The Cu
I atom of the title complex, [Cu(C
7H
8N
2S)
4]Cl, is located on a
inversion axis and has distorted tetrahedral coordination geometry, formed by four phenylthiourea S atoms. Within the phenylthiourea ligands, the C—N(imino) bonds [1.341 (2) Å] are significantly longer than the C—N(amino) bonds [1.316 (3) Å]. The Cl
− anion is located on another
inversion axis and links with four complex cations
via N—H
Cl hydrogen bonding.
Supporting information
CCDC reference: 248712
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.026
- wR factor = 0.065
- Data-to-parameter ratio = 18.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cu - S .. 20.62 su
Alert level C
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .... C5
PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2B ... ?
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.50
From the CIF: _reflns_number_total 1957
Count of symmetry unique reflns 1028
Completeness (_total/calc) 190.37%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 929
Fraction of Friedel pairs measured 0.904
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Cu(C7H8N2S)4]Cl | Dx = 1.386 Mg m−3 |
Mr = 707.85 | Mo Kα radiation, λ = 0.71069 Å |
Tetragonal, I4 | Cell parameters from 7866 reflections |
Hall symbol: I -4 | θ = 2.5–26.0° |
a = 11.4847 (3) Å | µ = 1.00 mm−1 |
c = 12.8612 (4) Å | T = 295 K |
V = 1696.37 (8) Å3 | Prism, pale-yellow |
Z = 2 | 0.38 × 0.26 × 0.24 mm |
F(000) = 732 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 1957 independent reflections |
Radiation source: fine-focus sealed tube | 1868 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.4° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.68, Tmax = 0.78 | l = −16→16 |
8326 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.2897P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
1957 reflections | Δρmax = 0.13 e Å−3 |
104 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 932 Friedel Pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.001 (12) |
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 | x | y | z | Uiso*/Ueq | |
Cu | 0.5000 | 0.0000 | 0.7500 | 0.05386 (14) | |
Cl | 0.5000 | 0.5000 | 0.5000 | 0.0527 (2) | |
S | 0.51034 (5) | 0.17313 (4) | 0.65581 (4) | 0.05544 (14) | |
N1 | 0.35821 (16) | 0.06011 (13) | 0.53791 (13) | 0.0517 (4) | |
N2 | 0.3862 (2) | 0.25346 (15) | 0.50004 (19) | 0.0717 (6) | |
C1 | 0.29141 (16) | 0.03378 (16) | 0.44721 (15) | 0.0473 (4) | |
C2 | 0.19393 (19) | 0.0962 (2) | 0.4208 (2) | 0.0651 (6) | |
H2 | 0.1679 | 0.1560 | 0.4637 | 0.078* | |
C3 | 0.1345 (2) | 0.0700 (3) | 0.3303 (2) | 0.0807 (8) | |
H3 | 0.0703 | 0.1145 | 0.3111 | 0.097* | |
C4 | 0.1688 (2) | −0.0199 (3) | 0.2694 (2) | 0.0857 (8) | |
H4 | 0.1283 | −0.0370 | 0.2086 | 0.103* | |
C5 | 0.2643 (3) | −0.0863 (3) | 0.2979 (2) | 0.0935 (10) | |
