research communications
κ3N,N′,N′′}dichloridocopper(II) diethyl ether hemisolvate
of {(but-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine-aDepartment of Chemistry & Physics, Saint Mary's College, Notre Dame, IN 46556, USA, bDepartment of Chemistry & Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA, and cDepartment of Chemistry & Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
*Correspondence e-mail: koshin@saintmarys.edu
The five-coordinate CuII atom in the title complex [CuCl2(C16H19N3)]·0.5C4H10O, adopts a near-ideal square-pyramidal geometry (τ-5 = 0.01). The apical Cu—Cl distance is 0.2626 (6) Å longer than the basal Cu—Cl distance. Weak C—H⋯Cl interactions between pyridine rings and the Cl atoms of adjacent complex molecules are present. The solvent molecule, located on a twofold rotation axis, is situated in the voids of this arrangement. Copper atoms coordinated by tridentate nitrogen-containing ligands have been found to be excellent promoters of Atom Transfer Radical Addition (ATRA) reactions.
Keywords: crystal structure; five-coordinate copper(II) complex; Atom Transfer Radical Addition (ATRA) reactions.
CCDC reference: 1050406
1. Chemical context
Transition-metal-catalyzed Atom Transfer Radical Addition (ATRA) reactions of haloalkanes and α-halocarbonyls to α-olefins have emerged as some of the most atom economical methods for simultaneously forming C—C and C—X bonds, leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities (Pintauer & Matyjaszewski, 2005). Copper(I) complexes with tridentate and tetradentate nitrogen-based ligands are currently some of the most active multidentate ligand structures developed for use in ATRA reactions (Matyjaszewski et al., 2001). In view of the importance of these types of complexes, we report the synthesis and structural characterization of the title compound {(but-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine-κ3N,N′,N′′} dichloridocopper(II) diethyl ether hemisolvate, (I).
2. Structural commentary
The title complex, (I) (Fig. 1), adopts a typical-for-this-class of compounds (vide infra), slightly distorted square-pyramidal geometry, as shown in the bond angles about the CuII atom. A τ-5 analysis of the distortions about the CuII atom yields a value of 0.01, close to an ideal value of zero for a perfect square-pyramidal geometry [Addison et al., 1984; τ-5 = (β − α)/60 where β and α are the angles formed by atoms trans across the metal atom that do not include the apical atom]. In the complex, the CuII atom lies 0.2761 (5) Å out of the mean basal plane formed by the three coordinating N atoms and atom Cl1, reflecting the slight distortion from a true square plane. The Cu—N bond lengths are all similar [1.9980 (11)–2.0700 (10) Å] and the apical Cu—Cl2 distance is considerably longer [2.5134 (4) Å] than that of Cu—Cl1 [2.2508 (4) Å] in the basal plane. The diethyl ether molecule of crystallization is located in the with the O atom on the crystallographic twofold rotation axis at [, y, ].
3. Supramolecular features
Despite an open coordination site on the CuII atom, the complex does not dimerize through a chloride bridge, that is often observed in similar complexes (vide infra). There are weak electrostatic C—H⋯Cl interactions between pyridine rings and the basal chlorine of adjacent molecules (Table 1 and Fig. 2). Close contacts about the butenyl chain are typical van der Waals contacts. The orientation of the butenyl chain is such that it is anti to the apical Cl ligand, effectively proximal to the vacant sixth coordination site of the CuII atom. Instead, the diethyl ether molecule of crystallization is located in the pocket formed by the butenyl chain and the basal coordination plane of the CuII atom. Perhaps surprisingly, the ether O atom is not oriented towards, or spatially close to, the Cu atom [Cu⋯O1ii = 4.9130 (9) Å; symmetry code (ii) −x + , −y + , −z + 1] and merely serves to occupy a void space that would otherwise be formed by molecular packing.
4. Database survey
Although there are 80 copper chloride structures that incorporate the bis(pyridin-2-ylmethyl)amine ligand (Groom & Allen, 2014; CSD Version 5.36 plus one update), only 20 have a sole bis(pyridin-2-ylmethyl)amine ligand chelating to a CuCl2 moiety within an overall five coordination. The remaining 60 structures either have a tethered pair or tethered tiplet of ligands, or have the bridging chlorines between two complexes and are thus the more common geometry adopted by copper coordinated by a bis(pyridin-2-ylmethyl)amine based ligand. The geometry of the ligand and observed herein, is also a common feature of these structures, vis-a-vis, the is oriented anti to the apical chlorine.
