Chloridotetra-pyridine-copper(II) dicyanamidate pyridine disolvate.

In the crystal structure of the title compound, [CuCl(C(5)H(5)N)(4)][N(CN)(2)]·2C(6)H(5)N, the copper(II) cations are coordinated by one chloride anion and four N-bonded pyridine ligands into discrete complexes. The copper(II) cation shows a square-pyramidal coordination environment, with the chloride anion in the apical position. However, there is one additional chloride anion at 3.0065 (9) Å, leading to a disorted octa-hedral coordination mode for copper. The copper(II) cation, the chloride ligand and the central N atom of the dicyanamide anion are located on twofold rotation axes. Two pyridine solvent molecules are observed in general positions.

Related literature

For background to this work, see: Wriedt et al. (2009a ▶,b ▶). For structures of transition metal dicyanamides, see: Wriedt & Näther (2011 ▶) and for a related structure, see: Potočňák et al. (2006) ▶. For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[CuCl(C5H5N)4](C2N3)·2C6H5N

M = 639.64

Orthorhombic,

a = 15.2859 (6) Å

b = 17.6577 (9) Å

c = 11.4818 (9) Å

V = 3099.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.83 mm−1

T = 170 K

0.48 × 0.18 × 0.08 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) ▶ T min = 0.825, T max = 0.941

16623 measured reflections

3708 independent reflections

3220 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.093

S = 1.03

3708 reflections

198 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.56 e Å−3

Absolute structure: Flack (1983 ▶), 1771 Friedel pairs

Flack parameter: 0.00 (2)

Data collection: IPDS (Stoe & Cie, 1998) ▶; cell refinement: IPDS ▶; data reduction: IPDS ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CIFTAB in SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016187/im2272sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016187/im2272Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CuCl(C5H5N)4](C2N3)·2C6H5N	F(000) = 1324
Mr = 639.64	Dx = 1.371 Mg m−3
Orthorhombic, Iba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2 -2c	Cell parameters from 16623 reflections
a = 15.2859 (6) Å	θ = 2.7–28°
b = 17.6577 (9) Å	µ = 0.83 mm−1
c = 11.4818 (9) Å	T = 170 K
V = 3099.1 (3) Å3	Block, blue
Z = 4	0.48 × 0.18 × 0.08 mm

Stoe IPDS-1 diffractometer	3708 independent reflections
Radiation source: fine-focus sealed tube	3220 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ scans	θmax = 28.0°, θmin = 2.7°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	h = −20→20
Tmin = 0.825, Tmax = 0.941	k = −23→23
16623 measured reflections	l = −15→15

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0648P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.71 e Å−3
3708 reflections	Δρmin = −0.56 e Å−3
198 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0056 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1740 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (2)

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. 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.78178 (3)	0.01901 (12)
Cl1	0.5000	0.5000	1.01993 (7)	0.01916 (17)
N1	0.51436 (10)	0.38455 (9)	0.77683 (18)	0.0175 (3)
C2	0.49213 (17)	0.26597 (16)	0.6798 (2)	0.0291 (6)
H2	0.4664	0.2383	0.6177	0.035*
C3	0.54374 (17)	0.22991 (13)	0.7620 (2)	0.0310 (5)
H3	0.5538	0.1769	0.7570	0.037*
C4	0.58055 (16)	0.27172 (12)	0.8518 (2)	0.0288 (5)
H4	0.6160	0.2479	0.9091	0.035*
C5	0.56461 (14)	0.34873 (12)	0.8560 (2)	0.0222 (4)
H5	0.5900	0.3775	0.9172	0.027*
N11	0.63287 (11)	0.50796 (9)	0.77505 (18)	0.0169 (3)
C11	0.67644 (14)	0.54903 (11)	0.8549 (2)	0.0193 (4)
H11	0.6440	0.5768	0.9112	0.023*
C12	0.76675 (16)	0.55225 (14)	0.8580 (2)	0.0257 (5)
H12	0.7960	0.5824	0.9144	0.031*
C13	0.81395 (14)	0.51051 (14)	0.7770 (3)	0.0294 (5)
H13	0.8761	0.5114	0.7777	0.035*
C14	0.76982 (15)	0.46773 (14)	0.6956 (2)	0.0264 (5)
H14	0.8010	0.4386	0.6397	0.032*
C15	0.67906 (14)	0.46793 (13)	0.6968 (2)	0.0210 (4)
H15	0.6485	0.4388	0.6404	0.025*
C1	0.47896 (16)	0.34335 (13)	0.6904 (2)	0.0225 (4)
H1	0.4435	0.3683	0.6342	0.027*
N21	0.79940 (15)	0.79986 (11)	0.5241 (2)	0.0355 (5)
C21	0.7555 (2)	0.75937 (16)	0.6032 (2)	0.0369 (6)
H21	0.7249	0.7859	0.6625	0.044*
C22	0.7521 (2)	0.68134 (18)	0.6039 (3)	0.0413 (7)
H22	0.7193	0.6552	0.6615	0.050*
C23	0.79745 (19)	0.64167 (15)	0.5190 (3)	0.0444 (7)
H23	0.7970	0.5879	0.5178	0.053*
C24	0.8428 (2)	0.68182 (16)	0.4368 (3)	0.0401 (7)
H24	0.8741	0.6566	0.3767	0.048*
C25	0.8419 (2)	0.75980 (16)	0.4435 (3)	0.0378 (6)
H25	0.8740	0.7870	0.3864	0.045*
N30	0.93807 (17)	0.38709 (14)	0.5329 (4)	0.0628 (8)
C30	0.96901 (19)	0.44145 (16)	0.5161 (4)	0.0527 (9)
N31	1.0000	0.5000	0.4511 (5)	0.0835 (19)

