Tetra-kis(quinolin-8-olato-κN,O)hafnium(IV) toluene disolvate.

In the title compound, [Hf(C(9)H(6)NO)(4)]·2C(7)H(8), the hafnium metal centre is coordinated by four N,O-donating bidentate quinolin-8-olate ligands arranged to give a square-anti-prismatic coordination polyhedron with a slightly distorted dodeca-hedral geometry. The average Hf-O and Hf-N distances are 2.096 (3) and 2.398 (3) Å, respectively, and the average O-Hf-N bite angle is 70.99 (11)°. The crystal packing is controlled by π-π inter-actions between quinoline ligands of neighbouring mol-ecules and hydrogen-bonding inter-actions. The inter-planar distances vary between 3.138 (1) and 3.208 (2) Å, while the centroid-centroid distances range from 3.576 (1) to 4.074 (1) Å.

Related literature

For a Zr analogue of the title compound, see: Lewis & Fay (1974 ▶). For n class="Chemical">hafnium and zirconium β-diketonato complexes, see: Viljoen et al. (2008 ▶, 2009 ▶); Demakopoulos et al. (1995 ▶), Zherikova et al. (2005 ▶, 2006 ▶, 2008 ▶); Steyn et al. (2008 ▶); Calderazzo et al. (1998 ▶).

Experimental

Crystal data

[Hf(C9H6NO)4]·2n class="Chemical">C7H8

M = 939.35

Triclinic,

a = 11.3323 (5) Å

b = 12.5539 (5) Å

c = 15.7126 (7) Å

α = 69.746 (2)°

β = 69.700 (2)°

γ = 75.787 (2)°

V = 1946.79 (14) Å3

Z = 2

Mo Kα radiation

μ = 2.73 mm−1

T = 100 K

0.22 × 0.10 × 0.04 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.585, T max = 0.899

22928 measured reflections

8458 independent reflections

7551 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.100

S = 1.04

8458 reflections

534 parameters

H-atom parameters constrained

Δρmax = 1.16 e Å−3

Δρmin = −0.81 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAIn class="Chemical">NT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043244/bg2301sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043244/bg2301Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Hf(C9H6NO)4]·2C7H8	Z = 2
Mr = 939.35	F(000) = 944
Triclinic, P1	Dx = 1.602 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.3323 (5) Å	Cell parameters from 9377 reflections
b = 12.5539 (5) Å	θ = 2.6–28.1°
c = 15.7126 (7) Å	µ = 2.73 mm−1
α = 69.746 (2)°	T = 100 K
β = 69.700 (2)°	Plate, yellow
γ = 75.787 (2)°	0.22 × 0.10 × 0.04 mm
V = 1946.79 (14) Å3

Bruker X8 APEXII 4K Kappa CCD diffractometer	8458 independent reflections
Radiation source: fine-focus sealed tube	7551 reflections with I > 2σ(I)
graphite	Rint = 0.044
ω and φ scans	θmax = 27°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
Tmin = 0.585, Tmax = 0.899	k = −16→16
22928 measured reflections	l = −20→20

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0618P)2] where P = (Fo2 + 2Fc2)/3
8458 reflections	(Δ/σ)max = 0.002
534 parameters	Δρmax = 1.16 e Å−3
0 restraints	Δρmin = −0.81 e Å−3

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.

