Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107015387/sf3036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107015387/sf3036Isup2.hkl |
CCDC reference: 652486
For related literature, see: Batten & Murray (2003); Batten et al. (1999, 2000); Biswas et al. (2006); Dance & Scudder (1996); Jager et al. (2001); Kini et al. (1990); Kmety et al. (2000); Kurmoo & Kepert (1998, 1999); Manskaya et al. (1999); Manson (2005); Manson et al. (1998, 1999, 2001); Miller & Manson (2001); Raebiger et al. (2001); Schlueter et al. (2005); Schlueter, Geiser & Manson (2004); Schlueter, Manson & Geiser (2006); Schlueter, Manson, Hyzer & Geiser (2004, 2006); Scudder & Dance (1998a, 1998b); Spek (2003); Tong et al. (2003); Wang et al. (1990, 1992, 2002, 2003); Werff et al. (2004, 2005); Werff, Batten, Jensen, Moubaraki & Murray (2001); Werff, Batten, Jensen, Moubaraki, Murray & Tan (2001); Williams et al. (1990).
Tetraphenylphosphonium copper(I) dicyanamide was prepared according to the literature procedure of Wang et al. (1990). An acetonitrile solution containing CuBr and two equivalents of PPh4(dca) was refluxed for 16 h. Upon slow cooling, crystals of PPh4Cu(dca)2 formed.
H atoms on aromatic C atoms were positioned geometrically, with C—H = 0.95 Å, and refined with a riding model, with Uiso(H) = 1.2Ueq(C). [Please check added text]
The dicyanamide pseudohalide anion [N(CN)2-, hereinafter abbreviated dca] has become a component of a growing number of coordination polymers because its large variety of bonding modes enables the formation of a wide range of structural types (Miller & Manson, 2001; Batten & Murray, 2003; Manson, 2005). With divalent first row transition elements, neutral binary M(dca)2 complexes with rutile-like structures form, in which the dca anion is coordinated in a µ1,3,5 fashion. Long-range magnetic order is observed in the cobalt and nickel compounds, which order ferromagnetically (Manson et al., 1998; Kurmoo & Kepert, 1998), while the vanadium, chromium, manganese and iron analogs possess antiferromagnetic ground states (Kurmoo & Kepert, 1998; Manson et al., 1999, 2001; Kmety et al., 2000; Batten et al., 1999). The isostructural Cu(dca)2 complex is paramagnetic to temperatures as low as 2 K (Kurmoo & Kepert, 1998, 1999).
There has recently been a rapid increase in the study of anionic dca complexes in which the use of diverse cationic templates has led to an increasing variety of structural types with various dimensionalities. Various trans and cis µ1,5-dibridged chains have been reported (Raebiger et al., 2001; Jager et al., 2001; Wang et al., 2002). Ladder-type structures represent an intermediate motif between one- and two-dimensional systems (van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Wang et al., 2003). Three two-dimensional anionic structural types are known, namely square (Raebiger et al., 2001; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Biswas et al., 2006), hexagonal honeycombs (Batten et al., 2000) and triangular (Schlueter, Geiser & Manson, 2004) Three-dimensional topologies with cubelike (Tong et al., 2003; Schlueter, Manson et al., 2004; Schlueter et al., 2005; van der Werff et al., 2005), triple rutile (Schlueter et al., 2005; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff et al., 2004) and lithium antimonate (Schlueter et al., 2005) packing motifs have also been identified. These various structural types differ in the ratio and arrangement of single and double dca bridges. The vast majority of these complexes contain divalent first row transition elements.
