metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Tri­chlorido­{meth­yl[4-(methyl­imino)­pent-2-en-2-yl]aza­nido-κ2N,N′}hafnium(IV)

aDepartment of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
*Correspondence e-mail: masuda.hideki@nitech.ac.jp

(Received 2 May 2013; accepted 13 August 2013; online 21 August 2013)

The title complex, [Hf(C29H41N2)Cl3], was synthesized from HfCl4 and HC[C(Me)N(iPr2C6H3)]2Li(Et2O) in toluene. The structure is isotypic with those of TiIV and ZrIV complexes reported previously [Nikiforov et al. (2007[Nikiforov, G. B., Roesky, H. W., Jones, P. G., Oswald, R. B. & Noltemeyer, M. (2007). Dalton Trans. pp. 4149-4159.]). Dalton Trans. pp. 4149–4159; Kakaliou et al. (1999[Kakaliou, L., Scanlon, W. J., Qian, B. S., Baek, S. W., Smith, M. R. & Motry, D. H. (1999). Inorg. Chem. 38, 5964-5977.]). Inorg. Chem. 38, 5964–5977]. There is a crystallographic mirror plane containing the Hf atom, one chloride ligand and the central diketiminate C atom. The HfIV ion has slightly distorted square-pyramidal geometry surrounded by two N atoms from the β-diketiminate ligand and by three Cl anions. Coordination bond lengths are Hf—N = 2.181 (3) Å, and Hf—Cl = 2.3148 (15) and 2.3727 (12) Å.

Related literature

For complexes bearing β-diketiminate ligands, see: Bourget-Merle et al. (2002[Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev. 102, 3031-3065.]); Hamaki et al. (2006[Hamaki, H., Takeda, N. & Tokitoh, N. (2006). Organometallics, 25, 2457-2464.]). For the synthesis of the precursor of the β-diketiminate in the title compound, see: Stender et al. (2001[Stender, M., Wright, R. J., Eichler, B. E., Prust, J., Olmstead, M. M., Roesky, H. W. & Power, P. P. (2001). J. Chem. Soc. Dalton Trans. pp. 3465-3469.]). For isotypic TiIV and ZrIV complexes, see: Nikiforov et al. (2007[Nikiforov, G. B., Roesky, H. W., Jones, P. G., Oswald, R. B. & Noltemeyer, M. (2007). Dalton Trans. pp. 4149-4159.]) and Kakaliou et al. (1999[Kakaliou, L., Scanlon, W. J., Qian, B. S., Baek, S. W., Smith, M. R. & Motry, D. H. (1999). Inorg. Chem. 38, 5964-5977.]), respectively.

[Scheme 1]

Experimental

Crystal data
  • [Hf(C29H41N2)Cl3]

  • Mr = 702.51

  • Orthorhombic, P n m a

  • a = 13.980 (3) Å

  • b = 21.808 (4) Å

  • c = 9.8492 (16) Å

  • V = 3002.8 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.75 mm−1

  • T = 173 K

  • 0.20 × 0.10 × 0.10 mm

Data collection
  • Rigaku Mercury70 diffractometer

  • 22083 measured reflections

  • 3527 independent reflections

  • 3132 reflections with F2 > 2σ(F2)

  • Rint = 0.049

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.068

  • S = 1.10

  • 3527 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 2.65 e Å−3

  • Δρmin = −1.02 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2006[Rigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: CrystalStructure (Rigaku/MSC, 2006[Rigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); software used to prepare material for publication: CrystalStructure.

Supporting information


Comment top

Recently, both main element and transition metal complexes with bulky β-diketiminates as a supporting ligand have attracted considerable attention to small molecule activation (Bourget-Merle et al., 2002). Especially, in the group 4, metal complexes of β-diketiminate were sometimes reported as pro-catalysts for the polymerization of olefins (Bourget-Merle et al., 2002), nevertheless only one example of hafnium complex with a bulky β-diketiminate is known, to our best knowledge (Hamaki et al., 2006). In this paper, we report a novel Hf(IV) complex with β-diketiminate, HC[C(Me)N(iPr2C6H3)]2HfCl3. The central Hf(IV) ion has slightly distorted square-pyramidal geometry surrounded by two N atoms from β-diketiminate ligand and by three Cl- anions. The selected geometric parameters are Hf—Cl2 = 2.3148 (15), Hf—Cl3 = 2.3727 (12), and Hf—N4 = 2.181 (3) Å. The reported complex is isomorphous to analogous complexes based on Titanium (Nikiforov et al., 2007) and Zirconium (Kakaliou et al., 1999).

