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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): m801.
Published online 2009 June 20. doi:  10.1107/S1600536809023009
PMCID: PMC2969286

catena-Poly[hemi[bis­(4′-phenyl-2,2′:6′,2′′-terpyridine-κ3 N)copper(II)] [cuprate(I)-di-μ2-thio­cyanato-κ2 N:S2 S:N]]

Abstract

Reaction of 4′-phenyl-2,2′:6′,2′′-terpyridine (phtpy), copper acetate hydrate and ammonium thio­cyanate under solvothermal conditions led to the formation of the title compound, {[Cu(C21H15N3)2][Cu2(NCS)4]}n. The structure is composed of discrete [Cu(phtpy)2]2+ cations and polymeric anionic {[Cu(SCN)2]} chains propagating along [010]. The central Cu2+ ion in the cation is coordinated by two tridentate chelating phtpy ligands in a distorted octa­hedral geometry. In each of the two crystallographically independent centrosymmetric anions, the CuI atoms are bridged in a 1,3-μ2-bridging mode by two S and two N atoms, resulting in a distorted tetrahedral CuN2S2 coordination. The [Cu(phtpy)2]2+ cations are fixed between these polymers by inter­molecular C—H(...)S hydrogen bonds.

Related literature

For related 2,2′:6′,2′′-terpyridine derivatives and their complexes, see: Heller & Schubert (2003 [triangle]); Hofmeier & Schubert (2004 [triangle]); Shi et al. (2007 [triangle]). For the isostructural 4′-(3-pyridyl)-2,2′:6′,2′′-terpyridine (3-pytpy) analogue, see: Shi (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m801-scheme1.jpg

Experimental

Crystal data

  • [Cu(C21H15N3)2][Cu2(NCS)4]
  • M r = 1041.66
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m801-efi1.jpg
  • a = 10.1803 (6) Å
  • b = 10.1829 (6) Å
  • c = 21.3203 (12) Å
  • α = 83.571 (1)°
  • β = 89.566 (1)°
  • γ = 81.676 (1)°
  • V = 2173.0 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.70 mm−1
  • T = 295 K
  • 0.15 × 0.14 × 0.12 mm

Data collection

  • Bruker SMART APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.785, T max = 0.823
  • 17217 measured reflections
  • 8453 independent reflections
  • 5988 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.141
  • S = 1.03
  • 8453 reflections
  • 568 parameters
  • 54 restraints
  • H-atom parameters constrained
  • Δρmax = 1.53 e Å−3
  • Δρmin = −0.89 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023009/at2820sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023009/at2820Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Jiangxi Science and Technology Normal University for supporting this study.

supplementary crystallographic information

Comment

2,2':6',2''-Terpyridine and its derivatives have attracted considerable interest as ligands in metal complexes because of their versatility as building blocks for supramolecular assembles and polymers (Heller & Schubert, 2003; Hofmeier & Schubert, 2004). As a continuing effort of our research on complexes of terpyridine derivatives (Shi et al., 2007), we here report the title compound by using 4'-phenyl-2,2':6',2''-terpyridine (phtpy) as ligand, containing discrete cations [Cu(phtpy)2]2+ and one-dimensional polymeric anionic chains [Cu(SCN)2]nn-.

As shown in Fig. 1, the molecular structure of the title compound consists of three independent fragments. The central Cu2+ ion in the cation is coordinated by two tridentate chelating phtpy ligands to form a distorted octahedral geometry. The phtpy ligands are approximately orthogonal to one another, with a dihedral angle of 76.4 (2) ° between planes through the three six-membered rings of the two ligands. The pendent and central pyridine in one phtpy are almost coplanar with a dihedral angle of 1.4 (1) °, but in the other phtpy, a corresponding serious tilt of 35.3 (2) ° is formed. There exists two independent crystallographically centrosymmetric [Cu(SCN)2]- anions, in which each Cu+ centre is coordinated by two S atoms and two N atoms from four isothiocyanate ligands with a distorted tetrahedron geometry. Each isothiocyanate anion acts as a 1,3-µ2 bridging ligand to bridge two Cu+ ions, resulting in the formation of polymeric [Cu(SCN)2]nn- anionic chains. All the SCN- groups are almost linear with the S–C–N bond angles in the range 176.3 (7) °–179.1 (4) °.

Two –CH groups in the [Cu(phtpy)2]2+ cation interact with two S atoms form two polymeric [Cu(SCN)2]nn- anionic chains through C–H···S hydrogen bonds [C···S = 3.697 (5) Å and 3.657 (5) Å, respectively] to form a two-dimensional supramolecular array (Fig.ure 2).

Experimental

A mixture of copper acetate hydrate (39.9 mg, 0.20 mmol), phtpy (30.9 mg, 0.10 mmol) and ammonium thiocyanate (15.2 mg, 0.20 mmol) in ethanol (12 ml) was sealed in a 15 ml Teflon-lined reactor, heated to 423 K for 72 h, and then cooled to room temperature at a rate of 6 K/h to give black crystals of the title compound [yield: 12 mg (22%)].

