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Acta Cryst. (2012). E68, m1344-m1345    [ doi:10.1107/S1600536812042092 ]

Tetrakis(5,7-dimethylquinolin-8-olato-[kappa]2N,O)zirconium(IV) dimethylformamide disolvate

M. Steyn, H. G. Visser and A. Roodt

Abstract top

In the title compound, [Zr(C11H10NO)4]·2C3H7NO, the ZrIV ion is coordinated by four bidentate 5,7-dimethylquinolin-8-olate ligands in a slightly distorted square-antiprismatic coordination environment. The asymmetric unit also contains two N,N'-dimethylformamide (DMF) solvent molecules. In the crystal, a weak C-H...O hydrogen bond links the complex molecule to a solvent molecule and weak [pi]-[pi] stacking interactions [centroid-centroid distance = 3.671 (3) Å] also occur. One of the DMF solvent molecules was refined as disordered over three sets of sites, with refined occupancies in the ratio of 0.391 (9):0.342 (10):0.267 (7).

Comment top

This study forms part of our ongoing research of structure reactivity relationships in catalysis, separation chemistry and other industrial reaction mechanisms including radio pharmacy (Roodt et al. 2011; Schutte et al. 2011; Brink et al. 2010; Ferreira et al. 2007; Haumann et al. 2004; Steyn et al. 2008, 2011; Viljoen et al. 2008, 2009a,b, 2010a,b).

The asymmetric unit of the title compound, [Zr(C10H11NO)4].2C3H7NO, with C10H11NO (diMeOx) = 5,7-Dimethyl-8-quinolinol, consists of a ZrIV ion coordinated to four bidentate ligands (diMeOx), as well as two N,N'-dimethylformamide (DMF) solvent molecules. In the complex molecule (Fig. 1) the ZrIV ion lies at the centre of an approximate square antiprismatic coordination polyhedron of the N,O-coordination ligand atoms, with a small distortion towards dodecahedral geometry. The Zr—N and Zr—O bond distances range from 2.094 (2) to 2.117 (2) Å and 2.398 (2) to 2.438 (2) Å, respectively. The N—Zr—O bite angles range from 69.70 (8)° to 70.55 (8)°.

In the crystal, a weak C—H···O hydrogen bond connects the complex molecule to a solvent molecule (Table 1). In addition, weak π–π interactions exist between the pyridine rings of the diMeOx ligand and symmetry related molecules (1 - x, 1 - y, 1/2 + z) , with interplanar and centroid-to-centroid distances of 3.433 (4) Å and 3.671 (3) Å, respectively (Figure 2).

Related literature top

For N,O- and O,O'-bidentate ligand complexes of zirconium and hafnium, see: Calderazzo et al. (1998); Demakopoulos et al. (1995); Steyn et al. (2008, 2011); Viljoen et al. (2008, 2009a,b; 2010a,b); Zherikova et al. (2005, 2006, 2008). For our ongoing research of structure reactivity relationships in catalysis, separation chemistry and other industrial reaction mechanisms, see: Roodt et al. (2011); Schutte et al. (2011); Brink et al. (2010); Ferreira et al. (2007); Haumann et al. (2004). Scheme - show DMF in full

Experimental top

Chemicals were purchased from Sigma-Aldrich and used as received. ZrCl4 (101.3 mg, 0.435 mmol) and 5,7-Dimethyl-8-quinolinol (diMeOxH) (228.2 mg, 1.317 mmol) was separately dissolved in DMF (2.5 ml ea) and heated to 60°C. The diMeOxH solution as added drop-wise to the zirconium solution and stirred at 333 K for 30 minutes. The reaction solution was removed from heating, covered and left to stand. Red cuboid crystals, suitable for single X-Ray diffraction, formed after 10 days. (Yield: 203 mg, 79%).

Refinement top

H atoms were placed inidealized positions (C—H = 0.93–0.96Å) and constrained to ride on their parent atoms with Uiso(H) = 1.2–1.5Ueq(C). The highest residual electron density was located 0.95 Å from O102. One of the DMF solvent molecules was refined as disordered over three sets of sites with refined occupancies in a ratio of 0.391 (9):0.342 (10):0.267 (7).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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).