Related literature top

For complexes bearing β-diketiminate ligands, see: Bourget-Merle et al. (2002); Hamaki et al. (2006). For the synthesis of the precursor of the β-diketiminate in the title compound, see: Stender et al. (2001). For isotypic TiIV and ZrIV complexes, see: Nikiforov et al. (2007) and Kakaliou et al. (1999), respectively.

Experimental top

A solution of crude HC[C(Me)N(iPr2C6H3)]2Li(Et2O) (2.0 g, 4.01 mmol, Stender et al., 2001) in toluene (20 ml) was slowly added to HfCl4 (1.28 g, 4.01 mmol) and stirred overnight at room temperature. The solution was filtered through celite and the filtrate was concentrated under reduced pressure to afford a yellow solid. The yellow solid was extracted with n-pentane (20 ml) and cooled to -40 °C to yield yellow single crystals (1.52 g, 2.16 mmol, 54% yield).

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 (aromatic CH), 0.98 (methyl CH3) or 1.00 Å (methine CH), and Uiso(H) = 1.2 Ueq(carrier C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku/MSC, 2006); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with displacement ellipsoids at the 50% probability level.
Trichlorido{methyl[4-(methylimino)pent-2-en-2-yl]azanido-κ2N,N'}hafnium(IV) top
Crystal data top
[Hf(C29H41N2)Cl3]F(000) = 1408.00
Mr = 702.51Dx = 1.554 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2nCell parameters from 7615 reflections
a = 13.980 (3) Åθ = 3.2–27.5°
b = 21.808 (4) ŵ = 3.75 mm1
c = 9.8492 (16) ÅT = 173 K
V = 3002.8 (9) Å3Chip, yellow
Z = 40.20 × 0.10 × 0.10 mm
Data collection top
Rigaku Mercury70
diffractometer
Rint = 0.049
Detector resolution: 7.314 pixels mm-1θmax = 27.5°
ω scansh = 1818
22083 measured reflectionsk = 2823
3527 independent reflectionsl = 1212
3132 reflections with F2 > 2σ(F2)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.029Secondary atom site location: difference Fourier map
wR(F2) = 0.068Hydrogen site location: inferred from neighbouring sites
S = 1.10H-atom parameters constrained
3527 reflections w = 1/[σ2(Fo2) + (0.0262P)2 + 3.927P]
where P = (Fo2 + 2Fc2)/3
163 parameters(Δ/σ)max = 0.001
0 restraintsΔρmax = 2.65 e Å3
0 constraintsΔρmin = 1.02 e Å3
Crystal data top
[Hf(C29H41N2)Cl3]V = 3002.8 (9) Å3
Mr = 702.51Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 13.980 (3) ŵ = 3.75 mm1
b = 21.808 (4) ÅT = 173 K
c = 9.8492 (16) Å0.20 × 0.10 × 0.10 mm
Data collection top
Rigaku Mercury70
diffractometer
3132 reflections with F2 > 2σ(F2)
22083 measured reflectionsRint = 0.049
3527 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 1.10Δρmax = 2.65 e Å3
3527 reflectionsΔρmin = 1.02 e Å3
163 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hf10.351205 (13)0.25000.235799 (18)0.02245 (7)
Cl20.45574 (11)0.25000.41806 (13)0.0426 (4)
