Buy article online - an online subscription or single-article purchase is required to access this article.
From the system CuCl2–biq–NaN(CN)2 (biq is 2,2′-biquinoline), the binuclear molecular complex bis(μ-dicyanamido-κ2N1:N5)bis[(2,2′-biquinoline-κ2N,N′)(dicyanamido-κN1)copper(II)], [Cu2(C2N3)4(C18H12N2)2] or [Cu2(biq)2(dca)2(μ1,5-dca)2] (1) [dca is dicyanamide, N(CN)2−] was isolated and characterized by crystal structure analysis, and spectral, thermal and magnetic measurements. IR spectroscopy confirmed the presence of the biq and dca ligands in 1. Its solid-state structure consists of discrete centrosymmetric binuclear copper(II) units with double end-to-end dca bridges. Each CuII atom is in a distorted square-pyramidal environment with the equatorial plane formed by two nitrile N atoms from bridging dca groups, one of the two N atoms of the chelate biq molecule and one nitrile N atom from a terminal dca ligand, whereas the second biq N atom occupies the axial position. Thermal decomposition of 1 in an air atmosphere proceeds gradually, with copper(I) cyanide being the final decomposition product. Magnetic measurements revealed the formation of alternating spin chains and a relatively strong exchange interaction within the binuclear units was also confirmed by Broken Symmetry DFT (density functional theory) calculations.
Supporting information
CCDC reference: 1870270
Data collection: CrysAlis PRO (Rigaku OD, 2017); cell refinement: CrysAlis PRO (Rigaku OD, 2017); data reduction: CrysAlis PRO (Rigaku OD, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Bis(µ-dicyanamido-
κ2N1:
N5)bis[(2,2'-biquinoline-
κ2N,
N')(dicyanamido-
κN1)copper(II)]
top
Crystal data top
[Cu2(C2N3)4(C18H12N2)2] | Z = 1 |
Mr = 903.87 | F(000) = 458 |
Triclinic, P1 | Dx = 1.575 Mg m−3 |
a = 9.5158 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.6393 (4) Å | Cell parameters from 7968 reflections |
c = 11.0824 (7) Å | θ = 4.3–29.1° |
α = 88.441 (4)° | µ = 1.18 mm−1 |
β = 71.611 (5)° | T = 120 K |
γ = 81.106 (4)° | Prism, blue |
V = 952.78 (9) Å3 | 0.33 × 0.24 × 0.13 mm |
Data collection top
Rigaku Xcalibur AtlasS2 Gemini ultra diffractometer | 4642 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4219 reflections with I > 2σ(I) |
Detector resolution: 5.1783 pixels mm-1 | Rint = 0.025 |
ω scans | θmax = 29.4°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2017) | h = −12→12 |
Tmin = 0.804, Tmax = 1.000 | k = −12→12 |
14202 measured reflections | l = −15→13 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.8125P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
4642 reflections | Δρmax = 1.09 e Å−3 |
280 parameters | Δρmin = −0.35 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. |
Refinement. Crystal structure of 1 was determined using an
Oxford Diffraction Xcalibur Gemini ultra diffractometer equipped with an
AtlasS2 CCD detector using MoKα radiation. CrysAlis PRO 1.171.39.35c (Rigaku
Oxford Diffraction, 2017) was used for data collection, cell refinement, data
reduction and absorption correction. The structure was solved by SHELXT
(Sheldrick, 2015a) and subsequent Fourier syntheses using SHELXL2014
(Sheldrick, 2015b), implemented in WinGX program suite (Farrugia, 2012).
Anisotropic displacement parameters were refined for all non-H atoms.
