—C14—H14	120.0	C33—C32—C31	119.7 (3)
C13—C14—H14	120.0	C33—C32—H32	120.1
C14—C15—C16	120.3 (3)	C31—C32—H32	120.1
C14—C15—H15	119.8	C32—C33—C34	120.3 (3)
C16—C15—H15	119.8	C32—C33—H33	119.9
C15—C16—C17	120.2 (3)	C34—C33—H33	119.9
C15—C16—H16	119.9	C33—C34—C29	121.1 (3)
C17—C16—H16	119.9	C33—C34—H34	119.5
C16—C17—C12	120.4 (3)	C29—C34—H34	119.5
C16—C17—H17	119.8
O1—P1—C1—C2	−51.6 (2)	C13—C12—C17—C16	−0.2 (4)
C12—P1—C1—C2	71.8 (2)	P1—C12—C17—C16	179.8 (2)
C6—P1—C1—C2	−174.7 (2)	C23—P2—C18—C19	171.0 (2)
C3—N1—C2—C5	−1.3 (3)	C29—P2—C18—C19	−84.6 (2)
C3—N1—C2—C1	178.3 (2)	C20—N2—C19—C22	−0.3 (3)
P1—C1—C2—C5	−115.8 (3)	C20—N2—C19—C18	−179.6 (3)
P1—C1—C2—N1	64.7 (3)	P2—C18—C19—C22	113.9 (3)
C2—N1—C3—C4	0.9 (3)	P2—C18—C19—N2	−66.9 (3)
N1—C3—C4—C5	−0.2 (3)	C19—N2—C20—C21	0.2 (4)
N1—C2—C5—C4	1.1 (3)	N2—C20—C21—C22	−0.1 (4)
C1—C2—C5—C4	−178.5 (3)	N2—C19—C22—C21	0.2 (3)
C3—C4—C5—C2	−0.6 (4)	C18—C19—C22—C21	179.5 (3)
O1—P1—C6—C11	−135.9 (3)	C20—C21—C22—C19	−0.1 (4)
C12—P1—C6—C11	100.4 (3)	C29—P2—C23—C24	−95.6 (3)
C1—P1—C6—C11	−13.1 (3)	C18—P2—C23—C24	7.3 (3)
O1—P1—C6—C7	43.2 (3)	C29—P2—C23—C28	88.2 (2)
C12—P1—C6—C7	−80.5 (3)	C18—P2—C23—C28	−168.9 (2)
C1—P1—C6—C7	166.0 (2)	C28—C23—C24—C25	0.7 (4)
C11—C6—C7—C8	0.1 (5)	P2—C23—C24—C25	−175.5 (2)
P1—C6—C7—C8	−179.0 (2)	C23—C24—C25—C26	−1.5 (5)
C6—C7—C8—C9	0.5 (5)	C24—C25—C26—C27	0.9 (5)
C7—C8—C9—C10	−1.0 (5)	C25—C26—C27—C28	0.5 (5)
C8—C9—C10—C11	1.0 (5)	C26—C27—C28—C23	−1.3 (5)
C7—C6—C11—C10	−0.2 (4)	C24—C23—C28—C27	0.8 (4)
P1—C6—C11—C10	178.9 (2)	P2—C23—C28—C27	177.2 (2)
C9—C10—C11—C6	−0.4 (5)	C23—P2—C29—C34	0.1 (3)
O1—P1—C12—C13	−131.6 (2)	C18—P2—C29—C34	−104.1 (3)
C6—P1—C12—C13	−8.3 (3)	C23—P2—C29—C30	−179.1 (2)
C1—P1—C12—C13	105.8 (2)	C18—P2—C29—C30	76.6 (2)
O1—P1—C12—C17	48.4 (3)	C34—C29—C30—C31	1.2 (4)
C6—P1—C12—C17	171.8 (2)	P2—C29—C30—C31	−179.6 (2)
C1—P1—C12—C17	−74.2 (2)	C29—C30—C31—C32	−1.3 (5)
C17—C12—C13—C14	0.4 (4)	C30—C31—C32—C33	0.6 (5)
P1—C12—C13—C14	−179.6 (2)	C31—C32—C33—C34	0.1 (5)
C12—C13—C14—C15	−0.3 (5)	C32—C33—C34—C29	−0.2 (5)
C13—C14—C15—C16	0.1 (5)	C30—C29—C34—C33	−0.4 (4)
C14—C15—C16—C17	0.1 (5)	P2—C29—C34—C33	−179.7 (2)
C15—C16—C17—C12	−0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.88 (3)	1.91 (3)	2.790 (3)	174 (3)
N1—H1···O1^i	0.86 (3)	1.99 (3)	2.821 (4)	164 (3)

Symmetry code: (i) −x, −y+1, −z.