Cl30.23188 (8)0.17538 (5)0.28104 (13)0.0590 (4)
N40.41607 (18)0.31701 (12)0.0996 (3)0.0211 (6)
C50.5517 (3)0.36044 (15)0.0307 (4)0.0324 (8)
C60.4993 (3)0.30737 (15)0.0335 (3)0.0241 (7)
C70.5401 (3)0.25000.0146 (4)0.0245 (9)
C80.3782 (3)0.37893 (15)0.0859 (4)0.0237 (7)
C90.4094 (3)0.42552 (15)0.1743 (4)0.0263 (7)
C100.3725 (3)0.48427 (16)0.1540 (4)0.0337 (8)
C110.3085 (3)0.49681 (16)0.0516 (4)0.0355 (8)
C120.2790 (3)0.45035 (16)0.0334 (4)0.0354 (9)
C130.3121 (3)0.39080 (15)0.0172 (4)0.0288 (7)
C140.4806 (3)0.41495 (16)0.2885 (4)0.0317 (8)
C150.4313 (3)0.4205 (2)0.4270 (4)0.0454 (10)
C160.5654 (3)0.4587 (2)0.2813 (5)0.0466 (11)
C170.2757 (3)0.34099 (18)0.1115 (5)0.0450 (11)
C180.3140 (5)0.3483 (3)0.2541 (5)0.0707 (17)
C190.1663 (4)0.3385 (3)0.1144 (6)0.0633 (14)
H20B0.50930.38130.09500.0389*
H21C0.60830.34520.07870.0389*
H22A0.57160.38930.04010.0389*
H230.60470.25000.01540.0294*
H240.39220.51650.21250.0404*
H250.28480.53730.03960.0426*
H260.23520.45920.10440.0425*
H270.50570.37220.27980.0380*
H28A0.37830.39120.43200.0545*
H29C0.47760.41160.49910.0545*
H30B0.40660.46220.43840.0545*
H31C0.61390.44610.34760.0559*
H32A0.54390.50040.30190.0559*
H33B0.59300.45760.18980.0559*
H340.29910.30080.07580.0540*
H35B0.14170.37340.16650.0760*
H36A0.14560.30020.15700.0760*
H37C0.14160.34040.02130.0760*
H38A0.28930.31510.31130.0849*
H39B0.38400.34660.25230.0849*
H40C0.29330.38780.29100.0849*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hf10.02264 (11)0.02380 (12)0.02091 (11)0.00000.00470 (7)0.0000
Cl20.0552 (9)0.0443 (8)0.0284 (7)0.00000.0114 (6)0.0000
Cl30.0439 (6)0.0417 (6)0.0914 (9)0.0175 (5)0.0394 (6)0.0235 (6)
N40.0225 (12)0.0220 (15)0.0188 (13)0.0011 (11)0.0019 (10)0.0003 (10)
C50.0320 (18)0.0295 (19)0.0358 (19)0.0063 (15)0.0100 (15)0.0021 (15)
C60.0233 (15)0.0288 (17)0.0201 (15)0.0045 (13)0.0006 (12)0.0006 (13)
C70.021 (2)0.027 (3)0.026 (3)0.00000.0042 (17)0.0000
C80.0251 (15)0.0218 (17)0.0242 (16)0.0010 (13)0.0063 (13)0.0033 (13)
C90.0282 (17)0.0245 (18)0.0261 (17)0.0020 (13)0.0062 (13)0.0026 (14)
C100.0374 (19)0.0248 (19)0.039 (2)0.0017 (15)0.0094 (16)0.0045 (15)
C110.0376 (19)0.0228 (19)0.046 (3)0.0050 (15)0.0081 (17)0.0058 (16)
C120.0345 (19)0.032 (2)0.040 (2)0.0035 (15)0.0027 (16)0.0115 (16)
C130.0316 (17)0.0270 (18)0.0277 (17)0.0015 (14)0.0009 (14)0.0050 (14)
C140.0343 (19)0.0293 (19)0.0314 (18)0.0014 (15)0.0009 (15)0.0084 (14)
C150.055 (3)0.050 (3)0.031 (2)0.003 (2)0.0006 (18)0.0088 (18)
C160.039 (3)0.049 (3)0.052 (3)0.011 (2)0.0043 (19)0.0146 (19)
C170.058 (3)0.029 (2)0.048 (3)0.0022 (18)0.027 (2)0.0018 (17)
C180.073 (4)0.088 (5)0.051 (3)0.014 (4)0.014 (3)0.032 (3)
C190.068 (4)0.061 (4)0.060 (3)0.023 (3)0.025 (3)0.005 (3)
Geometric parameters (Å, º) top
