The complex (2,2′-biquinoline-κ2N,N′)(carbamoylcyanonitrosomethanide-κ2N,O)chloridocopper(II) acetonitrile monosolvate, [Cu(C3H2N3O2)Cl(C18H12N2)]·CH3CN or [Cu(ccnm)Cl(biq)]·acn (acn is acetonitrile, biq is 2,2′-biquinoline and ccnm is carbamoylcyanonitrosomethanide), (I), was prepared as a result of nucleophilic addition of water to the dicyanonitrosomethanide ion in the presence of CuII and biq. IR spectroscopy confirmed the presence of ccnm, biq and acn in (I). The solid-state structure consists of the neutral complex containing ccnm and biq ligands, coordinated to the CuII atom in a bidendate chelating manner, and a chloride ligand, resulting in a distorted tetragonal pyramidal coordination of CuII. The asymmetric unit is supplemented by one molecule of solvated acn which, along with the nitrile group of ccnm, serves as an acceptor in intermolecular hydrogen bonding, creating infinite chains along the b axis. Magnetic measurements revealed a paramagnetic behaviour with a very small Weiss temperature Θ = −0.32 K and high anisotropy of the g tensor (gx = 2.036, gy = 2.120 and gz = 2.205).
Supporting information
CCDC reference: 1836379
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, 2015b) in WinGX (Farrugia, 2012); molecular graphics: DIAMOND (Brandenburg, 2009).
(2,2'-Biquinoline-
κ2N,
N')(carbamoylcyanonitrosomethanide-\
κ2N,
O)chloridocopper(II) acetonitrile monosolvate
top
Crystal data top
[Cu(C3H2N3O2)Cl(C18H12N2)]·C2H3N | F(000) = 1036 |
Mr = 508.42 | Dx = 1.504 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 11.8203 (1) Å | Cell parameters from 21847 reflections |
b = 9.1276 (1) Å | θ = 4.2–67.7° |
c = 21.1575 (1) Å | µ = 2.75 mm−1 |
β = 100.468 (1)° | T = 120 K |
V = 2244.71 (3) Å3 | Plate, dark green |
Z = 4 | 0.31 × 0.11 × 0.03 mm |
Data collection top
Rigaku Xcalibur AtlasS2 Gemini ultra diffractometer | 4034 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3765 reflections with I > 2σ(I) |
Detector resolution: 5.1783 pixels mm-1 | Rint = 0.030 |
ω scans | θmax = 67.6°, θmin = 3.8° |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2017), based on expressions
derived by Clark & Reid (1995)] | h = −14→14 |
Tmin = 0.593, Tmax = 0.927 | k = −10→10 |
40629 measured reflections | l = −25→25 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0332P)2 + 1.4117P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
4034 reflections | Δρmax = 0.29 e Å−3 |
318 parameters | Δρmin = −0.29 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 | |
