Bromidobis(1,10-phenanthroline-κN,N')copper(II) dicyanamidate.

The title compound, [CuBr(C(12)H(8)N(2))(2)][N(CN)(2)], is formed of discrete [CuBr(phen)(2)](+) complex cations and uncoordinated [N(CN)(2)](-) anions (phen is 1,10-phenanthroline). The Cu atom is five-coordinated in a distorted trigonal-bipyramidal geometry by two phen mol-ecules and one bromide ligand, which coordinates in the equatorial plane at a distance of 2.5228 (4) Å and lying along with the Cu and the amide N atoms on a twofold rotation axis. The two axial Cu-N distances [1.9926 (15) Å] are slightly shorter than the two equatorial Cu-N bonds [2.0979 (15) Å]. The structure is stabilized by a weak C-H⋯N hydrogen bond, with a cyanide N atom of the dicyanamide ligand as an acceptor, and π-π inter-actions between nearly parallel phenyl and pyridine rings of two adjacent phen mol-ecules [centroid-centroid distance = 3.589 (1) Å], and between π electrons of the dicyanamide anion and the pyridine ring [N⋯Cg(pyridine) = 3.511 (3) Å; C-N⋯Cg(pyridine) = 80.2 (2)°].

Related literature

For structures containing [Cu(phen)2Br]+ cations, see: Murphy et al. (1998 ▶); Parker et al. (1994 ▶); Lu et al. (2004 ▶). For n class="Chemical">penta­coordinated Cu(II) in [Cu(L)2dca]Y complexes [L = 1,10- phenanthroline (phen) and 2,2′-bipyridine (bpy), Y is a monovalent anion], see: Potočňák et al. (2005 ▶, 2006 ▶, 2008a ▶,b ▶). For π–π inter­actions, see: Janiak (2000 ▶). For the τ parameter, see: Addison et al. (1984 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For reference bond lengths, see: Jolly (1991 ▶).

Experimental

Crystal data

[CuBr(C12H8N2)2]C2N3

M = 569.91

Monoclinic,

a = 15.2317 (4) Å

b = 10.8270 (3) Å

c = 14.7408 (5) Å

β = 114.030 (4)°

V = 2220.27 (11) Å3

Z = 4

Mo Kα radiation

μ = 2.82 mm−1

T = 293 K

0.68 × 0.17 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.328, T max = 0.819

11517 measured reflections

2182 independent reflections

1799 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.062

S = 1.06

2182 reflections

160 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.43 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data n class="Disease">reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037979/kp2274sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037979/kp2274Isup2.hkl

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

[CuBr(C12H8N2)2]C2N3	F(000) = 1140
Mr = 569.91	Dx = 1.705 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 7148 reflections
a = 15.2317 (4) Å	θ = 3.0–29.5°
b = 10.8270 (3) Å	µ = 2.82 mm−1
c = 14.7408 (5) Å	T = 293 K
β = 114.030 (4)°	Prism, green
V = 2220.27 (11) Å3	0.68 × 0.17 × 0.09 mm
Z = 4