Figures top
[Figure 1] Fig. 1. The molecular structre of the Zr complex of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms and the solvent molecules are omitted for clarity.
[Figure 2] Fig. 2. Part of the crystal structure with weak π–π interactions shown as dashed lines.
Tetrakis(5,7-dimethylquinolin-8-olato-κ2N,O)zirconium(IV) dimethylformamide disolvate top
Crystal data top
[Zr(C11H10NO)4]·2C3H7NOF(000) = 1936
Mr = 926.21Dx = 1.332 Mg m−3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 9914 reflections
a = 15.572 (5) Åθ = 2.6–24.6°
b = 18.706 (5) ŵ = 0.29 mm−1
c = 15.853 (5) ÅT = 100 K
V = 4618 (2) Å3Cuboid, red
Z = 40.26 × 0.14 × 0.13 mm
Data collection top
Bruker APEXII CCD
diffractometer		11142 independent reflections
Radiation source: sealed tube8497 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
φ and ω scansθmax = 28°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −20→20
Tmin = 0.928, Tmax = 0.963k = −22→24
61276 measured reflectionsl = −20→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0485P)2 + 0.3005P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.002
11142 reflectionsΔρmax = 0.42 e Å−3
671 parametersΔρmin = −0.39 e Å−3
299 restraintsAbsolute structure: Flack (1983), 5375 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (3)
Crystal data top
[Zr(C11H10NO)4]·2C3H7NOV = 4618 (2) Å3
Mr = 926.21Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 15.572 (5) ŵ = 0.29 mm−1
b = 18.706 (5) ÅT = 100 K
c = 15.853 (5) Å0.26 × 0.14 × 0.13 mm
Data collection top
Bruker APEXII CCD
diffractometer		11142 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		8497 reflections with I > 2σ(I)
Tmin = 0.928, Tmax = 0.963Rint = 0.064
61276 measured reflectionsθmax = 28°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.42 e Å−3
S = 1.02Δρmin = −0.39 e Å−3
11142 reflectionsAbsolute structure: Flack (1983), 5375 Friedel pairs
671 parametersFlack parameter: −0.01 (3)
299 restraints
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Zr010.966490 (14)0.144904 (13)0.35471 (2)0.02304 (7)
N1020.96042 (15)0.03648 (14)0.43981 (17)0.0262 (6)
O1010.89103 (13)0.17184 (11)0.46024 (13)0.0297 (5)
O1041.02836 (11)0.19244 (11)0.24980 (13)0.0271 (5)
N1040.87759 (15)0.23775 (13)0.29748 (17)0.0262 (6)
O1030.85773 (12)0.09319 (11)0.30675 (14)0.0279 (5)
N1011.01720 (16)0.25663 (13)0.41574 (17)0.0294 (6)
N1031.01035 (15)0.04558 (13)0.26899 (16)0.0251 (6)
O1021.08748 (12)0.12297 (11)0.40715 (14)0.0271 (5)
C1161.1890 (2)0.04673 (17)0.4780 (2)0.0326 (7)
C1280.79960 (18)0.25709 (16)0.3227 (2)0.0295 (7)
H1280.77610.23490.36980.035*
C1100.8931 (2)−0.00201 (18)0.4599 (2)0.0339 (8)
H1100.83920.01350.44270.041*
C1220.95422 (19)−0.05997 (17)0.1978 (2)0.0260 (7)
C1070.8621 (2)0.23826 (18)0.5857 (2)0.0352 (8)
C1250.79013 (19)−0.00990 (18)0.2458 (2)0.0363 (8)
C1211.03962 (19)−0.07799 (19)0.1757 (2)0.0320 (8)
H1211.0504−0.11930.14480.038*
C1181.03964 (18)0.01552 (17)0.46759 (19)0.0247 (6)
C1110.8992 (2)−0.0659 (2)0.5063 (2)0.0423 (9)
H1110.8502−0.09220.5190.051*
C1090.97617 (19)0.27293 (17)0.4900 (2)0.0291 (7)
C1201.1060 (2)−0.03520 (18)0.1995 (2)0.0352 (8)