	x	y	z	Uiso*/Ueq
C11	0.0301 (4)	0.2510 (4)	0.5067 (3)	0.0187 (9)
H11	0.0671	0.3158	0.4665	0.022*
C12	−0.0455 (4)	0.2069 (4)	0.4758 (3)	0.0221 (10)
H12	−0.057	0.2415	0.4159	0.026*
C13	−0.1014 (5)	0.1134 (4)	0.5345 (3)	0.0237 (10)
H13	−0.1498	0.0829	0.5139	0.028*
C14	−0.0872 (4)	0.0617 (4)	0.6263 (3)	0.0184 (9)
C15	−0.1430 (5)	−0.0332 (4)	0.6941 (4)	0.0244 (10)
H15	−0.195	−0.0678	0.6801	0.029*
C16	−0.1200 (5)	−0.0747 (4)	0.7813 (3)	0.0239 (10)
H16	−0.1573	−0.1376	0.8256	0.029*
C17	−0.0420 (4)	−0.0252 (4)	0.8055 (3)	0.0200 (9)
H17	−0.0293	−0.0549	0.8652	0.024*
C18	0.0159 (4)	0.0675 (3)	0.7407 (3)	0.0151 (8)
C19	−0.0091 (4)	0.1124 (3)	0.6511 (3)	0.0125 (8)
C21	0.1816 (4)	0.2455 (3)	0.8712 (3)	0.0158 (9)
H21	0.2533	0.1901	0.8658	0.019*
C22	0.1269 (5)	0.2752 (4)	0.9567 (3)	0.0202 (9)
H22	0.1611	0.2386	1.0072	0.024*
C23	0.0237 (5)	0.3580 (4)	0.9650 (3)	0.0205 (10)
H23	−0.0115	0.3791	1.0209	0.025*
C24	−0.0297 (4)	0.4116 (4)	0.8891 (3)	0.0168 (9)
C25	−0.1373 (5)	0.4969 (4)	0.8906 (3)	0.0219 (10)
H25	−0.1785	0.5219	0.9443	0.026*
C26	−0.1805 (5)	0.5423 (4)	0.8124 (3)	0.0249 (10)
H26	−0.2515	0.5984	0.814	0.03*
C27	−0.1215 (4)	0.5072 (3)	0.7294 (3)	0.0177 (9)
H27	−0.1534	0.5403	0.6776	0.021*
C28	−0.0158 (4)	0.4235 (3)	0.7253 (3)	0.0151 (9)
C29	0.0305 (4)	0.3765 (3)	0.8060 (3)	0.0139 (8)
C31	0.2648 (4)	0.5148 (3)	0.5866 (3)	0.0148 (8)
H31	0.1885	0.5379	0.5712	0.018*
C32	0.3397 (5)	0.5985 (4)	0.5694 (3)	0.0191 (9)
H32	0.3126	0.6756	0.5433	0.023*
C33	0.4522 (5)	0.5659 (4)	0.5911 (3)	0.0203 (10)
H33	0.5025	0.6207	0.5796	0.024*
C34	0.4924 (4)	0.4487 (4)	0.6312 (3)	0.0157 (9)
C35	0.6077 (4)	0.4046 (4)	0.6546 (3)	0.0205 (9)
H35	0.6635	0.454	0.6446	0.025*
C36	0.6377 (5)	0.2882 (4)	0.6923 (3)	0.0224 (10)
H36	0.7137	0.2598	0.7079	0.027*
C37	0.5553 (4)	0.2116 (4)	0.7076 (3)	0.0199 (9)
H37	0.5773	0.1336	0.734	0.024*
C38	0.4435 (4)	0.2497 (3)	0.6844 (3)	0.0147 (8)
C39	0.4106 (4)	0.3707 (3)	0.6462 (3)	0.0137 (8)
C41	0.2922 (4)	−0.0275 (3)	0.6404 (3)	0.0124 (8)
H41	0.2627	−0.0479	0.7062	0.015*
C42	0.3422 (4)	−0.1154 (3)	0.5959 (3)	0.0165 (9)
H42	0.3453	−0.1919	0.6319	0.02*