An analysis of the bond lengths and angles was
performed using SHELXL2014 while PLATON (Spek, 2009) running under WinGX
was used to analyze
the π–π interactions. DIAMOND (Brandenburg, 2009) was used for molecular
graphics. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.30516 (3) | 0.25748 (2) | 0.24715 (2) | 0.01807 (9) | |
N10 | 0.11429 (19) | 0.39324 (17) | 0.27427 (16) | 0.0183 (3) | |
N20 | 0.15998 (18) | 0.18501 (17) | 0.42799 (15) | 0.0181 (3) | |
N2 | 0.5031 (2) | 0.1424 (2) | 0.18965 (17) | 0.0258 (4) | |
N3 | 0.7546 (2) | −0.1474 (2) | −0.12686 (17) | 0.0262 (4) | |
N1 | 0.7337 (2) | 0.0036 (2) | 0.05344 (18) | 0.0263 (4) | |
N5 | 0.3950 (2) | 0.4106 (2) | 0.3069 (2) | 0.0322 (4) | |
C21 | 0.0269 (2) | 0.2656 (2) | 0.46555 (18) | 0.0189 (4) | |
C11 | −0.0001 (2) | 0.3787 (2) | 0.37726 (18) | 0.0189 (4) | |
C2 | 0.6072 (2) | 0.0757 (2) | 0.12148 (19) | 0.0202 (4) | |
C3 | 0.7361 (2) | −0.0747 (2) | −0.04102 (19) | 0.0201 (4) | |
C22 | 0.1892 (2) | 0.0761 (2) | 0.50342 (19) | 0.0202 (4) | |
C12 | 0.0987 (2) | 0.4946 (2) | 0.18738 (19) | 0.0215 (4) | |
C27 | 0.0820 (2) | 0.0500 (2) | 0.62095 (19) | 0.0232 (4) | |
C19 | −0.1403 (2) | 0.4656 (2) | 0.4009 (2) | 0.0261 (4) | |
H19 | −0.2208 | 0.4539 | 0.4753 | 0.031* | |
C23 | 0.3281 (2) | −0.0141 (2) | 0.4617 (2) | 0.0253 (4) | |
H23 | 0.4002 | 0.0018 | 0.3831 | 0.030* | |
C29 | −0.0855 (2) | 0.2457 (2) | 0.58108 (19) | 0.0239 (4) | |
H29 | −0.1794 | 0.3057 | 0.6048 | 0.029* | |
C5 | 0.4456 (2) | 0.5057 (3) | 0.2812 (2) | 0.0321 (5) | |
C18 | −0.1592 (3) | 0.5664 (2) | 0.3162 (2) | 0.0290 (5) | |
H18 | −0.2535 | 0.6246 | 0.3313 | 0.035* | |
C28 | −0.0571 (3) | 0.1391 (2) | 0.6580 (2) | 0.0270 (5) | |
H28 | −0.1309 | 0.1251 | 0.7363 | 0.032* | |
C25 | 0.2529 (3) | −0.1502 (3) | 0.6520 (2) | 0.0312 (5) | |
H25 | 0.2758 | −0.2272 | 0.7015 | 0.037* | |
C17 | −0.0394 (3) | 0.5846 (2) | 0.2065 (2) | 0.0253 (4) | |
C24 | 0.3588 (3) | −0.1248 (2) | 0.5349 (2) | 0.0292 (5) | |
H24 | 0.4524 | −0.1849 | 0.5064 | 0.035* | |
C26 | 0.1182 (3) | −0.0651 (3) | 0.6943 (2) | 0.0301 (5) | |
H26 | 0.0479 | −0.0828 | 0.7735 | 0.036* | |
C13 | 0.2216 (3) | 0.5100 (2) | 0.0788 (2) | 0.0288 (5) | |
H13 | 0.3139 | 0.4485 | 0.0640 | 0.035* | |
C14 | 0.2069 (3) | 0.6144 (3) | −0.0051 (2) | 0.0380 (6) | |
H14 | 0.2902 | 0.6259 | −0.0773 | 0.046* | |
N6 | 0.4470 (3) | 0.8162 (3) | 0.1354 (3) | 0.0546 (7) | |