	U11	U22	U33	U12	U13	U23
Cu1	0.01452 (16)	0.01243 (16)	0.0301 (2)	−0.00084 (13)	0.000	0.000
Cl1	0.0229 (3)	0.0194 (3)	0.0151 (4)	0.0001 (3)	0.000	0.000
N1	0.0189 (8)	0.0146 (7)	0.0188 (7)	−0.0016 (6)	0.0009 (7)	0.0003 (7)
C2	0.0405 (16)	0.0208 (12)	0.0259 (13)	−0.0078 (10)	0.0045 (9)	−0.0045 (7)
C3	0.0379 (13)	0.0177 (10)	0.0375 (15)	0.0035 (10)	0.0098 (10)	0.0000 (8)
C4	0.0334 (12)	0.0230 (11)	0.0299 (11)	0.0106 (10)	0.0009 (10)	0.0057 (9)
C5	0.0251 (11)	0.0206 (9)	0.0210 (9)	0.0034 (9)	−0.0008 (8)	0.0023 (8)
N11	0.0163 (6)	0.0175 (8)	0.0169 (8)	−0.0007 (6)	−0.0013 (7)	−0.0001 (6)
C11	0.0228 (10)	0.0172 (9)	0.0179 (9)	−0.0039 (8)	0.0000 (8)	−0.0005 (8)
C12	0.0233 (11)	0.0296 (11)	0.0241 (10)	−0.0074 (9)	−0.0035 (9)	0.0011 (9)
C13	0.0178 (8)	0.0386 (13)	0.0317 (11)	−0.0009 (9)	0.0028 (11)	0.0067 (10)
C14	0.0220 (12)	0.0289 (12)	0.0282 (11)	0.0027 (10)	0.0037 (9)	0.0021 (10)
C15	0.0214 (11)	0.0214 (10)	0.0201 (9)	0.0007 (9)	0.0021 (9)	−0.0017 (8)
C1	0.0274 (11)	0.0200 (10)	0.0202 (8)	−0.0050 (9)	−0.0013 (9)	−0.0002 (9)
N21	0.0417 (12)	0.0274 (9)	0.0375 (10)	0.0003 (9)	0.0084 (11)	0.0080 (9)
C21	0.0384 (15)	0.0408 (16)	0.0314 (12)	0.0044 (13)	0.0074 (9)	0.0092 (10)
C22	0.0395 (15)	0.0433 (16)	0.0412 (15)	−0.0056 (13)	0.0035 (11)	0.0181 (12)
C23	0.0511 (16)	0.0258 (11)	0.0562 (17)	−0.0071 (12)	−0.0008 (14)	0.0103 (12)
C24	0.0467 (19)	0.0304 (13)	0.0431 (14)	−0.0018 (13)	0.0081 (11)	0.0023 (11)
C25	0.0447 (17)	0.0327 (13)	0.0362 (12)	−0.0063 (12)	0.0129 (11)	0.0090 (11)
N30	0.0391 (13)	0.0320 (12)	0.117 (2)	0.0062 (11)	−0.0058 (16)	0.0096 (19)
C30	0.0252 (11)	0.0321 (15)	0.101 (3)	−0.0010 (12)	0.0075 (16)	−0.0040 (16)
N31	0.105 (5)	0.091 (4)	0.054 (3)	−0.054 (3)	0.000	0.000