C43	0.3857 (4)	−0.0878 (3)	0.4999 (3)	0.0152 (9)
H43	0.4185	−0.1453	0.4698	0.018*
C44	0.3809 (4)	0.0293 (3)	0.4459 (3)	0.0136 (8)
C45	0.4271 (4)	0.0700 (3)	0.3460 (3)	0.0158 (9)
H45	0.4624	0.0183	0.3103	0.019*
C46	0.4198 (4)	0.1852 (4)	0.3018 (3)	0.0163 (9)
H46	0.4487	0.2105	0.2361	0.02*
C47	0.3701 (4)	0.2663 (3)	0.3526 (3)	0.0159 (9)
H47	0.3674	0.3441	0.3202	0.019*
C48	0.3249 (4)	0.2319 (3)	0.4504 (3)	0.0121 (8)
C49	0.3295 (4)	0.1114 (3)	0.4969 (3)	0.0115 (8)
C101	0.4169 (5)	0.8733 (4)	0.9727 (4)	0.0242 (10)
C102	0.3554 (5)	0.8060 (4)	1.0597 (3)	0.0287 (11)
H102	0.4019	0.7609	1.1014	0.034*
C103	0.2263 (5)	0.8043 (4)	1.0863 (4)	0.0286 (11)
H103	0.1871	0.7571	1.1449	0.034*
C104	0.1550 (5)	0.8725 (4)	1.0261 (3)	0.0233 (10)
H104	0.0679	0.8716	1.0438	0.028*
C105	0.2150 (5)	0.9418 (4)	0.9396 (3)	0.0233 (10)
H105	0.1678	0.9886	0.8988	0.028*
C106	0.3449 (5)	0.9423 (4)	0.9129 (3)	0.0197 (9)
H106	0.3843	0.9895	0.8542	0.024*
C107	0.5587 (5)	0.8748 (5)	0.9431 (4)	0.0414 (14)
H10A	0.5795	0.8976	0.9879	0.062*
H10B	0.5836	0.9283	0.8814	0.062*
H10C	0.6029	0.7996	0.9411	0.062*
C201	0.2346 (5)	0.6255 (4)	0.8215 (3)	0.0232 (10)
C202	0.2835 (4)	0.5123 (4)	0.8235 (3)	0.0206 (9)
H202	0.248	0.474	0.7994	0.025*
C203	0.3829 (5)	0.4553 (4)	0.8601 (3)	0.0281 (11)
H203	0.4145	0.3796	0.8599	0.034*
C204	0.4356 (6)	0.5098 (5)	0.8971 (4)	0.0394 (14)
H204	0.5034	0.4712	0.9215	0.047*
C205	0.3890 (7)	0.6201 (5)	0.8981 (4)	0.0459 (17)
H205	0.4239	0.6565	0.9242	0.055*
C206	0.2888 (6)	0.6785 (4)	0.8601 (3)	0.0389 (15)
H206	0.2578	0.7542	0.8607	0.047*
C207	0.1292 (5)	0.6861 (4)	0.7794 (4)	0.0353 (13)
H20A	0.1627	0.7132	0.7117	0.053*
H20B	0.0867	0.7501	0.8039	0.053*
H20C	0.0699	0.6344	0.7951	0.053*
N1	0.0504 (3)	0.2037 (3)	0.5909 (2)	0.0148 (7)
N2	0.1342 (3)	0.2939 (3)	0.7981 (2)	0.0140 (7)
N3	0.2993 (3)	0.4043 (3)	0.6239 (2)	0.0141 (7)
N4	0.2853 (3)	0.0823 (3)	0.5933 (2)	0.0130 (7)
O1	0.0910 (3)	0.1197 (2)	0.75695 (19)	0.0144 (6)
O2	0.0440 (3)	0.3817 (2)	0.6519 (2)	0.0141 (6)
O3	0.3619 (3)	0.1828 (2)	0.6929 (2)	0.0142 (6)
O4	0.2786 (3)	0.3022 (2)	0.5050 (2)	0.0134 (6)
Hf	0.194221 (16)	0.246881 (12)	0.651652 (11)	0.01143 (7)