H1201.1621−0.04640.18410.042*
C1141.1373 (2)−0.06654 (18)0.5408 (2)0.0332 (8)
C1171.10771 (19)0.06285 (17)0.4490 (2)0.0278 (7)
C1290.75120 (19)0.30983 (17)0.2808 (2)0.0348 (8)
H1290.69650.32160.29970.042*
C1191.0886 (2)0.02635 (18)0.2479 (2)0.0307 (7)
H1191.13440.05450.26570.037*
C1341.03493 (19)0.27832 (19)0.1369 (2)0.0355 (8)
C1270.94307 (19)0.00394 (16)0.2438 (2)0.0251 (7)
C1350.9944 (2)0.24636 (17)0.2046 (2)0.0270 (7)
C1310.8681 (2)0.32476 (19)0.1829 (2)0.0343 (7)
C1120.9788 (2)−0.0889 (2)0.5328 (2)0.0389 (9)
H1120.9837−0.13130.5630.047*
C1151.2008 (2)−0.01833 (18)0.5218 (2)0.0381 (8)
H1151.2562−0.02940.53910.046*
C1011.0838 (2)0.29617 (16)0.3917 (2)0.0341 (8)
H1011.11070.28590.34070.041*
C1131.0527 (2)−0.04862 (17)0.5143 (2)0.0296 (7)
C1021.1149 (2)0.35297 (18)0.4411 (3)0.0429 (9)
H1021.16210.37940.42310.051*
C1041.0026 (2)0.32912 (19)0.5431 (3)0.0400 (9)
C1360.91150 (19)0.27068 (17)0.2282 (2)0.0294 (7)
C14B1.1235 (2)0.2566 (2)0.1106 (2)0.0412 (9)
H14A1.1650.28180.14410.062*
H14B1.13180.2680.05210.062*
H14C1.13040.20610.11870.062*
C1330.9898 (3)0.3325 (2)0.0928 (3)0.0465 (10)
H1331.01690.35340.04670.056*
C1260.86090 (18)0.03010 (16)0.2668 (2)0.0272 (7)
C12A1.1540 (2)−0.13471 (18)0.5890 (2)0.0427 (9)
H12A1.2146−0.14020.59780.064*
H12B1.1327−0.17470.55720.064*
H12C1.1252−0.13270.64250.064*
C1240.8028 (2)−0.07534 (18)0.2024 (2)0.0428 (9)
H1240.7545−0.10240.18970.051*
C1080.9078 (2)0.22615 (17)0.5113 (2)0.0302 (7)
C1031.0751 (2)0.36913 (19)0.5161 (3)0.0460 (10)
H1031.09570.40640.54920.055*
C13A0.8899 (2)−0.17105 (18)0.1312 (3)0.0425 (9)
H13A0.8342−0.19140.12160.064*
H13B0.924−0.20350.1640.064*
H13C0.9176−0.16250.0780.064*
C1060.8905 (2)0.2956 (2)0.6375 (2)0.0469 (10)
H1060.86120.3030.68780.056*
C11B0.7879 (2)0.1918 (2)0.6073 (2)0.0416 (9)
H11A0.73880.2060.57470.062*
H11B0.7750.19660.66630.062*
H11C0.80180.1430.5950.062*
C1050.9568 (3)0.3407 (2)0.6200 (3)0.0506 (12)
C13B0.7013 (2)0.0169 (2)0.2666 (3)0.0574 (12)
H13D0.68540.0010.3220.086*
H13E0.6611−0.00140.22610.086*
H13F0.70080.06820.26490.086*
C12B1.2621 (2)0.09893 (19)0.4674 (3)0.0428 (9)
H12D1.28820.0920.41310.064*
H12E1.3040.0910.51080.064*
H12F1.24060.14690.47140.064*
C14A0.8651 (3)0.4165 (3)0.0639 (3)0.0684 (14)
H14D0.90450.43560.02310.103*
H14E0.8480.45360.10220.103*
H14F0.81540.3980.03560.103*
C1300.7850 (2)0.34339 (18)0.2126 (2)0.0377 (8)
H1300.75360.37870.18520.045*
C1230.8805 (2)−0.10150 (17)0.1781 (2)0.0328 (8)
C1320.9089 (3)0.3563 (2)0.1132 (3)0.0496 (10)
C11A0.9852 (3)0.3981 (3)0.6804 (3)0.0790 (17)
H11D0.9760.44420.65530.119*
H11E1.04510.39220.69290.119*
H11F0.95250.39460.73160.119*
N2010.5982 (2)0.0128 (2)0.8446 (3)0.0738 (11)
C2020.5442 (3)−0.0454 (3)0.8137 (3)0.0685 (13)
H20A0.5562−0.05370.75510.103*
H20B0.4848−0.03260.82020.103*
H20C0.5559−0.0880.84530.103*
C2030.5743 (5)0.0405 (5)0.9247 (5)0.144 (3)
H20D0.60920.08130.93770.216*
H20E0.58240.00450.96710.216*
H20F0.5150.05450.92350.216*
C2010.6631 (3)0.0338 (3)0.7986 (5)0.0925 (18)
H2010.6960.06950.82370.111*
O2010.6878 (2)0.0165 (2)0.7320 (3)0.0958 (13)
N310.372 (2)0.2574 (12)0.8644 (9)0.142 (6)0.342 (10)
