Acetonitrilebis(2,9-dimethylphenanthroline)copper(II) bis(tetrafluoridoborate) acetonitrile disolvate

Watton, S.P.

doi:10.1107/S1600536809012331

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m585-m586

doi:10.1107/S1600536809012331

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Acetonitrilebis(2,9-dimethylphenanthroline)copper(II) bis(tetrafluoridoborate) acetonitrile disolvate

Stephen P. Watton ^a ^*

^aDepartment of Chemistry, Central Connecticut State University, 1615 Stanley Street, New Britain, CT 06050, USA
^*Correspondence e-mail: wattonstp@ccsu.edu

(Received 10 March 2009; accepted 1 April 2009; online 30 April 2009)

In the title compound, [Cu(CH₃CN)(C₁₄H₁₂N₂)₂](BF₄)₂·2CH₃CN, the Cu^II atom shows a distorted CuN₅ square-pyramidal geometry with the acetonitrile N atom in an equatorial site, which differs substantially from the distorted trigonal-bipyramidal arrangement usually observed for five-coordinate complexes of Cu^II with two phenanthroline-type ligands and one other ligand. The B atom of one of the BF₄⁻ anions is disordered over two sites in a 0.825 (2):0.175 (2) ratio. In the crystal, C—H⋯F hydrogen bonds help to establish the packing.

Related literature

For related structures, see: Bush et al. (2001 ); Vega et al. (1985 ); Aligo et al. (2005 ). For background, see: Kepert (1973 ); Rossi & Hoffman (1975 ); James & Williams (1961 ).

Experimental

Crystal data

[Cu(C₂H₃N)(C₁₄H₁₂N₂)₂](BF₄)₂·2C₂H₃N
M_r = 776.83
Triclinic, $[P \overline 1]$
a = 11.2865 (19) Å
b = 12.070 (2) Å
c = 13.802 (2) Å
α = 72.843 (15)°
β = 83.746 (15)°
γ = 73.933 (15)°
V = 1725.7 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Sapphire diffractometer
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD, CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ). T_min = 0.997, T_max = 1.000 (expected range = 0.864–0.867)
10543 measured reflections
8129 independent reflections
4935 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 0.89
8129 reflections
489 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N5	2.0123 (18)
Cu1—N2	2.0297 (17)
Cu1—N3	2.0305 (18)
Cu1—N4	2.0348 (17)
Cu1—N1	2.1760 (18)
N3—C25	1.351 (3)
N3—C28	1.359 (3)
N4—C16	1.333 (2)
N4—C27	1.365 (3)

N5—Cu1—N2	84.42 (7)
N5—Cu1—N3	89.07 (7)
N2—Cu1—N3	165.23 (7)
N5—Cu1—N4	150.90 (7)
N2—Cu1—N4	98.14 (7)
N3—Cu1—N4	81.25 (7)
N5—Cu1—N1	100.93 (7)
N2—Cu1—N1	80.17 (7)
N3—Cu1—N1	114.15 (7)
N4—Cu1—N1	108.09 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12C⋯F8ⁱ	0.96	2.36	3.120 (3)	135
C18—H18⋯F5ⁱⁱ	0.93	2.36	3.279 (3)	171
C20—H20⋯F8ⁱⁱ	0.93	2.53	3.423 (3)	161
C30—H30A⋯F8	0.96	2.47	3.375 (4)	158
C30—H30B⋯F6ⁱⁱⁱ	0.96	2.38	3.314 (3)	165
C32—H32B⋯F7^iv	0.96	2.37	3.191 (3)	143
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z+1; (iii) -x, -y, -z+1; (iv) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD, CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD, CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012331/hb2926sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012331/hb2926Isup2.hkl

checkCIF report

Comment top

The copper-containing cation (Fig. 1) of the title compound, (I), consists of a 5-coordinate Cu center, with the geometry about copper being best described (Kepert, 1973) as distorted square pyramidal, rather than as a distorted TBP structure, which is most commonly observed for five-coordinate copper bis-phenanthroline complexes (Bush, et al., 2001). Most of the distortion from idealized square pyramidal can be explained in terms of the restricted bite angles of the rigid phenanthroline rings. It is assumed that steric strain associated with the presence of the 2,9-dimethyl groups on the ligand overrides electronic considerations (Rossi and Hoffman, 1975), resulting in formation of the disfavored square pyramidal geometry for the d⁹ complex. The steric strain inherent in the structure is also reflected in the copper being located considerably outside of the normal coordination plane of the phenanthroline [0.470 (1) and 0.636 (1)Å from the least squares planes of the two rings], and in a clear bowing of the phenanthroline ligand itself.