C16 | −0.0506 (3) | 0.6896 (3) | 0.1163 (3) | 0.0368 (6) | |
H16 | −0.1430 | 0.7498 | 0.1274 | 0.044* | |
C6 | 0.4737 (3) | 0.7222 (3) | 0.1928 (3) | 0.0401 (6) | |
C15 | 0.0702 (3) | 0.7045 (3) | 0.0143 (3) | 0.0425 (6) | |
H15 | 0.0623 | 0.7764 | −0.0445 | 0.051* | |
N4 | 0.5117 (4) | 0.6184 (3) | 0.2628 (4) | 0.0712 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01698 (13) | 0.01921 (13) | 0.01593 (13) | 0.00010 (9) | −0.00346 (9) | −0.00140 (9) |
N10 | 0.0193 (8) | 0.0174 (8) | 0.0186 (8) | −0.0015 (6) | −0.0071 (6) | −0.0015 (6) |
N20 | 0.0182 (8) | 0.0202 (8) | 0.0169 (8) | −0.0046 (6) | −0.0062 (6) | −0.0003 (6) |
N2 | 0.0233 (9) | 0.0301 (10) | 0.0240 (9) | 0.0018 (7) | −0.0093 (7) | −0.0069 (7) |
N3 | 0.0213 (9) | 0.0310 (10) | 0.0245 (9) | 0.0022 (7) | −0.0068 (7) | −0.0080 (7) |
N1 | 0.0181 (8) | 0.0329 (10) | 0.0278 (9) | 0.0017 (7) | −0.0088 (7) | −0.0116 (7) |
N5 | 0.0286 (10) | 0.0278 (10) | 0.0353 (11) | 0.0072 (8) | −0.0080 (8) | −0.0056 (8) |
C21 | 0.0196 (9) | 0.0215 (9) | 0.0169 (9) | −0.0055 (7) | −0.0063 (7) | −0.0026 (7) |
C11 | 0.0186 (9) | 0.0201 (9) | 0.0185 (9) | −0.0026 (7) | −0.0062 (7) | −0.0042 (7) |
C2 | 0.0203 (10) | 0.0222 (10) | 0.0202 (9) | −0.0021 (8) | −0.0099 (8) | −0.0018 (7) |
C3 | 0.0136 (9) | 0.0214 (9) | 0.0236 (10) | 0.0004 (7) | −0.0051 (7) | 0.0011 (8) |
C22 | 0.0224 (10) | 0.0227 (10) | 0.0202 (9) | −0.0085 (8) | −0.0110 (8) | 0.0022 (7) |
C12 | 0.0273 (11) | 0.0182 (9) | 0.0223 (10) | −0.0036 (8) | −0.0122 (8) | 0.0001 (7) |
C27 | 0.0277 (11) | 0.0286 (11) | 0.0184 (10) | −0.0115 (9) | −0.0115 (8) | 0.0026 (8) |
C19 | 0.0187 (10) | 0.0303 (11) | 0.0271 (11) | −0.0002 (8) | −0.0053 (8) | −0.0042 (8) |
C23 | 0.0245 (11) | 0.0265 (11) | 0.0277 (11) | −0.0066 (8) | −0.0114 (9) | 0.0045 (8) |
C29 | 0.0196 (10) | 0.0315 (11) | 0.0192 (10) | −0.0054 (8) | −0.0030 (8) | −0.0034 (8) |
C5 | 0.0175 (10) | 0.0344 (13) | 0.0450 (14) | 0.0022 (9) | −0.0125 (10) | −0.0112 (10) |
C18 | 0.0231 (11) | 0.0268 (11) | 0.0382 (13) | 0.0042 (8) | −0.0147 (9) | −0.0040 (9) |
C28 | 0.0269 (11) | 0.0375 (12) | 0.0165 (9) | −0.0131 (9) | −0.0032 (8) | 0.0019 (8) |
C25 | 0.0395 (13) | 0.0320 (12) | 0.0350 (12) | −0.0170 (10) | −0.0258 (11) | 0.0148 (10) |
C17 | 0.0296 (11) | 0.0199 (10) | 0.0314 (11) | −0.0019 (8) | −0.0173 (9) | −0.0005 (8) |
C24 | 0.0286 (11) | 0.0268 (11) | 0.0396 (13) | −0.0066 (9) | −0.0205 (10) | 0.0070 (9) |