Refinement

The carbon-bound H atoms were placed at calculated positions (C—H = 0.93 Å) and refined as riding, with U(H) = 1.2Ueq(C).

Figures

Fig. 1.
The title compound with displacement ellipsoids drawn at the 30% probability level. The H atoms are omitted for clarity.
Fig. 2.
A packing diagram of the title compound, showing the intermolecular C–H···S hydrogen bonds as dashed lines. The H atoms not involved in hydrogen bonds have been omitted for clarity.

Crystal data

[Cu(C21H15N3)2][Cu2(NCS)4]Z = 2
Mr = 1041.66F(000) = 1054
Triclinic, P1Dx = 1.592 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.1803 (6) ÅCell parameters from 3113 reflections
b = 10.1829 (6) Åθ = 2.6–22.6°
c = 21.3203 (12) ŵ = 1.70 mm1
α = 83.571 (1)°T = 295 K
β = 89.566 (1)°Block, black
γ = 81.676 (1)°0.15 × 0.14 × 0.12 mm
V = 2173.0 (2) Å3

Data collection

Bruker SMART APEX area-detector diffractometer8453 independent reflections
Radiation source: fine-focus sealed tube5988 reflections with I > 2σ(I)
graphiteRint = 0.031
[var phi] and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.785, Tmax = 0.823k = −12→12
17217 measured reflectionsl = −26→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0609P)2 + 1.919P] where P = (Fo2 + 2Fc2)/3
8453 reflections(Δ/σ)max = 0.001
568 parametersΔρmax = 1.53 e Å3
54 restraintsΔρmin = −0.89 e Å3

Special details

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)