The observation of an electronically high-energy structure is fully consistent with electrochemical data (James and Williams, 1961) which show the 2,9-disubstituted phenanthroline complex to be significantly easier to reduce than the analogous complexes lacking the 2,9- substituents. Reduction of the [Cu(neocuproine)₂(solv)]²⁺ complexes affords the air-stable [Cu(neocuproine)₂]⁺ species, which adopt pseudo-tetrahedral geometries that alleviate the steric strain between the substituents.

In the structure of (I), close contact of the disordered BF₄^- and the coordinated CH₃CN suggest that a C—H hydrogen bonding interaction exists (see, for example: Vega, et al., 1985). Similar interactions between BF₄^- ions and Cu-bound acetonitrile ligands have been observed previously (Aligo, et al., 2005). The packing of (I) is shown in Fig. 2 and the H bonds are listed in Table 2.

Related literature top

For related structures, see: Bush et al. (2001); Vega et al. (1985); Aligo et al. (2005). For background, see: Kepert (1973); Rossi & Hoffman (1975); James & Williams (1961);

Experimental top

Copper (II) tetrafluoroborate hydrate (0.100 g, 0.42 mmol) was dissolved in 5 ml of acetonitrile and 2,9-dimethylphenanthroline (0.190 g, 0.92 mmol) was added as a solution in 5 ml of acetonitrile. Vapor diffusion of ether into the solution afforded green blocks of (I). Yield 0.182 g (56%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction ,2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXLTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the cation in (I) with H atoms omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The packing for (I): H atoms are omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.

Acetonitrilebis(2,9-dimethylphenanthroline)copper(II) bis(tetrafluoroborate) acetonitrile disolvate top

Crystal data top

[Cu(C₂H₃N)(C₁₄H₁₂N₂)₂](BF₄)₂·2C₂H₃N	Z = 2
M_r = 776.83	F(000) = 794
Triclinic, P1	D_x = 1.495 Mg m⁻³
Hall symbol: -P 1	Melting point > 523 K
a = 11.2865 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.070 (2) Å	Cell parameters from 4074 reflections
c = 13.802 (2) Å	θ = 3.9–32.1°
α = 72.843 (15)°	µ = 0.71 mm⁻¹
β = 83.746 (15)°	T = 293 K
γ = 73.933 (15)°	Block, green
V = 1725.7 (5) Å³	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Sapphire diffractometer	8129 independent reflections
Radiation source: fine-focus sealed tube	4935 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 32.2°, θ_min = 3.9°
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis RED; Oxford Diffraction, 2006).	h = −16→13
T_min = 0.997, T_max = 1.000	k = −17→17
10543 measured reflections	l = −20→18

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0558P)²] where P = (F_o² + 2F_c²)/3
8129 reflections	(Δ/σ)_max = 0.009
489 parameters	Δρ_max = 0.54 e Å⁻³
30 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Cu(C₂H₃N)(C₁₄H₁₂N₂)₂](BF₄)₂·2C₂H₃N	γ = 73.933 (15)°
M_r = 776.83	V = 1725.7 (5) Å³
Triclinic, P1	Z = 2
a = 11.2865 (19) Å	Mo Kα radiation
b = 12.070 (2) Å	µ = 0.71 mm⁻¹
c = 13.802 (2) Å	T = 293 K
α = 72.843 (15)°	0.3 × 0.2 × 0.2 mm
β = 83.746 (15)°