C31A0.464 (2)0.2579 (16)0.8591 (10)0.141 (8)0.342 (10)
H31A0.4850.20970.85640.211*0.342 (10)
H31B0.48750.28110.9080.211*0.342 (10)
H31C0.48150.28330.80930.211*0.342 (10)
C31B0.331 (2)0.3202 (14)0.8686 (13)0.158 (9)0.342 (10)
H31D0.37210.35850.86490.237*0.342 (10)
H31E0.30090.32340.92120.237*0.342 (10)
H31F0.29110.32370.82280.237*0.342 (10)
C31C0.3383 (19)0.1890 (12)0.8670 (13)0.151 (6)0.342 (10)
H31J0.28080.17670.8740.181*0.342 (10)
O310.4022 (14)0.1459 (8)0.8578 (11)0.169 (7)0.342 (10)
N320.5527 (18)0.2747 (12)0.8555 (18)0.163 (8)0.267 (7)
C32B0.476 (2)0.3148 (16)0.848 (3)0.171 (10)0.267 (7)
H32A0.4890.36270.83070.257*0.267 (7)
H32B0.44640.31570.90110.257*0.267 (7)
H32C0.43920.29290.80620.257*0.267 (7)
C32C0.546 (2)0.2060 (11)0.8783 (12)0.169 (10)0.267 (7)
H32D0.48690.19310.88260.253*0.267 (7)
H32E0.57380.19920.9320.253*0.267 (7)
H32F0.57380.17650.83680.253*0.267 (7)
C32A0.6322 (19)0.3019 (16)0.841 (2)0.198 (11)0.267 (7)
H32J0.63790.34970.82570.238*0.267 (7)
O320.6989 (19)0.2633 (15)0.8475 (15)0.237 (12)0.267 (7)
N330.3685 (14)0.2750 (9)0.8788 (12)0.127 (5)0.391 (9)
C33A0.4579 (15)0.2793 (11)0.8624 (16)0.112 (6)0.391 (9)
H33A0.48570.23720.88360.167*0.391 (9)
H33B0.48110.32070.88990.167*0.391 (9)
H33C0.46720.28290.80270.167*0.391 (9)
C33C0.3514 (15)0.2052 (7)0.9044 (9)0.122 (6)0.391 (9)
H33D0.40440.18120.91660.183*0.391 (9)
H33E0.32170.18030.86030.183*0.391 (9)
H33F0.31630.20610.95420.183*0.391 (9)
C33B0.3106 (17)0.3250 (11)0.8571 (17)0.130 (6)0.391 (9)
H33J0.32850.36430.82580.156*0.391 (9)
O330.2314 (12)0.3201 (7)0.8785 (8)0.142 (6)0.391 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zr010.01669 (11)0.02212 (12)0.03031 (13)0.00031 (10)−0.00125 (16)−0.00248 (17)
N1020.0214 (13)0.0287 (15)0.0285 (15)0.0003 (11)0.0024 (11)−0.0051 (12)
O1010.0275 (11)0.0256 (11)0.0360 (13)0.0039 (9)0.0014 (9)−0.0050 (10)
O1040.0177 (10)0.0272 (11)0.0365 (12)−0.0001 (8)−0.0009 (9)−0.0015 (10)
N1040.0174 (11)0.0264 (13)0.0347 (15)0.0011 (10)−0.0020 (10)−0.0047 (12)
O1030.0164 (9)0.0280 (11)0.0393 (12)0.0005 (8)−0.0008 (9)−0.0068 (10)
N1010.0253 (13)0.0243 (13)0.0387 (16)0.0033 (10)−0.0082 (11)−0.0033 (12)
N1030.0167 (12)0.0252 (14)0.0335 (15)0.0006 (10)0.0018 (11)−0.0004 (12)
O1020.0196 (10)0.0249 (11)0.0370 (12)0.0015 (8)−0.0035 (9)−0.0004 (10)
C1160.0258 (16)0.0304 (18)0.0415 (19)0.0009 (13)−0.0038 (14)0.0018 (15)
C1280.0205 (14)0.0276 (16)0.0403 (17)0.0005 (12)0.0012 (12)−0.0038 (13)
C1100.0227 (16)0.042 (2)0.0371 (19)0.0007 (14)0.0033 (14)0.0016 (16)
C1220.0219 (15)0.0226 (16)0.0334 (17)0.0000 (12)−0.0004 (13)−0.0030 (14)
C1070.0315 (17)0.041 (2)0.0326 (18)0.0204 (15)−0.0063 (14)−0.0057 (16)
C1250.0208 (15)0.0357 (19)0.052 (2)−0.0039 (13)0.0038 (14)−0.0126 (17)
C1210.0267 (17)0.032 (2)0.037 (2)0.0015 (14)0.0043 (14)−0.0106 (16)
C1180.0213 (15)0.0269 (16)0.0258 (16)0.0031 (12)0.0046 (13)−0.0007 (13)
C1110.0301 (18)0.044 (2)0.053 (2)−0.0066 (16)0.0078 (17)0.0118 (19)
C1090.0299 (17)0.0240 (17)0.0334 (18)0.0102 (13)−0.0109 (14)−0.0072 (14)
C1200.0206 (15)0.040 (2)0.045 (2)0.0000 (14)0.0039 (14)−0.0122 (17)
C1140.0279 (16)0.0340 (19)0.0377 (19)0.0061 (14)−0.0001 (14)0.0048 (16)
