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The structure of the title compound, {[Cu(C11H19N4O2)(H2O)0.5]ClO4}n, consists of perchlorate anions and infinite chain cations. Each Cu atom has a distorted square-pyramidal or octa­hedral environment, with two oxime and two imine N atoms from the tetra­dentate ligand in a square-planar arrangement and one or two weak bonds to O atoms in trans positions through the coordination of the half-occupancy water mol­ecule and an oxime O atom of the adjacent unit. The dihedral angle between the planes of coordination of the tetra­dentate ligand in adjacent units of the polymeric cation is 61.92 (4)°. The perchlorate anions are hydrogen bonded to the aqua ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703886X/cf2129sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680703886X/cf2129Isup2.hkl
Contains datablock I

CCDC reference: 660093

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • Disorder in main residue
  • R factor = 0.034
  • wR factor = 0.081
  • Data-to-parameter ratio = 21.3

checkCIF/PLATON results

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Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

An investigation to assess the possible use of dioxime–diimine compounds as tetradentate ligands in the production of metal complexes with the copper(II) ion which demonstrates solvatochromism (Asadi et al., 2005; Movahedi & Golchoubian, 2006) motivated us to synthesize the title compound (I). This compound was previously prepared and its structure was investigated by Bertrand et al. (1977), but their reported structure has the formula [Cu(C11H19N4O2)]+ClO4-.0.5CH3OH with a triclinic space group and a density of 1.60 Mg m-3. However, our results show the presence of a water molecule in place of methanol, with a monoclinic space group and a density of 1.684 Mg m-3 as well as a different color of the crystals. On the other hand, Wisemann & Krebs (2000) reported a structure for the title compound. The structure appears to be the same as ours except for the full occupancy modeling of the water molecule and the lower precision. Other complexes of this tetradentate ligand with different transition metals and their derivatives have been synthesized (Wang, Chung et al., 1990; Wang, Wang et al., 1990; Wang et al., 1991) and their structures have been examined (Tahirov et al., 1995; Lu et al., 1993). The structure of the title compound contains infinite-chain cations. The dihedral angle between the CuN4 coordination planes of adjacent monomer units is 61.92 (4)°. In each unit the tetradentate ligand is coordinated to copper as shown in Fig. 1 through the two oxime and two imine nitrogen atoms. This coordination forms a six-membered and two five-membered chelate rings. Each five-membered chelate ring includes an imine nitrogen and an oxime nitrogen atoms. However, the six-membered chelate ring includes two imine nitrogen atoms. The four nitrogen atoms of the ligand are coplanar. The displacement of Cu out of this plane is 0.079 Å. The six-membered ring CuN2C5C6C7N3 is puckered with C6 positioned 0.701 Å out of the ring mean plane. This produces an overall chair-like conformation of the ligand. Cationic units are linked together by a weak bond between the copper atom of one unit and an oxygen atom of the oxime of the next unit. The coordination of each copper atom also includes a water molecule which bonds weakly to the other site of the CuN4 plane to complete a distorted octahedron. The water site is only half-occupied, so that only half of the Cu atoms have their coordination completed by the water molecule, the other half being square pyramidal. Full occupancy would give unacceptably short contacts between water molecules of adjacent chains, so the disorder is correlated between chains, but is random within chains.

The cationic chains are offset, resulting in a zigzag pattern of copper atoms as shown in Fig. 2. The structure is consolidated by hydrogen bonds which form a three-dimensional framework.

Related literature top

For related literature, see: Bertrand et al. (1977); Wang et al. (1991); Wang, Chung et al. (1990); Wang, Wang et al. (1990); Tahirov et al. (1995); Lu et al. (1993); Asadi et al. (2005); Movahedi & Golchoubian (2006); Wisemann & Krebs (2000).

Experimental top

The complex was prepared by a procedure given by Bertrand et al. (1977).