Data collection top

Oxford Diffraction Sapphire diffractometer	8129 independent reflections
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlis RED; Oxford Diffraction, 2006).	4935 reflections with I > 2σ(I)
T_min = 0.997, T_max = 1.000	R_int = 0.025
10543 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	30 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 0.89	Δρ_max = 0.54 e Å⁻³
8129 reflections	Δρ_min = −0.35 e Å⁻³
489 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.22719 (2)	0.09638 (2)	0.73647 (2)	0.02082 (9)
N1	0.27230 (16)	0.23116 (14)	0.60440 (13)	0.0205 (4)
N2	0.05462 (16)	0.19388 (14)	0.69210 (13)	0.0193 (4)
C1	−0.0467 (2)	0.0955 (2)	0.84546 (18)	0.0323 (6)
H1A	−0.0745	0.0276	0.8442	0.048*
H1B	−0.0993	0.1359	0.8909	0.048*
H1C	0.0365	0.0687	0.8683	0.048*
C2	−0.0512 (2)	0.17993 (18)	0.74111 (18)	0.0257 (5)
C3	−0.1658 (2)	0.24420 (19)	0.69496 (19)	0.0289 (5)
H3	−0.2392	0.2375	0.7311	0.035*
C4	−0.1685 (2)	0.31611 (18)	0.59724 (18)	0.0284 (5)
H4	−0.2437	0.3563	0.5665	0.034*
C5	−0.0576 (2)	0.32924 (17)	0.54323 (17)	0.0230 (5)
C6	−0.0512 (2)	0.40115 (17)	0.44062 (17)	0.0275 (5)
H6	−0.1233	0.4388	0.4046	0.033*
C7	0.0580 (2)	0.41503 (18)	0.39547 (18)	0.0273 (5)
H7	0.0600	0.4603	0.3282	0.033*
C8	0.1698 (2)	0.36192 (17)	0.44850 (16)	0.0227 (5)
C9	0.2844 (2)	0.38422 (17)	0.40945 (17)	0.0273 (5)
H9	0.2910	0.4319	0.3435	0.033*
C10	0.3853 (2)	0.33573 (18)	0.46848 (17)	0.0268 (5)
H10	0.4598	0.3539	0.4439	0.032*
C11	0.3777 (2)	0.25780 (17)	0.56708 (17)	0.0227 (5)
C12	0.4879 (2)	0.2062 (2)	0.63242 (19)	0.0320 (6)
H12A	0.4655	0.1590	0.6974	0.048*
H12B	0.5170	0.2701	0.6412	0.048*
H12C	0.5518	0.1564	0.6007	0.048*
C13	0.05311 (19)	0.26752 (16)	0.59555 (16)	0.0203 (5)
C14	0.16866 (19)	0.28576 (16)	0.54751 (16)	0.0197 (5)
N3	0.37614 (16)	−0.03179 (14)	0.80310 (14)	0.0224 (4)
N4	0.23061 (15)	0.15164 (14)	0.86165 (13)	0.0193 (4)
C15	0.1143 (2)	0.36074 (17)	0.80198 (17)	0.0273 (5)
H15A	0.1568	0.3556	0.7387	0.041*
H15B	0.1200	0.4320	0.8166	0.041*
H15C	0.0292	0.3637	0.7975	0.041*
C16	0.17194 (19)	0.25310 (17)	0.88480 (16)	0.0209 (5)
C17	0.1641 (2)	0.25959 (19)	0.98550 (17)	0.0263 (5)
H17	0.1211	0.3307	1.0002	0.032*
C18	0.2184 (2)	0.1634 (2)	1.06205 (18)	0.0280 (5)
H18	0.2099	0.1675	1.1288	0.034*
C19	0.2881 (2)	0.05700 (18)	1.03802 (17)	0.0237 (5)
C20	0.3561 (2)	−0.04595 (19)	1.11054 (18)	0.0287 (5)
H20	0.3505	−0.0479	1.1787	0.034*
C21	0.4291 (2)	−0.14124 (19)	1.08054 (18)	0.0309 (6)
H21	0.4723	−0.2079	1.1287	0.037*
C22	0.4403 (2)	−0.14037 (18)	0.97633 (18)	0.0266 (5)
C23	0.5219 (2)	−0.23138 (19)	0.9381 (2)	0.0327 (6)
H23	0.5680	−0.3003	0.9823	0.039*
C24	0.5322 (2)	−0.21712 (18)	0.8365 (2)	0.0329 (6)
H24	0.5889	−0.2751	0.8116	0.039*
C25	0.4591 (2)	−0.11654 (18)	0.76774 (18)	0.0284 (5)
C26	0.4755 (2)	−0.1021 (2)	0.65667 (19)	0.0356 (6)
H26A	0.4279	−0.0242	0.6207	0.053*
H26B	0.4482	−0.1628	0.6403	0.053*
H26C	0.5611	−0.1099	0.6373	0.053*
C27	0.29190 (19)	0.05730 (17)	0.93622 (16)	0.0200 (5)
C28	0.37000 (19)	−0.04304 (16)	0.90432 (17)	0.0211 (5)