Cu1 | 0.84543 (2) | 0.67370 (2) | 0.62482 (2) | 0.01704 (8) | |
Cl1 | 0.98942 (3) | 0.52820 (4) | 0.67748 (2) | 0.02252 (10) | |
O2 | 0.74668 (9) | 0.61544 (13) | 0.68669 (5) | 0.0218 (2) | |
O1 | 0.74223 (10) | 0.96188 (13) | 0.58230 (5) | 0.0254 (3) | |
N20 | 0.94414 (10) | 0.75413 (14) | 0.56619 (6) | 0.0168 (3) | |
N10 | 0.77747 (11) | 0.55355 (14) | 0.53480 (6) | 0.0180 (3) | |
N1 | 0.74096 (11) | 0.85218 (15) | 0.61833 (6) | 0.0183 (3) | |
N2 | 0.59380 (13) | 0.67900 (19) | 0.73050 (7) | 0.0266 (3) | |
N3 | 0.51050 (12) | 1.04133 (16) | 0.66124 (7) | 0.0286 (3) | |
C21 | 0.93414 (13) | 0.69337 (17) | 0.50823 (7) | 0.0175 (3) | |
C22 | 1.02823 (13) | 0.85627 (17) | 0.58589 (7) | 0.0175 (3) | |
C27 | 1.10787 (13) | 0.89555 (18) | 0.54590 (7) | 0.0190 (3) | |
N4 | 0.37291 (14) | 0.82051 (19) | 0.74661 (9) | 0.0387 (4) | |
C1 | 0.66365 (13) | 0.84313 (18) | 0.65695 (7) | 0.0185 (3) | |
C12 | 0.69170 (13) | 0.45126 (18) | 0.52100 (8) | 0.0204 (3) | |
C11 | 0.83902 (13) | 0.58648 (17) | 0.48996 (7) | 0.0185 (3) | |
C2 | 0.66930 (13) | 0.70659 (18) | 0.69295 (7) | 0.0199 (3) | |
C17 | 0.66875 (14) | 0.37865 (19) | 0.46055 (8) | 0.0243 (3) | |
C29 | 1.01142 (13) | 0.72761 (18) | 0.46644 (7) | 0.0204 (3) | |
H29 | 1.0036 | 0.6819 | 0.4255 | 0.024* | |
C3 | 0.58020 (13) | 0.95479 (18) | 0.65906 (7) | 0.0209 (3) | |
C28 | 1.09693 (13) | 0.82663 (18) | 0.48539 (8) | 0.0207 (3) | |
H28 | 1.1495 | 0.8494 | 0.4578 | 0.025* | |
C23 | 1.03632 (13) | 0.92393 (19) | 0.64663 (7) | 0.0216 (3) | |
H23 | 0.9838 | 0.8980 | 0.6739 | 0.026* | |
C26 | 1.19398 (13) | 1.00064 (19) | 0.56815 (8) | 0.0225 (3) | |
H26 | 1.2482 | 1.0268 | 0.5420 | 0.027* | |
C24 | 1.11937 (14) | 1.0264 (2) | 0.66624 (8) | 0.0253 (4) | |
H24 | 1.1234 | 1.0726 | 0.7068 | 0.030* | |
C19 | 0.81741 (14) | 0.5229 (2) | 0.42781 (8) | 0.0251 (4) | |
H19 | 0.8607 | 0.5522 | 0.3963 | 0.030* | |
C25 | 1.19955 (14) | 1.0645 (2) | 0.62684 (8) | 0.0256 (4) | |
H25 | 1.2576 | 1.1350 | 0.6414 | 0.031* | |
C13 | 0.62539 (14) | 0.41411 (19) | 0.56798 (8) | 0.0250 (4) | |
H13 | 0.6387 | 0.4627 | 0.6083 | 0.030* | |
C4 | 0.29640 (15) | 0.7813 (2) | 0.76818 (8) | 0.0276 (4) | |
C5 | 0.19909 (16) | 0.7316 (2) | 0.79585 (10) | 0.0299 (4) | |
C18 | 0.73392 (15) | 0.4194 (2) | 0.41403 (8) | 0.0279 (4) | |
H18 | 0.7196 | 0.3745 | 0.3728 | 0.033* | |
C16 | 0.58372 (15) | 0.2677 (2) | 0.45003 (9) | 0.0311 (4) | |
H16 | 0.5697 | 0.2168 | 0.4102 | 0.037* | |