Refinement top

C-bound hydrogen atoms were treated in a riding model with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) [1.5Ueq(C) for methyl groups]. The O-bound H atoms were located in a difference map and refined as riding in their as-found relative positions, with Uiso(H) = 1.5Ueq(O). Attempts to refine the model with full occupancy for water led to Ueq(O1s) = 0.105 Å2 and R1 = 0.045. Refinement of the water occupancy gave essentially half-occupancy, and this was fixed in the final refinement.

Structure description top

An investigation to assess the possible use of dioxime–diimine compounds as tetradentate ligands in the production of metal complexes with the copper(II) ion which demonstrates solvatochromism (Asadi et al., 2005; Movahedi & Golchoubian, 2006) motivated us to synthesize the title compound (I). This compound was previously prepared and its structure was investigated by Bertrand et al. (1977), but their reported structure has the formula [Cu(C11H19N4O2)]+ClO4-.0.5CH3OH with a triclinic space group and a density of 1.60 Mg m-3. However, our results show the presence of a water molecule in place of methanol, with a monoclinic space group and a density of 1.684 Mg m-3 as well as a different color of the crystals. On the other hand, Wisemann & Krebs (2000) reported a structure for the title compound. The structure appears to be the same as ours except for the full occupancy modeling of the water molecule and the lower precision. Other complexes of this tetradentate ligand with different transition metals and their derivatives have been synthesized (Wang, Chung et al., 1990; Wang, Wang et al., 1990; Wang et al., 1991) and their structures have been examined (Tahirov et al., 1995; Lu et al., 1993). The structure of the title compound contains infinite-chain cations. The dihedral angle between the CuN4 coordination planes of adjacent monomer units is 61.92 (4)°. In each unit the tetradentate ligand is coordinated to copper as shown in Fig. 1 through the two oxime and two imine nitrogen atoms. This coordination forms a six-membered and two five-membered chelate rings. Each five-membered chelate ring includes an imine nitrogen and an oxime nitrogen atoms. However, the six-membered chelate ring includes two imine nitrogen atoms. The four nitrogen atoms of the ligand are coplanar. The displacement of Cu out of this plane is 0.079 Å. The six-membered ring CuN2C5C6C7N3 is puckered with C6 positioned 0.701 Å out of the ring mean plane. This produces an overall chair-like conformation of the ligand. Cationic units are linked together by a weak bond between the copper atom of one unit and an oxygen atom of the oxime of the next unit. The coordination of each copper atom also includes a water molecule which bonds weakly to the other site of the CuN4 plane to complete a distorted octahedron. The water site is only half-occupied, so that only half of the Cu atoms have their coordination completed by the water molecule, the other half being square pyramidal. Full occupancy would give unacceptably short contacts between water molecules of adjacent chains, so the disorder is correlated between chains, but is random within chains.

The cationic chains are offset, resulting in a zigzag pattern of copper atoms as shown in Fig. 2. The structure is consolidated by hydrogen bonds which form a three-dimensional framework.