N5	0.19544 (17)	−0.02025 (15)	0.67040 (14)	0.0272 (4)
C29	0.1858 (2)	−0.08244 (18)	0.62641 (18)	0.0280 (5)
C30	0.1774 (2)	−0.1635 (2)	0.5691 (2)	0.0381 (6)
H30A	0.2111	−0.1384	0.5018	0.057*
H30B	0.0925	−0.1621	0.5656	0.057*
H30C	0.2230	−0.2435	0.6022	0.057*
N6	0.1570 (2)	0.8133 (2)	0.92492 (19)	0.0532 (6)
C31	0.1324 (2)	0.7532 (2)	0.8848 (2)	0.0393 (6)
C32	0.1015 (3)	0.6748 (2)	0.8345 (2)	0.0493 (7)
H32A	0.1717	0.6443	0.7951	0.074*
H32B	0.0336	0.7193	0.7907	0.074*
H32C	0.0788	0.6091	0.8845	0.074*
N7	0.1493 (2)	0.4854 (2)	0.0983 (2)	0.0571 (7)
C33	0.2350 (3)	0.5198 (2)	0.0862 (2)	0.0405 (6)
C34	0.3440 (3)	0.5640 (3)	0.0680 (3)	0.0680 (10)
H34A	0.3701	0.5745	−0.0019	0.102*
H34B	0.4085	0.5073	0.1103	0.102*
H34C	0.3258	0.6395	0.0835	0.102*
B1	0.5835 (3)	0.5036 (2)	0.2591 (2)	0.0350 (7)
F1	0.66138 (15)	0.48303 (17)	0.33530 (13)	0.0687 (5)
F2	0.46588 (13)	0.56703 (13)	0.28167 (12)	0.0502 (4)
F3	0.57688 (17)	0.39330 (14)	0.25247 (15)	0.0712 (5)
F4	0.62598 (14)	0.56564 (15)	0.16773 (13)	0.0653 (5)
B2	0.1702 (4)	0.0967 (3)	0.3432 (3)	0.0336 (9)	0.825 (2)
F5	0.20526 (15)	0.19999 (12)	0.28948 (11)	0.0480 (4)	0.825 (2)
F6	0.1266 (2)	0.10525 (16)	0.43944 (14)	0.0446 (5)	0.825 (2)
F7	0.07552 (17)	0.08275 (18)	0.29426 (15)	0.0543 (6)	0.825 (2)
F8	0.2690 (2)	−0.00073 (18)	0.34420 (18)	0.0602 (6)	0.825 (2)
B2B	0.2011 (15)	0.0932 (13)	0.3623 (11)	0.0336 (9)	0.175 (2)
F5B	0.20526 (15)	0.19999 (12)	0.28948 (11)	0.0480 (4)	0.175 (2)
F6B	0.2824 (8)	0.0556 (7)	0.4379 (6)	0.0446 (5)	0.175 (2)
F7B	0.0796 (9)	0.1141 (10)	0.4016 (9)	0.0543 (6)	0.175 (2)
F8B	0.2038 (10)	0.0053 (9)	0.3170 (9)	0.0602 (6)	0.175 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02490 (16)	0.01560 (12)	0.02076 (17)	−0.00460 (10)	0.00029 (11)	−0.00420 (9)
N1	0.0239 (10)	0.0171 (8)	0.0204 (10)	−0.0049 (7)	0.0026 (8)	−0.0064 (7)
N2	0.0234 (10)	0.0165 (8)	0.0197 (10)	−0.0072 (7)	0.0024 (8)	−0.0068 (7)
C1	0.0300 (13)	0.0371 (13)	0.0304 (15)	−0.0168 (11)	0.0073 (12)	−0.0053 (10)
C2	0.0280 (13)	0.0222 (10)	0.0316 (14)	−0.0113 (9)	0.0017 (11)	−0.0109 (9)
C3	0.0214 (12)	0.0273 (11)	0.0413 (16)	−0.0100 (9)	0.0011 (11)	−0.0117 (10)
C4	0.0257 (13)	0.0201 (10)	0.0420 (16)	−0.0031 (9)	−0.0104 (11)	−0.0115 (10)
C5	0.0245 (12)	0.0193 (10)	0.0284 (14)	−0.0062 (9)	−0.0035 (10)	−0.0097 (8)
C6	0.0356 (14)	0.0180 (10)	0.0285 (14)	−0.0017 (9)	−0.0153 (11)	−0.0055 (9)
C7	0.0388 (15)	0.0200 (10)	0.0215 (13)	−0.0054 (10)	−0.0049 (11)	−0.0037 (8)
C8	0.0319 (13)	0.0158 (9)	0.0193 (12)	−0.0032 (9)	0.0008 (10)	−0.0067 (8)
C9	0.0395 (14)	0.0189 (10)	0.0197 (13)	−0.0063 (10)	0.0072 (11)	−0.0039 (8)
C10	0.0290 (13)	0.0224 (10)	0.0267 (14)	−0.0088 (9)	0.0092 (11)	−0.0051 (9)
C11	0.0238 (12)	0.0176 (10)	0.0244 (13)	−0.0026 (9)	0.0056 (10)	−0.0070 (8)
C12	0.0243 (13)	0.0325 (12)	0.0345 (15)	−0.0076 (10)	0.0019 (11)	−0.0030 (10)
C13	0.0252 (12)	0.0140 (9)	0.0229 (13)	−0.0050 (8)	0.0007 (10)	−0.0077 (8)
C14	0.0249 (12)	0.0128 (9)	0.0219 (13)	−0.0038 (8)	−0.0002 (10)	−0.0068 (8)
N3	0.0248 (10)	0.0158 (8)	0.0253 (12)	−0.0048 (7)	0.0023 (9)	−0.0052 (7)
