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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 π–π 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).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812042092/lh5537sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536812042092/lh5537Isup2.hkl
Contains datablock I

CCDC reference: 909719

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in solvent or counterion
  • R factor = 0.041
  • wR factor = 0.099
  • Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT214_ALERT_2_C Atom N31 (Anion/Solvent) ADP max/min Ratio 4.1 prola PLAT214_ALERT_2_C Atom C32C (Anion/Solvent) ADP max/min Ratio 4.4 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.2 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of N201 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 11
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.00 From the CIF: _reflns_number_total 11142 Count of symmetry unique reflns 5780 Completeness (_total/calc) 192.77% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 5362 Fraction of Friedel pairs measured 0.928 Are heavy atom types Z>Si present yes PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 15 PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites .... 20 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT244_ALERT_4_G Low 'Solvent' Ueq as Compared to Neighbors of N32 PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ................... 50 Perc. PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Zr01 (IV) 4.23 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 299 PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ... 1
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 6 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check

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 ππ 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 ππ 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 m3
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 mm1
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 = 2020
Tmin = 0.928, Tmax = 0.963k = 2224
61276 measured reflectionsl = 2020
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 Å3
671 parametersΔρmin = 0.39 e Å3
299 restraintsAbsolute structure: Flack (1983), 5375 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.42 e Å3
S = 1.02Δρmin = 0.39 e Å3
11142 reflectionsAbsolute structure: Flack (1983), 5375 Friedel pairs
671 parametersAbsolute structure 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)
H1211.05040.11930.14480.038*
C1181.03964 (18)0.01552 (17)0.46759 (19)0.0247 (6)
C1110.8992 (2)0.0659 (2)0.5063 (2)0.0423 (9)
H1110.85020.09220.5190.051*
C1090.97617 (19)0.27293 (17)0.4900 (2)0.0291 (7)
C1201.1060 (2)0.03520 (18)0.1995 (2)0.0352 (8)
H1201.16210.04640.18410.042*
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)
H1120.98370.13130.5630.047*
C1151.2008 (2)0.01833 (18)0.5218 (2)0.0381 (8)
H1151.25620.02940.53910.046*
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)
H12A1.21460.14020.59780.064*
H12B1.13270.17470.55720.064*
H12C1.12520.13270.64250.064*
C1240.8028 (2)0.07534 (18)0.2024 (2)0.0428 (9)
H1240.75450.10240.18970.051*
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)
H13A0.83420.19140.12160.064*
H13B0.9240.20350.1640.064*
H13C0.91760.16250.0780.064*
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*
H13E0.66110.00140.22610.086*
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)
H20A0.55620.05370.75510.103*
H20B0.48480.03260.82020.103*
H20C0.55590.0880.84530.103*
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, z1/2.

Experimental details

Crystal data
Chemical formula[Zr(C11H10NO)4]·2C3H7NO
Mr926.21
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)100
a, b, c (Å)15.572 (5), 18.706 (5), 15.853 (5)
V3)4618 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.26 × 0.14 × 0.13
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.928, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
61276, 11142, 8497
Rint0.064
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.099, 1.02
No. of reflections11142
No. of parameters671
No. of restraints299
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.39
Absolute structureFlack (1983), 5375 Friedel pairs
Absolute structure parameter0.01 (3)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

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, z1/2.
 

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