C14 | 0.54218 (15) | 0.3085 (2) | 0.55557 (9) | 0.0307 (4) | |
H14 | 0.4975 | 0.2854 | 0.5873 | 0.037* | |
C15 | 0.52189 (15) | 0.2332 (2) | 0.49628 (10) | 0.0333 (4) | |
H15 | 0.4651 | 0.1585 | 0.4887 | 0.040* | |
H2N2 | 0.5987 (17) | 0.600 (3) | 0.7498 (10) | 0.027 (5)* | |
H1N2 | 0.5418 (19) | 0.736 (3) | 0.7336 (10) | 0.034 (6)* | |
H1C5 | 0.2262 (19) | 0.673 (3) | 0.8336 (11) | 0.042 (6)* | |
H3C5 | 0.154 (2) | 0.816 (3) | 0.8048 (11) | 0.046 (6)* | |
H2C5 | 0.149 (2) | 0.667 (3) | 0.7654 (12) | 0.047 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01632 (12) | 0.01982 (14) | 0.01701 (13) | 0.00012 (8) | 0.00846 (9) | 0.00151 (8) |
Cl1 | 0.02012 (18) | 0.0268 (2) | 0.02202 (18) | 0.00297 (15) | 0.00760 (14) | 0.00255 (15) |
O2 | 0.0196 (5) | 0.0246 (6) | 0.0236 (5) | 0.0032 (5) | 0.0106 (4) | 0.0058 (5) |
O1 | 0.0299 (6) | 0.0217 (6) | 0.0279 (6) | 0.0013 (5) | 0.0138 (5) | 0.0074 (5) |
N20 | 0.0157 (6) | 0.0191 (7) | 0.0165 (6) | 0.0022 (5) | 0.0052 (5) | 0.0013 (5) |
N10 | 0.0166 (6) | 0.0182 (7) | 0.0197 (6) | 0.0015 (5) | 0.0044 (5) | 0.0008 (5) |
N1 | 0.0187 (6) | 0.0198 (7) | 0.0178 (6) | −0.0028 (5) | 0.0069 (5) | 0.0000 (5) |
N2 | 0.0239 (8) | 0.0306 (9) | 0.0295 (8) | 0.0051 (7) | 0.0163 (6) | 0.0095 (7) |
N3 | 0.0281 (8) | 0.0245 (8) | 0.0369 (8) | 0.0007 (6) | 0.0156 (6) | −0.0017 (6) |
C21 | 0.0175 (7) | 0.0189 (8) | 0.0170 (7) | 0.0042 (6) | 0.0055 (6) | 0.0021 (6) |
C22 | 0.0161 (7) | 0.0186 (8) | 0.0185 (7) | 0.0025 (6) | 0.0047 (6) | 0.0036 (6) |
C27 | 0.0172 (7) | 0.0203 (8) | 0.0206 (7) | 0.0039 (6) | 0.0066 (6) | 0.0056 (6) |
N4 | 0.0338 (9) | 0.0378 (10) | 0.0497 (10) | 0.0097 (7) | 0.0212 (8) | 0.0090 (8) |
C1 | 0.0178 (7) | 0.0208 (8) | 0.0184 (7) | −0.0006 (6) | 0.0071 (6) | −0.0020 (6) |
C12 | 0.0169 (7) | 0.0186 (8) | 0.0252 (8) | 0.0027 (6) | 0.0019 (6) | 0.0019 (6) |
C11 | 0.0179 (7) | 0.0190 (8) | 0.0193 (7) | 0.0042 (6) | 0.0050 (6) | 0.0003 (6) |
C2 | 0.0171 (7) | 0.0263 (9) | 0.0170 (7) | −0.0016 (6) | 0.0051 (6) | 0.0002 (6) |
C17 | 0.0190 (8) | 0.0238 (9) | 0.0283 (8) | 0.0035 (7) | −0.0003 (6) | −0.0023 (7) |
C29 | 0.0238 (8) | 0.0224 (8) | 0.0169 (7) | 0.0050 (6) | 0.0091 (6) | 0.0020 (6) |
C3 | 0.0213 (8) | 0.0217 (9) | 0.0218 (8) | −0.0052 (7) | 0.0093 (6) | −0.0021 (6) |
C28 | 0.0216 (8) | 0.0227 (9) | 0.0212 (8) | 0.0040 (6) | 0.0128 (6) | 0.0055 (6) |
C23 | 0.0207 (8) | 0.0272 (9) | 0.0180 (7) | −0.0009 (7) | 0.0069 (6) | 0.0007 (6) |
C26 | 0.0180 (7) | 0.0247 (9) | 0.0262 (8) | −0.0005 (6) | 0.0076 (6) | 0.0058 (7) |