	U11	U22	U33	U12	U13	U23
C11	0.016 (2)	0.022 (2)	0.018 (2)	−0.0016 (18)	−0.0059 (18)	−0.0054 (17)
C12	0.018 (3)	0.032 (2)	0.017 (2)	0.000 (2)	−0.0085 (19)	−0.0083 (19)
C13	0.013 (2)	0.031 (2)	0.035 (3)	0.0034 (19)	−0.013 (2)	−0.016 (2)
C14	0.013 (2)	0.019 (2)	0.027 (2)	−0.0022 (17)	−0.0079 (19)	−0.0091 (18)
C15	0.017 (3)	0.024 (2)	0.038 (3)	−0.0043 (19)	−0.010 (2)	−0.012 (2)
C16	0.020 (3)	0.023 (2)	0.028 (3)	−0.0068 (19)	−0.005 (2)	−0.0058 (19)
C17	0.018 (2)	0.022 (2)	0.018 (2)	−0.0031 (18)	−0.0045 (19)	−0.0058 (18)
C18	0.012 (2)	0.0166 (19)	0.016 (2)	−0.0025 (17)	−0.0006 (17)	−0.0075 (16)
C19	0.008 (2)	0.0133 (18)	0.016 (2)	−0.0005 (16)	−0.0033 (17)	−0.0050 (16)
C21	0.015 (2)	0.0147 (19)	0.018 (2)	−0.0002 (16)	−0.0058 (18)	−0.0057 (16)
C22	0.023 (3)	0.024 (2)	0.015 (2)	−0.0067 (19)	−0.0075 (19)	−0.0038 (18)
C23	0.021 (3)	0.026 (2)	0.014 (2)	−0.0077 (19)	0.0015 (19)	−0.0096 (18)
C24	0.016 (2)	0.020 (2)	0.014 (2)	−0.0086 (18)	0.0002 (18)	−0.0039 (17)
C25	0.022 (3)	0.024 (2)	0.019 (2)	−0.0049 (19)	0.0013 (19)	−0.0109 (18)
C26	0.019 (3)	0.024 (2)	0.031 (3)	0.0039 (19)	−0.005 (2)	−0.013 (2)
C27	0.013 (2)	0.019 (2)	0.018 (2)	−0.0046 (17)	−0.0010 (18)	−0.0038 (17)
C28	0.019 (2)	0.0137 (18)	0.014 (2)	−0.0060 (17)	−0.0025 (18)	−0.0040 (16)
C29	0.012 (2)	0.0146 (19)	0.016 (2)	−0.0055 (16)	−0.0013 (17)	−0.0053 (16)
C31	0.015 (2)	0.0174 (19)	0.015 (2)	−0.0035 (17)	−0.0039 (17)	−0.0075 (16)
C32	0.024 (3)	0.016 (2)	0.016 (2)	−0.0032 (18)	−0.0039 (19)	−0.0054 (17)
C33	0.026 (3)	0.021 (2)	0.017 (2)	−0.0075 (19)	−0.0012 (19)	−0.0105 (18)
C34	0.015 (2)	0.021 (2)	0.013 (2)	−0.0083 (17)	0.0011 (17)	−0.0097 (17)
C35	0.017 (2)	0.029 (2)	0.021 (2)	−0.0114 (19)	−0.0008 (19)	−0.0129 (19)
C36	0.015 (2)	0.032 (2)	0.029 (3)	−0.0004 (19)	−0.008 (2)	−0.018 (2)
C37	0.019 (2)	0.023 (2)	0.022 (2)	−0.0014 (19)	−0.0065 (19)	−0.0122 (18)
C38	0.017 (2)	0.0164 (19)	0.015 (2)	−0.0048 (17)	−0.0049 (18)	−0.0077 (16)
C39	0.011 (2)	0.020 (2)	0.013 (2)	−0.0042 (17)	0.0010 (17)	−0.0102 (16)
C41	0.009 (2)	0.0159 (18)	0.014 (2)	−0.0028 (16)	−0.0040 (16)	−0.0046 (16)
C42	0.015 (2)	0.0141 (19)	0.022 (2)	−0.0016 (17)	−0.0059 (18)	−0.0061 (17)