5. Synthesis and crystallization
For the preparation of (but-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine (see Scheme 1 below), the bis(pyridin-2-ylmethyl)amine (BPMA) precursor was synthesized and purified following literature procedures (Carvalho et al., 2006). BPMA (8.064 g, 40.5 mmol) was dissolved in acetonitrile (15 ml) followed by the addition of triethylamine (4.098 g, 40.5 mmol) and 4-bromobutene (5.468 g, 40.5 mmol). The reaction vessel was sealed and allowed to mix for 4 d to ensure complete deprotonation and coupling occurred. Generation of the triethylamine hydrogen bromide salt, Et3NH+·Br−, was observed as white crystals in the brown-colored solution. The mixture was filtered and the desired product extracted from the filtrate using a hexane/water mixture. The hexane layer was separated and solvent removed to yield the ligand as a yellow colored oil (yield 8.516 g, 83%). The ligand was stored in a septum-sealed round-bottomed flask under argon gas in a refrigerator.
For the synthesis of the title compound, (I), 1-butene-BPMA (2.000 g, 7.900 mmol) was dissolved in acetonitrile (20 ml) in a 50 ml round-bottomed flask. CuCl2 (1.062 g, 7.900 mmol) was added to the flask to give a green-colored solution. The reaction was allowed to mix for 6 h, then pentane (20 ml) was added slowly to the solution to generate a bright-green precipitate. The solvent was removed from the round-bottomed flask by connecting it to a rotary evaporator. The precipitate obtained was washed twice by transferring two 15 ml aliquots of pentane into the flask and stirring vigorously for 30 min. The solvent was removed and the precipitate dried under vacuum for 2 h to yield a green solid (yield 2.909 g, 95%). Slow diffusion of diethyl ether into an acetonitrile solution of the complex at room temperature produced crystals of (I) suitable for X-ray analysis.
6. details
Crystal data, data collection and structure . All non-H atoms were refined with anisotropic displacement parameters. H atoms were included in idealized positions, with C—H = 0.95 (aromatic), 0.98 (methyl), and 0.99 Å (ethylinic/methylene). Methyl H atoms were allowed to rotate to minimize their electron-density contribution. The Uiso(H) values were set at 1.5Ueq(C) for methyl H atoms and at 1.2Ueq(C) otherwise.
details are summarized in Table 2Supporting information
CCDC reference: 1050406
10.1107/S2056989015003448/pk2546sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015003448/pk2546Isup2.hkl
Transition-metal-catalyzed Atom Transfer Radical Addition (ATRA) reactions of haloalkanes and α-halocarbonyls to α-olefins have emerged as some of the most atom economical methods for simultaneously forming C—C and C—X bonds, leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities (Pintauer & Matyjaszewski, 2005). Copper(I) complexes with tridentate and tetradentate nitrogen-based ligands are currently some of the most active multidentate ligand structures developed for use in ATRA reactions (Matyjaszewski et al., 2001). In view of the importance of these types of complexes, we report the synthesis and structural characterization of the title compound {(but-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine-κN,N',N''} dichloridocopper(II) diethyl ether monosolvate, (I).
The title complex, (I) (Fig. 1), adopts a typical-for-this-class of compounds (vide infra), slightly distorted square-pyramidal geometry, as shown in the bond angles about the Cu center. A τ-5 analysis of the distortions about the Cu center yields a value of 0.01, close to an ideal value of zero for a perfect square-pyramidal geometry [Addison et al., 1984; τ-5 = (β - α)/60 where β and α are the angles formed by atoms trans across the metal center that do not include the apical atom]. In the complex, the Cu center lies 0.2761 (5) Å out of the mean basal plane formed by the three coordinating N atoms and atom Cl1, reflecting the slight distortion from a true square plane. The Cu—N bond distances are all similar [1.9980 (11)–2.0700 (10) Å] and the apical Cu—Cl2 distance is considerably longer [2.5134 (4) Å] than that of Cu—Cl1 [2.2508 (4) Å] in the basal plane. The diethyl ether molecule of crystallization is located in the with the O atom on the crystallographic twofold axis at [1/2, y, 3/4].
