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The title compound, {(C9H14N)2[Cu3Cl8]}n, consists of parallel chains of alternating quasiplanar Cu2Cl6 and planar CuCl4 complexes separated by trimethyl­phenyl­ammonium cations. Both inorganic complexes possess inversion symmetry. Pairs of neighboring chloride ions of the CuCl4 complex each form a symmetric bridge and an asymmetric bridge to Cu2Cl6 complexes on either side. The Cu2Cl6 complex contains two symmetric chloride bridges between the copper cations with a terminal chloride bound to each five-coordinated CuII ion. The CuCl4 complex completes its coordination environment by forming two long semicoordinate contacts to the bridging chloride ions of neighboring Cu2Cl6 complexes. The use of the bridging rather than the terminal chloride ions to form semicoordinate contacts generates a new zigzag chain structure that differs from the straight chain structures found for other A2Cu3Cl8 compounds. The zigzag chain structure is adopted so as to conform to the shorter repeat distance dicta­ted by stacking of the organic cations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109054560/ga3139sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109054560/ga3139Isup2.hkl
Contains datablock I

CCDC reference: 774015

Comment top

Copper(II) halide chain compounds continue to show an amazing diversity of structure. A straighforward connection to other metal halide chain structures is exhibited by compounds such as CsCuCl3 (Schlueter et al., 1966) or (CH3)4NCuCl3 [Willett et al., 1988; refcode MATCCU01 in the Cambridge Structural Database (CSD; Allen, 2002)], which adopt the CsNiCl3 structure type. In the holotype structure, neighboring Ni2+ cations are linked by symmetric tri-µ-chloride bridging. For ACuCl3 compounds, however, two of the three bridges between neighboring Cu2+ ions in the chain are asymmetric as a result of Jahn–Teller distortion (Muller & Roy, 1974). For octahedral Cu2+ the Jahn–Teller distortion is primarily axial to produce a 4 + 2 coordination geometry in which Cu···Cl distances for the two semicoordinated ligands can range from 2.7 Å to well over 3 Å. It has long been recognized that semicoordinated ligands with Cu···Cl distances of 3 Å or more can still interact significantly with the Cu2+ ion and affect the geometrical arrangement of the coordinated ligands. In the extreme limit the distortion leads to complete removal of one or two axial ligands to give square-pyramidal or square-planar Cu2+, respectively (Smith, 1976; Reinen, 1983). Thus, strongly hydrogen bonding donor cations, such as cyclohexylammonium (Groenendijk et al., 1981; BAPYUM) or 2-amino-6-methylpyridinium (Geiser et al., 1986; CIGNOV10), can interact with the chain to stabilize terminal chloride ligands and yield symmetrically dibridged chains of CuCl5 square pyramids. Use of bulky cations leads to segmented chains in which tri-µ-halide-bridged segments of face-sharing octahedra are linked by two symmetrically bridging halide ions. These segments are of varying length as found in [(CH3)3NC2H5]4Cu5Cl14 (Bond et al., 1990; TABNOZ), [(CH3)2N(C2H5)2]3Cu4Cl11 (Fujii et al., 1995; ZACJES), [(C6H5)3PCH3]2Cu3Cl8 (El Essawi, 1997; NIJZEL), [(C6H5)3PCH3]2Cu3Br8 (Lorenzo et al., 2000; LITHEB), [(C6H5)3PCl]2Cu3Cl8 (Lorenzo et al., 2000; LITHAX), [(CH3CN)2(15-crown-5)Cu]Cu3Cl8 (Belsky et al., 1991; JIZBUP), and (1-n-butyl, 3-methylimidazolium)2Cu3Cl8 (Sun et al., 2005; FIYPUZ). In some cases, segmented chains form as stacks of quasiplanar di- or tri-copper complexes in which neighboring complexes are linked by two asymmetric bridges involving semicoordinate contacts, e.g. (i-C3H7NH3)2Cu2Cl6 (Roberts et al., 1981; IPAMCU01) and [1,2-(CH3)2C6H5N]2Cu3Br8 (Bond et al., 1995; ZACSAX). The (i-C3H7NH3)2Cu2Cl6 structure is especially interesting since it transforms to the CsNiCl3-type structure at higher temperature upon weakening of the hydrogen bonding from the organic cation. The charge compensation principle has successfully rationalized this wide array of chain structures by considering hydrogen bonding interactions from the organic cations that reduce ligand–ligand repulsion, stabilize square planar, 4 + 1 or 4 + 2 coordination geometries, or induce terminal (rather than bridging) halide formation in the chain (Willett, 1991). The structure presented here, catena-poly[bis(trimethylphenylammonium) [hexa-µ-chlorido-dichloridotricuprate(II)]], (I), contains terminal chain chloride ligands in the absence of strong NH hydrogen bonding, thus posing a challenge to these traditional rationalizations for copper(II) halide chain structures.