For related literature, see: Bertrand et al. (1977); Wang et al. (1991); Wang, Chung et al. (1990); Wang, Wang et al. (1990); Tahirov et al. (1995); Lu et al. (1993); Asadi et al. (2005); Movahedi & Golchoubian (2006); Wisemann & Krebs (2000).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines. Symmetry transformations used to generate equivalent atoms: A -x + 3/2, y + 1/2, -z + 1/2; B x - 1/2, -y + 1/2, z + 1/2; C -x, -y - 1, -z.
[Figure 2] Fig. 2. The crystal packing of the cationic chains (view approximately along the a axis). Anions and hydrogen atoms of ligands have been omitted for clarity, and all water sites are shown occupied, illustrating the unacceptably short contacts thus generated.
catena-Poly[[[hemiaquacopper(II)]-µ-3,9-dimethyl-4,8-diazaundeca-3,8-diene- 2,10-dione dioximato-κ4N,N',N'',N'':κO)] perchlorate] top
Crystal data top
[Cu(C11H19N4O2)(H2O)0.5]ClO4F(000) = 848
Mr = 411.30Dx = 1.684 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4849 reflections
a = 13.0833 (5) Åθ = 3.1–34.0°
b = 6.6401 (3) ŵ = 1.55 mm1
c = 18.6698 (7) ÅT = 100 K
β = 90.445 (1)°Prism, brown
V = 1621.88 (11) Å30.36 × 0.35 × 0.12 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
4717 independent reflections
Radiation source: fine-focus sealed tube3609 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scansθmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
h = 1818
Tmin = 0.577, Tmax = 0.832k = 98
15994 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: mixed
wR(F2) = 0.081H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.03P)2 + 1.5P]
where P = (Fo2 + 2Fc2)/3
4717 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.97 e Å3
Crystal data top
[Cu(C11H19N4O2)(H2O)0.5]ClO4V = 1621.88 (11) Å3
Mr = 411.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.0833 (5) ŵ = 1.55 mm1
b = 6.6401 (3) ÅT = 100 K
c = 18.6698 (7) Å0.36 × 0.35 × 0.12 mm
β = 90.445 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
4717 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
3609 reflections with I > 2σ(I)
Tmin = 0.577, Tmax = 0.832Rint = 0.035
15994 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.00Δρmax = 0.53 e Å3
4717 reflectionsΔρmin = 0.97 e Å3
221 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Cu10.337030 (18)0.28836 (4)0.333467 (15)0.02361 (8)
Cl10.73712 (4)0.02121 (8)0.07806 (3)0.02456 (11)
O10.23722 (10)0.6526 (2)0.28151 (7)0.0174 (3)
O20.42009 (10)0.6102 (2)0.24366 (7)0.0209 (3)
H2A0.35950.64610.25110.031*
O30.69075 (12)0.0705 (3)0.13955 (9)0.0362 (4)
O40.84578 (13)0.0135 (4)0.08157 (10)0.0483 (5)
O50.69497 (15)0.0660 (3)0.01428 (9)0.0374 (4)
O60.71672 (17)0.2335 (3)0.07880 (10)0.0469 (5)
N10.22697 (12)0.4842 (2)0.32114 (8)0.0155 (3)
N20.23733 (12)0.1622 (2)0.39627 (9)0.0176 (3)
N30.45279 (12)0.1049 (3)0.34784 (9)0.0181 (3)
N40.43956 (12)0.4366 (3)0.27955 (8)0.0156 (3)