C24 | 0.0255 (8) | 0.0302 (9) | 0.0196 (8) | −0.0027 (7) | 0.0024 (6) | −0.0016 (7) |
C19 | 0.0235 (8) | 0.0318 (10) | 0.0209 (8) | 0.0019 (7) | 0.0066 (6) | −0.0032 (7) |
C25 | 0.0209 (8) | 0.0272 (9) | 0.0276 (8) | −0.0051 (7) | 0.0018 (7) | 0.0029 (7) |
C13 | 0.0228 (8) | 0.0252 (9) | 0.0270 (8) | −0.0011 (7) | 0.0046 (7) | 0.0031 (7) |
C4 | 0.0287 (9) | 0.0257 (9) | 0.0290 (9) | 0.0082 (7) | 0.0067 (7) | 0.0003 (7) |
C5 | 0.0263 (9) | 0.0303 (10) | 0.0348 (10) | 0.0002 (8) | 0.0098 (8) | −0.0008 (8) |
C18 | 0.0262 (8) | 0.0334 (10) | 0.0230 (8) | 0.0031 (7) | 0.0016 (7) | −0.0085 (7) |
C16 | 0.0248 (9) | 0.0289 (10) | 0.0365 (10) | −0.0012 (7) | −0.0027 (7) | −0.0065 (8) |
C14 | 0.0239 (9) | 0.0297 (10) | 0.0380 (10) | −0.0041 (7) | 0.0044 (7) | 0.0084 (8) |
C15 | 0.0256 (9) | 0.0247 (10) | 0.0462 (11) | −0.0055 (7) | −0.0025 (8) | 0.0025 (8) |
Geometric parameters (Å, º) top
Cu1—O2 | 1.9785 (10) | C11—C19 | 1.418 (2) |
Cu1—N20 | 1.9912 (12) | C17—C18 | 1.406 (3) |
Cu1—N1 | 2.0337 (14) | C17—C16 | 1.416 (2) |
Cu1—N10 | 2.2179 (13) | C29—C28 | 1.361 (2) |
Cu1—Cl1 | 2.2832 (4) | C29—H29 | 0.9500 |
O2—C2 | 1.261 (2) | C28—H28 | 0.9500 |
O1—N1 | 1.2602 (17) | C23—C24 | 1.365 (2) |
N20—C21 | 1.331 (2) | C23—H23 | 0.9500 |
N20—C22 | 1.371 (2) | C26—C25 | 1.363 (2) |
N10—C11 | 1.331 (2) | C26—H26 | 0.9500 |
N10—C12 | 1.370 (2) | C24—C25 | 1.415 (2) |
N1—C1 | 1.334 (2) | C24—H24 | 0.9500 |
N2—C2 | 1.322 (2) | C19—C18 | 1.359 (3) |
N2—H2N2 | 0.82 (2) | C19—H19 | 0.9500 |
N2—H1N2 | 0.82 (2) | C25—H25 | 0.9500 |
N3—C3 | 1.148 (2) | C13—C14 | 1.368 (2) |
C21—C29 | 1.417 (2) | C13—H13 | 0.9500 |
C21—C11 | 1.486 (2) | C4—C5 | 1.455 (3) |
C22—C23 | 1.413 (2) | C5—H1C5 | 0.97 (2) |
C22—C27 | 1.421 (2) | C5—H3C5 | 0.98 (2) |
C27—C28 | 1.411 (2) | C5—H2C5 | 0.99 (2) |
C27—C26 | 1.416 (2) | C18—H18 | 0.9500 |
N4—C4 | 1.142 (2) | C16—C15 | 1.360 (3) |
C1—C3 | 1.425 (2) | C16—H16 | 0.9500 |
C1—C2 | 1.456 (2) | C14—C15 | 1.412 (3) |
C12—C13 | 1.414 (2) | C14—H14 | 0.9500 |
C12—C17 | 1.422 (2) | C15—H15 | 0.9500 |
| | | |
O2—Cu1—N20 | 173.84 (5) | C16—C17—C12 | 119.27 (16) |
O2—Cu1—N1 | 80.56 (5) | C28—C29—C21 | 119.42 (15) |
N20—Cu1—N1 | 94.59 (5) | C28—C29—H29 | 120.3 |
O2—Cu1—N10 | 105.67 (5) | C21—C29—H29 | 120.3 |
N20—Cu1—N10 | 79.00 (5) | N3—C3—C1 | 177.75 (17) |
N1—Cu1—N10 | 102.55 (5) | C29—C28—C27 | 120.28 (14) |
O2—Cu1—Cl1 | 89.88 (3) | C29—C28—H28 | 119.9 |
N20—Cu1—Cl1 | 92.82 (4) | C27—C28—H28 | 119.9 |
N1—Cu1—Cl1 | 152.69 (4) | C24—C23—C22 | 120.13 (14) |