xyzUiso*/Ueq
Cu10.49651 (5)0.79721 (6)0.75522 (2)0.04334 (17)
Cu2−0.00482 (7)0.74884 (6)1.01693 (3)0.0650 (2)
Cu30.02122 (6)0.24319 (6)0.52085 (3)0.05204 (18)
S10.18721 (14)0.64253 (13)0.95859 (6)0.0549 (3)
S2−0.14546 (18)0.86946 (15)0.93153 (9)0.0860 (6)
S30.19621 (12)0.07262 (12)0.56458 (6)0.0464 (3)
S4−0.04694 (14)0.35973 (13)0.60866 (6)0.0550 (3)
N10.3676 (4)0.9799 (4)0.77294 (17)0.0492 (9)
N20.5013 (3)0.7885 (4)0.84804 (16)0.0386 (8)
N30.6371 (4)0.6148 (4)0.78198 (16)0.0416 (9)
N40.6732 (4)0.8846 (4)0.72222 (17)0.0467 (9)
N50.4877 (3)0.7923 (3)0.66328 (15)0.0374 (8)
N60.3130 (4)0.7109 (4)0.74383 (17)0.0488 (10)
N70.0858 (5)0.4059 (4)0.9483 (2)0.0636 (12)
N8−0.0544 (5)1.1122 (5)0.9388 (2)0.0630 (12)
N9−0.0682 (4)0.6194 (4)0.54712 (18)0.0510 (10)
N100.1066 (4)−0.1400 (4)0.51346 (19)0.0504 (10)
C10.2992 (6)1.0712 (6)0.7315 (2)0.0692 (16)
H10.31851.06940.68880.083*
C20.2026 (7)1.1665 (7)0.7484 (3)0.0863 (18)
H20.15761.22910.71790.104*
C30.1727 (7)1.1693 (7)0.8105 (3)0.0926 (19)
H30.10731.23420.82330.111*
C40.2411 (6)1.0740 (6)0.8546 (3)0.0749 (18)
H40.22081.07290.89730.090*
C50.3388 (5)0.9815 (5)0.8345 (2)0.0450 (11)
C60.4210 (4)0.8776 (4)0.87713 (19)0.0378 (10)
C70.4160 (4)0.8682 (4)0.94226 (19)0.0401 (10)
H70.35940.93120.96170.048*
C80.4947 (4)0.7653 (4)0.97905 (19)0.0379 (10)
C90.5786 (4)0.6746 (4)0.94723 (19)0.0390 (10)
H90.63340.60470.97000.047*
C100.5807 (4)0.6884 (4)0.8820 (2)0.0384 (10)
C110.6651 (4)0.5962 (5)0.84408 (19)0.0404 (10)
C120.7644 (5)0.5007 (6)0.8694 (2)0.0631 (15)
H120.78280.49080.91250.076*
C130.8364 (6)0.4198 (6)0.8306 (3)0.0768 (19)
H130.90380.35360.84700.092*
C140.8086 (6)0.4371 (6)0.7673 (2)0.0657 (16)
H140.85610.38260.74020.079*
C150.7106 (5)0.5350 (5)0.7447 (2)0.0535 (13)
H150.69320.54770.70150.064*
C160.4897 (5)0.7524 (5)1.0481 (2)0.0674 (10)
C170.4049 (6)0.8408 (6)1.0785 (2)0.0786 (11)
H170.35290.91141.05490.094*
C180.3944 (6)0.8278 (6)1.1434 (2)0.0832 (11)
H180.33130.88611.16220.100*
C190.4748 (6)0.7313 (5)1.1807 (2)0.0796 (11)
H190.47230.72691.22450.095*
C200.5589 (6)0.6414 (6)1.1509 (2)0.0803 (11)
H200.61340.57301.17470.096*
C210.5640 (6)0.6510 (6)1.08594 (19)0.0762 (10)
H210.61980.58641.06710.091*
C220.7639 (6)0.9315 (6)0.7553 (2)0.0603 (14)
H220.75510.92810.79890.072*
C230.8678 (6)0.9834 (6)0.7278 (3)0.0698 (16)
H230.92821.01650.75220.084*
C240.8837 (6)0.9871 (6)0.6640 (3)0.0709 (17)
H240.95381.02420.64440.085*
C250.7956 (5)0.9358 (6)0.6293 (2)0.0581 (14)
H250.80600.93520.58590.070*
C260.6905 (4)0.8847 (4)0.6596 (2)0.0413 (10)
C270.5899 (4)0.8247 (4)0.62715 (19)0.0378 (10)
C280.5990 (5)0.7969 (5)0.5653 (2)0.0429 (11)
H280.67060.81860.54100.052*
C290.5018 (4)0.7367 (4)0.53914 (19)0.0405 (10)
C300.3948 (4)0.7099 (4)0.57630 (19)0.0374 (10)
H300.32630.67290.55960.045*
C310.3894 (4)0.7382 (4)0.63832 (19)0.0374 (10)
C320.2836 (4)0.7071 (4)0.68283 (19)0.0394 (10)
C330.1616 (5)0.6776 (5)0.6644 (2)0.0490 (12)
H330.14210.67680.62190.059*
C340.0712 (5)0.6499 (6)0.7093 (3)0.0665 (16)
H34−0.01030.62840.69780.080*
C350.1010 (6)0.6538 (6)0.7718 (3)0.0711 (17)
H350.03990.63590.80300.085*
C360.2221 (5)0.6846 (6)0.7870 (2)0.0644 (15)
H360.24200.68740.82920.077*
C370.5151 (4)0.6986 (5)0.47397 (19)0.0410 (10)
C380.6401 (5)0.6557 (4)0.4509 (2)0.0444 (11)
H380.71460.65090.47650.053*
C390.6547 (5)0.6202 (5)0.3905 (2)0.0517 (12)
H390.73890.59240.37550.062*
C400.5463 (6)0.6258 (6)0.3528 (2)0.0630 (15)
H400.55670.60050.31230.076*
C410.4217 (6)0.6686 (6)0.3744 (2)0.0692 (16)
H410.34800.67290.34830.083*
C420.4056 (5)0.7053 (5)0.4349 (2)0.0561 (13)
H420.32110.73460.44930.067*
C430.1256 (5)0.5044 (5)0.9518 (2)0.0467 (11)
C44−0.0890 (7)1.0120 (6)0.9343 (3)0.0790 (11)
C45−0.0607 (4)0.5133 (5)0.5729 (2)0.0400 (9)
C460.1439 (4)−0.0529 (5)0.5350 (2)0.0397 (10)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0446 (3)0.0535 (4)0.0328 (3)−0.0080 (3)0.0034 (2)−0.0079 (2)