C43	0.007 (2)	0.0175 (19)	0.024 (2)	−0.0026 (16)	−0.0027 (17)	−0.0105 (17)
C44	0.011 (2)	0.0152 (19)	0.019 (2)	−0.0030 (16)	−0.0063 (17)	−0.0071 (16)
C45	0.014 (2)	0.020 (2)	0.018 (2)	−0.0010 (17)	−0.0032 (18)	−0.0129 (17)
C46	0.012 (2)	0.026 (2)	0.014 (2)	−0.0055 (18)	−0.0057 (17)	−0.0061 (17)
C47	0.016 (2)	0.0165 (19)	0.017 (2)	0.0002 (17)	−0.0076 (18)	−0.0048 (16)
C48	0.008 (2)	0.0155 (19)	0.016 (2)	−0.0054 (16)	−0.0030 (16)	−0.0052 (16)
C49	0.013 (2)	0.0126 (18)	0.0120 (19)	−0.0058 (16)	−0.0041 (16)	−0.0036 (15)
C101	0.022 (3)	0.024 (2)	0.029 (3)	−0.002 (2)	−0.008 (2)	−0.012 (2)
C102	0.031 (3)	0.028 (2)	0.021 (3)	0.002 (2)	−0.012 (2)	−0.002 (2)
C103	0.032 (3)	0.027 (2)	0.021 (2)	−0.006 (2)	−0.005 (2)	−0.0017 (19)
C104	0.016 (2)	0.023 (2)	0.032 (3)	−0.0052 (19)	−0.003 (2)	−0.012 (2)
C105	0.029 (3)	0.018 (2)	0.029 (3)	0.0045 (19)	−0.018 (2)	−0.0111 (19)
C106	0.023 (3)	0.017 (2)	0.019 (2)	−0.0089 (18)	−0.0017 (19)	−0.0051 (17)
C107	0.024 (3)	0.051 (3)	0.045 (4)	−0.005 (3)	−0.005 (3)	−0.014 (3)
C201	0.027 (3)	0.021 (2)	0.013 (2)	−0.012 (2)	0.0096 (19)	−0.0033 (17)
C202	0.017 (2)	0.027 (2)	0.019 (2)	−0.0059 (19)	−0.0004 (19)	−0.0112 (18)
C203	0.028 (3)	0.036 (3)	0.018 (2)	−0.009 (2)	−0.003 (2)	−0.006 (2)
C204	0.034 (3)	0.069 (4)	0.017 (3)	−0.027 (3)	−0.004 (2)	−0.006 (3)
C205	0.071 (5)	0.063 (4)	0.020 (3)	−0.052 (4)	−0.005 (3)	−0.009 (3)
C206	0.068 (5)	0.025 (2)	0.020 (3)	−0.026 (3)	0.008 (3)	−0.009 (2)
C207	0.029 (3)	0.027 (3)	0.027 (3)	0.005 (2)	0.003 (2)	0.001 (2)
N1	0.0113 (19)	0.0180 (17)	0.0155 (18)	0.0010 (14)	−0.0043 (15)	−0.0068 (14)
N2	0.0152 (19)	0.0123 (15)	0.0143 (18)	−0.0064 (14)	−0.0028 (15)	−0.0021 (13)
N3	0.0129 (19)	0.0173 (17)	0.0130 (17)	−0.0036 (14)	−0.0005 (15)	−0.0076 (14)
N4	0.0104 (18)	0.0131 (16)	0.0185 (18)	−0.0021 (14)	−0.0061 (15)	−0.0061 (14)
O1	0.0159 (16)	0.0165 (13)	0.0131 (14)	−0.0052 (12)	−0.0043 (12)	−0.0049 (11)
O2	0.0149 (16)	0.0143 (13)	0.0139 (15)	0.0001 (12)	−0.0047 (12)	−0.0059 (11)
O3	0.0119 (16)	0.0149 (13)	0.0177 (15)	−0.0019 (11)	−0.0042 (12)	−0.0071 (11)
O4	0.0143 (16)	0.0118 (13)	0.0149 (15)	−0.0054 (11)	−0.0014 (12)	−0.0050 (11)
Hf	0.01205 (11)	0.01173 (10)	0.01191 (10)	−0.00236 (7)	−0.00353 (7)	−0.00454 (7)

