A Cu^II complex with an carbamoyl­cyano­nitro­somethanide ligand formed in situ by the nucleophilic addition of water to di­cyano­nitro­somethan­ide: structure, spectral and magnetic properties

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 Cu^II 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 Cu^II atom in a bidendate chelating manner, and a chloride ligand, resulting in a distorted tetra­gonal pyramidal coordination of Cu^II. 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 (g_x = 2.036, g_y = 2.120 and g_z = 2.205).

Computing details

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

Crystal data

[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) Å^3	Plate, dark green
Z = 4	0.31 × 0.11 × 0.03 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0332P)^2 + 1.4117P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···Cl1^i	0.95	2.67	3.4989 (17)	146
C13—H13···O2	0.95	2.36	3.230 (2)	153
N2—H2N2···N3^ii	0.82 (2)	2.53 (2)	3.061 (2)	123.8 (17)
N2—H2N2···N4^ii	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···O1^ii	0.97 (2)	2.60 (2)	3.541 (2)	163.6 (18)
C5—H3C5···Cl1^iii	0.98 (2)	2.65 (3)	3.615 (2)	173.0 (19)
C5—H2C5···Cl1^iv	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.