Cu20.0847 (5)0.0437 (4)0.0693 (5)−0.0180 (3)−0.0072 (4)−0.0058 (3)
Cu30.0624 (4)0.0423 (3)0.0525 (4)−0.0099 (3)−0.0023 (3)−0.0068 (3)
S10.0606 (8)0.0564 (8)0.0512 (7)−0.0212 (6)0.0085 (6)−0.0042 (6)
S20.1016 (13)0.0481 (8)0.1102 (13)−0.0130 (8)−0.0552 (10)−0.0106 (8)
S30.0529 (7)0.0451 (6)0.0422 (6)−0.0108 (5)−0.0074 (5)−0.0036 (5)
S40.0766 (9)0.0474 (7)0.0393 (6)−0.0059 (6)0.0072 (6)−0.0018 (5)
N10.052 (2)0.060 (2)0.033 (2)−0.0001 (15)−0.0021 (18)−0.0061 (18)
N20.036 (2)0.049 (2)0.0306 (19)−0.0035 (17)0.0009 (15)−0.0069 (16)
N30.044 (2)0.049 (2)0.0314 (19)−0.0029 (18)0.0034 (16)−0.0082 (17)
N40.056 (2)0.055 (2)0.032 (2)−0.010 (2)0.0024 (18)−0.0116 (18)
N50.041 (2)0.044 (2)0.0280 (18)−0.0059 (17)−0.0011 (16)−0.0059 (15)
N60.047 (2)0.069 (3)0.030 (2)−0.008 (2)−0.0007 (17)−0.0061 (18)
N70.068 (3)0.050 (3)0.075 (3)−0.017 (2)0.016 (2)−0.011 (2)
N80.078 (3)0.056 (3)0.055 (3)−0.010 (2)−0.013 (2)−0.007 (2)
N90.064 (3)0.045 (2)0.044 (2)−0.006 (2)−0.002 (2)−0.0060 (19)
N100.050 (2)0.045 (2)0.055 (3)−0.0014 (19)−0.011 (2)−0.0045 (19)
C10.078 (4)0.092 (4)0.035 (3)−0.016 (4)−0.009 (3)0.008 (3)
C20.086 (4)0.097 (4)0.058 (3)0.026 (3)−0.004 (3)0.019 (3)
C30.090 (4)0.102 (4)0.064 (3)0.041 (3)0.004 (3)0.015 (3)
C40.078 (4)0.088 (4)0.043 (3)0.033 (3)0.009 (3)0.003 (3)
C50.044 (3)0.055 (3)0.034 (2)0.000 (2)0.003 (2)−0.005 (2)
C60.038 (2)0.044 (3)0.029 (2)0.001 (2)−0.0004 (18)−0.0059 (19)
C70.041 (3)0.044 (3)0.033 (2)0.003 (2)0.0061 (19)−0.0080 (19)
C80.034 (2)0.047 (3)0.033 (2)−0.010 (2)−0.0011 (18)−0.0068 (19)
C90.040 (2)0.046 (3)0.029 (2)0.000 (2)−0.0009 (18)−0.0055 (19)
C100.035 (2)0.046 (3)0.034 (2)−0.002 (2)0.0022 (19)−0.0089 (19)
C110.040 (2)0.050 (3)0.031 (2)−0.005 (2)0.0024 (19)−0.006 (2)
C120.064 (3)0.087 (4)0.029 (3)0.021 (3)−0.001 (2)−0.007 (3)
C130.079 (4)0.091 (4)0.046 (3)0.036 (3)0.004 (3)−0.007 (3)
C140.082 (4)0.068 (4)0.044 (3)0.011 (3)0.017 (3)−0.020 (3)
C150.072 (4)0.061 (3)0.029 (2)−0.008 (3)0.008 (2)−0.013 (2)
C160.080 (2)0.080 (2)0.0313 (15)0.0226 (18)0.0027 (15)−0.0060 (15)
C170.094 (2)0.090 (2)0.0370 (16)0.0330 (18)0.0063 (16)−0.0037 (16)
C180.101 (2)0.095 (2)0.0386 (16)0.0338 (19)0.0078 (17)−0.0060 (16)
C190.096 (2)0.094 (2)0.0361 (16)0.0263 (19)0.0032 (16)−0.0038 (16)
C200.093 (2)0.095 (2)0.0380 (16)0.0294 (19)0.0019 (17)−0.0005 (16)
C210.088 (2)0.090 (2)0.0373 (16)0.0297 (18)0.0028 (16)−0.0028 (16)
C220.070 (4)0.076 (4)0.039 (3)−0.015 (3)0.000 (3)−0.019 (3)
C230.060 (4)0.093 (4)0.064 (4)−0.023 (3)−0.008 (3)−0.028 (3)
C240.060 (4)0.088 (4)0.076 (4)−0.042 (3)0.017 (3)−0.020 (3)
C250.062 (3)0.078 (4)0.043 (3)−0.031 (3)0.011 (2)−0.014 (3)
C260.048 (3)0.047 (3)0.030 (2)−0.011 (2)0.002 (2)−0.0064 (19)
C270.041 (2)0.042 (2)0.031 (2)−0.009 (2)0.0021 (19)−0.0033 (18)
C280.048 (3)0.053 (3)0.030 (2)−0.015 (2)0.004 (2)−0.004 (2)
C290.048 (3)0.044 (3)0.029 (2)−0.005 (2)−0.0034 (19)−0.0037 (19)
C300.039 (2)0.044 (2)0.030 (2)−0.005 (2)−0.0042 (18)−0.0023 (18)
C310.038 (2)0.039 (2)0.032 (2)−0.0018 (19)−0.0011 (19)0.0013 (18)
C320.038 (2)0.047 (3)0.033 (2)−0.004 (2)0.0006 (19)−0.0060 (19)
C330.045 (3)0.065 (3)0.039 (3)−0.014 (2)0.000 (2)−0.004 (2)
C340.049 (3)0.101 (5)0.055 (3)−0.027 (3)0.007 (3)−0.013 (3)
C350.057 (4)0.108 (5)0.050 (3)−0.024 (3)0.016 (3)0.001 (3)
C360.064 (4)0.097 (4)0.031 (3)−0.012 (3)0.007 (2)−0.004 (3)
C370.048 (3)0.048 (3)0.027 (2)−0.009 (2)0.0019 (19)−0.0034 (19)
C380.047 (3)0.049 (3)0.039 (2)−0.010 (2)0.001 (2)−0.007 (2)
C390.057 (3)0.054 (3)0.045 (3)−0.005 (2)0.011 (2)−0.011 (2)
C400.087 (4)0.066 (4)0.034 (3)−0.002 (3)0.001 (3)−0.011 (2)
C410.072 (4)0.093 (4)0.043 (3)0.001 (3)−0.017 (3)−0.019 (3)
C420.051 (3)0.077 (4)0.039 (3)0.000 (3)−0.005 (2)−0.015 (2)
C430.048 (3)0.049 (3)0.041 (3)−0.004 (2)0.007 (2)−0.001 (2)
C440.095 (2)0.0446 (18)0.098 (2)−0.0090 (18)−0.0519 (19)−0.0091 (18)
C450.041 (2)0.0463 (17)0.032 (2)−0.004 (2)−0.0011 (19)−0.0062 (16)
C460.038 (2)0.044 (3)0.034 (2)0.001 (2)−0.0030 (19)0.002 (2)