N4	0.0187 (9)	0.0168 (8)	0.0216 (11)	−0.0059 (7)	0.0009 (8)	−0.0035 (7)
C15	0.0319 (13)	0.0185 (10)	0.0298 (14)	−0.0018 (9)	−0.0015 (11)	−0.0084 (9)
C16	0.0197 (11)	0.0217 (10)	0.0223 (13)	−0.0074 (8)	0.0030 (10)	−0.0070 (8)
C17	0.0279 (13)	0.0281 (11)	0.0268 (14)	−0.0101 (10)	0.0042 (11)	−0.0127 (9)
C18	0.0308 (13)	0.0395 (13)	0.0195 (14)	−0.0191 (11)	0.0062 (11)	−0.0099 (10)
C19	0.0239 (12)	0.0296 (11)	0.0195 (13)	−0.0161 (9)	0.0013 (10)	−0.0017 (9)
C20	0.0298 (13)	0.0368 (13)	0.0192 (14)	−0.0186 (10)	−0.0047 (11)	0.0036 (9)
C21	0.0290 (13)	0.0283 (12)	0.0311 (16)	−0.0162 (10)	−0.0108 (11)	0.0099 (9)
C22	0.0215 (12)	0.0192 (10)	0.0366 (15)	−0.0101 (9)	−0.0061 (11)	0.0022 (9)
C23	0.0290 (13)	0.0185 (10)	0.0454 (18)	−0.0078 (9)	−0.0078 (12)	0.0028 (10)
C24	0.0242 (13)	0.0177 (10)	0.0544 (19)	−0.0018 (9)	−0.0023 (12)	−0.0092 (10)
C25	0.0262 (13)	0.0215 (10)	0.0361 (16)	−0.0056 (9)	0.0032 (11)	−0.0079 (9)
C26	0.0347 (14)	0.0294 (12)	0.0431 (17)	−0.0020 (11)	0.0056 (13)	−0.0186 (11)
C27	0.0211 (11)	0.0188 (9)	0.0205 (13)	−0.0105 (8)	−0.0007 (10)	−0.0011 (8)
C28	0.0219 (11)	0.0164 (9)	0.0241 (14)	−0.0105 (8)	−0.0005 (10)	0.0010 (8)
N5	0.0371 (11)	0.0189 (9)	0.0232 (11)	−0.0034 (8)	0.0008 (9)	−0.0063 (7)
C29	0.0303 (13)	0.0233 (11)	0.0271 (15)	−0.0045 (9)	−0.0017 (11)	−0.0041 (9)
C30	0.0491 (16)	0.0300 (12)	0.0393 (17)	−0.0109 (11)	−0.0029 (13)	−0.0146 (11)
N6	0.0573 (16)	0.0383 (13)	0.0632 (18)	−0.0169 (12)	0.0008 (13)	−0.0097 (12)
C31	0.0380 (15)	0.0279 (12)	0.0457 (18)	−0.0086 (11)	0.0070 (13)	−0.0037 (11)
C32	0.0546 (19)	0.0414 (15)	0.055 (2)	−0.0162 (14)	0.0111 (16)	−0.0195 (13)
N7	0.0549 (16)	0.0420 (13)	0.078 (2)	−0.0183 (13)	0.0175 (14)	−0.0231 (13)
C33	0.0471 (17)	0.0280 (12)	0.0450 (18)	−0.0105 (12)	0.0058 (14)	−0.0099 (11)
C34	0.053 (2)	0.0423 (16)	0.101 (3)	−0.0180 (15)	−0.0185 (19)	0.0030 (17)
B1	0.0279 (16)	0.0293 (14)	0.043 (2)	−0.0088 (12)	0.0002 (14)	−0.0022 (12)
F1	0.0476 (10)	0.0914 (14)	0.0596 (12)	−0.0102 (10)	−0.0204 (9)	−0.0101 (10)
F2	0.0346 (9)	0.0468 (9)	0.0636 (12)	−0.0047 (7)	0.0037 (8)	−0.0139 (8)
F3	0.0778 (13)	0.0413 (9)	0.0996 (16)	−0.0214 (9)	0.0141 (11)	−0.0272 (9)
F4	0.0410 (10)	0.0648 (11)	0.0601 (12)	−0.0121 (8)	0.0031 (9)	0.0246 (9)
B2	0.042 (3)	0.0327 (15)	0.026 (2)	−0.0028 (16)	0.0009 (17)	−0.0152 (14)
F5	0.0704 (11)	0.0442 (9)	0.0360 (10)	−0.0262 (8)	0.0093 (8)	−0.0143 (7)
F6	0.0712 (14)	0.0388 (9)	0.0236 (11)	−0.0134 (9)	0.0036 (10)	−0.0110 (8)
F7	0.0470 (12)	0.0763 (14)	0.0504 (14)	−0.0257 (10)	−0.0004 (10)	−0.0249 (10)
F8	0.0393 (13)	0.0447 (10)	0.0828 (17)	0.0122 (11)	0.0014 (12)	−0.0196 (10)
B2B	0.042 (3)	0.0327 (15)	0.026 (2)	−0.0028 (16)	0.0009 (17)	−0.0152 (14)
F5B	0.0704 (11)	0.0442 (9)	0.0360 (10)	−0.0262 (8)	0.0093 (8)	−0.0143 (7)
F6B	0.0712 (14)	0.0388 (9)	0.0236 (11)	−0.0134 (9)	0.0036 (10)	−0.0110 (8)
F7B	0.0470 (12)	0.0763 (14)	0.0504 (14)	−0.0257 (10)	−0.0004 (10)	−0.0249 (10)
F8B	0.0393 (13)	0.0447 (10)	0.0828 (17)	0.0122 (11)	0.0014 (12)	−0.0196 (10)