Anionic copper dicyanamide complexes are relatively unknown, but we have recently reported the first three structures that contain anionic copper(II) dicyanamide coordination polymers. The (PPh4)3[Cu4(dca)11] salt possesses a novel triple ladder structure, in which the rungs are comprised of single µ1,5-dca bridges while the sides are constructed of double µ1,5-dca bridges (Schlueter, Manson & Geiser, 2006). We have also found that the (PPh4)Cu(dca)3H2O salt contains singly bridged µ1,5-dca chains that are linked into a two-dimensional network through coordinated water molecules (Schlueter, Manson et al., 2006). Replacement of one of the cation phenyl groups with a butyl group results in the formation of the (PPh3Bu)2Cu(dca)4 salt, which contains doubly-bridged µ1,5-dca chains (Schlueter, Manson et al., 2006). Only two examples of anionic copper(I) dca salts have been reported to date, namely the [Rb(18-crown-6)]3Cu2(dca)5 salt, which contains both tetrahedrally and triangularly coordinated Cu, forming complex one-dimensional chains (Reference?), while [Tl(18-crown-6)]Cu(dca)2 contains only tetrahedrally coordinated Cu linked through single µ1,5-dca bridges into two-dimensional polymeric sheets (Manskaya et al., 1999). Here, we report the first example of a three-dimensional copper(I) dicyanamide network, PPh4Cu(dca)2, (I). This salt has been used as a precursor (Wang et al., 1990, 1992) for the electrochemical synthesis of the superconducting charge-transfer salts (BEDT-TTF)2Cu(dca)X (X is Br or Cl; BEDT-TTF is ? [Please define]) (Williams et al., 1990; Kini et al., 1990). In order to control the electrocrystallization process better, it is necessary to understand more fully the structure of the anionic network in electrolyte precursors.
The atom-numbering scheme of the tetraphenylphosphonium cation and the copper(I) dicyanamide anion of (I) are illustrated in Fig. 1. The geometry of the dca anions in the PPh4Cu(dca)2 structure is typical. The nitrile C≡ N bond lengths range from 1.148 (4) to 1.157 (4) Å, the amide N—C bond lengths range from 1.299 (4) to 1.320 (4) Å, the C—N—C bond angles are 120.1 (2) and 123.3 (3)° and the N≡C—N bond angles range from 172.9 (3) to 174.3 (3)°. The displacement ellipsoids of the amide N atoms are elongated, indicating a rocking thermal motion of the dca anion. The coordination about the CuI center is distorted tetrahedral, with the N—Cu—N bond angles ranging from 100.5 (1) to 119.0 (1)°. Two of the Cu—N bond lengths are slightly shorter (0.07 Å) than the other two. A polymeric network is formed by two sets of copper dicyanamide chains; one runs along the a axis, while the other runs along the b axis. These zigzag chains wind around 21 screw axes. The chain along the a axis has N—Cu—N bond angles of 111.0 (1)°, while for the b axis chain this angle is 110.6 (1)°. As illustrated in Fig. 2, each Cu atom is joined to four equivalent ones through dca linkages, resulting in Cu···Cu separations of 7.9641 (7) and 8.1075 (7) Å, thus forming a highly distorted single diamondoid net.
As seen in Fig. 1, the molecular structure of the tetraphenylphosphonium cation that templates the anionic pores is typical of that commonly described in the literature. The P—C bond lengths range from 1.795 (3) to 1.804 (3) Å with C—P—C bond angles slightly distorted from tetrahedral, ranging from 108.3 (1) to 110.8 (1)°. The C—C distances within the aromatic rings range from 1.375 (4) to 1.396 (4) Å and the C—C—C bond angles range from 119.2 (2) to 120.6 (3)°.
As illustrated in Fig. 3, zigzag chains of PPh4+ cations form along the b axis, with P···P separations of 7.2621 (7) Å. These chains are stabilized through multiple phenyl embraces of both the offset-face-to-face (off) and edge-to-face (ef) types. The most prominent off interaction is between phenyl rings defined by atoms C1–C6 and C13–C18, respectively. The centroid-to-centroid distance between these rings is 4.4080 Å, with a dihedral angle of 15.51° between their respective planes, confirming the presence of π–π interactions (Spek, 2003). The most significant ef interaction is between atom H10 and the phenyl ring defined by atoms C1–C6. The associated H-to-centroid distance is 3.28 Å. This type of concerted supramolecular motif is not one of the modes commonly observed for tetraphenylphosphonium salts (Dance & Scudder, 1996; Scudder & Dance, 1998a,b).