Geometric parameters (Å, °)

Cu1—N51.970 (3)C11—C121.366 (6)
Cu1—N21.972 (3)C12—C131.368 (7)
Cu1—N12.184 (4)C12—H120.9300
Cu1—N42.197 (4)C13—C141.368 (7)
Cu1—N32.198 (4)C13—H130.9300
Cu1—N62.203 (4)C14—C151.354 (7)
Cu2—N8i1.953 (5)C14—H140.9300
Cu2—N7ii1.954 (4)C15—H150.9300
Cu2—S22.4297 (17)C16—C171.369 (4)
Cu2—S12.4886 (16)C16—C211.373 (4)
Cu3—N10iii1.979 (4)C17—C181.378 (4)
Cu3—N9iv2.004 (4)C17—H170.9300
Cu3—S42.3738 (14)C18—C191.368 (4)
Cu3—S32.4137 (13)C18—H180.9300
S1—C431.642 (5)C19—C201.367 (4)
S2—C441.643 (6)C19—H190.9300
S3—C461.643 (5)C20—C211.378 (4)
S4—C451.648 (5)C20—H200.9300
N1—C11.330 (6)C21—H210.9300
N1—C51.345 (5)C22—C231.352 (7)
N2—C61.334 (5)C22—H220.9300
N2—C101.350 (5)C23—C241.366 (8)
N3—C111.343 (5)C23—H230.9300
N3—C151.346 (6)C24—C251.363 (7)
N4—C221.338 (6)C24—H240.9300
N4—C261.345 (5)C25—C261.382 (6)
N5—C271.347 (5)C25—H250.9300
N5—C311.349 (5)C26—C271.480 (6)
N6—C361.333 (6)C27—C281.379 (6)
N6—C321.343 (5)C28—C291.388 (6)
N7—C431.145 (6)C28—H280.9300
N7—Cu2ii1.954 (4)C29—C301.384 (6)
N8—C441.141 (6)C29—C371.484 (6)
N8—Cu2i1.953 (4)C30—C311.383 (6)
N9—C451.148 (5)C30—H300.9300
N9—Cu3iv2.004 (4)C31—C321.475 (6)
N10—C461.154 (6)C32—C331.390 (6)
N10—Cu3iii1.979 (4)C33—C341.358 (7)
C1—C21.355 (8)C33—H330.9300
C1—H10.9300C34—C351.374 (7)
C2—C31.360 (8)C34—H340.9300
C2—H20.9300C35—C361.365 (7)
C3—C41.386 (8)C35—H350.9300
C3—H30.9300C36—H360.9300
C4—C51.368 (7)C37—C421.386 (6)
C4—H40.9300C37—C381.389 (6)
C5—C61.478 (6)C38—C391.377 (6)
C6—C71.382 (5)C38—H380.9300
C7—C81.392 (6)C39—C401.361 (7)
C7—H70.9300C39—H390.9300
C8—C91.395 (6)C40—C411.373 (8)
C8—C161.464 (6)C40—H400.9300
C9—C101.382 (5)C41—C421.385 (7)
C9—H90.9300C41—H410.9300
C10—C111.483 (6)C42—H420.9300
N5—Cu1—N2175.67 (15)C15—C14—C13118.8 (5)
N5—Cu1—N1105.11 (14)C15—C14—H14120.6
N2—Cu1—N177.42 (14)C13—C14—H14120.6
N5—Cu1—N477.58 (14)N3—C15—C14122.9 (4)
N2—Cu1—N4105.65 (14)N3—C15—H15118.5
N1—Cu1—N499.01 (15)C14—C15—H15118.5
N5—Cu1—N3100.08 (14)C17—C16—C21116.0 (4)
N2—Cu1—N377.53 (14)C17—C16—C8120.6 (4)
N1—Cu1—N3154.77 (14)C21—C16—C8123.3 (4)
N4—Cu1—N384.97 (14)C16—C17—C18121.8 (5)
N5—Cu1—N677.55 (14)C16—C17—H17119.1
N2—Cu1—N699.24 (14)C18—C17—H17119.1
N1—Cu1—N686.46 (15)C19—C18—C17121.5 (5)
N4—Cu1—N6155.11 (13)C19—C18—H18119.2
N3—Cu1—N6100.42 (14)C17—C18—H18119.2
N8i—Cu2—N7ii128.70 (19)C20—C19—C18117.2 (5)
N8i—Cu2—S2104.74 (13)C20—C19—H19121.4
N7ii—Cu2—S2108.40 (15)C18—C19—H19121.4
N8i—Cu2—S1108.29 (15)C19—C20—C21120.8 (5)
N7ii—Cu2—S1101.83 (14)C19—C20—H20119.6
S2—Cu2—S1101.98 (7)C21—C20—H20119.6