Geometric parameters (Å, º) top

Cu1—N5	2.0123 (18)	C18—C19	1.419 (3)
Cu1—N2	2.0297 (17)	C18—H18	0.9300
Cu1—N3	2.0305 (18)	C19—C27	1.400 (3)
Cu1—N4	2.0348 (17)	C19—C20	1.429 (3)
Cu1—N1	2.1760 (18)	C20—C21	1.362 (3)
N1—C11	1.328 (3)	C20—H20	0.9300
N1—C14	1.374 (3)	C21—C22	1.427 (3)
N2—C2	1.334 (3)	C21—H21	0.9300
N2—C13	1.365 (3)	C22—C28	1.402 (3)
C1—C2	1.496 (3)	C22—C23	1.417 (3)
C1—H1A	0.9600	C23—C24	1.357 (3)
C1—H1B	0.9600	C23—H23	0.9300
C1—H1C	0.9600	C24—C25	1.411 (3)
C2—C3	1.419 (3)	C24—H24	0.9300
C3—C4	1.370 (3)	C25—C26	1.488 (3)
C3—H3	0.9300	C26—H26A	0.9600
C4—C5	1.408 (3)	C26—H26B	0.9600
C4—H4	0.9300	C26—H26C	0.9600
C5—C13	1.415 (3)	C27—C28	1.441 (3)
C5—C6	1.432 (3)	N5—C29	1.128 (3)
C6—C7	1.350 (3)	C29—C30	1.455 (3)
C6—H6	0.9300	C30—H30A	0.9600
C7—C8	1.420 (3)	C30—H30B	0.9600
C7—H7	0.9300	C30—H30C	0.9600
C8—C14	1.405 (3)	N6—C31	1.137 (3)
C8—C9	1.411 (3)	C31—C32	1.458 (4)
C9—C10	1.362 (3)	C32—H32A	0.9600
C9—H9	0.9300	C32—H32B	0.9600
C10—C11	1.417 (3)	C32—H32C	0.9600
C10—H10	0.9300	N7—C33	1.132 (3)
C11—C12	1.494 (3)	C33—C34	1.441 (4)
C12—H12A	0.9600	C34—H34A	0.9600
C12—H12B	0.9600	C34—H34B	0.9600
C12—H12C	0.9600	C34—H34C	0.9600
C13—C14	1.440 (3)	B1—F1	1.367 (3)
N3—C25	1.351 (3)	B1—F4	1.375 (3)
N3—C28	1.359 (3)	B1—F3	1.383 (3)
N4—C16	1.333 (2)	B1—F2	1.390 (3)
N4—C27	1.365 (3)	B2—F8	1.376 (4)
C15—C16	1.495 (3)	B2—F6	1.388 (4)
C15—H15A	0.9600	B2—F5	1.387 (4)
C15—H15B	0.9600	B2—F7	1.397 (4)
C15—H15C	0.9600	B2B—F6B	1.355 (14)
C16—C17	1.407 (3)	B2B—F8B	1.372 (14)
C17—C18	1.365 (3)	B2B—F7B	1.402 (15)
C17—H17	0.9300