We conclude that, although the three-dimensional Cu(dca)2- lattice of the PPh4+ salt breaks down in solution prior to electrocrystallization of (BEDT-TTF)2Cu(dca)X (X is Br and Cl), the one-dimensional zigzag anionic chain structure is retained in these BEDT-TTF salts. The presence of coordinating Br- or Cl- anions and the two-dimensional templating effect of the (BEDT-TTF)2+ cations likely cause the anionic structural transformation.
For related literature, see: Batten & Murray (2003); Batten et al. (1999, 2000); Biswas et al. (2006); Dance & Scudder (1996); Jager et al. (2001); Kini et al. (1990); Kmety et al. (2000); Kurmoo & Kepert (1998, 1999); Manskaya et al. (1999); Manson (2005); Manson et al. (1998, 1999, 2001); Miller & Manson (2001); Raebiger et al. (2001); Schlueter et al. (2005); Schlueter, Geiser & Manson (2004); Schlueter, Manson & Geiser (2006); Schlueter, Manson, Hyzer & Geiser (2004, 2006); Scudder & Dance (1998a, 1998b); Spek (2003); Tong et al. (2003); Wang et al. (1990, 1992, 2002, 2003); Werff et al. (2004, 2005); Werff, Batten, Jensen, Moubaraki & Murray (2001); Werff, Batten, Jensen, Moubaraki, Murray & Tan (2001); Williams et al. (1990).
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
(C24H20P)[Cu(C2N3)2] | Dx = 1.431 Mg m−3 |
Mr = 535.01 | Melting point: 433 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1784 reflections |
a = 12.7929 (12) Å | θ = 2.6–26.2° |
b = 13.4006 (12) Å | µ = 0.97 mm−1 |
c = 14.4847 (14) Å | T = 150 K |
V = 2483.1 (4) Å3 | Rod, colorless |
Z = 4 | 0.40 × 0.06 × 0.06 mm |
F(000) = 1096 |
Siemens SMART CCD area-detector diffractometer | 5978 independent reflections |
Radiation source: fine-focus sealed tube | 4855 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: integration (SHELXTL; Sheldrick, 2001) | h = −16→16 |
Tmin = 0.787, Tmax = 0.951 | k = −17→17 |
21614 measured reflections | l = −18→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0308P)2 + 0.4799P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.022 |
5978 reflections | Δρmax = 0.89 e Å−3 |
325 parameters | Δρmin = −0.63 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.061 (12) |
(C24H20P)[Cu(C2N3)2] | V = 2483.1 (4) Å3 |
Mr = 535.01 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.7929 (12) Å | µ = 0.97 mm−1 |
b = 13.4006 (12) Å | T = 150 K |
c = 14.4847 (14) Å | 0.40 × 0.06 × 0.06 mm |
Siemens SMART CCD area-detector diffractometer | 5978 independent reflections |