C1170.0276 (15)0.0256 (17)0.0300 (16)0.0041 (13)0.0012 (13)−0.0007 (14)
C1290.0192 (15)0.0328 (18)0.053 (2)0.0029 (13)−0.0028 (15)−0.0011 (17)
C1190.0221 (15)0.0333 (19)0.0368 (19)−0.0022 (13)0.0018 (14)−0.0028 (15)
C1340.0251 (16)0.044 (2)0.0375 (18)−0.0005 (15)−0.0014 (14)0.0034 (16)
C1270.0203 (14)0.0277 (17)0.0274 (17)−0.0025 (13)0.0007 (12)−0.0033 (14)
C1350.0213 (14)0.0269 (18)0.0328 (17)0.0000 (13)−0.0055 (13)−0.0013 (14)
C1310.0293 (16)0.0392 (19)0.0346 (19)0.0025 (14)−0.0048 (14)0.0047 (16)
C1120.0347 (19)0.034 (2)0.048 (2)0.0044 (15)0.0082 (16)0.0074 (17)
C1150.0284 (16)0.038 (2)0.048 (2)0.0093 (15)−0.0040 (15)0.0039 (17)
C1010.0267 (16)0.0250 (16)0.050 (2)0.0008 (13)−0.0088 (14)−0.0022 (15)
C1130.0319 (17)0.0268 (18)0.0302 (18)0.0027 (14)0.0051 (14)−0.0002 (15)
C1020.0318 (17)0.0267 (18)0.070 (3)0.0012 (14)−0.0184 (18)−0.0057 (18)
C1040.0320 (17)0.0313 (18)0.057 (2)0.0131 (16)−0.0177 (17)−0.0137 (18)
C1360.0231 (15)0.0304 (18)0.0346 (18)−0.0037 (13)−0.0023 (13)−0.0026 (15)
C14B0.0279 (16)0.052 (2)0.043 (2)0.0004 (15)0.0011 (15)0.0115 (18)
C1330.041 (2)0.060 (3)0.039 (2)0.008 (2)0.0059 (19)0.019 (2)
C1260.0219 (14)0.0234 (16)0.0363 (18)−0.0006 (12)0.0017 (13)−0.0039 (14)
C12A0.0377 (19)0.039 (2)0.052 (2)0.0090 (16)−0.0012 (17)0.0084 (18)
C1240.0273 (17)0.038 (2)0.063 (2)−0.0136 (15)−0.0015 (16)−0.0142 (19)
C1080.0289 (16)0.0291 (17)0.0324 (17)0.0119 (13)−0.0084 (14)−0.0044 (15)
C1030.0329 (19)0.034 (2)0.071 (3)0.0071 (15)−0.0234 (19)−0.0204 (19)
C13A0.0358 (19)0.0308 (18)0.061 (2)−0.0058 (15)−0.0002 (17)−0.0134 (18)
C1060.041 (2)0.062 (3)0.037 (2)0.029 (2)−0.0102 (16)−0.0189 (19)
C11B0.0334 (18)0.056 (2)0.0352 (19)0.0199 (17)−0.0002 (15)−0.0069 (18)
C1050.044 (2)0.054 (3)0.054 (3)0.0193 (19)−0.020 (2)−0.031 (2)
C13B0.0236 (17)0.056 (2)0.093 (3)−0.0054 (16)−0.0032 (19)−0.030 (2)
C12B0.0256 (16)0.043 (2)0.060 (2)−0.0029 (15)−0.0115 (16)0.0133 (19)
C14A0.056 (3)0.089 (4)0.061 (3)0.032 (2)0.006 (2)0.033 (3)
C1300.0277 (16)0.040 (2)0.045 (2)0.0102 (14)−0.0068 (15)0.0014 (17)
C1230.0296 (16)0.0275 (18)0.041 (2)−0.0038 (14)0.0031 (14)−0.0047 (15)
C1320.041 (2)0.062 (3)0.046 (2)0.0135 (19)0.0007 (18)0.017 (2)
C11A0.056 (3)0.092 (4)0.089 (4)0.020 (3)−0.021 (3)−0.064 (3)
N2010.0424 (18)0.081 (2)0.098 (3)0.0171 (18)0.001 (2)0.007 (3)
C2020.041 (2)0.080 (3)0.084 (3)0.003 (2)−0.001 (2)0.010 (3)
C2030.094 (5)0.185 (8)0.154 (7)0.070 (5)−0.007 (5)−0.073 (6)
C2010.049 (3)0.090 (4)0.138 (5)0.010 (3)0.004 (3)0.013 (4)
O2010.0446 (19)0.112 (3)0.131 (4)0.0012 (19)0.018 (2)0.028 (3)
N310.285 (12)0.108 (10)0.034 (7)0.057 (10)0.031 (9)−0.024 (9)
C31A0.296 (17)0.070 (15)0.055 (11)−0.019 (14)0.002 (15)0.018 (12)
C31B0.310 (19)0.106 (14)0.058 (13)0.036 (16)−0.054 (15)−0.004 (12)
C31C0.301 (14)0.100 (11)0.052 (10)0.057 (11)0.030 (12)0.010 (11)
O310.293 (19)0.149 (12)0.064 (7)0.061 (12)0.002 (15)0.001 (10)
N320.31 (2)0.136 (15)0.047 (9)0.014 (16)0.053 (16)0.010 (12)
C32B0.34 (2)0.13 (2)0.045 (13)−0.03 (2)0.010 (19)−0.013 (18)
C32C0.38 (3)0.095 (15)0.032 (11)0.051 (19)0.061 (15)0.000 (10)
C32A0.35 (2)0.17 (2)0.071 (15)0.027 (19)0.043 (19)0.029 (15)