C26 | 0.0370 (13) | 0.0376 (12) | 0.0238 (11) | −0.0174 (10) | −0.0167 (10) | 0.0113 (9) |
C13 | 0.0308 (12) | 0.0300 (11) | 0.0253 (11) | −0.0033 (9) | −0.0095 (9) | 0.0054 (9) |
C14 | 0.0473 (15) | 0.0390 (14) | 0.0298 (12) | −0.0109 (11) | −0.0141 (11) | 0.0142 (10) |
N6 | 0.0658 (18) | 0.0405 (14) | 0.0574 (16) | −0.0176 (13) | −0.0158 (14) | 0.0110 (12) |
C16 | 0.0437 (15) | 0.0281 (12) | 0.0463 (15) | 0.0013 (10) | −0.0285 (12) | 0.0066 (10) |
C6 | 0.0349 (14) | 0.0341 (13) | 0.0485 (16) | −0.0094 (11) | −0.0072 (12) | −0.0007 (11) |
C15 | 0.0581 (18) | 0.0355 (13) | 0.0418 (15) | −0.0081 (12) | −0.0278 (13) | 0.0180 (11) |
N4 | 0.0644 (19) | 0.0479 (16) | 0.129 (3) | −0.0260 (14) | −0.064 (2) | 0.0281 (17) |
Geometric parameters (Å, º) top
Cu1—N2 | 1.9546 (18) | C19—H19 | 0.9500 |
Cu1—N3i | 1.9919 (18) | C23—C24 | 1.374 (3) |
Cu1—N10 | 2.0109 (17) | C23—H23 | 0.9500 |
Cu1—N5 | 2.036 (2) | C29—C28 | 1.367 (3) |
Cu1—N20 | 2.2111 (16) | C29—H29 | 0.9500 |
N10—C11 | 1.327 (3) | C5—N4 | 1.316 (4) |
N10—C12 | 1.378 (3) | C18—C17 | 1.408 (3) |
N20—C21 | 1.327 (3) | C18—H18 | 0.9500 |
N20—C22 | 1.374 (3) | C28—H28 | 0.9500 |
N2—C2 | 1.150 (3) | C25—C26 | 1.361 (4) |
N3—C3 | 1.149 (3) | C25—C24 | 1.411 (3) |
N3—Cu1i | 1.9919 (18) | C25—H25 | 0.9500 |
N1—C3 | 1.299 (3) | C17—C16 | 1.419 (3) |
N1—C2 | 1.303 (3) | C24—H24 | 0.9500 |
N5—C5 | 1.091 (3) | C26—H26 | 0.9500 |
C21—C29 | 1.416 (3) | C13—C14 | 1.373 (3) |
C21—C11 | 1.492 (3) | C13—H13 | 0.9500 |
C11—C19 | 1.412 (3) | C14—C15 | 1.406 (4) |
C22—C23 | 1.413 (3) | C14—H14 | 0.9500 |
C22—C27 | 1.423 (3) | N6—C6 | 1.135 (4) |
C12—C13 | 1.412 (3) | C16—C15 | 1.357 (4) |
C12—C17 | 1.416 (3) | C16—H16 | 0.9500 |
C27—C28 | 1.408 (3) | C6—N4 | 1.326 (4) |
C27—C26 | 1.422 (3) | C15—H15 | 0.9500 |
C19—C18 | 1.364 (3) | | |
| | | |
N2—Cu1—N3i | 88.16 (7) | C24—C23—C22 | 120.0 (2) |
N2—Cu1—N10 | 169.15 (7) | C24—C23—H23 | 120.0 |
N3i—Cu1—N10 | 88.86 (7) | C22—C23—H23 | 120.0 |
N2—Cu1—N5 | 89.86 (8) | C28—C29—C21 | 119.2 (2) |
N3i—Cu1—N5 | 157.78 (9) | C28—C29—H29 | 120.4 |
N10—Cu1—N5 | 88.96 (7) | C21—C29—H29 | 120.4 |
N2—Cu1—N20 | 112.45 (7) | N5—C5—N4 | 173.0 (3) |
N3i—Cu1—N20 | 98.72 (7) | C19—C18—C17 | 120.2 (2) |
N10—Cu1—N20 | 78.32 (7) | C19—C18—H18 | 119.9 |
N5—Cu1—N20 | 102.48 (7) | C17—C18—H18 | 119.9 |
C11—N10—C12 | 120.35 (17) | C29—C28—C27 | 119.77 (19) |