The structure of (I) consists of parallel zigzag inorganic chains separated by trimethylphenylammonium cations (Figs. 1 and 2). Table 1 lists bond lengths and angles within the chloridocuprate(II) chain. At first glance the inorganic chain structure consists of alternating planar CuCl4 and quasi-planar Cu2Cl6 complexes with neighboring complexes linked by one symmetric (Cl3) and one asymmetric (Cl2) bridge. The CuCl4 complex has inversion symmetry (at Cu2) and closely approximates square planarity. The copper ions in the Cu2Cl6 complex are five-coordinate with a distorted square-pyramidal arrangement in which Cl2 is the axial ligand and lies out of the plane of the complex. The basal ligands all have short bond lengths: the bond length to Cl1, the terminal chloride, is the shortest. Atom Cu1 sits above the basal ligands slightly, as indicated by trans Cl—Cu—Cl angles of approximately 169°. The axial ligand that bridges to atom Cu2 is bent toward Cu2 as shown by the acute Cl2—Cu1—Cl3 angle of 82.31 (3)°. The Cu2Cl6 complex possesses inversion symmetry so that the axial ligands of the neighboring copper(II) ions are oriented in opposite directions. Neighboring CuCl4 and Cu2Cl6 complex planes form an angle of 61.53 (2)° with respect to each other.

The inorganic chain structures of the other A2Cu3Cl8 compounds listed above can be described in the same basic terms as an alternating chain of planar CuCl4 and quasi-planar Cu2Cl6 complexes. However, the chain structures in these cases are straight, rather than zigzag as in (I). This arises from a remarkable difference in the way the CuCl4 complex in (I) completes its coordination environment. In the straight-chain structures the CuCl4 complex forms long semicoordinate contacts to terminal chloride ions of neighboring Cu2Cl6 units to give itself 4 + 2 coordination and to produce the straight chain (e.g. NIJZEL, LITHEB, LITHAX, JIZBUP and FIYPUZ). This behavior is easily explained in terms of the charge compensation principle, since without strong hydrogen bonding from the organic cation the terminal chloride should interact more strongly with a neighboring copper cation to form an asymmetric bridge. In contrast, the CuCl4 complex in (I) completes its coordination environment by forming semicoordinate contacts to the bridging chlorides (Cl4) of neighboring Cu2Cl6 complexes, and leaving Cl1 as a completely terminal ligand. This occurs in spite of the fact that the quaternary N atom is incapable of the strong NH hydrogen bonding expected to stabilize terminal halide ligands within the chain (Willett, 1991). In both the linear and the zigzag chains, the CuCl4 complex also acts as the central complex of a tricopper segment linked to neighboring segments by the symmetric dibridging in the Cu2Cl6 complexes.

The semicoordinate contact angles about Cu2 are strained, as shown by the Cl···Cu—Cl angles, which deviate by an average of 10.04 (4)° from 90°. However, they are not as strained as those in the (C6H5)3PR+ salts where average deviations of 17.59 (4)° for NIJZEL (R = CH3) and 15.31 (6)° for LITHAX (R = Cl) are found. In these cases the larger strain arises from the straight chain stretching to accomodate the repeat distance enforced by the bulky cations. Indeed, the semicoordinate Cu···Cl contact distance in these latter salts is approximately 0.4 Å longer [Cu···Cl = 3.467 (3) Å for R = CH3 and 3.309 (3) Å for R = Cl] than here, even though the semicoordinated ligand in (I) is a bridging ligand. Other straight-chain Cu3Cl82- compounds with less bulky ligands are less strained, as shown by shorter Cu···Cl bonds [2.786 (5) Å for JIZBUP and 2.9582 (7) Å for FIYPUZ] and smaller distortions in average Cl···Cu—Cl angles [11.3 (2)° for JIZBUP and 9.30 (4) for FIYPUZ]. Repeat distances for the tricopper chain segment reflect these strains, with values of 9.539 (8) Å for NIJZEL and 9.480 (6) Å for LITHAX compared to the shorter values of 9.330 (3) Å for JIZBUP, 9.278 (1) Å for FIYPUZ, and 7.4496 (1) Å here.