Hf1—Cl22.3148 (15)C5—H20B0.980
Hf1—Cl32.3727 (12)C5—H21C0.980
Hf1—Cl3i2.3727 (12)C5—H22A0.980
Hf1—N42.181 (3)C7—H230.950
Hf1—N4i2.181 (3)C10—H240.950
N4—C61.349 (4)C11—H250.950
N4—C81.457 (5)C12—H260.950
C5—C61.509 (5)C14—H271.000
C6—C71.388 (4)C15—H28A0.980
C8—C91.407 (5)C15—H29C0.980
C8—C131.398 (5)C15—H30B0.980
C9—C101.395 (5)C16—H31C0.980
C9—C141.519 (5)C16—H32A0.980
C10—C111.376 (6)C16—H33B0.980
C11—C121.377 (6)C17—H341.000
C12—C131.387 (5)C18—H38A0.980
C13—C171.517 (6)C18—H39B0.980
C14—C151.533 (6)C18—H40C0.980
C14—C161.523 (6)C19—H35B0.980
C17—C181.511 (7)C19—H36A0.980
C17—C191.531 (7)C19—H37C0.980
Hf1···C6i3.134 (3)H36A···H40C3.1084
Hf1···C73.423 (5)H37C···H38A3.5678
Hf1···C8i3.198 (4)H37C···H40C3.5528
Cl3···C8i3.046 (4)H38A···H38Ai2.8376
Cl3···C9i3.480 (4)Cl2···H37Cii3.4172
Cl3···C13i3.460 (4)Cl2···H37Ciii3.4172
N4···C6i3.022 (5)Cl3···H21Civ3.4324
N4···C142.973 (5)Cl3···H22Aiv3.1806
N4···C172.906 (5)Cl3···H23iv3.3374
C5···C82.714 (5)Cl3···H27iv3.3816
C5···C93.169 (5)Cl3···H31Civ3.3684
C5···C133.418 (5)Cl3···H33Biv3.5015
C5···C143.505 (5)C5···H24v3.3202
C6···C93.184 (5)C5···H25v3.1951
C6···C133.226 (5)C5···H35Bvi3.2492
C6···C143.447 (5)C5···H36Avi3.5932
C6···C173.514 (6)C10···H20Bv3.4145
C8···C112.770 (5)C10···H22Av3.4442
C8···C153.558 (5)C10···H26vii3.0737
C8···C183.531 (6)C10···H35Bvii3.5779
C9···C122.793 (5)C11···H22Av3.1289
C10···C132.778 (5)C11···H26vii3.5735
C10···C153.137 (6)C11···H30Bviii3.3299
C10···C163.026 (6)C11···H31Cix3.0996
C12···C183.150 (7)C11···H33Bv2.9226
C12···C193.011 (7)C11···H40Cvii3.2803
Hf1···H273.4567C12···H24viii3.5377
Hf1···H27i3.4567C12···H30Bviii3.2326
Hf1···H343.3432C12···H31Cix2.9471
Hf1···H34i3.3432C12···H33Bv3.1000
Cl2···H273.0726C13···H31Cix3.4529
Cl2···H27i3.0726C15···H25vii3.3478
Cl2···H28A3.2664C15···H26vii3.5208
Cl2···H28Ai3.2664C15···H32Ax3.1979
Cl3···H28Ai2.9170C15···H37Ciii3.5433
Cl3···H37Ci3.2526C15···H40Cxi3.4560
N4···H20B2.7090C16···H30Bx3.2793
N4···H21C3.2680C18···H21Cxii3.3144
N4···H22A2.7492C18···H25viii3.5028
N4···H233.2201C18···H28Axiii3.3537
N4···H272.4832C19···H21Cxii3.1334
N4···H342.4045C19···H29Cix3.2847
N4···H34i3.5007C19···H31Cix3.5986
N4···H39B3.5534H20B···C10v3.4145
C5···H232.5242H20B···H24v2.8635
C5···H273.1349H20B···H25v3.4260
C5···H33B3.0880H20B···H32Av3.3703
C5···H39B3.2181H20B···H35Bvi2.9948
C6···H272.8088H20B···H36Avi3.5667
C6···H343.0015H21C···Cl3ii3.4324
C6···H39B3.3543H21C···C18vi3.3144
C7···H20B3.0904H21C···C19vi3.1334
C7···H20Bi3.0904H21C···H24v3.2920
C7···H21C2.4616H21C···H25v2.9928
C7···H21Ci2.4616H21C···H35Bvi2.6257
C7···H22A3.0807H21C···H36Avi2.8300
C7···H22Ai3.0807H21C···H38Avi2.8303
C8···H20B2.5573H21C···H40Cvi3.0341
C8···H22A2.7505H22A···Cl3ii3.1806
C8···H243.2554H22A···C10v3.4442
C8···H263.2523H22A···C11v3.1289
