The structure of the title compound is similar to that of the related complexes [Co(C12H8N4S)2(N3)2] and [Ni(C12H8N4S)2(N3)2] in which the azide ion is substituted by the thiocyanate group. The CuN4S2 octahedron is more distorted than the CoN6 and NiN6 octahedra.
Supporting information
CCDC reference: 1494615
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.036
- wR factor = 0.097
- Data-to-parameter ratio = 21.9
checkCIF/PLATON results
No syntax errors found
Alert level G
PLAT230_ALERT_2_G Hirshfeld Test Diff for S2 -- C13 .. 17.0 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for N5 -- C13 .. 15.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cu1 -- S2 .. 12.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cu1 -- N2 .. 5.0 s.u.
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.30 Ratio
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF: S1 -- S2 .. 4.01 Ang.
PLAT774_ALERT_1_G Suspect X-Y Bond in CIF: S2 -- S1 .. 4.01 Ang.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 9 Check
C1 -C2 -S1 1.555 1.555 1.555 28.52 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 30 Check
C7 -C8 -S1 1.555 1.555 1.555 32.59 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 50 Check
C1 -N2 -S1 1.555 1.555 1.555 38.12 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 54 Check
C7 -N3 -S1 1.555 1.555 1.555 37.70 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 59 Check
C13 -N5 -S2 1.555 1.555 1.555 1.19 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 76 Check
C1 -S1 -N2 1.555 1.555 1.555 28.28 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 79 Check
C7 -S1 -N3 1.555 1.555 1.555 27.38 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 80 Check
N2 -S1 -N3 1.555 1.555 1.555 31.13 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 82 Check
C7 -S1 -C8 1.555 1.555 1.555 27.14 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 85 Check
C1 -S1 -C2 1.555 1.555 1.555 23.90 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 94 Check
C8 -S1 -N4 1.555 1.555 1.555 27.13 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 103 Check
C13 -S2 -N5 1.555 1.555 1.555 0.81 Deg.
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1 (II) ..... 2.11 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min) 1 Note
PLAT933_ALERT_2_G Number of OMIT records in Embedded RES ......... 1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density 10 Note
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
23 ALERT level G = General information/check it is not something unexpected
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 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
13 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia,
2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