Absorption correction: integration (SHELXTL; Sheldrick, 2001) | 4855 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.951 | Rint = 0.049 |
21614 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.083 | Δρmax = 0.89 e Å−3 |
S = 1.03 | Δρmin = −0.63 e Å−3 |
5978 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
325 parameters | Absolute structure parameter: 0.061 (12) |
0 restraints |
Experimental. The data collection nominally covered over a hemisphere of reciprocal space by a combination of four sets of exposures; each set had a different φ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.974 cm. Coverage of the unique set was 100% complete to at least 26.3° in θ, 98.3% complete to at least 28.2° in θ. |
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 | ||
P1 | 0.54674 (5) | 0.59794 (5) | 0.66257 (4) | 0.02235 (13) | |
C1 | 0.4177 (2) | 0.62583 (18) | 0.70553 (18) | 0.0239 (6) | |
C2 | 0.3308 (2) | 0.5742 (2) | 0.67337 (18) | 0.0287 (6) | |
H2 | 0.3387 | 0.5240 | 0.6276 | 0.034* | |
C3 | 0.2326 (2) | 0.5960 (2) | 0.70824 (18) | 0.0315 (6) | |
H3 | 0.1730 | 0.5614 | 0.6858 | 0.038* | |
C4 | 0.2215 (2) | 0.6679 (2) | 0.7755 (2) | 0.0331 (7) | |
H4 | 0.1541 | 0.6831 | 0.7992 | 0.040* | |
C5 | 0.3084 (2) | 0.7179 (2) | 0.8087 (2) | 0.0391 (7) | |
H5 | 0.3004 | 0.7665 | 0.8559 | 0.047* | |
C6 | 0.4065 (2) | 0.6978 (2) | 0.7738 (2) | 0.0359 (7) | |
H6 | 0.4658 | 0.7329 | 0.7963 | 0.043* | |
C7 | 0.6150 (2) | 0.71322 (18) | 0.64187 (18) | 0.0246 (6) | |
C8 | 0.6701 (2) | 0.7571 (2) | 0.71444 (18) | 0.0300 (6) | |
H8 | 0.6777 | 0.7228 | 0.7714 | 0.036* | |
C9 | 0.7136 (2) | 0.8511 (2) | 0.7029 (2) | 0.0330 (7) | |
H9 | 0.7513 | 0.8812 | 0.7521 | 0.040* | |
C10 | 0.7024 (2) | 0.9008 (2) | 0.62045 (19) | 0.0329 (6) | |
H10 | 0.7312 | 0.9656 | 0.6133 | 0.039* | |
C11 | 0.6493 (2) | 0.8568 (2) | 0.5479 (2) | 0.0345 (7) | |
H11 | 0.6431 | 0.8910 | 0.4907 | 0.041* | |
C12 | 0.6051 (2) | 0.7633 (2) | 0.55822 (19) | 0.0300 (6) | |
H12 | 0.5682 | 0.7335 | 0.5085 | 0.036* | |
C13 | 0.6184 (2) | 0.5281 (2) | 0.74723 (18) | 0.0267 (6) | |
C14 | 0.7242 (2) | 0.5086 (2) | 0.73136 (19) | 0.0309 (6) | |
H14 | 0.7578 | 0.5356 | 0.6785 | 0.037* | |
C15 | 0.7796 (2) | 0.4504 (2) | 0.7924 (2) | 0.0389 (7) | |
H15 | 0.8510 | 0.4354 | 0.7810 | 0.047* | |
C16 | 0.7304 (3) | 0.4138 (3) | 0.8707 (2) | 0.0481 (9) | |
H16 | 0.7687 | 0.3742 | 0.9134 | 0.058* | |
C17 | 0.6266 (3) | 0.4343 (3) | 0.8873 (2) | 0.0490 (9) | |