Despite an open coordination site on the copper center, the complex does not dimerize through a chloride bridge, that is often observed in similar complexes (vide infra). There are weak electrostatic C—H···Cl interactions between pyridine rings and the basal chlorine of adjacent molecules (Table 1 and Fig. 2). Close contacts about the butenyl chain are typical van der Waals contacts. The orientation of the butenyl chain is such that it is anti to the apical Cl ligand, effectively proximal to the vacant sixth coordination site of the Cu center. Instead, the diethyl ether molecule of crystallization is located in the pocket formed by the butenyl chain and the basal coordination plane of the Cu center. Perhaps surprisingly, the ether O atom is not oriented towards, or spatially close to, the Cu atom [Cu···O1ii = 4.9130 (9) Å; symmetry code (ii) -x+1/2, -y+3/2, -z+1] and merely serves to occupy a void space that would otherwise be formed by molecular packing.
Although there are 80 copper chloride structures that incorporate the bis(pyridin-2-ylmethyl)amine ligand (Allen, 2002; CSD Version 5.36 +1 update), only 20 have a sole bis(pyridin-2-ylmethyl)amine ligand chelating a five-coordinate copper chloride center. The remaining sixty structures either have a tethered pair or tethered tiplet of ligands, or have the bridging chlorines between two complexes and are thus the more common geometry adopted by copper coordinated by a bis(pyridin-2-ylmethyl)amine based ligand. The geometry of the ligand and
observed herein, is also a common feature of these structures, vis-a-vis, the is oriented anti to the apical chlorine.For the preparation of (but-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine, the bis(pyridin-2-ylmethyl)amine (BPMA) precursor was synthesized and purified following literature procedures (Carvalho et al., 2006). BPMA (8.064 g, 40.5 mmol) was dissolved in acetonitrile (15 ml) followed by the addition of triethylamine (4.098 g, 40.5 mmol) and 4-bromobutene (5.468 g, 40.5 mmol). The reaction was sealed and allowed to mix for 4 d to ensure complete deprotonation and coupling occurred. Generation of the triethylamine hydrogen bromide salt, [Et3NH]+.Br-, was observed as white crystals in the brown-colored solution. The mixture was filtered and desired product extracted from the filtrate using a hexane/water mixture. The hexane layer was separated and solvent removed to yield the ligand as a yellow colored oil (yield 8.516 g, 83%). The ligand was stored in a septum-sealed round-bottomed flask under argon gas in a refrigerator.
For the synthesis of the title compound, (I), 1-butene-BPMA (2.000 g, 7.900 mmol) was dissolved in acetonitrile (20 ml) in a 50 ml round-bottomed flask. CuCl2 (1.062 g, 7.900 mmol) was added to the flask to give a green-colored solution. The reaction was allowed to mix for 6 h, then pentane (20 ml) was added slowly to the solution to generate a bright-green precipitate. The solvent was removed from the round-bottomed flask by connecting it to a rotary evaporator. The precipitate obtained was washed twice by transferring two 15 ml aliquots of pentane into the flask and stirring vigorously for 30 min. The solvent was removed and the precipitate dried under vacuum for 2 h to yield a green solid (yield 2.909 g, 95%). Slow diffusion of diethyl ether into an acetonitrile solution of the complex at room temperature produced crystals of (I) suitable for X-ray analysis.