Bis[2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-
κ2N2,
N3]bis(thiocyanato-
κS)copper(II)
top
Crystal data top
[Cu(NCS)2(C12H8N4S)2] | Dx = 1.635 Mg m−3 |
Mr = 660.27 | Melting point: 538 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0205 (3) Å | Cell parameters from 4089 reflections |
b = 7.8434 (3) Å | θ = 2.5–30.5° |
c = 21.3454 (9) Å | µ = 1.17 mm−1 |
β = 92.565 (2)° | T = 296 K |
V = 1341.45 (9) Å3 | Block, brown |
Z = 2 | 0.35 × 0.32 × 0.26 mm |
F(000) = 670 | |
Data collection top
Bruker X8 APEX diffractometer | 4089 independent reflections |
Radiation source: fine-focus sealed tube | 3155 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
φ and ω scans | θmax = 30.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.604, Tmax = 0.746 | k = −11→11 |
42199 measured reflections | l = −27→30 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0418P)2 + 0.834P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4089 reflections | Δρmax = 0.56 e Å−3 |
187 parameters | Δρmin = −0.51 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.4345 (2) | 0.6803 (2) | 0.38733 (8) | 0.0240 (4) | |
C2 | 0.5958 (2) | 0.6037 (2) | 0.37724 (8) | 0.0240 (4) | |
C3 | 0.6786 (3) | 0.6181 (3) | 0.32209 (9) | 0.0327 (4) | |
H3 | 0.6314 | 0.6778 | 0.2881 | 0.039* | |
C4 | 0.8333 (3) | 0.5416 (3) | 0.31863 (10) | 0.0372 (5) | |
H4 | 0.8909 | 0.5469 | 0.2818 | 0.045* | |
C5 | 0.9012 (3) | 0.4572 (3) | 0.37055 (11) | 0.0366 (5) | |
H5 | 1.0065 | 0.4079 | 0.3696 | 0.044* | |
C6 | 0.8102 (3) | 0.4473 (3) | 0.42395 (10) | 0.0320 (4) | |
H6 | 0.8563 | 0.3896 | 0.4586 | 0.038* | |
C7 | 0.1712 (2) | 0.8133 (2) | 0.39355 (9) | 0.0251 (4) | |
C8 | 0.0124 (2) | 0.9022 (3) | 0.38144 (9) | 0.0270 (4) | |
C9 | −0.1027 (3) | 0.9212 (3) | 0.42773 (10) | 0.0322 (4) | |
H9 | −0.0804 | 0.8796 | 0.4680 | 0.039* | |
C10 | −0.2511 (3) | 1.0036 (3) | 0.41222 (12) | 0.0387 (5) | |
H10 | −0.3306 | 1.0198 | 0.4421 | 0.046* | |
C11 | −0.2792 (3) | 1.0615 (3) | 0.35150 (12) | 0.0430 (5) | |
H11 | −0.3782 | 1.1168 | 0.3396 | 0.052* | |
C12 | −0.1570 (3) | 1.0356 (3) | 0.30870 (12) | 0.0439 (6) | |
H12 | −0.1772 | 1.0747 | 0.2679 | 0.053* | |
C13 | 0.3302 (3) | 0.2765 (3) | 0.36867 (13) | 0.0423 (5) | |
N1 | 0.65894 (19) | 0.5170 (2) | 0.42789 (7) | 0.0246 (3) | |
N2 | 0.36607 (19) | 0.6566 (2) | 0.44138 (7) | 0.0258 (3) | |
N3 | 0.2129 (2) | 0.7323 (2) | 0.44510 (7) | 0.0282 (3) | |
N4 | −0.0124 (2) | 0.9581 (2) | 0.32252 (8) | 0.0354 (4) | |
N5 | 0.3255 (3) | 0.3117 (3) | 0.31799 (10) | 0.0568 (6) | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.02713 (10) | |
S1 | 0.31614 (6) | 0.80256 (7) | 0.33603 (2) | 0.02941 (12) | |
S2 | 0.33021 (9) | 0.22277 (9) | 0.44310 (3) | 0.04809 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0269 (9) | 0.0275 (9) | 0.0174 (8) | −0.0018 (7) | 0.0005 (6) | 0.0016 (7) |