C11—N1	1.325 (5)	C41—C42	1.408 (5)
C11—C12	1.409 (6)	C41—H41	0.93
C11—H11	0.93	C42—C43	1.357 (6)
C12—C13	1.356 (7)	C42—H42	0.93
C12—H12	0.93	C43—C44	1.419 (5)
C13—C14	1.411 (6)	C43—H43	0.93
C13—H13	0.93	C44—C49	1.413 (5)
C14—C15	1.407 (6)	C44—C45	1.417 (6)
C14—C19	1.423 (6)	C45—C46	1.366 (6)
C15—C16	1.380 (7)	C45—H45	0.93
C15—H15	0.93	C46—C47	1.400 (6)
C16—C17	1.407 (6)	C46—H46	0.93
C16—H16	0.93	C47—C48	1.383 (6)
C17—C18	1.382 (6)	C47—H47	0.93
C17—H17	0.93	C48—O4	1.332 (5)
C18—O1	1.326 (5)	C48—C49	1.432 (5)
C18—C19	1.424 (6)	C49—N4	1.363 (5)
C19—N1	1.360 (5)	C101—C102	1.377 (7)
C21—N2	1.328 (5)	C101—C106	1.386 (6)
C21—C22	1.409 (6)	C101—C107	1.513 (7)
C21—H21	0.93	C102—C103	1.378 (7)
C22—C23	1.362 (6)	C102—H102	0.93
C22—H22	0.93	C103—C104	1.382 (7)
C23—C24	1.411 (6)	C103—H103	0.93
C23—H23	0.93	C104—C105	1.377 (7)
C24—C25	1.410 (6)	C104—H104	0.93
C24—C29	1.413 (6)	C105—C106	1.385 (7)
C25—C26	1.367 (6)	C105—H105	0.93
C25—H25	0.93	C106—H106	0.93
C26—C27	1.410 (6)	C107—H10A	0.96
C26—H26	0.93	C107—H10B	0.96
C27—C28	1.385 (6)	C107—H10C	0.96
C27—H27	0.93	C201—C202	1.386 (6)
C28—O2	1.329 (5)	C201—C206	1.389 (7)
C28—C29	1.422 (6)	C201—C207	1.482 (7)
C29—N2	1.365 (5)	C202—C203	1.371 (7)
C31—N3	1.322 (5)	C202—H202	0.93
C31—C32	1.407 (6)	C203—C204	1.371 (7)
C31—H31	0.93	C203—H203	0.93
C32—C33	1.364 (6)	C204—C205	1.359 (9)
C32—H32	0.93	C204—H204	0.93
C33—C34	1.414 (6)	C205—C206	1.393 (9)
C33—H33	0.93	C205—H205	0.93
C34—C35	1.409 (6)	C206—H206	0.93
C34—C39	1.418 (6)	C207—H20A	0.96
C35—C36	1.377 (6)	C207—H20B	0.96
C35—H35	0.93	C207—H20C	0.96
C36—C37	1.407 (6)	N1—Hf	2.395 (3)
C36—H36	0.93	N2—Hf	2.400 (3)
C37—C38	1.367 (6)	N3—Hf	2.391 (3)
C37—H37	0.93	N4—Hf	2.404 (3)
C38—O3	1.340 (5)	O1—Hf	2.098 (3)
C38—C39	1.433 (6)	O2—Hf	2.085 (3)
C39—N3	1.353 (5)	O3—Hf	2.103 (3)
C41—N4	1.317 (5)	O4—Hf	2.096 (3)
N1—C11—C12	122.4 (4)	C48—C47—H47	119.7
N1—C11—H11	118.8	C46—C47—H47	119.7
C12—C11—H11	118.8	O4—C48—C47	125.2 (4)
C13—C12—C11	119.2 (4)	O4—C48—C49	117.2 (3)
C13—C12—H12	120.4	C47—C48—C49	117.7 (4)
C11—C12—H12	120.4	N4—C49—C44	123.0 (4)