C8···H272.6160H22A···H24v3.2656
C8···H28A3.4192H22A···H25v2.6850
C8···H342.5814H23···Cl3ii3.3374
C8···H37C3.5718H23···Cl3iii3.3374
C8···H39B3.4060H23···H36Axiv3.4545
C9···H20B3.1492H23···H36Avi3.4545
C9···H22A2.7401H23···H38Axiv3.4045
C9···H253.2766H23···H38Avi3.4045
C9···H28A2.6818H24···C5v3.3202
C9···H29C3.3521H24···C12vii3.5377
C9···H30B2.7215H24···H20Bv2.8635
C9···H31C3.3598H24···H21Cv3.2920
C9···H32A2.7896H24···H22Av3.2656
C9···H33B2.6637H24···H26vii2.5889
C10···H263.2347H24···H35Bvii2.7218
C10···H273.3127H24···H40Cvii3.3290
C10···H28A3.4094H25···C5v3.1951
C10···H30B2.8813H25···C15viii3.3478
C10···H32A2.8258H25···C18vii3.5028
C10···H33B3.1557H25···H20Bv3.4260
C12···H243.2331H25···H21Cv2.9928
C12···H343.3005H25···H22Av2.6850
C12···H35B2.8678H25···H26vii3.5183
C12···H37C3.0741H25···H28Aviii2.9593
C12···H39B3.4533H25···H30Bviii2.8558
C12···H40C2.8877H25···H31Cix3.3002
C13···H20B2.8696H25···H33Bv2.8353
C13···H253.2652H25···H40Cvii2.5780
C13···H35B2.8250H26···C10viii3.0737
C13···H36A3.3496H26···C11viii3.5735
C13···H37C2.6241H26···C15viii3.5208
C13···H38A3.3496H26···H24viii2.5889
C13···H39B2.7022H26···H25viii3.5183
C13···H40C2.7100H26···H30Bviii2.6539
C14···H22A2.8131H26···H31Cix3.0590
C14···H242.6445H26···H33Bv3.1254
C15···H243.0241H27···Cl3ii3.3816
C15···H31C2.7278H27···H37Ciii3.1229
C15···H32A2.6519H28A···C18xi3.3537
C15···H33B3.3488H28A···H25vii2.9593
C16···H22A2.8170H28A···H38Axi3.2702
C16···H242.8133H28A···H39Bxi3.2591
C16···H28A3.3482H28A···H40Cxi2.9765
C16···H29C2.6767H29C···C19iii3.2847
C16···H30B2.7069H29C···H30Bx3.2514
C17···H20B3.3862H29C···H32Ax2.7591
C17···H262.6413H29C···H35Biii2.9453
C17···H34i3.1288H29C···H37Ciii2.7779
C18···H20B3.2300H29C···H39Bxi3.1172
C18···H263.0403H29C···H40Cxi3.3429
C18···H35B2.6163H30B···C11vii3.3299
C18···H36A2.7483H30B···C12vii3.2326
C18···H37C3.3298H30B···C16x3.2793
C19···H262.8053H30B···H25vii2.8558
C19···H34i3.5806H30B···H26vii2.6539
C19···H36Ai3.0673H30B···H29Cx3.2514
C19···H38A2.6427H30B···H30Bx3.3174
C19···H39B3.3372H30B···H31Cx2.9193
C19···H40C2.7087H30B···H32Ax2.7726
H20B···H233.2545H30B···H40Cxi3.4993
H20B···H33B3.4651H31C···Cl3ii3.3684
H20B···H343.4284H31C···C11iii3.0996
H20B···H39B2.4584H31C···C12iii2.9471
H20B···H40C3.5865H31C···C13iii3.4529
H21C···H232.1675H31C···C19iii3.5986
H21C···H39B3.5718H31C···H25iii3.3002
H22A···H233.1219H31C···H26iii3.0590
H22A···H272.5613H31C···H30Bx2.9193
H22A···H31C3.3247H31C···H35Biii3.5407
H22A···H32A3.5586H31C···H37Ciii2.8971
H22A···H33B2.1161H32A···C15x3.1979
H24···H252.3158H32A···H20Bv3.3703
H24···H273.5866H32A···H29Cx2.7591
H24···H28A3.4900H32A···H30Bx2.7726
H24···H30B2.5277H32A···H39Bv3.5202
H24···H32A2.3230H32A···H40Cv3.3360
H24···H33B3.0951H33B···Cl3ii3.5015
H25···H262.3209H33B···C11v2.9226