C2 | 0.0256 (8) | 0.0274 (9) | 0.0191 (8) | −0.0026 (7) | 0.0017 (6) | −0.0008 (7) |
C3 | 0.0359 (10) | 0.0429 (12) | 0.0196 (9) | −0.0034 (9) | 0.0058 (7) | 0.0018 (8) |
C4 | 0.0368 (11) | 0.0480 (13) | 0.0278 (11) | −0.0035 (9) | 0.0142 (8) | −0.0039 (9) |
C5 | 0.0309 (10) | 0.0421 (12) | 0.0379 (12) | 0.0034 (9) | 0.0140 (9) | −0.0007 (9) |
C6 | 0.0298 (10) | 0.0346 (10) | 0.0322 (11) | 0.0052 (8) | 0.0067 (8) | 0.0050 (8) |
C7 | 0.0244 (8) | 0.0291 (9) | 0.0219 (9) | −0.0009 (7) | 0.0004 (6) | 0.0005 (7) |
C8 | 0.0257 (9) | 0.0294 (9) | 0.0256 (9) | −0.0003 (7) | −0.0006 (7) | 0.0017 (7) |
C9 | 0.0327 (10) | 0.0371 (11) | 0.0269 (10) | 0.0007 (8) | 0.0020 (8) | 0.0004 (8) |
C10 | 0.0318 (10) | 0.0400 (12) | 0.0449 (13) | 0.0049 (9) | 0.0081 (9) | −0.0054 (10) |
C11 | 0.0314 (11) | 0.0419 (12) | 0.0554 (15) | 0.0082 (9) | −0.0016 (10) | 0.0047 (11) |
C12 | 0.0414 (12) | 0.0523 (14) | 0.0376 (13) | 0.0085 (11) | −0.0036 (10) | 0.0139 (11) |
C13 | 0.0331 (11) | 0.0369 (12) | 0.0568 (16) | 0.0028 (9) | 0.0003 (10) | −0.0137 (11) |
N1 | 0.0247 (7) | 0.0278 (8) | 0.0217 (8) | 0.0002 (6) | 0.0047 (6) | 0.0015 (6) |
N2 | 0.0246 (7) | 0.0311 (8) | 0.0216 (8) | 0.0017 (6) | 0.0016 (6) | 0.0026 (6) |
N3 | 0.0267 (8) | 0.0346 (9) | 0.0236 (8) | 0.0046 (7) | 0.0035 (6) | 0.0034 (7) |
N4 | 0.0319 (9) | 0.0440 (10) | 0.0304 (9) | 0.0065 (8) | 0.0022 (7) | 0.0108 (8) |
N5 | 0.0803 (17) | 0.0623 (15) | 0.0260 (10) | 0.0160 (13) | −0.0157 (10) | −0.0098 (10) |
Cu1 | 0.02419 (16) | 0.0377 (2) | 0.02004 (17) | 0.00875 (13) | 0.00685 (11) | 0.00895 (13) |
S1 | 0.0304 (2) | 0.0383 (3) | 0.0196 (2) | 0.0038 (2) | 0.00108 (17) | 0.00653 (19) |
S2 | 0.0581 (4) | 0.0487 (4) | 0.0380 (3) | −0.0128 (3) | 0.0077 (3) | −0.0015 (3) |
Geometric parameters (Å, º) top
C1—N2 | 1.313 (2) | C10—C11 | 1.382 (4) |
C1—C2 | 1.452 (3) | C10—H10 | 0.9300 |
C1—S1 | 1.7106 (18) | C11—C12 | 1.384 (4) |
C2—N1 | 1.356 (2) | C11—H11 | 0.9300 |
C2—C3 | 1.382 (3) | C12—N4 | 1.331 (3) |
C2—S1 | 2.8397 (19) | C12—H12 | 0.9300 |
C3—C4 | 1.383 (3) | C13—N5 | 1.115 (3) |
C3—H3 | 0.9300 | C13—S2 | 1.644 (3) |
C4—C5 | 1.382 (3) | N1—Cu1 | 2.0463 (15) |
C4—H4 | 0.9300 | N2—N3 | 1.370 (2) |
C5—C6 | 1.383 (3) | N2—Cu1 | 2.0267 (16) |
C5—H5 | 0.9300 | N2—S1 | 2.5392 (16) |
C6—N1 | 1.337 (2) | N3—S1 | 2.5657 (16) |
C6—H6 | 0.9300 | N4—S1 | 2.9062 (18) |
C7—N3 | 1.301 (2) | N5—S2 | 2.759 (2) |
C7—C8 | 1.465 (3) | Cu1—N2i | 2.0267 (16) |
C7—S1 | 1.7300 (19) | Cu1—N1i | 2.0463 (15) |
C8—N4 | 1.338 (3) | Cu1—S2i | 2.8124 (7) |
C8—C9 | 1.390 (3) | Cu1—S2 | 2.8125 (7) |
C8—S1 | 2.774 (2) | S1—S2ii | 4.0094 (9) |
C9—C10 | 1.382 (3) | S2—S1iii | 4.0094 (9) |
C9—H9 | 0.9300 | | |
| | | |
N2—C1—C2 | 118.82 (16) | N2—N3—S1 | 73.37 (9) |