C12—C13—C14	121.0 (4)	N4—C49—C48	115.2 (3)
C12—C13—H13	119.5	C44—C49—C48	121.8 (4)
C14—C13—H13	119.5	C102—C101—C106	118.2 (5)
C15—C14—C13	126.1 (4)	C102—C101—C107	121.5 (5)
C15—C14—C19	118.2 (4)	C106—C101—C107	120.2 (5)
C13—C14—C19	115.7 (4)	C101—C102—C103	121.4 (5)
C16—C15—C14	119.6 (4)	C101—C102—H102	119.3
C16—C15—H15	120.2	C103—C102—H102	119.3
C14—C15—H15	120.2	C102—C103—C104	120.2 (5)
C15—C16—C17	122.2 (4)	C102—C103—H103	119.9
C15—C16—H16	118.9	C104—C103—H103	119.9
C17—C16—H16	118.9	C105—C104—C103	119.0 (5)
C18—C17—C16	120.1 (4)	C105—C104—H104	120.5
C18—C17—H17	119.9	C103—C104—H104	120.5
C16—C17—H17	119.9	C104—C105—C106	120.6 (4)
O1—C18—C17	124.5 (4)	C104—C105—H105	119.7
O1—C18—C19	117.4 (4)	C106—C105—H105	119.7
C17—C18—C19	118.1 (4)	C105—C106—C101	120.6 (4)
N1—C19—C14	123.1 (4)	C105—C106—H106	119.7
N1—C19—C18	115.1 (4)	C101—C106—H106	119.7
C14—C19—C18	121.7 (4)	C101—C107—H10A	109.5
N2—C21—C22	122.1 (4)	C101—C107—H10B	109.5
N2—C21—H21	118.9	H10A—C107—H10B	109.5
C22—C21—H21	118.9	C101—C107—H10C	109.5
C23—C22—C21	119.7 (4)	H10A—C107—H10C	109.5
C23—C22—H22	120.1	H10B—C107—H10C	109.5
C21—C22—H22	120.1	C202—C201—C206	117.1 (5)
C22—C23—C24	120.0 (4)	C202—C201—C207	120.8 (4)
C22—C23—H23	120	C206—C201—C207	122.1 (5)
C24—C23—H23	120	C203—C202—C201	121.8 (4)
C25—C24—C23	124.7 (4)	C203—C202—H202	119.1
C25—C24—C29	118.6 (4)	C201—C202—H202	119.1
C23—C24—C29	116.7 (4)	C204—C203—C202	120.0 (5)
C26—C25—C24	119.3 (4)	C204—C203—H203	120
C26—C25—H25	120.4	C202—C203—H203	120
C24—C25—H25	120.4	C205—C204—C203	120.1 (6)
C25—C26—C27	122.5 (4)	C205—C204—H204	120
C25—C26—H26	118.7	C203—C204—H204	120
C27—C26—H26	118.7	C204—C205—C206	120.0 (5)
C28—C27—C26	119.9 (4)	C204—C205—H205	120
C28—C27—H27	120	C206—C205—H205	120
C26—C27—H27	120	C201—C206—C205	121.0 (5)
O2—C28—C27	124.6 (4)	C201—C206—H206	119.5
O2—C28—C29	117.3 (4)	C205—C206—H206	119.5
C27—C28—C29	118.0 (4)	C201—C207—H20A	109.5
N2—C29—C24	122.8 (4)	C201—C207—H20B	109.5
N2—C29—C28	115.4 (4)	H20A—C207—H20B	109.5
C24—C29—C28	121.7 (4)	C201—C207—H20C	109.5