C11—N10—Cu1 | 117.64 (13) | C29—C28—H28 | 120.1 |
C12—N10—Cu1 | 121.95 (14) | C27—C28—H28 | 120.1 |
C21—N20—C22 | 118.59 (17) | C26—C25—C24 | 120.4 (2) |
C21—N20—Cu1 | 111.27 (13) | C26—C25—H25 | 119.8 |
C22—N20—Cu1 | 130.12 (13) | C24—C25—H25 | 119.8 |
C2—N2—Cu1 | 158.34 (17) | C18—C17—C12 | 117.95 (19) |
C3—N3—Cu1i | 156.25 (17) | C18—C17—C16 | 123.0 (2) |
C3—N1—C2 | 119.41 (18) | C12—C17—C16 | 119.0 (2) |
C5—N5—Cu1 | 145.8 (2) | C23—C24—C25 | 120.8 (2) |
N20—C21—C29 | 122.89 (19) | C23—C24—H24 | 119.6 |
N20—C21—C11 | 116.06 (17) | C25—C24—H24 | 119.6 |
C29—C21—C11 | 121.05 (18) | C25—C26—C27 | 120.5 (2) |
N10—C11—C19 | 121.39 (19) | C25—C26—H26 | 119.8 |
N10—C11—C21 | 116.58 (17) | C27—C26—H26 | 119.8 |
C19—C11—C21 | 122.03 (18) | C14—C13—C12 | 119.6 (2) |
N2—C2—N1 | 173.1 (2) | C14—C13—H13 | 120.2 |
N3—C3—N1 | 172.7 (2) | C12—C13—H13 | 120.2 |
N20—C22—C23 | 119.08 (18) | C13—C14—C15 | 120.9 (2) |
N20—C22—C27 | 121.67 (19) | C13—C14—H14 | 119.6 |
C23—C22—C27 | 119.24 (19) | C15—C14—H14 | 119.6 |
N10—C12—C13 | 119.83 (19) | C15—C16—C17 | 120.3 (2) |
N10—C12—C17 | 120.56 (19) | C15—C16—H16 | 119.9 |
C13—C12—C17 | 119.60 (19) | C17—C16—H16 | 119.9 |
C28—C27—C26 | 123.0 (2) | N6—C6—N4 | 175.4 (3) |
C28—C27—C22 | 117.91 (19) | C16—C15—C14 | 120.6 (2) |
C26—C27—C22 | 119.1 (2) | C16—C15—H15 | 119.7 |
C18—C19—C11 | 119.5 (2) | C14—C15—H15 | 119.7 |
C18—C19—H19 | 120.2 | C5—N4—C6 | 120.9 (3) |
C11—C19—H19 | 120.2 | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···N2 | 0.95 | 2.51 | 3.391 (3) | 154 |
Cg···Cg distances and angles (Å, °) characterizing π–π
interactions in 1 topCg(I)···Cg(J) | Cg···Cg | α | β | γ |
Cg1···Cg1ii | 3.6275 (2) | 0 | 20.8 | 20.8 |
Cg1···Cg2ii | 3.6358 (2) | 2 | 22.8 | 21.0 |
Cg3···Cg1iii | 3.8779 (2) | 5 | 25.5 | 29.8 |
Cg4···Cg4iv | 3.8195 (2) | 0 | 10.1 | 10.1 |
Symmetry codes: (ii) -x, -y, -z+1;
(iii) -x, -y+1, -z+1;
(iv) -x, -y+1, -z.
α is the dihedral angle between planes I and J. β is the angle
between the Cg(I)···Cg(J) vector and the normal to
plane I. γ is the angle between
Cg(I)···Cg(J) vector and normal to plane J.
Cg1 and Cg2 represent the centroids of the pyridine and phenyl
rings of the quinoline moiety containing atom N10, while Cg3 and
Cg4 represent the centroids of the pyridine and phenyl rings of the
quinoline moiety containing atom N20. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.