N10iii—Cu3—N9iv109.16 (16)C16—C21—C20122.4 (5)
N10iii—Cu3—S4117.43 (13)C16—C21—H21118.8
N9iv—Cu3—S4106.20 (12)C20—C21—H21118.8
N10iii—Cu3—S3103.38 (12)N4—C22—C23122.5 (5)
N9iv—Cu3—S3118.10 (12)N4—C22—H22118.8
S4—Cu3—S3103.02 (5)C23—C22—H22118.8
C43—S1—Cu295.54 (17)C22—C23—C24119.6 (5)
C44—S2—Cu295.2 (2)C22—C23—H23120.2
C46—S3—Cu396.74 (15)C24—C23—H23120.2
C45—S4—Cu398.45 (16)C25—C24—C23119.3 (5)
C1—N1—C5118.5 (4)C25—C24—H24120.4
C1—N1—Cu1128.4 (4)C23—C24—H24120.4
C5—N1—Cu1111.8 (3)C24—C25—C26118.8 (5)
C6—N2—C10120.3 (4)C24—C25—H25120.6
C6—N2—Cu1119.8 (3)C26—C25—H25120.6
C10—N2—Cu1119.8 (3)N4—C26—C25121.7 (4)
C11—N3—C15117.6 (4)N4—C26—C27114.6 (4)
C11—N3—Cu1112.4 (3)C25—C26—C27123.7 (4)
C15—N3—Cu1129.1 (3)N5—C27—C28120.6 (4)
C22—N4—C26118.1 (4)N5—C27—C26115.1 (4)
C22—N4—Cu1129.5 (3)C28—C27—C26124.2 (4)
C26—N4—Cu1112.4 (3)C27—C28—C29120.3 (4)
C27—N5—C31120.2 (3)C27—C28—H28119.8
C27—N5—Cu1119.5 (3)C29—C28—H28119.8
C31—N5—Cu1119.6 (3)C30—C29—C28118.0 (4)
C36—N6—C32118.4 (4)C30—C29—C37121.3 (4)
C36—N6—Cu1128.7 (3)C28—C29—C37120.7 (4)
C32—N6—Cu1111.9 (3)C31—C30—C29120.1 (4)
C43—N7—Cu2ii153.4 (4)C31—C30—H30120.0
C44—N8—Cu2i156.0 (5)C29—C30—H30120.0
C45—N9—Cu3iv154.1 (4)N5—C31—C30120.7 (4)
C46—N10—Cu3iii158.2 (4)N5—C31—C32114.8 (4)
N1—C1—C2123.1 (5)C30—C31—C32124.4 (4)
N1—C1—H1118.5N6—C32—C33121.4 (4)
C2—C1—H1118.5N6—C32—C31114.8 (4)
C1—C2—C3119.0 (5)C33—C32—C31123.8 (4)
C1—C2—H2120.5C34—C33—C32119.0 (5)
C3—C2—H2120.5C34—C33—H33120.5
C2—C3—C4119.1 (6)C32—C33—H33120.5
C2—C3—H3120.5C33—C34—C35119.6 (5)
C4—C3—H3120.5C33—C34—H34120.2
C5—C4—C3119.1 (5)C35—C34—H34120.2
C5—C4—H4120.5C36—C35—C34118.7 (5)
C3—C4—H4120.5C36—C35—H35120.7
N1—C5—C4121.3 (4)C34—C35—H35120.7
N1—C5—C6114.7 (4)N6—C36—C35122.9 (5)
C4—C5—C6124.1 (4)N6—C36—H36118.6
N2—C6—C7120.9 (4)C35—C36—H36118.6
N2—C6—C5114.9 (4)C42—C37—C38118.6 (4)
C7—C6—C5124.3 (4)C42—C37—C29121.7 (4)
C6—C7—C8120.7 (4)C38—C37—C29119.6 (4)
C6—C7—H7119.6C39—C38—C37120.6 (4)
C8—C7—H7119.6C39—C38—H38119.7
C7—C8—C9117.0 (4)C37—C38—H38119.7
C7—C8—C16121.6 (4)C40—C39—C38120.3 (5)
C9—C8—C16121.3 (4)C40—C39—H39119.9
C10—C9—C8120.2 (4)C38—C39—H39119.9
C10—C9—H9119.9C39—C40—C41120.3 (5)
C8—C9—H9119.9C39—C40—H40119.9
N2—C10—C9120.9 (4)C41—C40—H40119.9
N2—C10—C11115.0 (4)C40—C41—C42120.1 (5)
C9—C10—C11124.1 (4)C40—C41—H41120.0
N3—C11—C12122.1 (4)C42—C41—H41120.0
N3—C11—C10114.5 (4)C41—C42—C37120.1 (5)
C12—C11—C10123.4 (4)C41—C42—H42119.9
C11—C12—C13119.1 (5)C37—C42—H42119.9
C11—C12—H12120.5N7—C43—S1177.8 (5)
C13—C12—H12120.5N8—C44—S2176.3 (7)