C10.05749 (14)0.5895 (3)0.36414 (11)0.0205 (4)
H1A0.07440.71790.34120.031*
H1B0.04150.61280.41470.031*
H1C0.00190.52960.33990.031*
C20.14635 (13)0.4499 (3)0.35890 (10)0.0151 (4)
C30.15169 (14)0.2563 (3)0.39869 (10)0.0158 (4)
C40.05944 (15)0.1835 (3)0.43799 (11)0.0233 (4)
H4B0.05410.03690.43320.035*
H4C0.00190.24680.41770.035*
H4D0.06580.21910.48880.035*
C50.25740 (16)0.0270 (3)0.43378 (11)0.0221 (4)
H5B0.23760.14140.40260.026*
H5C0.21540.03320.47760.026*
C60.36965 (17)0.0454 (3)0.45408 (11)0.0243 (4)
H6B0.37750.15940.48780.029*
H6C0.39040.07860.47980.029*
C70.44309 (16)0.0778 (3)0.39138 (11)0.0235 (4)
H7A0.51120.11660.41030.028*
H7B0.41750.18940.36100.028*
C80.63399 (16)0.0489 (4)0.31626 (12)0.0300 (5)
H8A0.62790.07230.34580.045*
H8B0.68850.13490.33550.045*
H8C0.65030.01040.26700.045*
C90.53527 (14)0.1615 (3)0.31692 (10)0.0193 (4)
C100.52860 (14)0.3557 (3)0.27613 (10)0.0187 (4)
C110.61537 (14)0.4418 (4)0.23499 (11)0.0271 (5)
H11A0.59510.57210.21470.041*
H11B0.63370.34950.19620.041*
H11C0.67430.46040.26700.041*
O1S0.4279 (2)0.4681 (5)0.44200 (16)0.0267 (7)0.50
H1S0.49250.46070.44640.032*0.50
H2S0.38880.48510.47770.032*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01772 (12)0.01642 (13)0.03693 (16)0.00581 (10)0.01567 (10)0.00905 (11)
Cl10.0289 (2)0.0278 (3)0.0169 (2)0.0001 (2)0.00467 (18)0.00056 (19)
O10.0180 (6)0.0159 (7)0.0184 (7)0.0006 (5)0.0031 (5)0.0046 (5)
O20.0188 (7)0.0231 (8)0.0208 (7)0.0013 (6)0.0045 (5)0.0053 (6)
O30.0218 (8)0.0559 (12)0.0308 (9)0.0033 (8)0.0004 (6)0.0138 (8)
O40.0239 (8)0.0888 (17)0.0321 (9)0.0020 (9)0.0055 (7)0.0093 (10)
O50.0602 (11)0.0255 (9)0.0262 (8)0.0064 (8)0.0182 (8)0.0078 (7)
O60.0786 (14)0.0260 (10)0.0360 (10)0.0010 (9)0.0077 (10)0.0084 (8)
N10.0167 (7)0.0142 (8)0.0155 (7)0.0009 (6)0.0037 (6)0.0010 (6)
N20.0202 (8)0.0147 (8)0.0179 (8)0.0010 (6)0.0059 (6)0.0011 (6)
N30.0176 (7)0.0202 (9)0.0166 (8)0.0031 (6)0.0016 (6)0.0010 (7)
N40.0152 (7)0.0193 (8)0.0122 (7)0.0023 (6)0.0003 (6)0.0014 (6)
C10.0125 (8)0.0301 (11)0.0191 (9)0.0030 (7)0.0014 (7)0.0027 (8)
C20.0137 (8)0.0186 (9)0.0130 (8)0.0015 (7)0.0010 (6)0.0023 (7)
C30.0160 (8)0.0184 (10)0.0129 (8)0.0037 (7)0.0033 (6)0.0019 (7)
C40.0193 (9)0.0265 (12)0.0241 (10)0.0057 (8)0.0073 (8)0.0013 (9)
C50.0272 (10)0.0155 (10)0.0236 (10)0.0012 (8)0.0053 (8)0.0024 (8)
C60.0327 (11)0.0207 (10)0.0196 (9)0.0027 (9)0.0011 (8)0.0029 (8)
C70.0261 (10)0.0211 (11)0.0233 (10)0.0063 (8)0.0015 (8)0.0009 (8)
C80.0164 (9)0.0431 (14)0.0304 (11)0.0087 (9)0.0017 (8)0.0027 (10)
C90.0147 (8)0.0285 (11)0.0148 (9)0.0032 (7)0.0031 (7)0.0056 (8)
C100.0117 (8)0.0300 (11)0.0143 (8)0.0031 (7)0.0009 (6)0.0063 (8)
C110.0116 (8)0.0478 (15)0.0220 (10)0.0042 (9)0.0031 (7)0.0002 (10)
O1S0.0223 (14)0.0324 (18)0.0254 (15)0.0045 (13)0.0071 (12)0.0054 (13)
Geometric parameters (Å, º) top
Cu1—N21.9499 (16)C4—H4B0.980
Cu1—N41.9502 (16)C4—H4C0.980
Cu1—N11.9525 (16)C4—H4D0.980
Cu1—N31.9607 (16)C5—C61.519 (3)