Crystal data, data collection and structure
details are summarized in Table 2. All non-H atoms were refined with anisotropic displacement parameters. H atoms were included in idealized positions, with C—H = 0.95 (aromatic), 0.98 (methyl), and 0.99 Å (ethylinic/methylene). Methyl H atoms were allowed to rotate to minimize their electron-density contribution. The Uiso(H) values were set at 1.5Ueq(C) for methyl H atoms and at 1.2Ueq(C) otherwise.Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006) and POV-RAY (Cason, 2013); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The structure and atom-labeling scheme for (I). Displacement parameters are depicted at the 50% probability level. [Symmetry code: (i) -x+1, y, -z+3/2.] | |
Fig. 2. Packing diagram viewed along the a direction demonstrating the linear C—H···Cl electrostatic interactions (blue dashed lines). |
[CuCl2(C16H19N3)]·0.5C4H10O | F(000) = 1760 |
Mr = 424.84 | Dx = 1.412 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.1614 (13) Å | Cell parameters from 8841 reflections |
b = 11.5738 (5) Å | θ = 2.2–32.2° |
c = 16.4530 (7) Å | µ = 1.37 mm−1 |
β = 108.771 (1)° | T = 150 K |
V = 3995.6 (3) Å3 | Rhomboid, blue |
Z = 8 | 0.50 × 0.28 × 0.10 mm |
Bruker APEXII diffractometer | 6872 independent reflections |
Radiation source: fine-focus sealed tube | 5660 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.33 pixels mm-1 | θmax = 32.6°, θmin = 1.9° |
ϕ and ω scans | h = −32→33 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −17→17 |
Tmin = 0.471, Tmax = 0.840 | l = −23→24 |
24823 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0348P)2 + 2.0749P] where P = (Fo2 + 2Fc2)/3 |
6872 reflections | (Δ/σ)max = 0.002 |
223 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
[CuCl2(C16H19N3)]·0.5C4H10O | V = 3995.6 (3) Å3 |
Mr = 424.84 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.1614 (13) Å | µ = 1.37 mm−1 |
b = 11.5738 (5) Å | T = 150 K |
c = 16.4530 (7) Å | 0.50 × 0.28 × 0.10 mm |
β = 108.771 (1)° |
Bruker APEXII diffractometer | 6872 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 5660 reflections with I > 2σ(I) |
Tmin = 0.471, Tmax = 0.840 | Rint = 0.025 |
24823 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.53 e Å−3 |
6872 reflections | Δρmin = −0.43 e Å−3 |
223 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.15616 (2) | 0.59899 (2) | 0.13662 (2) | 0.01989 (5) | |
Cl1 | 0.09795 (2) | 0.43892 (3) | 0.13435 (2) | 0.03418 (8) | |
Cl2 | 0.25976 (2) | 0.52731 (3) | 0.12375 (2) | 0.02394 (7) | |
N1 | 0.18137 (5) | 0.77181 (9) | 0.14348 (6) | 0.01978 (19) | |
N2 | 0.11788 (5) | 0.64014 (9) | 0.01190 (7) | 0.0215 (2) | |