N2—C1—S1 | 113.60 (14) | C12—N4—C8 | 116.71 (19) |
C2—C1—S1 | 127.58 (14) | C12—N4—S1 | 172.31 (16) |
N1—C2—C3 | 122.97 (18) | C8—N4—S1 | 70.92 (11) |
N1—C2—C1 | 113.12 (15) | C13—N5—S2 | 1.19 (15) |
C3—C2—C1 | 123.91 (18) | N2—Cu1—N2i | 180.0 |
N1—C2—S1 | 141.62 (12) | N2—Cu1—N1i | 99.96 (6) |
C3—C2—S1 | 95.40 (13) | N2i—Cu1—N1i | 80.04 (6) |
C1—C2—S1 | 28.52 (8) | N2—Cu1—N1 | 80.04 (6) |
C2—C3—C4 | 118.45 (19) | N2i—Cu1—N1 | 99.96 (6) |
C2—C3—H3 | 120.8 | N1i—Cu1—N1 | 180.0 |
C4—C3—H3 | 120.8 | N2—Cu1—S2i | 91.78 (5) |
C5—C4—C3 | 119.16 (19) | N2i—Cu1—S2i | 88.22 (5) |
C5—C4—H4 | 120.4 | N1i—Cu1—S2i | 91.80 (5) |
C3—C4—H4 | 120.4 | N1—Cu1—S2i | 88.20 (5) |
C4—C5—C6 | 119.0 (2) | N2—Cu1—S2 | 88.22 (5) |
C4—C5—H5 | 120.5 | N2i—Cu1—S2 | 91.78 (5) |
C6—C5—H5 | 120.5 | N1i—Cu1—S2 | 88.20 (5) |
N1—C6—C5 | 122.9 (2) | N1—Cu1—S2 | 91.80 (5) |
N1—C6—H6 | 118.6 | S2i—Cu1—S2 | 180.00 (2) |
C5—C6—H6 | 118.6 | C1—S1—C7 | 86.79 (9) |
N3—C7—C8 | 124.76 (17) | C1—S1—N2 | 28.28 (7) |
N3—C7—S1 | 114.92 (14) | C7—S1—N2 | 58.51 (7) |
C8—C7—S1 | 120.27 (14) | C1—S1—N3 | 59.41 (7) |
N4—C8—C9 | 123.86 (18) | C7—S1—N3 | 27.38 (7) |
N4—C8—C7 | 114.43 (17) | N2—S1—N3 | 31.13 (5) |
C9—C8—C7 | 121.69 (18) | C1—S1—C8 | 113.89 (8) |
N4—C8—S1 | 81.95 (12) | C7—S1—C8 | 27.14 (7) |
C9—C8—S1 | 154.16 (14) | N2—S1—C8 | 85.63 (5) |
C7—C8—S1 | 32.59 (9) | N3—S1—C8 | 54.50 (5) |
C10—C9—C8 | 118.2 (2) | C1—S1—C2 | 23.90 (7) |
C10—C9—H9 | 120.9 | C7—S1—C2 | 110.69 (7) |
C8—C9—H9 | 120.9 | N2—S1—C2 | 52.18 (5) |
C9—C10—C11 | 118.7 (2) | N3—S1—C2 | 83.31 (5) |
C9—C10—H10 | 120.6 | C8—S1—C2 | 137.77 (6) |
C11—C10—H10 | 120.6 | C1—S1—N4 | 140.66 (7) |
C10—C11—C12 | 118.7 (2) | C7—S1—N4 | 54.21 (7) |
C10—C11—H11 | 120.6 | N2—S1—N4 | 112.55 (5) |
C12—C11—H11 | 120.6 | N3—S1—N4 | 81.50 (5) |
N4—C12—C11 | 123.8 (2) | C8—S1—N4 | 27.13 (5) |
N4—C12—H12 | 118.1 | C2—S1—N4 | 164.06 (5) |
C11—C12—H12 | 118.1 | C1—S1—S2ii | 95.46 (7) |
N5—C13—S2 | 178.0 (3) | C7—S1—S2ii | 63.79 (7) |
C6—N1—C2 | 117.53 (16) | N2—S1—S2ii | 82.33 (4) |
C6—N1—Cu1 | 128.20 (13) | N3—S1—S2ii | 70.21 (4) |
C2—N1—Cu1 | 114.18 (12) | C8—S1—S2ii | 64.66 (4) |
C1—N2—N3 | 113.62 (15) | C2—S1—S2ii | 105.86 (4) |
C1—N2—Cu1 | 113.43 (13) | N4—S1—S2ii | 73.36 (4) |
N3—N2—Cu1 | 132.74 (12) | C13—S2—N5 | 0.81 (10) |
C1—N2—S1 | 38.12 (9) | C13—S2—Cu1 | 101.44 (9) |
N3—N2—S1 | 75.50 (9) | N5—S2—Cu1 | 102.00 (6) |
Cu1—N2—S1 | 151.43 (8) | C13—S2—S1iii | 70.19 (8) |
C7—N3—N2 | 111.07 (15) | N5—S2—S1iii | 69.96 (5) |
C7—N3—S1 | 37.70 (9) | Cu1—S2—S1iii | 151.94 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N5iv | 0.93 | 2.53 | 3.353 (3) | 147 |
C6—H6···N3i | 0.93 | 2.35 | 3.143 (3) | 142 |
C4—H4···N4v | 0.93 | 2.57 | 3.458 (3) | 161 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2. |