The segmented chain structures arise as a means of accomodating bulkier organic cations. In (CH3)4NCuCl3, a uniformly tribridged chain occurs (MATCCU01), but the slightly bulkier (CH3)3N(C2H5)+ cation yields a chain of pentacopper segments (TABNOZ). The even bulkier (CH3)2N(C2H5)2+ cation yields a chain of tetracopper segments (ZACJES). Shorter chain segments require more frequent dibridging along the chain. Since the dibridging is charge neutral, it requires no counter-ion. Thus the presence of more dibridging provides more room to pack bulkier cations. It is not surprising, then, that a chain of [Cu5Cl14]4- segments is found with the N,N-dimethylpiperidinium cation (Talley et al., 1999). While this cation is larger than (CH3)3N(C2H5)2+ by one C atom, the organic ring structure is more constrained than the two ethyl groups of (CH3)3N(C2H5)2+, so the cation is, arguably, less bulky. The trimethylphenylammonium cation of (I) replaces one methyl group of (CH3)4N+ (MATCCU01) with a phenyl group that should be less bulky than the saturated organic ring structure in N,N-dimethylpiperidinium. So the formation of a [Cu3Cl8]2- rather than a [Cu5Cl14]4- segmented chain at first seems puzzling.

The longest dimension of the trimethylphenylammonium cation, as measured by the H4···H12B distance plus twice the van der Waals radius of hydrogen (1.2 Å), can be generously estimated as 9.27 Å. This value is close to the lower limit of the repeat distance of the [Cu3Cl8]2- segments found in FIYPUZ. Hence it is conceivable that a straight-chain structure of tricopper segments could arise if trimethylphenylammonium cations were to stack end-to-end along their longest dimension, but it is unlikely that this would be an efficient packing mode for them. In this regard the folding back of the [Cu3Cl8]2- segment to form a zigzag chain can be explained as a means of accomodating the packing requirements of a cation of considerably less bulk than those that normally are found with segmented [Cu3Cl8]2- chains. The use of bridging ligands in (I) to form semicoordinate contacts arises to meet the packing needs of the organic cation, with charge compensation now a secondary factor at best.

Lorenzo et al. (2000) have carefully analyzed the LITHEB, LITHAX and JIZBUP structures and concluded that `it is likely that the details of coordination and bridging of copper have been controlled by the requirements of the [(C6H5)3PR+] cation motif'. In this regard it is worthwhile considering the organic cation packing motif here. The trimethylphenylammonium cations form parallel stacks of inversion-related pairs along the a axis, as shown in Fig. 2. Each inorganic chain is surrounded by four neighboring cation pair stacks and vice versa. The aromatic rings of each pair are coplanar and are separated by an interplanar spacing of 3.934 (6) Å. The normal to the aromatic ring plane forms an angle of 49.92 (6)° with respect to the a axis and is almost perpendicular to the b axis. This tilt angle efficiently allows the cations to aggregate phenyl rings inside the stack while placing two of the three methyl groups on the periphery. Neighboring cation pairs are also related by inversion, so that the cation stack follows a similar line of inversion centers along the a axis as does the inorganic chain. The cation pair inversion center is at the same x coordinate as the Cu2Cl6 inversion center, and the inversion center between cation pairs is at the same x coordinate as the CuCl4 inversion center. The methyl group of a cation in one pair abuts the phenyl ring of a cation in the neighboring pair with a contact distance [C4···C11iii = 3.549 (5) Å; symmetry code: (iii) x + 1, y, z] close to the sum of the van der Waals radii. The packing modes of the trimethylphenylammonium cation are varied in other structures, but cation stacking with the phenyl ring tilted relative to the stacking axis is a common motif. In particular, trimethylphenylammonium ozonide (Korber & Jansen, 1992; KUDYOX) contains stacking of inversion-related cation pairs with a repeat distance of 7.130 (2) Å, which very closely resembles the cation pair stacking in (I). In KUDYOX the tilt angle and the interplanar spacing are slightly smaller than those in (I), thus contributing to the marginally lower repeat distance.