H26···H343.5806H33B···C12v3.1000
H26···H35B2.3646H33B···H25v2.8353
H26···H37C3.0160H33B···H26v3.1254
H26···H39B3.5336H35B···C5xii3.2492
H26···H40C2.5425H35B···C10viii3.5779
H27···H28A2.3643H35B···H20Bxii2.9948
H27···H29C2.3585H35B···H21Cxii2.6257
H27···H30B2.8660H35B···H24viii2.7218
H27···H31C2.3106H35B···H29Cix2.9453
H27···H32A2.8556H35B···H31Cix3.5407
H27···H33B2.3963H36A···C5xii3.5932
H28A···H32A3.5603H36A···H20Bxii3.5667
H29C···H31C2.5357H36A···H21Cxii2.8300
H29C···H32A2.8958H36A···H23xv3.4545
H29C···H33B3.5899H37C···Cl2iv3.4172
H30B···H31C3.0532H37C···C15ix3.5433
H30B···H32A2.4868H37C···H27ix3.1229
H30B···H33B3.5759H37C···H29Cix2.7779
H34···H34i2.2148H37C···H31Cix2.8971
H34···H35B2.8549H38A···H21Cxii2.8303
H34···H36A2.2909H38A···H23xv3.4045
H34···H36Ai3.1772H38A···H28Axiii3.2702
H34···H37C2.4257H39B···H28Axiii3.2591
H34···H38A2.3444H39B···H29Cxiii3.1172
H34···H38Ai3.4323H39B···H32Av3.5202
H34···H39B2.3292H40C···C11viii3.2803
H34···H40C2.8463H40C···C15xiii3.4560
H35B···H38A2.8131H40C···H21Cxii3.0341
H35B···H39B3.5400H40C···H24viii3.3290
H35B···H40C2.4696H40C···H25viii2.5780
H36A···H36Ai2.1882H40C···H28Axiii2.9765
H36A···H37Ci3.3453H40C···H29Cxiii3.3429
H36A···H38A2.5404H40C···H30Bxiii3.4993
H36A···H38Ai3.5585H40C···H32Av3.3360
Cl2—Hf1—Cl3107.35 (4)H21C—C5—H22A109.466
Cl2—Hf1—Cl3i107.35 (4)C6—C7—H23115.628
Cl2—Hf1—N4102.39 (8)C6i—C7—H23115.628
Cl2—Hf1—N4i102.39 (8)C9—C10—H24119.072
Cl3—Hf1—Cl3i86.61 (4)C11—C10—H24119.075
Cl3—Hf1—N4150.14 (8)C10—C11—H25120.198
Cl3—Hf1—N4i87.04 (8)C12—C11—H25120.205
Cl3i—Hf1—N487.04 (8)C11—C12—H26119.356
Cl3i—Hf1—N4i150.14 (8)C13—C12—H26119.357
N4—Hf1—N4i84.12 (10)C9—C14—H27107.891
Hf1—N4—C6123.4 (2)C15—C14—H27107.901
Hf1—N4—C8121.8 (2)C16—C14—H27107.895
C6—N4—C8114.4 (3)C14—C15—H28A109.471
N4—C6—C5120.1 (3)C14—C15—H29C109.465
N4—C6—C7124.0 (3)C14—C15—H30B109.478
C5—C6—C7115.8 (3)H28A—C15—H29C109.472
C6—C7—C6i128.7 (4)H28A—C15—H30B109.472
N4—C8—C9120.0 (3)H29C—C15—H30B109.470
N4—C8—C13118.6 (3)C14—C16—H31C109.474
C9—C8—C13121.4 (3)C14—C16—H32A109.459
C8—C9—C10117.4 (3)C14—C16—H33B109.477
C8—C9—C14123.5 (3)H31C—C16—H32A109.468
C10—C9—C14119.2 (3)H31C—C16—H33B109.482
C9—C10—C11121.9 (4)H32A—C16—H33B109.467
C10—C11—C12119.6 (4)C13—C17—H34107.625
C11—C12—C13121.3 (4)C18—C17—H34107.627
C8—C13—C12118.5 (3)C19—C17—H34107.628
C8—C13—C17122.3 (3)C17—C18—H38A109.459
C12—C13—C17119.2 (4)C17—C18—H39B109.471
C9—C14—C15110.6 (3)C17—C18—H40C109.474
C9—C14—C16112.4 (3)H38A—C18—H39B109.469
C15—C14—C16110.0 (3)H38A—C18—H40C109.473
C13—C17—C18112.0 (4)H39B—C18—H40C109.481
C13—C17—C19111.8 (4)C17—C19—H35B109.477
C18—C17—C19109.9 (4)C17—C19—H36A109.473
C6—C5—H20B109.467C17—C19—H37C109.470
C6—C5—H21C109.476H35B—C19—H36A109.468
C6—C5—H22A109.471H35B—C19—H37C109.471