N10—Cu1—Cl1 | 104.66 (4) | C24—C23—H23 | 119.9 |
C2—O2—Cu1 | 114.74 (10) | C22—C23—H23 | 119.9 |
C21—N20—C22 | 120.09 (13) | C25—C26—C27 | 120.39 (15) |
C21—N20—Cu1 | 117.14 (11) | C25—C26—H26 | 119.8 |
C22—N20—Cu1 | 122.39 (10) | C27—C26—H26 | 119.8 |
C11—N10—C12 | 118.77 (13) | C23—C24—C25 | 120.76 (15) |
C11—N10—Cu1 | 109.93 (10) | C23—C24—H24 | 119.6 |
C12—N10—Cu1 | 131.18 (10) | C25—C24—H24 | 119.6 |
O1—N1—C1 | 120.28 (13) | C18—C19—C11 | 119.01 (16) |
O1—N1—Cu1 | 127.12 (10) | C18—C19—H19 | 120.5 |
C1—N1—Cu1 | 112.58 (10) | C11—C19—H19 | 120.5 |
C2—N2—H2N2 | 118.1 (14) | C26—C25—C24 | 120.33 (16) |
C2—N2—H1N2 | 121.6 (15) | C26—C25—H25 | 119.8 |
H2N2—N2—H1N2 | 120 (2) | C24—C25—H25 | 119.8 |
N20—C21—C29 | 121.57 (15) | C14—C13—C12 | 120.33 (16) |
N20—C21—C11 | 116.71 (13) | C14—C13—H13 | 119.8 |
C29—C21—C11 | 121.72 (14) | C12—C13—H13 | 119.8 |
N20—C22—C23 | 119.94 (13) | N4—C4—C5 | 179.8 (2) |
N20—C22—C27 | 120.83 (14) | C4—C5—H1C5 | 109.7 (14) |
C23—C22—C27 | 119.23 (14) | C4—C5—H3C5 | 109.1 (14) |
C28—C27—C26 | 123.07 (14) | H1C5—C5—H3C5 | 112.9 (19) |
C28—C27—C22 | 117.79 (15) | C4—C5—H2C5 | 110.4 (14) |
C26—C27—C22 | 119.14 (14) | H1C5—C5—H2C5 | 106.3 (19) |
N1—C1—C3 | 122.00 (14) | H3C5—C5—H2C5 | 108.4 (19) |
N1—C1—C2 | 113.70 (14) | C19—C18—C17 | 120.19 (15) |
C3—C1—C2 | 124.21 (14) | C19—C18—H18 | 119.9 |
N10—C12—C13 | 119.78 (14) | C17—C18—H18 | 119.9 |
N10—C12—C17 | 121.48 (15) | C15—C16—C17 | 120.76 (17) |
C13—C12—C17 | 118.73 (15) | C15—C16—H16 | 119.6 |
N10—C11—C19 | 122.64 (15) | C17—C16—H16 | 119.6 |
N10—C11—C21 | 116.67 (13) | C13—C14—C15 | 120.89 (17) |
C19—C11—C21 | 120.69 (14) | C13—C14—H14 | 119.6 |
O2—C2—N2 | 121.27 (16) | C15—C14—H14 | 119.6 |
O2—C2—C1 | 118.36 (13) | C16—C15—C14 | 119.97 (17) |
N2—C2—C1 | 120.37 (15) | C16—C15—H15 | 120.0 |
C18—C17—C16 | 122.89 (16) | C14—C15—H15 | 120.0 |
C18—C17—C12 | 117.84 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···Cl1i | 0.95 | 2.67 | 3.4989 (17) | 146 |
C13—H13···O2 | 0.95 | 2.36 | 3.230 (2) | 153 |
N2—H2N2···N3ii | 0.82 (2) | 2.53 (2) | 3.061 (2) | 123.8 (17) |
N2—H2N2···N4ii | 0.82 (2) | 2.57 (2) | 3.321 (3) | 151.3 (18) |
N2—H1N2···N4 | 0.82 (2) | 2.20 (2) | 2.987 (2) | 161 (2) |
C5—H1C5···O1ii | 0.97 (2) | 2.60 (2) | 3.541 (2) | 163.6 (18) |
C5—H3C5···Cl1iii | 0.98 (2) | 2.65 (3) | 3.615 (2) | 173.0 (19) |
C5—H2C5···Cl1iv | 0.99 (2) | 2.71 (3) | 3.688 (2) | 171.0 (19) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x−1, y, z. |