O320.39 (3)0.26 (3)0.061 (11)0.14 (2)−0.011 (18)0.060 (16)
N330.261 (11)0.078 (8)0.043 (7)0.057 (9)0.005 (8)−0.020 (7)
C33A0.243 (15)0.049 (12)0.043 (10)−0.032 (11)0.019 (12)−0.018 (9)
C33C0.307 (17)0.030 (7)0.029 (7)0.007 (9)−0.020 (10)−0.005 (6)
C33B0.267 (14)0.083 (9)0.040 (7)0.059 (11)−0.025 (11)−0.009 (9)
O330.236 (15)0.097 (8)0.094 (10)0.040 (11)−0.001 (10)0.003 (7)
Geometric parameters (Å, º) top
Zr01—O1032.093 (2)C12A—H12A0.96
Zr01—O1022.100 (2)C12A—H12B0.96
Zr01—O1012.106 (2)C12A—H12C0.96
Zr01—O1042.118 (2)C124—C1231.360 (4)
Zr01—N1042.399 (2)C124—H1240.93
Zr01—N1032.401 (3)C103—H1030.93
Zr01—N1012.435 (3)C13A—C1231.505 (5)
Zr01—N1022.438 (3)C13A—H13A0.96
N102—C1101.310 (4)C13A—H13B0.96
N102—C1181.367 (4)C13A—H13C0.96
O101—C1081.325 (4)C106—C1051.361 (6)
O104—C1351.345 (4)C106—H1060.93
N104—C1281.329 (4)C11B—H11A0.96
N104—C1361.365 (4)C11B—H11B0.96
O103—C1261.340 (4)C11B—H11C0.96
N101—C1011.330 (4)C105—C11A1.506 (6)
N101—C1091.374 (4)C13B—H13D0.96
N103—C1191.314 (4)C13B—H13E0.96
N103—C1271.365 (4)C13B—H13F0.96
O102—C1171.343 (4)C12B—H12D0.96
C116—C1171.380 (4)C12B—H12E0.96
C116—C1151.413 (5)C12B—H12F0.96
C116—C12B1.510 (4)C14A—C1321.531 (5)
C128—C1291.408 (4)C14A—H14D0.96
C128—H1280.93C14A—H14E0.96
C110—C1111.407 (5)C14A—H14F0.96
C110—H1100.93C130—H1300.93
C122—C1271.412 (4)C11A—H11D0.96
C122—C1211.416 (4)C11A—H11E0.96
C122—C1231.421 (4)C11A—H11F0.96
C107—C1081.395 (5)N201—C2011.307 (7)
C107—C1061.422 (5)N201—C2031.422 (8)
C107—C11B1.486 (5)N201—C2021.461 (6)
C125—C1261.373 (4)C202—H20A0.96
C125—C1241.418 (5)C202—H20B0.96
C125—C13B1.508 (4)C202—H20C0.96
C121—C1201.361 (4)C203—H20D0.96
C121—H1210.93C203—H20E0.96
C118—C1171.412 (4)C203—H20F0.96
C118—C1131.424 (5)C201—O2011.169 (7)
C111—C1121.377 (5)C201—H2010.93
C111—H1110.93N31—C31B1.341 (17)
C109—C1041.408 (5)N31—C31C1.387 (17)
C109—C1081.419 (5)N31—C31A1.430 (16)
C120—C1191.410 (5)C31A—H31A0.96
C120—H1200.93C31A—H31B0.96
C114—C1151.372 (4)C31A—H31C0.96
C114—C1131.424 (4)C31B—H31D0.96
C114—C12A1.509 (5)C31B—H31E0.96
C129—C1301.356 (5)C31B—H31F0.96
C129—H1290.93C31C—O311.29 (2)
C119—H1190.93C31C—H31J0.93
C134—C1351.381 (5)N32—C32C1.338 (17)
C134—C1331.417 (5)N32—C32A1.359 (18)
C134—C14B1.497 (4)N32—C32B1.422 (18)
C127—C1261.417 (4)C32B—H32A0.96
C135—C1361.419 (4)C32B—H32B0.96
C131—C1321.405 (5)C32B—H32C0.96
C131—C1361.413 (4)C32C—H32D0.96
C131—C1301.421 (4)C32C—H32E0.96
C112—C1131.406 (5)C32C—H32F0.96
C112—H1120.93C32A—O321.27 (2)
C115—H1150.93C32A—H32J0.93
C101—C1021.406 (5)N33—C33B1.343 (16)
C101—H1010.93N33—C33C1.392 (15)
C102—C1031.375 (6)N33—C33A1.418 (15)
C102—H1020.93C33A—H33A0.96
C104—C1031.421 (6)C33A—H33B0.96
C104—C1051.428 (6)C33A—H33C0.96
C14B—H14A0.96C33C—H33D0.96
C14B—H14B0.96C33C—H33E0.96
C14B—H14C0.96C33C—H33F0.96
C133—C1321.374 (5)C33B—O331.28 (2)
C133—H1330.93C33B—H33J0.93
O103—Zr01—O102141.21 (8)H12A—C12A—H12B109.5
O103—Zr01—O10187.00 (8)C114—C12A—H12C109.5
O102—Zr01—O101103.47 (9)H12A—C12A—H12C109.5
O103—Zr01—O104106.07 (8)H12B—C12A—H12C109.5
O102—Zr01—O10489.13 (8)C123—C124—C125124.9 (3)
O101—Zr01—O104141.02 (8)C123—C124—H124117.5