H17 | 0.5940 | 0.4095 | 0.9416 | 0.059* | |
C18 | 0.5696 (2) | 0.4910 (2) | 0.82533 (19) | 0.0369 (7) | |
H18 | 0.4977 | 0.5043 | 0.8362 | 0.044* | |
C19 | 0.5363 (2) | 0.52615 (18) | 0.55795 (17) | 0.0237 (6) | |
C20 | 0.5928 (2) | 0.4376 (2) | 0.5492 (2) | 0.0352 (7) | |
H20 | 0.6356 | 0.4151 | 0.5986 | 0.042* | |
C21 | 0.5864 (3) | 0.3824 (2) | 0.4684 (2) | 0.0433 (8) | |
H21 | 0.6239 | 0.3215 | 0.4628 | 0.052* | |
C22 | 0.5257 (2) | 0.4161 (2) | 0.39650 (19) | 0.0348 (7) | |
H22 | 0.5227 | 0.3791 | 0.3407 | 0.042* | |
C23 | 0.4692 (2) | 0.50331 (19) | 0.40480 (18) | 0.0287 (6) | |
H23 | 0.4268 | 0.5254 | 0.3549 | 0.034* | |
C24 | 0.4737 (2) | 0.55907 (19) | 0.48554 (17) | 0.0252 (6) | |
H24 | 0.4345 | 0.6190 | 0.4912 | 0.030* | |
Cu1 | 0.50274 (3) | 0.09989 (2) | 0.39858 (2) | 0.03329 (10) | |
N31 | 0.5245 (2) | 0.17433 (17) | 0.27500 (16) | 0.0360 (6) | |
N32 | 0.5541 (3) | 0.27550 (19) | 0.13528 (16) | 0.0472 (7) | |
N33 | 0.53432 (19) | 0.45741 (18) | 0.12412 (16) | 0.0353 (6) | |
N34 | 0.4065 (2) | 0.1838 (2) | 0.4730 (2) | 0.0519 (8) | |
N35 | 0.3303 (2) | 0.3264 (3) | 0.5561 (2) | 0.0594 (9) | |
N36 | 0.1536 (2) | 0.3955 (2) | 0.54821 (18) | 0.0477 (7) | |
C31 | 0.5369 (2) | 0.2252 (2) | 0.2121 (2) | 0.0321 (6) | |
C33 | 0.5425 (2) | 0.3722 (2) | 0.13384 (17) | 0.0302 (6) | |
C34 | 0.3659 (2) | 0.2495 (3) | 0.5103 (2) | 0.0391 (7) | |
C36 | 0.2353 (3) | 0.3595 (2) | 0.54799 (19) | 0.0336 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0207 (3) | 0.0234 (3) | 0.0230 (3) | −0.0017 (3) | −0.0017 (3) | −0.0009 (3) |
C1 | 0.0203 (14) | 0.0261 (14) | 0.0252 (13) | 0.0018 (10) | 0.0022 (11) | −0.0016 (11) |
C2 | 0.0265 (14) | 0.0322 (15) | 0.0273 (13) | −0.0028 (11) | 0.0005 (12) | −0.0016 (11) |
C3 | 0.0235 (14) | 0.0404 (15) | 0.0305 (13) | −0.0052 (14) | −0.0025 (11) | 0.0038 (14) |
C4 | 0.0271 (16) | 0.0316 (15) | 0.0406 (16) | 0.0050 (13) | 0.0055 (13) | 0.0069 (13) |
C5 | 0.0385 (18) | 0.0293 (16) | 0.0494 (18) | −0.0022 (13) | 0.0128 (15) | −0.0139 (13) |
C6 | 0.0297 (17) | 0.0340 (16) | 0.0439 (18) | −0.0079 (13) | 0.0022 (14) | −0.0116 (14) |
C7 | 0.0216 (14) | 0.0232 (13) | 0.0290 (14) | −0.0031 (11) | 0.0023 (11) | −0.0045 (11) |
C8 | 0.0315 (16) | 0.0307 (15) | 0.0278 (13) | −0.0033 (12) | −0.0030 (12) | −0.0016 (12) |
C9 | 0.0300 (16) | 0.0341 (16) | 0.0348 (15) | −0.0074 (13) | −0.0055 (13) | −0.0084 (13) |
C10 | 0.0245 (14) | 0.0288 (13) | 0.0455 (16) | −0.0062 (14) | 0.0007 (12) | 0.0023 (14) |