Lorenzo et al. (2000) ask the question is the crystal packing in halidocuprate(II) compounds dominated or determined by organic cation supramolecular motifs, or by coordination within the halidocuprate anion? Their answer, with respect to the (C6H5)3PRCu3X8 compounds, is that cation supramoleuclar motifs dominate, but that validation is still required by geometrical information from related compounds. The structural details of (I) support the conclusion of Lorenzo et al. that cation supramolecular motifs indeed do determine the overall crystal packing, at least for cations bulkier than (CH3)4N+. Specifically, the zigzag chain structure in (I) is adopted to match the repeat distance dictated by the stacking of organic cation pairs. In this regard it is significant that the organic cation packing in (I) is rational and with precedent, while the halidocuprate chain structure defies traditional rationalizations (Willett, 1991).

C—H···Cl hydrogen bonding seems to be of little importance in the structure. Two of the three shortest H···Cl contact distances are to the terminal chloride (see Table 2). These short interactions might provide some weak CH hydrogen bonding to the terminal chloride that could further stabilize the zigzag chain structure. However, these contacts are significantly longer than those in the dibridged ACuCl3 chains, such as BAPYUM or CIGNOV10, in which H···Cl contact distances to the terminal ligand are less than 2.5 Å.

Bond lengths and angles within the trimethylphenylammonium cation agree with expected values (Ladd & Palmer, 1994). The conformation of the phenyl ring plane is staggered with respect to the methyl groups, and forms C2—C1—N1—C1X torsion angles of 85.6 (3)° with C11, 154.2 (3)° with C12 and 34.4 (3)° with C13. A study of similar torsion angles of trimethylphenylammonium cations compiled from the CSD indicates this staggered arrangement of the phenyl ring is less frequent than the eclipsed conformation. A histogram of these torsion angles (Fig. 3) shows that the more frequent torsion angles are approximately 0, 60, 120 and 180°, corresponding to an eclipsed conformation of the aromatic ring with one of the methyl groups. Less frequent torsion angles occur at approximately 30, 90 and 150° and correspond to the staggered conformation seen in (I). Elongated ring C atom displacement ellipsoids perpendicular to the ring plane indicate a high degree of librational motion. Librational motion of the methyl groups at higher temperature may render the eclipsed conformation untenable. The large displacement parameters perpendicular to the ring then arise as it is buffeted by non-bonding repulsive interactions with the methyl groups. Below 200 K a phase transition to a triclinic unit cell is observed, although crystal damage during the transition has so far prevented a completely suitable structure determination of the low-temperature phase. The best structure determination yet, obtained at 100 K [R = 0.0932 and F2 > 2σ(F2)], has established connectivity and shows a rearrangement of the organic cation to an eclipsed conformation while maintaining the gross structure of the inorganic chain (Bond, 2009).

Related literature top

For related literature, see: Allen (2002); Belsky et al. (1991); Bond (2009); Bond et al. (1990, 1995); El Essawi (1997); Fujii et al. (1995); Geiser et al. (1986); Groenendijk et al. (1981); Korber & Jansen (1992); Ladd & Palmer (1994); Lorenzo et al. (2000); Muller & Roy (1974); Reinen (1983); Roberts et al. (1981); Schlueter et al. (1966); Smith (1976); Sun et al. (2005); Talley et al. (1999); Willett (1991); Willett et al. (1988).

Experimental top

Trimethylphenylammonium iodide was prepared by reaction of N,N-dimethylaniline (5 ml, 0.04 mol) with a molar excess of iodomethane. The chloride salt was prepared by halide ion exchange with a molar excess of silver chloride. Trimethylphenylammonium chloride and copper(II) chloride were dissolved in a 1:1 ratio in 100 ml of approximately 6 M HCl solution. Red crystals of (I) were obtained upon evaporation.