O103—Zr01—N10474.36 (8)C125—C124—H124117.5
O102—Zr01—N104143.99 (8)O101—C108—C107122.7 (3)
O101—Zr01—N10478.77 (9)O101—C108—C109118.3 (3)
O104—Zr01—N10470.22 (8)C107—C108—C109118.9 (3)
O103—Zr01—N10370.55 (8)C102—C103—C104120.3 (3)
O102—Zr01—N10379.49 (8)C102—C103—H103119.9
O101—Zr01—N103142.52 (8)C104—C103—H103119.9
O104—Zr01—N10375.58 (8)C123—C13A—H13A109.5
N104—Zr01—N103120.68 (9)C123—C13A—H13B109.5
O103—Zr01—N101143.46 (8)H13A—C13A—H13B109.5
O102—Zr01—N10173.70 (8)C123—C13A—H13C109.5
O101—Zr01—N10170.11 (9)H13A—C13A—H13C109.5
O104—Zr01—N10178.70 (9)H13B—C13A—H13C109.5
N104—Zr01—N10173.50 (8)C105—C106—C107125.9 (4)
N103—Zr01—N101142.84 (8)C105—C106—H106117.1
O103—Zr01—N10277.60 (8)C107—C106—H106117.1
O102—Zr01—N10269.70 (8)C107—C11B—H11A109.5
O101—Zr01—N10274.80 (8)C107—C11B—H11B109.5
O104—Zr01—N102143.28 (8)H11A—C11B—H11B109.5
N104—Zr01—N102142.11 (8)C107—C11B—H11C109.5
N103—Zr01—N10271.36 (8)H11A—C11B—H11C109.5
N101—Zr01—N102120.46 (9)H11B—C11B—H11C109.5
C110—N102—C118119.1 (3)C106—C105—C104117.3 (4)
C110—N102—Zr01128.5 (2)C106—C105—C11A122.3 (4)
C118—N102—Zr01112.45 (19)C104—C105—C11A120.3 (4)
C108—O101—Zr01124.0 (2)C125—C13B—H13D109.5
C135—O104—Zr01123.64 (18)C125—C13B—H13E109.5
C128—N104—C136118.2 (3)H13D—C13B—H13E109.5
C128—N104—Zr01127.7 (2)C125—C13B—H13F109.5
C136—N104—Zr01114.05 (18)H13D—C13B—H13F109.5
C126—O103—Zr01123.28 (17)H13E—C13B—H13F109.5
C101—N101—C109119.0 (3)C116—C12B—H12D109.5
C101—N101—Zr01128.1 (2)C116—C12B—H12E109.5
C109—N101—Zr01112.3 (2)H12D—C12B—H12E109.5
C119—N103—C127118.8 (3)C116—C12B—H12F109.5
C119—N103—Zr01128.3 (2)H12D—C12B—H12F109.5
C127—N103—Zr01112.86 (19)H12E—C12B—H12F109.5
C117—O102—Zr01124.72 (18)C132—C14A—H14D109.5
C117—C116—C115118.1 (3)C132—C14A—H14E109.5
C117—C116—C12B120.9 (3)H14D—C14A—H14E109.5
C115—C116—C12B120.9 (3)C132—C14A—H14F109.5
N104—C128—C129122.6 (3)H14D—C14A—H14F109.5
N104—C128—H128118.7H14E—C14A—H14F109.5
C129—C128—H128118.7C129—C130—C131120.3 (3)
N102—C110—C111122.7 (3)C129—C130—H130119.9
N102—C110—H110118.7C131—C130—H130119.9
C111—C110—H110118.7C124—C123—C122117.3 (3)
C127—C122—C121116.4 (3)C124—C123—C13A122.5 (3)
C127—C122—C123118.5 (3)C122—C123—C13A120.1 (3)
C121—C122—C123125.1 (3)C133—C132—C131117.6 (3)
C108—C107—C106116.8 (3)C133—C132—C14A121.8 (4)
C108—C107—C11B119.8 (3)C131—C132—C14A120.6 (3)
C106—C107—C11B123.4 (3)C105—C11A—H11D109.5
C126—C125—C124118.4 (3)C105—C11A—H11E109.5
C126—C125—C13B120.1 (3)H11D—C11A—H11E109.5
C124—C125—C13B121.4 (3)C105—C11A—H11F109.5
C120—C121—C122120.3 (3)H11D—C11A—H11F109.5
C120—C121—H121119.8H11E—C11A—H11F109.5
C122—C121—H121119.8C201—N201—C203126.3 (6)
N102—C118—C117115.5 (3)C201—N201—C202118.9 (5)
N102—C118—C113122.5 (3)C203—N201—C202114.9 (5)
C117—C118—C113122.0 (3)N201—C202—H20A109.5
C112—C111—C110119.0 (3)N201—C202—H20B109.5
C112—C111—H111120.5H20A—C202—H20B109.5
C110—C111—H111120.5N201—C202—H20C109.5
N101—C109—C104122.8 (3)H20A—C202—H20C109.5
N101—C109—C108114.6 (3)H20B—C202—H20C109.5
C104—C109—C108122.5 (3)N201—C203—H20D109.5
C121—C120—C119119.0 (3)N201—C203—H20E109.5
C121—C120—H120120.5H20D—C203—H20E109.5
C119—C120—H120120.5N201—C203—H20F109.5