N3 | 0.19179 (5) | 0.61566 (9) | 0.26406 (7) | 0.0223 (2) | |
C1 | 0.19332 (6) | 0.79568 (11) | 0.06162 (8) | 0.0219 (2) | |
H1A | 0.2363 | 0.7679 | 0.0650 | 0.026* | |
H1B | 0.1915 | 0.8800 | 0.0508 | 0.026* | |
C2 | 0.14371 (6) | 0.73526 (11) | −0.01065 (8) | 0.0205 (2) | |
C3 | 0.12747 (6) | 0.77160 (12) | −0.09536 (8) | 0.0240 (2) | |
H3 | 0.1460 | 0.8393 | −0.1099 | 0.029* | |
C4 | 0.08364 (6) | 0.70725 (13) | −0.15849 (8) | 0.0275 (3) | |
H4 | 0.0728 | 0.7289 | −0.2171 | 0.033* | |
C5 | 0.05600 (7) | 0.61125 (13) | −0.13490 (9) | 0.0287 (3) | |
H5 | 0.0251 | 0.5674 | −0.1770 | 0.034* | |
C6 | 0.07399 (6) | 0.57991 (12) | −0.04920 (9) | 0.0263 (3) | |
H6 | 0.0549 | 0.5141 | −0.0331 | 0.032* | |
C7 | 0.23897 (6) | 0.78269 (11) | 0.22018 (8) | 0.0223 (2) | |
H7A | 0.2440 | 0.8638 | 0.2403 | 0.027* | |
H7B | 0.2773 | 0.7607 | 0.2053 | 0.027* | |
C8 | 0.23224 (6) | 0.70480 (11) | 0.29021 (8) | 0.0219 (2) | |
C9 | 0.26692 (7) | 0.72191 (12) | 0.37617 (9) | 0.0284 (3) | |
H9 | 0.2956 | 0.7850 | 0.3935 | 0.034* | |
C10 | 0.25854 (8) | 0.64431 (13) | 0.43618 (9) | 0.0315 (3) | |
H10 | 0.2825 | 0.6525 | 0.4952 | 0.038* | |
C11 | 0.21516 (7) | 0.55514 (13) | 0.40935 (9) | 0.0298 (3) | |
H11 | 0.2076 | 0.5034 | 0.4499 | 0.036* | |
C12 | 0.18308 (7) | 0.54244 (12) | 0.32283 (9) | 0.0263 (3) | |
H12 | 0.1540 | 0.4802 | 0.3042 | 0.032* | |
C13 | 0.12613 (6) | 0.83899 (11) | 0.15197 (9) | 0.0250 (2) | |
H13A | 0.1182 | 0.8139 | 0.2052 | 0.030* | |
H13B | 0.0879 | 0.8187 | 0.1031 | 0.030* | |
C14 | 0.13334 (8) | 0.97031 (13) | 0.15463 (11) | 0.0370 (3) | |
H14A | 0.1719 | 0.9922 | 0.2024 | 0.044* | |
H14B | 0.1387 | 0.9976 | 0.1003 | 0.044* | |
C15 | 0.07651 (10) | 1.02672 (16) | 0.16678 (14) | 0.0517 (5) | |
H15 | 0.0648 | 1.0031 | 0.2150 | 0.062* | |
C16 | 0.04196 (14) | 1.1043 (2) | 0.1180 (2) | 0.0866 (9) | |
H16A | 0.0519 | 1.1306 | 0.0691 | 0.104* | |
H16B | 0.0064 | 1.1356 | 0.1308 | 0.104* | |
O1 | 0.5000 | 0.71720 (17) | 0.7500 | 0.0552 (5) | |
C17 | 0.46509 (12) | 0.7851 (2) | 0.6791 (2) | 0.0809 (9) | |
H17A | 0.4948 | 0.8292 | 0.6570 | 0.097* | |
H17B | 0.4381 | 0.8409 | 0.6973 | 0.097* | |
C18 | 0.42468 (16) | 0.7095 (4) | 0.6110 (2) | 0.1069 (12) | |
H18A | 0.4016 | 0.7564 | 0.5610 | 0.160* | |
H18B | 0.3941 | 0.6687 | 0.6323 | 0.160* | |
H18C | 0.4515 | 0.6531 | 0.5942 | 0.160* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02130 (8) | 0.01992 (8) | 0.01888 (8) | −0.00387 (5) | 0.00706 (6) | 0.00069 (5) |
Cl1 | 0.03288 (17) | 0.03282 (17) | 0.03443 (18) | −0.01494 (14) | 0.00746 (14) | 0.00510 (13) |
Cl2 | 0.02487 (14) | 0.02391 (14) | 0.02458 (14) | −0.00119 (11) | 0.01009 (11) | −0.00181 (11) |