H20B—C5—H21C109.476H36A—C19—H37C109.467
H20B—C5—H22A109.470
Cl2—Hf1—N4—C669.28 (18)N4—C6—C7—C6i13.4 (6)
Cl2—Hf1—N4—C8103.09 (16)C5—C6—C7—C6i164.0 (4)
Cl2—Hf1—N4i—C6i69.28 (18)N4—C8—C9—C10178.3 (3)
Cl2—Hf1—N4i—C8i103.09 (16)N4—C8—C9—C141.4 (5)
Cl3—Hf1—N4—C6105.67 (19)N4—C8—C13—C12177.5 (3)
Cl3—Hf1—N4—C882.0 (3)N4—C8—C13—C172.4 (5)
Cl3—Hf1—N4i—C6i176.40 (18)C9—C8—C13—C121.5 (5)
Cl3—Hf1—N4i—C8i4.03 (16)C9—C8—C13—C17178.6 (3)
Cl3i—Hf1—N4—C6176.40 (18)C13—C8—C9—C100.7 (5)
Cl3i—Hf1—N4—C84.03 (16)C13—C8—C9—C14179.6 (3)
Cl3i—Hf1—N4i—C6i105.67 (19)C8—C9—C10—C110.3 (5)
Cl3i—Hf1—N4i—C8i82.0 (3)C8—C9—C14—C15110.5 (4)
N4—Hf1—N4i—C6i32.15 (18)C8—C9—C14—C16126.1 (3)
N4—Hf1—N4i—C8i155.47 (18)C10—C9—C14—C1569.8 (4)
N4i—Hf1—N4—C632.15 (18)C10—C9—C14—C1653.6 (4)
N4i—Hf1—N4—C8155.47 (18)C14—C9—C10—C11179.4 (3)
Hf1—N4—C6—C5164.94 (16)C9—C10—C11—C120.4 (6)
Hf1—N4—C6—C717.8 (4)C10—C11—C12—C130.5 (6)
Hf1—N4—C8—C987.6 (3)C11—C12—C13—C81.5 (5)
Hf1—N4—C8—C1393.4 (3)C11—C12—C13—C17178.6 (3)
C6—N4—C8—C985.4 (4)C8—C13—C17—C18109.4 (4)
C6—N4—C8—C1393.6 (4)C8—C13—C17—C19126.7 (4)
C8—N4—C6—C57.9 (4)C12—C13—C17—C1870.5 (5)
C8—N4—C6—C7169.3 (3)C12—C13—C17—C1953.4 (5)
Symmetry codes: (i) x, y+1/2, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y, z+1/2; (iv) x1/2, y+1/2, z+1/2; (v) x+1, y+1, z; (vi) x+1/2, y, z1/2; (vii) x+1/2, y+1, z+1/2; (viii) x+1/2, y+1, z1/2; (ix) x1/2, y, z+1/2; (x) x+1, y+1, z+1; (xi) x, y, z+1; (xii) x1/2, y, z1/2; (xiii) x, y, z1; (xiv) x+1/2, y+1/2, z1/2; (xv) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Hf(C29H41N2)Cl3]
Mr702.51
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)173
a, b, c (Å)13.980 (3), 21.808 (4), 9.8492 (16)
V3)3002.8 (9)
Z4
Radiation typeMo Kα
µ (mm1)3.75
Crystal size (mm)0.20 × 0.10 × 0.10
Data collection
DiffractometerRigaku Mercury70
diffractometer
Absorption correction
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
22083, 3527, 3132
Rint0.049
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.068, 1.10
No. of reflections3527
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.65, 1.02

Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2006).

 

Acknowledgements

We gratefully acknowledge support of this work by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, and in part by a grant from the Knowledge Cluster Program.

References

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First citationRigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.
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First citationStender, M., Wright, R. J., Eichler, B. E., Prust, J., Olmstead, M. M., Roesky, H. W. & Power, P. P. (2001). J. Chem. Soc. Dalton Trans. pp. 3465–3469.  Web of Science CSD CrossRef

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