C115—C114—C113116.5 (3)H20D—C203—H20F109.5
C115—C114—C12A122.9 (3)H20E—C203—H20F109.5
C113—C114—C12A120.5 (3)O201—C201—N201132.4 (7)
O102—C117—C116124.3 (3)O201—C201—H201113.8
O102—C117—C118116.9 (3)N201—C201—H201113.8
C116—C117—C118118.8 (3)C31B—N31—C31C129 (2)
C130—C129—C128119.5 (3)C31B—N31—C31A118.4 (19)
C130—C129—H129120.2C31C—N31—C31A113.1 (16)
C128—C129—H129120.2N31—C31A—H31A109.5
N103—C119—C120122.7 (3)N31—C31A—H31B109.5
N103—C119—H119118.6H31A—C31A—H31B109.5
C120—C119—H119118.6N31—C31A—H31C109.5
C135—C134—C133117.8 (3)H31A—C31A—H31C109.5
C135—C134—C14B121.3 (3)H31B—C31A—H31C109.5
C133—C134—C14B120.9 (3)N31—C31B—H31D109.5
N103—C127—C122122.7 (3)N31—C31B—H31E109.5
N103—C127—C126114.9 (3)H31D—C31B—H31E109.5
C122—C127—C126122.4 (3)N31—C31B—H31F109.5
O104—C135—C134124.0 (3)H31D—C31B—H31F109.5
O104—C135—C136117.2 (3)H31E—C31B—H31F109.5
C134—C135—C136118.8 (3)O31—C31C—N31106.0 (18)
C132—C131—C136119.0 (3)O31—C31C—H31J127
C132—C131—C130124.7 (3)N31—C31C—H31J127
C136—C131—C130116.3 (3)C32C—N32—C32A118.3 (18)
C111—C112—C113120.4 (4)C32C—N32—C32B117.8 (19)
C111—C112—H112119.8C32A—N32—C32B123.9 (19)
C113—C112—H112119.8N32—C32B—H32A109.5
C114—C115—C116125.5 (3)N32—C32B—H32B109.5
C114—C115—H115117.2H32A—C32B—H32B109.5
C116—C115—H115117.2N32—C32B—H32C109.5
N101—C101—C102122.0 (3)H32A—C32B—H32C109.5
N101—C101—H101119H32B—C32B—H32C109.5
C102—C101—H101119N32—C32C—H32D109.5
C112—C113—C114124.7 (3)N32—C32C—H32E109.5
C112—C113—C118116.3 (3)H32D—C32C—H32E109.5
C114—C113—C118118.9 (3)N32—C32C—H32F109.5
C103—C102—C101119.5 (3)H32D—C32C—H32F109.5
C103—C102—H102120.3H32E—C32C—H32F109.5
C101—C102—H102120.3O32—C32A—N32121 (3)
C109—C104—C103116.4 (3)O32—C32A—H32J119.4
C109—C104—C105118.5 (4)N32—C32A—H32J119.4
C103—C104—C105125.1 (3)C33B—N33—C33C126.8 (17)
N104—C136—C131123.2 (3)C33B—N33—C33A124.9 (17)
N104—C136—C135114.8 (3)C33C—N33—C33A107.1 (14)
C131—C136—C135122.0 (3)N33—C33A—H33A109.5
C134—C14B—H14A109.5N33—C33A—H33B109.5
C134—C14B—H14B109.5H33A—C33A—H33B109.5
H14A—C14B—H14B109.5N33—C33A—H33C109.5
C134—C14B—H14C109.5H33A—C33A—H33C109.5
H14A—C14B—H14C109.5H33B—C33A—H33C109.5
H14B—C14B—H14C109.5N33—C33C—H33D109.5
C132—C133—C134124.8 (4)N33—C33C—H33E109.5
C132—C133—H133117.6H33D—C33C—H33E109.5
C134—C133—H133117.6N33—C33C—H33F109.5
O103—C126—C125124.4 (3)H33D—C33C—H33F109.5
O103—C126—C127117.3 (2)H33E—C33C—H33F109.5
C125—C126—C127118.3 (3)O33—C33B—N33122 (2)
C114—C12A—H12A109.5O33—C33B—H33J119.1
C114—C12A—H12B109.5N33—C33B—H33J119.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14A—H14E···O201i0.962.433.358 (7)161
Symmetry code: (i) −x+3/2, y+1/2, z−1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14A—H14E···O201i0.962.433.358 (7)161.3
Symmetry code: (i) −x+3/2, y+1/2, z−1/2.
Acknowledgements top

Financial assistance from the Advanced Metals Initiative (AMI) and the Department of Science and Technology (DST) of South Africa, as well as the New Metals Development Network (NMDN) and the South African Nuclear Energy Corporation Limited (Necsa), is gratefully acknowledged.

references
References top

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