N5—Cu1—N2	84.42 (7)	C17—C16—C15	120.15 (18)
N5—Cu1—N3	89.07 (7)	C18—C17—C16	121.2 (2)
N2—Cu1—N3	165.23 (7)	C18—C17—H17	119.4
N5—Cu1—N4	150.90 (7)	C16—C17—H17	119.4
N2—Cu1—N4	98.14 (7)	C17—C18—C19	118.8 (2)
N3—Cu1—N4	81.25 (7)	C17—C18—H18	120.6
N5—Cu1—N1	100.93 (7)	C19—C18—H18	120.6
N2—Cu1—N1	80.17 (7)	C27—C19—C18	116.6 (2)
N3—Cu1—N1	114.15 (7)	C27—C19—C20	119.6 (2)
N4—Cu1—N1	108.09 (6)	C18—C19—C20	123.7 (2)
C11—N1—C14	118.58 (18)	C21—C20—C19	120.5 (2)
C11—N1—Cu1	132.80 (14)	C21—C20—H20	119.8
C14—N1—Cu1	108.16 (13)	C19—C20—H20	119.8
C2—N2—C13	119.90 (19)	C20—C21—C22	121.0 (2)
C2—N2—Cu1	126.65 (15)	C20—C21—H21	119.5
C13—N2—Cu1	112.75 (14)	C22—C21—H21	119.5
C2—C1—H1A	109.5	C28—C22—C23	116.0 (2)
C2—C1—H1B	109.5	C28—C22—C21	119.6 (2)
H1A—C1—H1B	109.5	C23—C22—C21	124.3 (2)
C2—C1—H1C	109.5	C24—C23—C22	119.5 (2)
H1A—C1—H1C	109.5	C24—C23—H23	120.3
H1B—C1—H1C	109.5	C22—C23—H23	120.3
N2—C2—C3	120.5 (2)	C23—C24—C25	121.7 (2)
N2—C2—C1	118.8 (2)	C23—C24—H24	119.1
C3—C2—C1	120.7 (2)	C25—C24—H24	119.1
C4—C3—C2	120.1 (2)	N3—C25—C24	119.7 (2)
C4—C3—H3	120.0	N3—C25—C26	120.1 (2)
C2—C3—H3	120.0	C24—C25—C26	120.2 (2)
C3—C4—C5	120.1 (2)	C25—C26—H26A	109.5
C3—C4—H4	119.9	C25—C26—H26B	109.5
C5—C4—H4	119.9	H26A—C26—H26B	109.5
C4—C5—C13	116.8 (2)	C25—C26—H26C	109.5
C4—C5—C6	124.1 (2)	H26A—C26—H26C	109.5
C13—C5—C6	119.1 (2)	H26B—C26—H26C	109.5
C7—C6—C5	120.9 (2)	N4—C27—C19	123.75 (18)
C7—C6—H6	119.6	N4—C27—C28	116.32 (19)
C5—C6—H6	119.6	C19—C27—C28	119.81 (19)
C6—C7—C8	121.4 (2)	N3—C28—C22	124.35 (19)
C6—C7—H7	119.3	N3—C28—C27	116.23 (18)
C8—C7—H7	119.3	C22—C28—C27	119.3 (2)
C14—C8—C9	116.5 (2)	C29—N5—Cu1	173.4 (2)
C14—C8—C7	119.5 (2)	N5—C29—C30	178.3 (3)
C9—C8—C7	124.0 (2)	C29—C30—H30A	109.5
C10—C9—C8	119.9 (2)	C29—C30—H30B	109.5
C10—C9—H9	120.1	H30A—C30—H30B	109.5
C8—C9—H9	120.1	C29—C30—H30C	109.5
C9—C10—C11	120.5 (2)	H30A—C30—H30C	109.5
C9—C10—H10	119.8	H30B—C30—H30C	109.5
C11—C10—H10	119.8	N6—C31—C32	179.2 (3)
N1—C11—C10	121.0 (2)	C31—C32—H32A	109.5
N1—C11—C12	118.5 (2)	C31—C32—H32B	109.5
C10—C11—C12	120.4 (2)	H32A—C32—H32B	109.5
C11—C12—H12A	109.5	C31—C32—H32C	109.5
C11—C12—H12B	109.5	H32A—C32—H32C	109.5
H12A—C12—H12B	109.5	H32B—C32—H32C	109.5
C11—C12—H12C	109.5	N7—C33—C34	178.5 (3)
H12A—C12—H12C	109.5	C33—C34—H34A	109.5
H12B—C12—H12C	109.5	C33—C34—H34B	109.5
N2—C13—C5	122.4 (2)	H34A—C34—H34B	109.5
N2—C13—C14	118.18 (19)	C33—C34—H34C	109.5
C5—C13—C14	119.38 (19)	H34A—C34—H34C	109.5
N1—C14—C8	123.4 (2)	H34B—C34—H34C	109.5
N1—C14—C13	117.07 (18)	F1—B1—F4	111.3 (2)
C8—C14—C13	119.45 (19)	F1—B1—F3	107.7 (2)
C25—N3—C28	118.60 (19)	F4—B1—F3	109.3 (2)
C25—N3—Cu1	130.46 (16)	F1—B1—F2	110.3 (2)
C28—N3—Cu1	109.46 (13)	F4—B1—F2	109.8 (2)
C16—N4—C27	118.45 (18)	F3—B1—F2	108.5 (2)
C16—N4—Cu1	131.53 (15)	F8—B2—F6	113.5 (3)
C27—N4—Cu1	109.30 (12)	F8—B2—F5	108.5 (3)
C16—C15—H15A	109.5	F6—B2—F5	109.6 (3)
C16—C15—H15B	109.5	F8—B2—F7	106.8 (3)
H15A—C15—H15B	109.5	F6—B2—F7	108.0 (3)
C16—C15—H15C	109.5	F5—B2—F7	110.3 (3)
H15A—C15—H15C	109.5	F6B—B2B—F8B	112.7 (12)
H15B—C15—H15C	109.5	F6B—B2B—F7B	110.6 (12)
N4—C16—C17	120.81 (19)	F8B—B2B—F7B	101.0 (12)
N4—C16—C15	119.04 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···F8ⁱ	0.96	2.36	3.120 (3)	135
C18—H18···F5ⁱⁱ	0.93	2.36	3.279 (3)	171
C20—H20···F8ⁱⁱ	0.93	2.53	3.423 (3)	161
C30—H30A···F8	0.96	2.47	3.375 (4)	158
C30—H30B···F6ⁱⁱⁱ	0.96	2.38	3.314 (3)	165
C32—H32B···F7^iv	0.96	2.37	3.191 (3)	143