(IV) tetrachlorido(5-diphenylphosphinomethyl-2H-pyrrole- κ²N,P)titanium(IV)

Crystal data

[TiCl4(C17H16NP)]	Z = 2
Mr = 454.98	F(000) = 460
Triclinic, P1	Dx = 1.581 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1481 (17) Å	Cell parameters from 1842 reflections
b = 8.6323 (16) Å	θ = 3.5–27.5°
c = 14.202 (3) Å	µ = 1.09 mm^−1
α = 98.159 (15)°	T = 140 K
β = 98.727 (16)°	Needle, orange
γ = 100.588 (16)°	0.14 × 0.06 × 0.06 mm
V = 955.6 (3) Å^3

Data collection

Oxford Diffraction Xcalibur 3/CCD diffractometer	3347 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1864 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.112
Detector resolution: 16.0050 pixels mm^-1	θmax = 25.0°, θmin = 3.5°
Thin slice ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006)	k = −10→10
Tmin = 0.905, Tmax = 0.937	l = −16→16
10184 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0307P)^2] where P = (Fo^2 + 2Fc^2)/3
3347 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Ti1	0.26998 (13)	0.27029 (11)	0.21430 (7)	0.0204 (3)
C1	0.2003 (7)	0.6387 (6)	0.1838 (3)	0.0185 (13)
H1A	0.0814	0.6171	0.1942	0.022*
H1B	0.2358	0.7540	0.1819	0.022*
C2	0.2159 (6)	0.5402 (6)	0.0921 (4)	0.0176 (13)
C3	0.2492 (7)	0.3295 (6)	−0.0073 (4)	0.0253 (14)
H3A	0.1562	0.2354	−0.0345	0.030*
H3B	0.3593	0.2974	−0.0094	0.030*
C4	0.2342 (7)	0.4612 (7)	−0.0612 (4)	0.0246 (14)
H4	0.2386	0.4575	−0.1279	0.030*
C5	0.2135 (7)	0.5852 (6)	−0.0017 (4)	0.0250 (14)
H5	0.1996	0.6857	−0.0179	0.030*
C6	0.5492 (7)	0.6938 (6)	0.2772 (4)	0.0189 (13)
C7	0.6838 (7)	0.6629 (6)	0.3385 (4)	0.0271 (14)
H7	0.6633	0.5861	0.3794	0.032*
C8	0.8448 (7)	0.7418 (6)	0.3405 (4)	0.0293 (15)
H8	0.9364	0.7177	0.3818	0.035*
C9	0.8775 (7)	0.8567 (6)	0.2834 (4)	0.0283 (15)
H9	0.9904	0.9124	0.2857	0.034*
C10	0.7446 (7)	0.8889 (6)	0.2236 (4)	0.0248 (14)
H10	0.7655	0.9675	0.1839	0.030*
C11	0.5816 (7)	0.8089 (6)	0.2204 (4)	0.0226 (14)
H11	0.4903	0.8329	0.1789	0.027*
C12	0.2900 (7)	0.6707 (6)	0.3933 (4)	0.0175 (13)
C13	0.3162 (7)	0.8355 (6)	0.4170 (4)	0.0258 (14)
H13	0.3632	0.9005	0.3750	0.031*
C14	0.2747 (7)	0.9073 (7)	0.5018 (4)	0.0293 (15)
H14	0.2921	1.0205	0.5178	0.035*
C15	0.2078 (7)	0.8110 (7)	0.5619 (4)	0.0243 (14)