N3—C31—C32	122.3 (4)	H20A—C207—H20C	109.5
N3—C31—H31	118.9	H20B—C207—H20C	109.5
C32—C31—H31	118.9	C11—N1—C19	118.5 (4)
C33—C32—C31	119.6 (4)	C11—N1—Hf	128.7 (3)
C33—C32—H32	120.2	C19—N1—Hf	112.7 (3)
C31—C32—H32	120.2	C21—N2—C29	118.5 (4)
C32—C33—C34	119.9 (4)	C21—N2—Hf	129.1 (3)
C32—C33—H33	120	C29—N2—Hf	112.2 (3)
C34—C33—H33	120	C31—N3—C39	118.9 (4)
C35—C34—C33	125.0 (4)	C31—N3—Hf	128.1 (3)
C35—C34—C39	118.5 (4)	C39—N3—Hf	112.9 (2)
C33—C34—C39	116.4 (4)	C41—N4—C49	118.0 (3)
C36—C35—C34	119.9 (4)	C41—N4—Hf	129.4 (3)
C36—C35—H35	120	C49—N4—Hf	112.5 (2)
C34—C35—H35	120	C18—O1—Hf	123.2 (3)
C35—C36—C37	121.2 (4)	C28—O2—Hf	123.8 (3)
C35—C36—H36	119.4	C38—O3—Hf	123.4 (2)
C37—C36—H36	119.4	C48—O4—Hf	123.6 (2)
C38—C37—C36	121.3 (4)	O2—Hf—O4	94.50 (11)
C38—C37—H37	119.4	O2—Hf—O1	97.00 (11)
C36—C37—H37	119.4	O4—Hf—O1	141.84 (10)
O3—C38—C37	125.4 (4)	O2—Hf—O3	142.31 (11)
O3—C38—C39	116.5 (4)	O4—Hf—O3	97.89 (11)
C37—C38—C39	118.1 (4)	O1—Hf—O3	94.85 (11)
N3—C39—C34	122.9 (4)	O2—Hf—N3	78.53 (12)
N3—C39—C38	116.0 (4)	O4—Hf—N3	73.74 (11)
C34—C39—C38	121.0 (4)	O1—Hf—N3	144.27 (11)
N4—C41—C42	123.1 (4)	O3—Hf—N3	71.16 (11)
N4—C41—H41	118.4	O2—Hf—N1	73.68 (11)
C42—C41—H41	118.4	O4—Hf—N1	77.94 (11)
C43—C42—C41	119.6 (4)	O1—Hf—N1	70.73 (11)
C43—C42—H42	120.2	O3—Hf—N1	143.78 (11)
C41—C42—H42	120.2	N3—Hf—N1	138.19 (12)
C42—C43—C44	119.5 (4)	O2—Hf—N2	71.04 (11)
C42—C43—H43	120.2	O4—Hf—N2	145.17 (11)
C44—C43—H43	120.2	O1—Hf—N2	72.67 (11)
C49—C44—C45	117.8 (4)	O3—Hf—N2	78.70 (11)
C49—C44—C43	116.8 (4)	N3—Hf—N2	72.39 (11)
C45—C44—C43	125.4 (4)	N1—Hf—N2	124.51 (12)
C46—C45—C44	120.1 (4)	O2—Hf—N4	142.23 (11)
C46—C45—H45	119.9	O4—Hf—N4	70.84 (11)
C44—C45—H45	119.9	O1—Hf—N4	77.98 (11)
C45—C46—C47	122.0 (4)	O3—Hf—N4	75.31 (11)
C45—C46—H46	119	N3—Hf—N4	126.37 (12)
C47—C46—H46	119	N1—Hf—N4	69.32 (11)
C48—C47—C46	120.6 (4)	N2—Hf—N4	138.57 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C105—H105···O1i	0.93	2.56	3.467 (5)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C105—H105⋯O1i	0.93	2.56	3.467 (5)	166

Symmetry code: (i) .