Oxford Diffraction Xcalibur2 CCD diffractometer	2182 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1799 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 8.3438 pixels mm-1	θmax = 26.0°, θmin = 3.0°
Rotation method data acquisition using ω scans	h = −18→18
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007)	k = −13→13
Tmin = 0.328, Tmax = 0.819	l = −18→18
11517 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0401P)2] where P = (Fo2 + 2Fc2)/3
2182 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.72646 (3)	0.2500	0.03323 (11)
N10	0.62123 (11)	0.71984 (14)	0.22918 (11)	0.0327 (4)
N20	0.59053 (11)	0.64969 (13)	0.38697 (12)	0.0321 (4)
Br1	0.5000	0.95947 (2)	0.2500	0.03604 (10)
C11	0.69628 (13)	0.66725 (15)	0.30537 (13)	0.0308 (4)
C12	0.63710 (15)	0.76473 (19)	0.15301 (15)	0.0396 (5)
H12	0.5869	0.8039	0.1017	0.047*
C13	0.72584 (16)	0.75547 (19)	0.14697 (16)	0.0434 (5)
H13	0.7342	0.7877	0.0925	0.052*
C14	0.80010 (15)	0.6989 (2)	0.22157 (16)	0.0415 (5)
H14	0.8590	0.6898	0.2173	0.050*
C15	0.78767 (14)	0.65401 (16)	0.30513 (15)	0.0348 (4)
C16	0.86264 (14)	0.6003 (2)	0.38968 (15)	0.0445 (5)
H16	0.9231	0.5888	0.3894	0.053*
C21	0.67959 (13)	0.63020 (16)	0.39026 (14)	0.0295 (4)
C22	0.57510 (15)	0.62008 (19)	0.46690 (15)	0.0380 (5)
H22	0.5139	0.6310	0.4651	0.046*
C23	0.64771 (16)	0.57311 (19)	0.55360 (15)	0.0443 (5)
H23	0.6347	0.5552	0.6086	0.053*
C24	0.73686 (16)	0.55385 (18)	0.55692 (15)	0.0428 (5)
H24	0.7853	0.5224	0.6142	0.051*
C25	0.75581 (14)	0.58155 (17)	0.47343 (14)	0.0356 (4)
C26	0.84725 (16)	0.56610 (19)	0.46978 (16)	0.0455 (5)
H26	0.8974	0.5316	0.5240	0.055*
N1	0.5000	0.4095 (4)	0.2500	0.0987 (14)
C2	0.5311 (2)	0.3506 (2)	0.3332 (2)	0.0560 (6)
N2	0.56044 (18)	0.3068 (3)	0.41052 (18)	0.0749 (7)

	U11	U22	U33	U12	U13	U23
Cu1	0.02710 (19)	0.0454 (2)	0.03011 (19)	0.000	0.01467 (14)	0.000
N10	0.0319 (9)	0.0372 (9)	0.0308 (9)	0.0010 (7)	0.0146 (7)	0.0012 (7)
N20	0.0348 (9)	0.0320 (8)	0.0295 (9)	−0.0022 (7)	0.0131 (7)	−0.0029 (6)
Br1	0.03279 (16)	0.03849 (17)	0.03668 (17)	0.000	0.01399 (12)	0.000
C11	0.0322 (10)	0.0290 (10)	0.0307 (10)	−0.0017 (8)	0.0122 (8)	−0.0071 (8)
C12	0.0405 (12)	0.0453 (12)	0.0371 (11)	0.0029 (9)	0.0200 (9)	0.0040 (9)
C13	0.0479 (13)	0.0485 (12)	0.0450 (12)	−0.0028 (10)	0.0303 (11)	−0.0002 (10)
C14	0.0358 (11)	0.0456 (11)	0.0522 (13)	−0.0021 (10)	0.0271 (10)	−0.0103 (10)
C15	0.0323 (10)	0.0347 (10)	0.0397 (11)	−0.0015 (8)	0.0169 (8)	−0.0103 (8)
C16	0.0288 (11)	0.0509 (12)	0.0500 (14)	0.0032 (10)	0.0121 (10)	−0.0099 (11)
C21	0.0320 (10)	0.0265 (9)	0.0290 (10)	−0.0029 (7)	0.0114 (8)	−0.0056 (7)
C22	0.0418 (12)	0.0423 (11)	0.0338 (11)	−0.0044 (9)	0.0194 (9)	−0.0004 (9)
C23	0.0558 (14)	0.0457 (13)	0.0304 (11)	−0.0075 (10)	0.0164 (10)	0.0021 (9)
C24	0.0463 (13)	0.0424 (12)	0.0299 (11)	−0.0039 (9)	0.0055 (10)	0.0018 (9)
C25	0.0368 (11)	0.0319 (10)	0.0318 (10)	−0.0020 (9)	0.0075 (9)	−0.0059 (9)
C26	0.0346 (11)	0.0499 (13)	0.0413 (12)	0.0059 (9)	0.0048 (10)	−0.0021 (10)
N1	0.139 (4)	0.065 (2)	0.055 (2)	0.000	0.001 (2)	0.000
C2	0.0556 (15)	0.0599 (15)	0.0556 (16)	−0.0062 (12)	0.0257 (13)	−0.0226 (14)
N2	0.0795 (17)	0.1034 (18)	0.0465 (14)	−0.0076 (15)	0.0304 (12)	−0.0144 (13)