Refinement top

All H atoms were visible in electron density difference maps. Positions for H atoms were calculated to give an idealized geometry in a riding model, with C—H bond lengths of 0.93 Å for aromatic H atoms and C—H bond lengths of 0.96 Å for methyl H atoms. Uiso(H) values were fixed at 1.2Ueq(C) for aromatic H atoms and 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEPIII (Burnett & Johnson, 1996) diagram with atom labels of the organic cation and a section of the chloridocuprate(II) chain. Displacement ellipsoids are drawn at the 50% level. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z + 1; (iii) x + 1, y, z.] DONT MATCH TABLES
[Figure 2] Fig. 2. Unit-cell packing diagram viewed down the b axis and showing the cation pair stacking and inorganic chain parallel to the a axis. For clarity, H atoms have been omitted, N and Cu atoms are drawn as large circles, and C and Cl atoms are drawn as small circles.
[Figure 3] Fig. 3. A histogram compiled from data in the CSD of C2,6—C1—N1—C1X torsion angles [atom-numbering scheme for (I) is used] in the range 0–180° for trimethylphenylammonium cations (Allen, 2002).
catena-Poly[bis(trimethylphenylammonium) [hexa-µ-chlorido-dichloridotricuprate(II)]] top
Crystal data top
(C9H14N)2[Cu3Cl8]F(000) = 746
Mr = 746.7Dx = 1.823 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6226 reflections
a = 7.4496 (1) Åθ = 2.9–35.0°
b = 10.0211 (2) ŵ = 3.12 mm1
c = 18.4713 (4) ÅT = 200 K
β = 99.420 (1)°Irregular, red
V = 1360.35 (4) Å30.30 × 0.24 × 0.18 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer
5947 independent reflections
Radiation source: Enraf Nonius FR5904127 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 9 pixels mm-1θmax = 35.0°, θmin = 3.5°
CCD rotation images, thick slices scansh = 1112
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
k = 1616
Tmin = 0.416, Tmax = 0.548l = 2929
11596 measured reflections
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0517P)2 + 1.7348P]
where P = (Fo2 + 2Fc2)/3
5947 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 1.32 e Å3
0 restraintsΔρmin = 1.70 e Å3
Crystal data top
(C9H14N)2[Cu3Cl8]V = 1360.35 (4) Å3
Mr = 746.7Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.4496 (1) ŵ = 3.12 mm1
b = 10.0211 (2) ÅT = 200 K
c = 18.4713 (4) Å0.30 × 0.24 × 0.18 mm
β = 99.420 (1)°
Data collection top
Nonius KappaCCD
diffractometer
5947 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
4127 reflections with I > 2σ(I)
Tmin = 0.416, Tmax = 0.548Rint = 0.033
11596 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.08Δρmax = 1.32 e Å3
5947 reflectionsΔρmin = 1.70 e Å3
145 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*/Ueq
Cu10.33640 (5)0.46628 (3)0.424383 (18)0.02878 (9)
Cu20.00000.50000.50000.02953 (11)
Cl30.07601 (9)0.33905 (7)0.41827 (4)0.03081 (14)
Cl10.33054 (10)0.46660 (8)0.30362 (4)0.03568 (15)
Cl20.10950 (10)0.66049 (7)0.43452 (4)0.03309 (14)
Cl40.61720 (10)0.56436 (8)0.44752 (4)0.03591 (16)
N10.7632 (3)0.4761 (2)0.20224 (12)0.0278 (4)
C10.5871 (3)0.5010 (3)0.15177 (14)0.0259 (5)
C110.9168 (4)0.4862 (3)0.15900 (18)0.0379 (6)
H11A1.03060.47520.19130.057*
H11B0.91390.57210.13580.057*
H11C0.90410.41760.12220.057*
C120.7672 (5)0.3402 (3)0.23681 (18)0.0421 (7)
H12A0.87700.33040.27170.063*
H12B0.76340.27310.19950.063*
H12C0.66390.33010.26130.063*
C130.7934 (5)0.5762 (4)0.26341 (18)0.0447 (8)
H13A0.90070.55270.29730.067*
H13B0.69030.57670.28850.067*
H13C0.80880.66330.24360.067*
C40.2688 (4)0.5509 (4)0.05547 (18)0.0402 (7)
H40.16250.56770.02270.048*
C20.5276 (4)0.6303 (3)0.13867 (18)0.0390 (7)
H20.59460.70110.16180.047*
C30.3669 (4)0.6543 (3)0.0906 (2)0.0451 (8)
H30.32560.74140.08230.054*