H15	0.1784	0.8583	0.6199	0.029*
C16	0.1833 (7)	0.6489 (7)	0.5395 (4)	0.0248 (14)
H16	0.1393	0.5844	0.5825	0.030*
C17	0.2219 (7)	0.5774 (6)	0.4547 (4)	0.0243 (14)
H17	0.2016	0.4641	0.4388	0.029*
Cl1	0.54140 (19)	0.28949 (17)	0.19072 (11)	0.0306 (4)
Cl2	0.00233 (18)	0.30511 (16)	0.23398 (10)	0.0270 (4)
Cl3	0.3352 (2)	0.21919 (17)	0.36339 (10)	0.0314 (4)
Cl4	0.1693 (2)	0.02861 (16)	0.11559 (11)	0.0325 (4)
N1	0.2376 (5)	0.3943 (5)	0.0920 (3)	0.0208 (11)
P1	0.33927 (19)	0.58169 (16)	0.27991 (10)	0.0180 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0231 (6)	0.0184 (6)	0.0219 (6)	0.0043 (5)	0.0077 (5)	0.0068 (5)
C1	0.022 (3)	0.013 (3)	0.020 (3)	0.002 (2)	0.004 (3)	0.005 (3)
C2	0.012 (3)	0.016 (3)	0.022 (3)	−0.001 (2)	−0.001 (2)	0.002 (3)
C3	0.030 (4)	0.032 (4)	0.014 (3)	0.007 (3)	0.006 (3)	0.001 (3)
C4	0.026 (4)	0.030 (4)	0.015 (3)	−0.002 (3)	0.004 (3)	0.008 (3)
C5	0.028 (4)	0.021 (3)	0.025 (3)	−0.001 (3)	0.001 (3)	0.011 (3)
C6	0.024 (4)	0.015 (3)	0.017 (3)	0.006 (3)	0.007 (3)	−0.002 (3)
C7	0.025 (4)	0.026 (3)	0.030 (4)	0.001 (3)	0.006 (3)	0.009 (3)
C8	0.022 (4)	0.029 (4)	0.040 (4)	0.013 (3)	0.007 (3)	0.004 (3)
C9	0.024 (4)	0.017 (3)	0.043 (4)	−0.001 (3)	0.020 (3)	−0.008 (3)
C10	0.033 (4)	0.020 (3)	0.020 (3)	0.002 (3)	0.012 (3)	−0.001 (3)
C11	0.029 (4)	0.022 (3)	0.018 (3)	0.006 (3)	0.007 (3)	0.005 (3)
C12	0.020 (3)	0.015 (3)	0.016 (3)	0.003 (2)	0.003 (2)	−0.001 (2)
C13	0.031 (4)	0.023 (3)	0.026 (4)	0.007 (3)	0.011 (3)	0.006 (3)
C14	0.037 (4)	0.021 (3)	0.029 (4)	0.009 (3)	0.011 (3)	−0.005 (3)
C15	0.028 (4)	0.031 (4)	0.015 (3)	0.008 (3)	0.009 (3)	−0.002 (3)
C16	0.026 (4)	0.034 (4)	0.020 (3)	0.011 (3)	0.008 (3)	0.009 (3)
C17	0.029 (4)	0.016 (3)	0.030 (4)	0.006 (3)	0.008 (3)	0.007 (3)
Cl1	0.0256 (9)	0.0310 (9)	0.0413 (10)	0.0107 (7)	0.0139 (7)	0.0116 (7)
Cl2	0.0223 (9)	0.0311 (9)	0.0301 (9)	0.0044 (7)	0.0106 (7)	0.0095 (7)
Cl3	0.0423 (10)	0.0313 (9)	0.0273 (9)	0.0145 (7)	0.0094 (7)	0.0152 (7)
Cl4	0.0453 (11)	0.0172 (8)	0.0333 (9)	0.0026 (7)	0.0096 (8)	0.0012 (7)
N1	0.020 (3)	0.025 (3)	0.017 (3)	0.004 (2)	0.008 (2)	0.001 (2)
P1	0.0202 (9)	0.0179 (8)	0.0179 (8)	0.0053 (7)	0.0057 (7)	0.0057 (7)

Geometric parameters (Å, º)