Cu1—N11	2.0374 (16)	C13—C14	1.378 (4)
Cu1—N11i	2.0374 (16)	C13—H13	0.9500
Cu1—N1	2.0511 (16)	C14—C15	1.387 (3)
Cu1—N1i	2.0511 (16)	C14—H14	0.9500
Cu1—Cl1	2.7344 (9)	C15—H15	0.9500
N1—C1	1.345 (3)	C1—H1	0.9500
N1—C5	1.348 (3)	N21—C25	1.333 (4)
C2—C3	1.385 (4)	N21—C21	1.337 (3)
C2—C1	1.386 (4)	C21—C22	1.379 (4)
C2—H2	0.9500	C21—H21	0.9500
C3—C4	1.387 (3)	C22—C23	1.386 (5)
C3—H3	0.9500	C22—H22	0.9500
C4—C5	1.382 (3)	C23—C24	1.368 (4)
C4—H4	0.9500	C23—H23	0.9500
C5—H5	0.9500	C24—C25	1.379 (4)
N11—C15	1.344 (3)	C24—H24	0.9500
N11—C11	1.346 (3)	C25—H25	0.9500
C11—C12	1.382 (3)	N30—C30	1.087 (4)
C11—H11	0.9500	C30—N31	1.360 (4)
C12—C13	1.389 (4)	N31—C30ii	1.360 (4)
C12—H12	0.9500
N11—Cu1—N11i	175.66 (12)	C11—C12—H12	120.7
N11—Cu1—N1	87.76 (6)	C13—C12—H12	120.7
N11i—Cu1—N1	92.12 (6)	C14—C13—C12	119.39 (19)
N11—Cu1—N1i	92.12 (6)	C14—C13—H13	120.3
N11i—Cu1—N1i	87.76 (6)	C12—C13—H13	120.3
N1—Cu1—N1i	176.83 (12)	C13—C14—C15	118.8 (2)
N11—Cu1—Cl1	92.17 (6)	C13—C14—H14	120.6
N11i—Cu1—Cl1	92.17 (6)	C15—C14—H14	120.6
N1—Cu1—Cl1	91.59 (6)	N11—C15—C14	122.2 (2)
N1i—Cu1—Cl1	91.59 (6)	N11—C15—H15	118.9
C1—N1—C5	118.27 (18)	C14—C15—H15	118.9
C1—N1—Cu1	121.01 (15)	N1—C1—C2	122.6 (2)
C5—N1—Cu1	120.58 (15)	N1—C1—H1	118.7
C3—C2—C1	118.4 (2)	C2—C1—H1	118.7
C3—C2—H2	120.8	C25—N21—C21	115.6 (2)
C1—C2—H2	120.8	N21—C21—C22	123.9 (3)
C2—C3—C4	119.5 (2)	N21—C21—H21	118.1
C2—C3—H3	120.2	C22—C21—H21	118.1
C4—C3—H3	120.2	C21—C22—C23	118.8 (2)
C5—C4—C3	118.6 (2)	C21—C22—H22	120.6
C5—C4—H4	120.7	C23—C22—H22	120.6
C3—C4—H4	120.7	C24—C23—C22	118.4 (2)
N1—C5—C4	122.5 (2)	C24—C23—H23	120.8
N1—C5—H5	118.7	C22—C23—H23	120.8
C4—C5—H5	118.7	C23—C24—C25	118.3 (3)
C15—N11—C11	118.64 (17)	C23—C24—H24	120.9
C15—N11—Cu1	120.85 (14)	C25—C24—H24	120.9
C11—N11—Cu1	120.31 (15)	N21—C25—C24	125.0 (2)
N11—C11—C12	122.3 (2)	N21—C25—H25	117.5
N11—C11—H11	118.9	C24—C25—H25	117.5
C12—C11—H11	118.9	N30—C30—N31	156.9 (5)
C11—C12—C13	118.7 (2)	C30ii—N31—C30	113.5 (5)