Cu1—N10i	1.9926 (15)	C14—H14	0.9300
Cu1—N10	1.9926 (15)	C15—C16	1.427 (3)
Cu1—N20i	2.0979 (15)	C16—C26	1.346 (3)
Cu1—N20	2.0979 (15)	C16—H16	0.9300
Cu1—Br1	2.5228 (4)	C21—C25	1.403 (3)
N10—C12	1.333 (3)	C22—C23	1.401 (3)
N10—C11	1.359 (2)	C22—H22	0.9300
N20—C22	1.331 (2)	C23—C24	1.355 (3)
N20—C21	1.354 (2)	C23—H23	0.9300
C11—C15	1.401 (3)	C24—C25	1.406 (3)
C11—C21	1.432 (3)	C24—H24	0.9300
C12—C13	1.394 (3)	C25—C26	1.425 (3)
C12—H12	0.9300	C26—H26	0.9300
C13—C14	1.361 (3)	N1—C2	1.288 (4)
C13—H13	0.9300	N1—C2i	1.288 (4)
C14—C15	1.407 (3)	C2—N2	1.145 (3)
N10i—Cu1—N10	175.88 (9)	C15—C14—H14	120.0
N10i—Cu1—N20i	81.19 (6)	C11—C15—C14	117.07 (18)
N10—Cu1—N20i	97.16 (6)	C11—C15—C16	118.83 (19)
N10i—Cu1—N20	97.16 (6)	C14—C15—C16	124.07 (19)
N10—Cu1—N20	81.19 (6)	C26—C16—C15	121.0 (2)
N20i—Cu1—N20	133.32 (8)	C26—C16—H16	119.5
N10i—Cu1—Br1	92.06 (4)	C15—C16—H16	119.5
N10—Cu1—Br1	92.06 (4)	N20—C21—C25	123.38 (18)
N20i—Cu1—Br1	113.34 (4)	N20—C21—C11	117.18 (16)
N20—Cu1—Br1	113.34 (4)	C25—C21—C11	119.38 (18)
C12—N10—C11	117.96 (17)	N20—C22—C23	122.4 (2)
C12—N10—Cu1	127.88 (14)	N20—C22—H22	118.8
C11—N10—Cu1	114.09 (12)	C23—C22—H22	118.8
C22—N20—C21	117.78 (17)	C24—C23—C22	119.7 (2)
C22—N20—Cu1	131.57 (14)	C24—C23—H23	120.1
C21—N20—Cu1	110.64 (12)	C22—C23—H23	120.1
N10—C11—C15	122.90 (18)	C23—C24—C25	119.70 (19)
N10—C11—C21	116.79 (16)	C23—C24—H24	120.1
C15—C11—C21	120.25 (17)	C25—C24—H24	120.1
N10—C12—C13	122.74 (19)	C21—C25—C24	116.94 (19)
N10—C12—H12	118.6	C21—C25—C26	118.98 (19)
C13—C12—H12	118.6	C24—C25—C26	124.06 (19)
C14—C13—C12	119.3 (2)	C16—C26—C25	121.52 (19)
C14—C13—H13	120.3	C16—C26—H26	119.2
C12—C13—H13	120.3	C25—C26—H26	119.2
C13—C14—C15	119.94 (19)	C2—N1—C2i	120.7 (4)
C13—C14—H14	120.0	N2—C2—N1	174.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···N2ii	0.93	2.60	3.346 (3)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯N2i	0.93	2.60	3.346 (3)	137

Symmetry code: (i) .