C14—C13—C12119.5 (5)N9—C45—S4178.5 (5)
C14—C13—H13120.3N10—C46—S3179.1 (4)
C12—C13—H13120.3
N8i—Cu2—S1—C43159.5 (2)C16—C8—C9—C10179.5 (5)
N7ii—Cu2—S1—C4321.6 (2)C6—N2—C10—C91.2 (6)
S2—Cu2—S1—C43−90.40 (18)Cu1—N2—C10—C9−175.3 (3)
N8i—Cu2—S2—C4418.0 (3)C6—N2—C10—C11−180.0 (4)
N7ii—Cu2—S2—C44158.2 (3)Cu1—N2—C10—C113.6 (5)
S1—Cu2—S2—C44−94.9 (3)C8—C9—C10—N2−0.5 (7)
N10iii—Cu3—S3—C469.68 (19)C8—C9—C10—C11−179.2 (4)
N9iv—Cu3—S3—C46−110.9 (2)C15—N3—C11—C120.3 (7)
S4—Cu3—S3—C46132.43 (16)Cu1—N3—C11—C12−170.1 (4)
N10iii—Cu3—S4—C45−110.1 (2)C15—N3—C11—C10179.6 (4)
N9iv—Cu3—S4—C4512.3 (2)Cu1—N3—C11—C109.3 (5)
S3—Cu3—S4—C45137.04 (16)N2—C10—C11—N3−8.8 (6)
N5—Cu1—N1—C1−1.3 (5)C9—C10—C11—N3170.0 (4)
N2—Cu1—N1—C1−177.7 (5)N2—C10—C11—C12170.6 (5)
N4—Cu1—N1—C178.2 (5)C9—C10—C11—C12−10.7 (7)
N3—Cu1—N1—C1175.5 (4)N3—C11—C12—C13−1.1 (8)
N6—Cu1—N1—C1−77.4 (5)C10—C11—C12—C13179.6 (5)
N5—Cu1—N1—C5165.4 (3)C11—C12—C13—C140.7 (10)
N2—Cu1—N1—C5−11.0 (3)C12—C13—C14—C150.5 (10)
N4—Cu1—N1—C5−115.1 (3)C11—N3—C15—C141.0 (7)
N3—Cu1—N1—C5−17.8 (6)Cu1—N3—C15—C14169.5 (4)
N6—Cu1—N1—C589.3 (3)C13—C14—C15—N3−1.4 (9)
N1—Cu1—N2—C67.5 (3)C7—C8—C16—C171.2 (9)
N4—Cu1—N2—C6103.5 (3)C9—C8—C16—C17−178.7 (6)
N3—Cu1—N2—C6−175.4 (4)C7—C8—C16—C21178.8 (6)
N6—Cu1—N2—C6−76.7 (3)C9—C8—C16—C21−1.1 (9)
N1—Cu1—N2—C10−176.0 (3)C21—C16—C17—C18−0.4 (11)
N4—Cu1—N2—C10−80.0 (3)C8—C16—C17—C18177.4 (6)
N3—Cu1—N2—C101.1 (3)C16—C17—C18—C194.5 (12)
N6—Cu1—N2—C1099.8 (3)C17—C18—C19—C20−5.0 (11)
N5—Cu1—N3—C11177.8 (3)C18—C19—C20—C211.6 (11)
N2—Cu1—N3—C11−5.9 (3)C17—C16—C21—C20−3.0 (11)
N1—Cu1—N3—C110.9 (5)C8—C16—C21—C20179.3 (6)
N4—Cu1—N3—C11101.4 (3)C19—C20—C21—C162.4 (11)
N6—Cu1—N3—C11−103.2 (3)C26—N4—C22—C232.9 (8)
N5—Cu1—N3—C158.9 (4)Cu1—N4—C22—C23−179.6 (4)
N2—Cu1—N3—C15−174.8 (4)N4—C22—C23—C24−1.1 (9)
N1—Cu1—N3—C15−168.0 (4)C22—C23—C24—C25−1.3 (10)
N4—Cu1—N3—C15−67.6 (4)C23—C24—C25—C261.8 (9)
N6—Cu1—N3—C1587.9 (4)C22—N4—C26—C25−2.3 (7)
N5—Cu1—N4—C22179.2 (5)Cu1—N4—C26—C25179.8 (4)
N2—Cu1—N4—C22−3.8 (5)C22—N4—C26—C27176.8 (4)
N1—Cu1—N4—C2275.6 (4)Cu1—N4—C26—C27−1.1 (5)
N3—Cu1—N4—C22−79.3 (4)C24—C25—C26—N40.1 (8)
N6—Cu1—N4—C22176.7 (4)C24—C25—C26—C27−179.0 (5)
N5—Cu1—N4—C26−3.2 (3)C31—N5—C27—C28−3.3 (6)
N2—Cu1—N4—C26173.8 (3)Cu1—N5—C27—C28166.9 (3)
N1—Cu1—N4—C26−106.8 (3)C31—N5—C27—C26179.3 (4)
N3—Cu1—N4—C2698.3 (3)Cu1—N5—C27—C26−10.5 (5)
N6—Cu1—N4—C26−5.7 (6)N4—C26—C27—N57.1 (6)
N1—Cu1—N5—C27103.7 (3)C25—C26—C27—N5−173.7 (5)
N4—Cu1—N5—C277.6 (3)N4—C26—C27—C28−170.2 (4)
N3—Cu1—N5—C27−75.0 (3)C25—C26—C27—C288.9 (7)