Ti1—N1	2.174 (5)	C7—C8	1.357 (7)
Ti1—Cl3	2.2293 (18)	C7—H7	0.9500
Ti1—Cl1	2.2663 (19)	C8—C9	1.382 (8)
Ti1—Cl4	2.2766 (17)	C8—H8	0.9500
Ti1—Cl2	2.3079 (19)	C9—C10	1.367 (7)
Ti1—P1	2.6428 (17)	C9—H9	0.9500
C1—C2	1.487 (7)	C10—C11	1.371 (7)
C1—P1	1.820 (5)	C10—H10	0.9500
C1—H1A	0.9900	C11—H11	0.9500
C1—H1B	0.9900	C12—C17	1.378 (7)
C2—N1	1.303 (6)	C12—C13	1.384 (7)
C2—C5	1.439 (7)	C12—P1	1.817 (5)
C3—N1	1.464 (6)	C13—C14	1.392 (7)
C3—C4	1.471 (7)	C13—H13	0.9500
C3—H3A	0.9900	C14—C15	1.376 (8)
C3—H3B	0.9900	C14—H14	0.9500
C4—C5	1.320 (7)	C15—C16	1.361 (7)
C4—H4	0.9500	C15—H15	0.9500
C5—H5	0.9500	C16—C17	1.380 (7)
C6—C11	1.379 (7)	C16—H16	0.9500
C6—C7	1.384 (7)	C17—H17	0.9500
C6—P1	1.813 (5)
N1—Ti1—Cl3	162.51 (12)	C6—C7—H7	119.9
N1—Ti1—Cl1	85.23 (13)	C7—C8—C9	120.9 (6)
Cl3—Ti1—Cl1	92.25 (7)	C7—C8—H8	119.5
N1—Ti1—Cl4	91.10 (12)	C9—C8—H8	119.5
Cl3—Ti1—Cl4	106.38 (7)	C10—C9—C8	118.9 (6)
Cl1—Ti1—Cl4	95.06 (7)	C10—C9—H9	120.6
N1—Ti1—Cl2	86.30 (13)	C8—C9—H9	120.6
Cl3—Ti1—Cl2	93.35 (7)	C9—C10—C11	120.6 (5)
Cl1—Ti1—Cl2	168.17 (7)	C9—C10—H10	119.7
Cl4—Ti1—Cl2	93.35 (7)	C11—C10—H10	119.7
N1—Ti1—P1	71.36 (11)	C10—C11—C6	120.4 (5)
Cl3—Ti1—P1	91.32 (6)	C10—C11—H11	119.8
Cl1—Ti1—P1	89.10 (6)	C6—C11—H11	119.8
Cl4—Ti1—P1	161.60 (6)	C17—C12—C13	119.2 (5)
Cl2—Ti1—P1	80.36 (6)	C17—C12—P1	121.4 (4)
C2—C1—P1	106.2 (3)	C13—C12—P1	119.3 (4)
C2—C1—H1A	110.5	C12—C13—C14	120.7 (5)
P1—C1—H1A	110.5	C12—C13—H13	119.6
C2—C1—H1B	110.5	C14—C13—H13	119.6
P1—C1—H1B	110.5	C15—C14—C13	118.7 (5)
H1A—C1—H1B	108.7	C15—C14—H14	120.7
N1—C2—C5	112.2 (5)	C13—C14—H14	120.7
N1—C2—C1	119.5 (5)	C16—C15—C14	120.9 (5)
C5—C2—C1	128.2 (5)	C16—C15—H15	119.6
N1—C3—C4	104.9 (4)	C14—C15—H15	119.6
N1—C3—H3A	110.8	C15—C16—C17	120.5 (6)
C4—C3—H3A	110.8	C15—C16—H16	119.7
N1—C3—H3B	110.8	C17—C16—H16	119.7
C4—C3—H3B	110.8	C12—C17—C16	119.9 (5)
H3A—C3—H3B	108.8	C12—C17—H17	120.0
C5—C4—C3	108.8 (5)	C16—C17—H17	120.0
C5—C4—H4	125.6	C2—N1—C3	106.7 (5)
C3—C4—H4	125.6	C2—N1—Ti1	128.2 (4)
C4—C5—C2	107.4 (5)	C3—N1—Ti1	125.0 (3)
C4—C5—H5	126.3	C6—P1—C12	104.3 (2)
C2—C5—H5	126.3	C6—P1—C1	104.4 (2)
C11—C6—C7	118.8 (5)	C12—P1—C1	106.5 (2)
C11—C6—P1	124.4 (4)	C6—P1—Ti1	117.80 (17)
C7—C6—P1	116.8 (4)	C12—P1—Ti1	123.63 (18)
C8—C7—C6	120.3 (6)	C1—P1—Ti1	97.79 (16)
C8—C7—H7	119.9