N1 | 0.0212 (5) | 0.0208 (5) | 0.0182 (5) | −0.0017 (4) | 0.0076 (4) | −0.0003 (4) |
N2 | 0.0209 (5) | 0.0229 (5) | 0.0205 (5) | −0.0029 (4) | 0.0064 (4) | −0.0002 (4) |
N3 | 0.0255 (5) | 0.0233 (5) | 0.0203 (5) | 0.0010 (4) | 0.0106 (4) | 0.0013 (4) |
C1 | 0.0241 (6) | 0.0234 (6) | 0.0193 (5) | −0.0051 (4) | 0.0083 (5) | −0.0001 (4) |
C2 | 0.0202 (5) | 0.0217 (6) | 0.0207 (5) | −0.0004 (4) | 0.0081 (4) | −0.0004 (4) |
C3 | 0.0223 (6) | 0.0292 (6) | 0.0214 (6) | 0.0015 (5) | 0.0082 (5) | 0.0034 (5) |
C4 | 0.0254 (6) | 0.0367 (7) | 0.0195 (6) | 0.0040 (5) | 0.0058 (5) | 0.0017 (5) |
C5 | 0.0243 (6) | 0.0344 (7) | 0.0237 (6) | −0.0024 (5) | 0.0024 (5) | −0.0041 (5) |
C6 | 0.0228 (6) | 0.0290 (7) | 0.0250 (6) | −0.0049 (5) | 0.0048 (5) | −0.0016 (5) |
C7 | 0.0247 (6) | 0.0214 (6) | 0.0199 (5) | −0.0034 (4) | 0.0061 (5) | −0.0011 (4) |
C8 | 0.0251 (6) | 0.0212 (6) | 0.0202 (5) | 0.0029 (4) | 0.0081 (5) | −0.0011 (4) |
C9 | 0.0364 (7) | 0.0254 (6) | 0.0211 (6) | 0.0046 (5) | 0.0060 (5) | −0.0027 (5) |
C10 | 0.0433 (8) | 0.0305 (7) | 0.0196 (6) | 0.0122 (6) | 0.0089 (6) | 0.0005 (5) |
C11 | 0.0383 (7) | 0.0302 (7) | 0.0251 (6) | 0.0110 (6) | 0.0161 (6) | 0.0078 (5) |
C12 | 0.0303 (6) | 0.0267 (6) | 0.0257 (6) | 0.0031 (5) | 0.0142 (5) | 0.0056 (5) |
C13 | 0.0271 (6) | 0.0240 (6) | 0.0255 (6) | 0.0033 (5) | 0.0107 (5) | 0.0002 (5) |
C14 | 0.0349 (8) | 0.0245 (7) | 0.0458 (9) | 0.0048 (6) | 0.0048 (7) | −0.0025 (6) |
C15 | 0.0609 (12) | 0.0382 (9) | 0.0612 (12) | 0.0139 (8) | 0.0269 (10) | −0.0075 (8) |
C16 | 0.0783 (18) | 0.0776 (18) | 0.095 (2) | 0.0474 (15) | 0.0156 (16) | −0.0047 (15) |
O1 | 0.0521 (11) | 0.0461 (11) | 0.0708 (13) | 0.000 | 0.0244 (10) | 0.000 |
C17 | 0.0600 (14) | 0.0728 (17) | 0.124 (2) | 0.0280 (13) | 0.0496 (16) | 0.0421 (16) |
C18 | 0.0760 (19) | 0.158 (4) | 0.078 (2) | 0.036 (2) | 0.0130 (16) | 0.035 (2) |
Cu1—N3 | 1.9980 (11) | C8—C9 | 1.3895 (18) |
Cu1—N2 | 2.0093 (11) | C9—C10 | 1.391 (2) |
Cu1—N1 | 2.0700 (10) | C9—H9 | 0.9500 |
Cu1—Cl1 | 2.2508 (4) | C10—C11 | 1.383 (2) |
Cu1—Cl2 | 2.5134 (4) | C10—H10 | 0.9500 |
N1—C1 | 1.4800 (15) | C11—C12 | 1.379 (2) |
N1—C7 | 1.4837 (16) | C11—H11 | 0.9500 |
N1—C13 | 1.4942 (16) | C12—H12 | 0.9500 |
N2—C6 | 1.3466 (16) | C13—C14 | 1.527 (2) |
N2—C2 | 1.3469 (16) | C13—H13A | 0.9900 |
N3—C8 | 1.3434 (17) | C13—H13B | 0.9900 |
N3—C12 | 1.3455 (16) | C14—C15 | 1.488 (2) |
C1—C2 | 1.5067 (17) | C14—H14A | 0.9900 |
C1—H1A | 0.9900 | C14—H14B | 0.9900 |
C1—H1B | 0.9900 | C15—C16 | 1.281 (3) |
C2—C3 | 1.3878 (17) | C15—H15 | 0.9500 |
C3—C4 | 1.3883 (19) | C16—H16A | 0.9500 |
C3—H3 | 0.9500 | C16—H16B | 0.9500 |
C4—C5 | 1.383 (2) | O1—C17i | 1.413 (3) |