C60.4899 (5)0.3957 (3)0.1173 (2)0.0479 (9)
H60.53050.30850.12590.057*
C50.3283 (5)0.4223 (4)0.0688 (2)0.0536 (10)
H50.26070.35200.04550.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03094 (16)0.02784 (17)0.02452 (15)0.00009 (12)0.00449 (12)0.00067 (12)
Cu20.0323 (2)0.0264 (2)0.0285 (2)0.00246 (17)0.00080 (17)0.00053 (17)
Cl30.0313 (3)0.0301 (3)0.0297 (3)0.0039 (2)0.0013 (2)0.0047 (2)
Cl10.0373 (3)0.0422 (4)0.0254 (3)0.0001 (3)0.0012 (2)0.0009 (3)
Cl20.0390 (3)0.0263 (3)0.0335 (3)0.0008 (2)0.0045 (3)0.0027 (2)
Cl40.0356 (3)0.0398 (4)0.0281 (3)0.0072 (3)0.0073 (2)0.0073 (3)
N10.0272 (10)0.0277 (11)0.0259 (10)0.0019 (8)0.0030 (8)0.0014 (8)
C10.0267 (11)0.0268 (11)0.0227 (10)0.0013 (9)0.0003 (9)0.0006 (9)
C110.0278 (13)0.0462 (18)0.0385 (15)0.0003 (12)0.0025 (11)0.0014 (13)
C120.0490 (17)0.0353 (15)0.0375 (15)0.0024 (13)0.0061 (13)0.0107 (13)
C130.0461 (17)0.0455 (18)0.0364 (15)0.0041 (14)0.0118 (13)0.0152 (14)
C40.0291 (13)0.0510 (19)0.0369 (14)0.0030 (13)0.0054 (11)0.0027 (13)
C20.0387 (14)0.0256 (13)0.0469 (17)0.0019 (11)0.0098 (12)0.0041 (12)
C30.0393 (15)0.0371 (16)0.0530 (19)0.0097 (13)0.0103 (14)0.0071 (14)
C60.0468 (17)0.0310 (15)0.056 (2)0.0045 (13)0.0198 (15)0.0117 (14)
C50.0458 (18)0.0429 (18)0.061 (2)0.0026 (15)0.0237 (16)0.0124 (17)
Geometric parameters (Å, º) top
Cu1—Cl12.2240 (8)N1—C131.500 (4)
Cu1—Cl22.6045 (8)C13—H13A0.9600
Cu1—Cl32.3085 (7)C13—H13B0.9600
Cu1—Cl42.2873 (8)C13—H13C0.9600
Cu1—Cl4i2.3547 (7)N1—C11.501 (3)
Cu2—Cl22.2446 (7)C1—C21.378 (4)
Cu2—Cl32.3411 (7)C2—H20.9300
Cu2—Cl4i2.9297 (7)C1—C61.376 (4)
N1—C111.502 (4)C2—C31.389 (4)
C11—H11A0.9600C3—H30.9300
C11—H11B0.9600C3—C41.369 (5)
C11—H11C0.9600C4—H40.9300
N1—C121.503 (4)C4—C51.371 (5)
C12—H12A0.9600C5—H50.9300
C12—H12B0.9600C5—C61.403 (4)
C12—H12C0.9600C6—H60.9300
Cl1—Cu1—Cl299.47 (3)N1—C12—H12C109.5
Cl1—Cu1—Cl394.21 (3)H12A—C12—H12C109.5
Cl1—Cu1—Cl493.10 (3)H12B—C12—H12C109.5
Cl1—Cu1—Cl4i169.62 (3)C12—N1—C13107.2 (2)
Cl2—Cu1—Cl382.31 (3)N1—C13—H13A109.5
Cl2—Cu1—Cl4104.47 (3)N1—C13—H13B109.5
Cl2—Cu1—Cl4i90.89 (3)H13A—C13—H13B109.5
Cl3—Cu1—Cl4169.08 (3)N1—C13—H13C109.5
Cl3—Cu1—Cl4i87.77 (3)H13A—C13—H13C109.5
Cl4—Cu1—Cl4i83.62 (3)H13B—C13—H13C109.5
Cl2—Cu2—Cl389.92 (3)C1—N1—C13111.4 (2)
Cl2—Cu2—Cl4i85.19 (2)N1—C1—C2119.3 (2)
Cl3—Cu2—Cl4i74.73 (2)N1—C1—C6120.0 (2)
Cu1—Cl4—Cu1i96.38 (3)C2—C1—C6120.7 (3)
Cu1—Cl2—Cu278.50 (2)C1—C2—C3119.6 (3)
Cu1—Cl3—Cu282.99 (2)C1—C2—H2120.2
Cu1—Cl4—Cu2i141.09 (3)C3—C2—H2120.2
C1—N1—C11108.9 (2)C2—C3—C4120.6 (3)
N1—C11—H11A109.5C2—C3—H3119.7
N1—C11—H11B109.5C4—C3—H3119.7
H11A—C11—H11B109.5C3—C4—C5119.6 (3)
N1—C11—H11C109.5C3—C4—H4120.2
H11A—C11—H11C109.5C5—C4—H4120.2
H11B—C11—H11C109.5C4—C5—C6120.8 (3)
C11—N1—C12108.8 (2)C4—C5—H5119.6
C11—N1—C13108.8 (2)C6—C5—H5119.6
C1—N1—C12111.7 (2)C5—C6—C1118.8 (3)
N1—C12—H12A109.5C1—C6—H6120.6
N1—C12—H12B109.5C5—C6—H6120.6
H12A—C12—H12B109.5
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1ii0.932.77 (1)3.639 (3)156 (1)
C11—H11A···Cl1iii0.962.79 (1)3.739 (3)170 (1)
C11—H11C···Cl2iv0.962.78 (1)3.683 (3)158 (1)
Symmetry codes: (ii) x+1, y+1/2, z+1/2; (iii) x+1, y, z; (iv) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula(C9H14N)2[Cu3Cl8]
Mr746.7
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)7.4496 (1), 10.0211 (2), 18.4713 (4)
β (°) 99.420 (1)
V3)1360.35 (4)
Z2
Radiation typeMo Kα
µ (mm1)3.12
Crystal size (mm)0.30 × 0.24 × 0.18
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.416, 0.548
No. of measured, independent and
observed [I > 2σ(I)] reflections
11596, 5947, 4127
Rint0.033
(sin θ/λ)max1)0.806
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.129, 1.08
No. of reflections5947
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.32, 1.70