Cl1—O51.4309 (16)C5—H5B0.990
Cl1—O61.4346 (19)C5—H5C0.990
Cl1—O31.4380 (17)C6—C71.535 (3)
Cl1—O41.4411 (18)C6—H6B0.990
O1—N11.348 (2)C6—H6C0.990
O2—N41.357 (2)C7—H7A0.990
O2—H2A0.840C7—H7B0.990
N1—C21.293 (2)C8—C91.492 (3)
N2—C31.284 (2)C8—H8A0.980
N2—C51.461 (3)C8—H8B0.980
N3—C91.284 (2)C8—H8C0.980
N3—C71.466 (3)C9—C101.499 (3)
N4—C101.285 (2)C10—C111.490 (3)
C1—C21.491 (3)C11—H11A0.980
C1—H1A0.980C11—H11B0.980
C1—H1B0.980C11—H11C0.980
C1—H1C0.980O1S—H1S0.850
C2—C31.486 (3)O1S—H2S0.850
C3—C41.498 (2)
N2—Cu1—N4173.41 (7)C3—C4—H4D109.5
N2—Cu1—N182.00 (7)H4B—C4—H4D109.5
N4—Cu1—N196.46 (7)H4C—C4—H4D109.5
N2—Cu1—N399.81 (7)N2—C5—C6111.00 (17)
N4—Cu1—N381.41 (7)N2—C5—H5B109.4
N1—Cu1—N3176.58 (7)C6—C5—H5B109.4
O5—Cl1—O6109.57 (11)N2—C5—H5C109.4
O5—Cl1—O3109.31 (11)C6—C5—H5C109.4
O6—Cl1—O3109.19 (12)H5B—C5—H5C108.0
O5—Cl1—O4110.29 (12)C5—C6—C7115.52 (17)
O6—Cl1—O4109.90 (14)C5—C6—H6B108.4
O3—Cl1—O4108.55 (10)C7—C6—H6B108.4
N4—O2—H2A109.5C5—C6—H6C108.4
C2—N1—O1122.01 (16)C7—C6—H6C108.4
C2—N1—Cu1114.99 (13)H6B—C6—H6C107.5
O1—N1—Cu1122.74 (11)N3—C7—C6111.36 (17)
C3—N2—C5123.73 (16)N3—C7—H7A109.4
C3—N2—Cu1113.58 (13)C6—C7—H7A109.4
C5—N2—Cu1122.62 (12)N3—C7—H7B109.4
C9—N3—C7124.64 (17)C6—C7—H7B109.4
C9—N3—Cu1114.03 (14)H7A—C7—H7B108.0
C7—N3—Cu1121.33 (13)C9—C8—H8A109.5
C10—N4—O2119.86 (16)C9—C8—H8B109.5
C10—N4—Cu1116.23 (14)H8A—C8—H8B109.5
O2—N4—Cu1123.83 (11)C9—C8—H8C109.5
C2—C1—H1A109.5H8A—C8—H8C109.5
C2—C1—H1B109.5H8B—C8—H8C109.5
H1A—C1—H1B109.5N3—C9—C8126.0 (2)
C2—C1—H1C109.5N3—C9—C10115.75 (17)
H1A—C1—H1C109.5C8—C9—C10118.26 (18)
H1B—C1—H1C109.5N4—C10—C11124.0 (2)
N1—C2—C3112.90 (16)N4—C10—C9112.56 (16)
N1—C2—C1124.48 (18)C11—C10—C9123.38 (18)
C3—C2—C1122.60 (16)C10—C11—H11A109.5
N2—C3—C2116.17 (16)C10—C11—H11B109.5
N2—C3—C4124.53 (18)H11A—C11—H11B109.5
C2—C3—C4119.29 (17)C10—C11—H11C109.5
C3—C4—H4B109.5H11A—C11—H11C109.5
C3—C4—H4C109.5H11B—C11—H11C109.5
H4B—C4—H4C109.5H1S—O1S—H2S122.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O10.841.702.516 (2)162
O1S—H1S···O4i0.852.193.000 (2)159
O1S—H2S···O4ii0.852.032.842 (2)159
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C11H19N4O2)(H2O)0.5]ClO4
Mr411.30
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)13.0833 (5), 6.6401 (3), 18.6698 (7)
β (°) 90.445 (1)
V3)1621.88 (11)
Z4
Radiation typeMo Kα
µ (mm1)1.55
Crystal size (mm)0.36 × 0.35 × 0.12
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
Absorption correctionMulti-scan
(APEX2; Bruker, 2005)
Tmin, Tmax0.577, 0.832
No. of measured, independent and
observed [I > 2σ(I)] reflections
15994, 4717, 3609
Rint0.035
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.081, 1.00
No. of reflections4717
No. of parameters221
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.53, 0.97

Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998), SHELXTL.

 

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