C4—H4 | 0.9500 | O1—C17 | 1.413 (3) |
C5—C6 | 1.3845 (19) | C17—C18 | 1.476 (4) |
C5—H5 | 0.9500 | C17—H17A | 0.9900 |
C6—H6 | 0.9500 | C17—H17B | 0.9900 |
C7—C8 | 1.5077 (17) | C18—H18A | 0.9800 |
C7—H7A | 0.9900 | C18—H18B | 0.9800 |
C7—H7B | 0.9900 | C18—H18C | 0.9800 |
N3—Cu1—N2 | 160.62 (5) | H7A—C7—H7B | 108.3 |
N3—Cu1—N1 | 80.84 (4) | N3—C8—C9 | 121.93 (12) |
N2—Cu1—N1 | 81.05 (4) | N3—C8—C7 | 115.75 (11) |
N3—Cu1—Cl1 | 97.34 (3) | C9—C8—C7 | 122.30 (12) |
N2—Cu1—Cl1 | 97.28 (3) | C8—C9—C10 | 118.31 (13) |
N1—Cu1—Cl1 | 159.94 (3) | C8—C9—H9 | 120.8 |
N3—Cu1—Cl2 | 93.27 (3) | C10—C9—H9 | 120.8 |
N2—Cu1—Cl2 | 95.11 (3) | C11—C10—C9 | 119.57 (13) |
N1—Cu1—Cl2 | 94.92 (3) | C11—C10—H10 | 120.2 |
Cl1—Cu1—Cl2 | 105.136 (14) | C9—C10—H10 | 120.2 |
C1—N1—C7 | 113.65 (9) | C12—C11—C10 | 118.92 (13) |
C1—N1—C13 | 112.33 (10) | C12—C11—H11 | 120.5 |
C7—N1—C13 | 112.52 (10) | C10—C11—H11 | 120.5 |
C1—N1—Cu1 | 104.77 (7) | N3—C12—C11 | 121.94 (13) |
C7—N1—Cu1 | 105.76 (7) | N3—C12—H12 | 119.0 |
C13—N1—Cu1 | 107.05 (8) | C11—C12—H12 | 119.0 |
C6—N2—C2 | 119.11 (11) | N1—C13—C14 | 116.05 (11) |
C6—N2—Cu1 | 127.29 (9) | N1—C13—H13A | 108.3 |
C2—N2—Cu1 | 113.44 (8) | C14—C13—H13A | 108.3 |
C8—N3—C12 | 119.27 (11) | N1—C13—H13B | 108.3 |
C8—N3—Cu1 | 114.07 (8) | C14—C13—H13B | 108.3 |
C12—N3—Cu1 | 126.42 (9) | H13A—C13—H13B | 107.4 |
N1—C1—C2 | 109.43 (10) | C15—C14—C13 | 110.80 (14) |
N1—C1—H1A | 109.8 | C15—C14—H14A | 109.5 |
C2—C1—H1A | 109.8 | C13—C14—H14A | 109.5 |
N1—C1—H1B | 109.8 | C15—C14—H14B | 109.5 |
C2—C1—H1B | 109.8 | C13—C14—H14B | 109.5 |
H1A—C1—H1B | 108.2 | H14A—C14—H14B | 108.1 |
N2—C2—C3 | 121.90 (12) | C16—C15—C14 | 125.8 (2) |
N2—C2—C1 | 115.39 (10) | C16—C15—H15 | 117.1 |
C3—C2—C1 | 122.65 (11) | C14—C15—H15 | 117.1 |
C2—C3—C4 | 118.80 (12) | C15—C16—H16A | 120.0 |
C2—C3—H3 | 120.6 | C15—C16—H16B | 120.0 |
C4—C3—H3 | 120.6 | H16A—C16—H16B | 120.0 |
C5—C4—C3 | 119.17 (12) | C17i—O1—C17 | 112.4 (3) |
C5—C4—H4 | 120.4 | O1—C17—C18 | 109.5 (2) |
C3—C4—H4 | 120.4 | O1—C17—H17A | 109.8 |
C4—C5—C6 | 119.20 (13) | C18—C17—H17A | 109.8 |
C4—C5—H5 | 120.4 | O1—C17—H17B | 109.8 |
C6—C5—H5 | 120.4 | C18—C17—H17B | 109.8 |
N2—C6—C5 | 121.79 (13) | H17A—C17—H17B | 108.2 |
N2—C6—H6 | 119.1 | C17—C18—H18A | 109.5 |
C5—C6—H6 | 119.1 | C17—C18—H18B | 109.5 |
N1—C7—C8 | 109.24 (10) | H18A—C18—H18B | 109.5 |
N1—C7—H7A | 109.8 | C17—C18—H18C | 109.5 |
C8—C7—H7A | 109.8 | H18A—C18—H18C | 109.5 |
N1—C7—H7B | 109.8 | H18B—C18—H18C | 109.5 |
C8—C7—H7B | 109.8 | ||
C7—N1—C1—C2 | 155.62 (10) | C12—N3—C8—C9 | 1.93 (19) |
C13—N1—C1—C2 | −75.20 (13) | Cu1—N3—C8—C9 | −172.73 (10) |
Cu1—N1—C1—C2 | 40.65 (11) | C12—N3—C8—C7 | −179.82 (11) |