N6—Cu1—N5—C27−173.5 (3)N5—C27—C28—C290.8 (7)
N1—Cu1—N5—C31−86.1 (3)C26—C27—C28—C29178.0 (4)
N4—Cu1—N5—C31177.8 (3)C27—C28—C29—C302.1 (7)
N3—Cu1—N5—C3195.3 (3)C27—C28—C29—C37−176.1 (4)
N6—Cu1—N5—C31−3.2 (3)C28—C29—C30—C31−2.6 (6)
N5—Cu1—N6—C36−172.3 (5)C37—C29—C30—C31175.6 (4)
N2—Cu1—N6—C3610.6 (5)C27—N5—C31—C302.8 (6)
N1—Cu1—N6—C36−66.0 (5)Cu1—N5—C31—C30−167.4 (3)
N4—Cu1—N6—C36−169.8 (4)C27—N5—C31—C32179.9 (4)
N3—Cu1—N6—C3689.5 (5)Cu1—N5—C31—C329.7 (5)
N5—Cu1—N6—C32−4.2 (3)C29—C30—C31—N50.2 (6)
N2—Cu1—N6—C32178.8 (3)C29—C30—C31—C32−176.6 (4)
N1—Cu1—N6—C32102.2 (3)C36—N6—C32—C330.4 (7)
N4—Cu1—N6—C32−1.7 (6)Cu1—N6—C32—C33−169.1 (4)
N3—Cu1—N6—C32−102.3 (3)C36—N6—C32—C31179.6 (4)
C5—N1—C1—C20.7 (9)Cu1—N6—C32—C3110.1 (5)
Cu1—N1—C1—C2166.6 (5)N5—C31—C32—N6−13.1 (6)
N1—C1—C2—C3−0.6 (11)C30—C31—C32—N6163.9 (4)
C1—C2—C3—C4−0.5 (11)N5—C31—C32—C33166.1 (4)
C2—C3—C4—C51.4 (11)C30—C31—C32—C33−17.0 (7)
C1—N1—C5—C40.3 (8)N6—C32—C33—C34−1.1 (8)
Cu1—N1—C5—C4−167.9 (5)C31—C32—C33—C34179.8 (5)
C1—N1—C5—C6−179.2 (4)C32—C33—C34—C351.1 (9)
Cu1—N1—C5—C612.6 (5)C33—C34—C35—C36−0.6 (9)
C3—C4—C5—N1−1.3 (9)C32—N6—C36—C350.2 (8)
C3—C4—C5—C6178.2 (6)Cu1—N6—C36—C35167.7 (5)
C10—N2—C6—C7−0.9 (6)C34—C35—C36—N6−0.1 (10)
Cu1—N2—C6—C7175.5 (3)C30—C29—C37—C4236.2 (7)
C10—N2—C6—C5−179.6 (4)C28—C29—C37—C42−145.7 (5)
Cu1—N2—C6—C5−3.1 (5)C30—C29—C37—C38−144.1 (4)
N1—C5—C6—N2−7.1 (6)C28—C29—C37—C3834.0 (6)
C4—C5—C6—N2173.4 (5)C42—C37—C38—C39−0.2 (7)
N1—C5—C6—C7174.3 (4)C29—C37—C38—C39−179.9 (4)
C4—C5—C6—C7−5.2 (8)C37—C38—C39—C40−0.6 (7)
N2—C6—C7—C80.0 (7)C38—C39—C40—C410.9 (8)
C5—C6—C7—C8178.5 (4)C39—C40—C41—C42−0.5 (9)
C6—C7—C8—C90.7 (6)C40—C41—C42—C37−0.2 (9)
C6—C7—C8—C16−179.2 (5)C38—C37—C42—C410.6 (8)
C7—C8—C9—C10−0.4 (6)C29—C37—C42—C41−179.8 (5)

Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x, −y+1, −z+2; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C28—H28···S3v0.932.823.697 (5)158
C36—H36···S10.932.813.657 (5)152

Symmetry codes: (v) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2820).

References

  • Bruker (2002). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Heller, M. & Schubert, U. S. (2003). Eur. J. Org. Chem. pp. 947–961.
  • Hofmeier, H. & Schubert, U. S. (2004). Chem. Soc. Rev.33, 373–399. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shi, W.-J. (2009). Acta Cryst. E65, m814. [PMC free article] [PubMed]
  • Shi, W.-J., Hou, L., Li, D. & Yin, Y.-G. (2007). Inorg. Chim. Acta, 360, 588–598.

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