H5 | 0.2864 | −0.1498 | 0.2576 | 0.112* | |
C6 | 0.3268 (2) | −0.0582 (2) | 0.38591 (19) | 0.0666 (6) | |
H6 | 0.3925 | −0.1011 | 0.4039 | 0.080* | |
C7 | 0.41019 (18) | 0.16215 (15) | 0.55805 (15) | 0.0480 (4) | |
H1A | 0.383 (2) | −0.003 (3) | 0.575 (2) | 0.080* | |
H2A | 0.424 (3) | 0.314 (3) | 0.510 (3) | 0.080* | |
H2B | 0.345 (3) | 0.238 (3) | 0.446 (2) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.06454 (19) | 0.06454 (19) | 0.0325 (2) | 0.000 | 0.000 | 0.000 |
Cl | 0.0348 (2) | 0.0348 (2) | 0.0886 (7) | 0.000 | 0.000 | 0.000 |
S | 0.0771 (3) | 0.0434 (2) | 0.0458 (2) | −0.0088 (2) | −0.0116 (2) | −0.00645 (18) |
N1 | 0.0673 (10) | 0.0396 (7) | 0.0481 (9) | −0.0108 (7) | −0.0098 (7) | 0.0034 (6) |
N2 | 0.0946 (14) | 0.0458 (9) | 0.0746 (13) | −0.0247 (9) | −0.0329 (12) | 0.0174 (9) |
C1 | 0.0503 (10) | 0.0460 (9) | 0.0455 (9) | −0.0128 (7) | −0.0023 (7) | 0.0006 (7) |
C2 | 0.0533 (11) | 0.0559 (11) | 0.0860 (16) | −0.0036 (9) | −0.0096 (11) | −0.0098 (11) |
C3 | 0.0541 (12) | 0.0882 (17) | 0.100 (2) | −0.0045 (12) | −0.0266 (13) | 0.0076 (16) |
C4 | 0.0666 (14) | 0.127 (2) | 0.0630 (16) | −0.0126 (15) | −0.0177 (12) | −0.0115 (15) |
C5 | 0.0809 (17) | 0.130 (3) | 0.0696 (16) | 0.0138 (18) | −0.0133 (14) | −0.0448 (17) |
C6 | 0.0590 (11) | 0.0766 (14) | 0.0640 (13) | 0.0086 (10) | −0.0110 (10) | −0.0192 (11) |
C7 | 0.0606 (10) | 0.0399 (8) | 0.0434 (9) | −0.0080 (7) | −0.0011 (8) | −0.0003 (7) |
Geometric parameters (Å, º) top
Cu—S | 2.3313 (5) | C2—C3 | 1.383 (4) |
S—C7 | 1.709 (2) | C2—H2 | 0.9300 |
N1—C7 | 1.341 (2) | C3—C4 | 1.355 (4) |
N1—C1 | 1.429 (2) | C3—H3 | 0.9300 |
N1—H1A | 0.92 (3) | C4—C5 | 1.386 (4) |
N2—C7 | 1.316 (3) | C4—H4 | 0.9300 |
N2—H2A | 0.83 (3) | C5—C6 | 1.379 (3) |
N2—H2B | 0.86 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.372 (3) | C6—H6 | 0.9300 |
C1—C6 | 1.380 (3) | | |
| | | |
S—Cu—Si | 117.38 (2) | C4—C3—C2 | 120.6 (2) |
S—Cu—Sii | 105.666 (10) | C4—C3—H3 | 119.7 |
C7—S—Cu | 106.57 (6) | C2—C3—H3 | 119.7 |
C7—N1—C1 | 125.59 (16) | C3—C4—C5 | 119.8 (2) |
C7—N1—H1A | 116.8 (17) | C3—C4—H4 | 120.1 |
C1—N1—H1A | 115.4 (17) | C5—C4—H4 | 120.1 |
C7—N2—H2A | 118 (2) | C6—C5—C4 | 120.0 (3) |
C7—N2—H2B | 114 (2) | C6—C5—H5 | 120.0 |
H2A—N2—H2B | 125 (3) | C4—C5—H5 | 120.0 |
C2—C1—C6 | 119.97 (19) | C5—C6—C1 | 119.7 (2) |
C2—C1—N1 | 121.97 (19) | C5—C6—H6 | 120.2 |
C6—C1—N1 | 118.07 (18) | C1—C6—H6 | 120.2 |
C1—C2—C3 | 119.8 (2) | N2—C7—N1 | 119.59 (18) |
C1—C2—H2 | 120.1 | N2—C7—S | 119.95 (14) |
C3—C2—H2 | 120.1 | N1—C7—S | 120.43 (14) |
Symmetry codes: (i) −x+1, −y, z; (ii) y+1/2, −x+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Si | 0.91 (3) | 2.53 (3) | 3.4284 (17) | 168 (2) |
N2—H2A···Cl | 0.83 (4) | 2.31 (3) | 3.1185 (18) | 164 (4) |
Symmetry code: (i) −x+1, −y, z. |