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃N)(C₁₄H₁₂N₂)₂](BF₄)₂·2C₂H₃N
M_r	776.83
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.2865 (19), 12.070 (2), 13.802 (2)
α, β, γ (°)	72.843 (15), 83.746 (15), 73.933 (15)
V (Å³)	1725.7 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Sapphire diffractometer
Absorption correction	Multi-scan (SCALE3 ABSPACK in CrysAlis RED; Oxford Diffraction, 2006).
T_min, T_max	0.997, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10543, 8129, 4935
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.750

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 0.89
No. of reflections	8129
No. of parameters	489
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.35

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction ,2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXLTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—N5	2.0123 (18)	N3—C25	1.351 (3)
Cu1—N2	2.0297 (17)	N3—C28	1.359 (3)
Cu1—N3	2.0305 (18)	N4—C16	1.333 (2)
Cu1—N4	2.0348 (17)	N4—C27	1.365 (3)
Cu1—N1	2.1760 (18)

N5—Cu1—N2	84.42 (7)	N3—Cu1—N4	81.25 (7)
N5—Cu1—N3	89.07 (7)	N5—Cu1—N1	100.93 (7)
N2—Cu1—N3	165.23 (7)	N2—Cu1—N1	80.17 (7)
N5—Cu1—N4	150.90 (7)	N3—Cu1—N1	114.15 (7)
N2—Cu1—N4	98.14 (7)	N4—Cu1—N1	108.09 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···F8ⁱ	0.96	2.36	3.120 (3)	135
C18—H18···F5ⁱⁱ	0.93	2.36	3.279 (3)	171
C20—H20···F8ⁱⁱ	0.93	2.53	3.423 (3)	161
C30—H30A···F8	0.96	2.47	3.375 (4)	158
C30—H30B···F6ⁱⁱⁱ	0.96	2.38	3.314 (3)	165
C32—H32B···F7^iv	0.96	2.37	3.191 (3)	143

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1.

Acknowledgements

I thank Dr Guy Crundwell for his assistance with the disorder modeling, and with preparation of this manuscript, and I thank Dr Laura Pence for helpful discussions concerning the geometry of the complex.

References

Aligo, J. A., Smith, L., Eglin, J. E. & Pence, L. E. (2005). Inorg. Chem. 44, 4001–4007. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bush, P. M., Whitehead, J. P., Pink, C. C., Gramm, E. C., Eglin, J. C., Watton, S. P. & Pence, L. E. (2001). Inorg. Chem. 40, 1871–1877. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
James, B. R. & Williams, R. J. P. (1961). J. Chem. Soc. pp. 2007–2019. CrossRef Web of Science Google Scholar
Kepert, D. L. (1973). Inorg. Chem. 12, 1938–1942. CrossRef CAS Web of Science Google Scholar
Oxford Diffraction (2006). CrysAlis CCD, CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Rossi, A. R. & Hoffman, R. (1975). Inorg. Chem. 14, 365–374. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vega, I. E. D., Gale, P. A., Lighta, M. E. & Loeb, S. J. (1985). Chem. Commun. 39, 4913–4915. Google Scholar

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Volume 65| Part 5| May 2009| Pages m585-m586

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Aceto­nitrilebis(2,9-di­methylphenanthroline)copper(II) bis­(tetra­fluoridoborate) aceto­nitrile disolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Acetonitrilebis(2,9-dimethylphenanthroline)copper(II) bis(tetrafluoridoborate) acetonitrile disolvate