Computer programs: COLLECT (Bruker, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cu1—Cl12.2240 (8)Cu1—Cl4i2.3547 (7)
Cu1—Cl22.6045 (8)Cu2—Cl22.2446 (7)
Cu1—Cl32.3085 (7)Cu2—Cl32.3411 (7)
Cu1—Cl42.2873 (8)Cu2—Cl4i2.9297 (7)
Cl1—Cu1—Cl299.47 (3)Cl4—Cu1—Cl4i83.62 (3)
Cl1—Cu1—Cl394.21 (3)Cl2—Cu2—Cl389.92 (3)
Cl1—Cu1—Cl493.10 (3)Cl2—Cu2—Cl4i85.19 (2)
Cl1—Cu1—Cl4i169.62 (3)Cl3—Cu2—Cl4i74.73 (2)
Cl2—Cu1—Cl382.31 (3)Cu1—Cl4—Cu1i96.38 (3)
Cl2—Cu1—Cl4104.47 (3)Cu1—Cl2—Cu278.50 (2)
Cl2—Cu1—Cl4i90.89 (3)Cu1—Cl3—Cu282.99 (2)
Cl3—Cu1—Cl4169.08 (3)Cu1—Cl4—Cu2i141.09 (3)
Cl3—Cu1—Cl4i87.77 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1ii0.932.771 (1)3.639 (3)155.6 (2)
C11—H11A···Cl1iii0.962.790 (1)3.739 (3)169.8 (2)
C11—H11C···Cl2iv0.962.777 (1)3.683 (3)157.5 (2)
Symmetry codes: (ii) x+1, y+1/2, z+1/2; (iii) x+1, y, z; (iv) x+1, y1/2, z+1/2.
 

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