C6—N2—C2—C3 | −1.47 (18) | Cu1—N3—C8—C7 | 5.52 (14) |
Cu1—N2—C2—C3 | 174.32 (10) | N1—C7—C8—N3 | 22.88 (15) |
C6—N2—C2—C1 | −178.80 (11) | N1—C7—C8—C9 | −158.88 (12) |
Cu1—N2—C2—C1 | −3.00 (13) | N3—C8—C9—C10 | −0.6 (2) |
N1—C1—C2—N2 | −26.50 (15) | C7—C8—C9—C10 | −178.72 (12) |
N1—C1—C2—C3 | 156.20 (11) | C8—C9—C10—C11 | −1.8 (2) |
N2—C2—C3—C4 | −0.47 (19) | C9—C10—C11—C12 | 2.7 (2) |
C1—C2—C3—C4 | 176.66 (12) | C8—N3—C12—C11 | −0.91 (19) |
C2—C3—C4—C5 | 2.0 (2) | Cu1—N3—C12—C11 | 173.03 (10) |
C3—C4—C5—C6 | −1.7 (2) | C10—C11—C12—N3 | −1.4 (2) |
C2—N2—C6—C5 | 1.8 (2) | C1—N1—C13—C14 | −63.24 (15) |
Cu1—N2—C6—C5 | −173.32 (10) | C7—N1—C13—C14 | 66.53 (14) |
C4—C5—C6—N2 | −0.2 (2) | Cu1—N1—C13—C14 | −177.71 (10) |
C1—N1—C7—C8 | −152.29 (10) | N1—C13—C14—C15 | −177.66 (13) |
C13—N1—C7—C8 | 78.63 (12) | C13—C14—C15—C16 | −125.1 (3) |
Cu1—N1—C7—C8 | −37.91 (11) | C17i—O1—C17—C18 | −174.1 (3) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2ii | 0.95 | 2.67 | 3.5541 (15) | 156 |
C11—H11···Cl2iii | 0.95 | 2.74 | 3.4767 (15) | 135 |
C14—H14A···Cl2iv | 0.99 | 2.80 | 3.7127 (18) | 153 |
Symmetry codes: (ii) −x+1/2, −y+3/2, −z; (iii) x, −y+1, z+1/2; (iv) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2i | 0.95 | 2.67 | 3.5541 (15) | 156 |
C11—H11···Cl2ii | 0.95 | 2.74 | 3.4767 (15) | 135 |
C14—H14A···Cl2iii | 0.99 | 2.80 | 3.7127 (18) | 153 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) x, −y+1, z+1/2; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl2(C16H19N3)]·0.5C4H10O |
Mr | 424.84 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 22.1614 (13), 11.5738 (5), 16.4530 (7) |
β (°) | 108.771 (1) |
V (Å3) | 3995.6 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.50 × 0.28 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Krause et al., 2015) |
Tmin, Tmax | 0.471, 0.840 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24823, 6872, 5660 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.758 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.072, 1.03 |
No. of reflections | 6872 |
No. of parameters | 223 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.43 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2006) and POV-RAY (Cason, 2013), publCIF (Westrip, 2010).
Acknowledgements
KDO wishes to thank all undergraduate research students listed for their contributions to this project; Duquesne University and the University of Notre Dame for instrumentation support; Cambridge Isotope Laboratories Inc., the American Chemical Society, Saint Mary's College, and Eli Lilly & Company for funding support.
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