C11 | 0.0347 (17) | 0.0352 (16) | 0.0337 (15) | −0.0090 (13) | 0.0007 (13) | 0.0049 (13) |
C12 | 0.0294 (16) | 0.0340 (15) | 0.0267 (14) | −0.0053 (13) | −0.0004 (12) | 0.0002 (12) |
C13 | 0.0223 (15) | 0.0309 (15) | 0.0270 (14) | −0.0019 (12) | −0.0029 (11) | −0.0019 (11) |
C14 | 0.0251 (16) | 0.0373 (16) | 0.0304 (14) | −0.0023 (13) | 0.0008 (12) | −0.0013 (12) |
C15 | 0.0272 (17) | 0.0468 (19) | 0.0427 (17) | 0.0023 (14) | −0.0107 (14) | −0.0026 (14) |
C16 | 0.045 (2) | 0.061 (2) | 0.0384 (17) | 0.0021 (19) | −0.0170 (15) | 0.0109 (16) |
C17 | 0.048 (2) | 0.070 (2) | 0.0287 (17) | 0.0017 (18) | −0.0013 (15) | 0.0156 (15) |
C18 | 0.0288 (16) | 0.0529 (19) | 0.0289 (15) | 0.0004 (14) | 0.0012 (13) | 0.0048 (14) |
C19 | 0.0254 (15) | 0.0206 (12) | 0.0252 (12) | −0.0030 (11) | 0.0015 (11) | −0.0044 (10) |
C20 | 0.0410 (18) | 0.0258 (13) | 0.0387 (17) | 0.0084 (13) | −0.0126 (15) | −0.0043 (12) |
C21 | 0.0452 (19) | 0.0306 (16) | 0.0542 (19) | 0.0128 (14) | −0.0090 (15) | −0.0142 (14) |
C22 | 0.0368 (18) | 0.0341 (15) | 0.0334 (14) | −0.0050 (12) | 0.0040 (13) | −0.0130 (12) |
C23 | 0.0294 (16) | 0.0318 (13) | 0.0249 (13) | −0.0062 (11) | −0.0002 (12) | 0.0022 (11) |
C24 | 0.0248 (16) | 0.0225 (12) | 0.0283 (13) | −0.0023 (10) | −0.0012 (11) | −0.0013 (10) |
Cu1 | 0.02837 (17) | 0.02200 (14) | 0.0495 (2) | 0.00307 (18) | 0.00123 (18) | −0.00661 (15) |
N31 | 0.0413 (18) | 0.0307 (13) | 0.0361 (13) | 0.0031 (11) | 0.0048 (11) | −0.0019 (10) |
N32 | 0.079 (2) | 0.0343 (13) | 0.0285 (13) | 0.0154 (15) | 0.0033 (14) | −0.0008 (11) |
N33 | 0.0323 (15) | 0.0364 (13) | 0.0371 (13) | −0.0049 (11) | −0.0034 (10) | 0.0050 (11) |
N34 | 0.0479 (18) | 0.0366 (15) | 0.071 (2) | 0.0035 (14) | 0.0127 (16) | 0.0025 (15) |
N35 | 0.0357 (17) | 0.084 (2) | 0.0585 (18) | 0.0054 (16) | 0.0031 (15) | −0.0369 (17) |
N36 | 0.0511 (18) | 0.0406 (15) | 0.0515 (16) | 0.0061 (15) | 0.0046 (13) | −0.0151 (14) |
C31 | 0.0346 (17) | 0.0254 (14) | 0.0363 (15) | 0.0059 (12) | −0.0043 (13) | −0.0063 (12) |
C33 | 0.0293 (15) | 0.0398 (16) | 0.0215 (12) | 0.0010 (13) | −0.0045 (12) | −0.0003 (11) |
C34 | 0.0346 (18) | 0.0452 (19) | 0.0376 (16) | 0.0026 (15) | 0.0049 (14) | 0.0037 (15) |
C36 | 0.042 (2) | 0.0273 (14) | 0.0316 (16) | −0.0087 (14) | 0.0090 (15) | −0.0084 (12) |
P1—C13 | 1.795 (3) | C15—C16 | 1.387 (4) |
P1—C7 | 1.800 (3) | C15—H15 | 0.9500 |
P1—C19 | 1.800 (3) | C16—C17 | 1.377 (5) |
P1—C1 | 1.804 (3) | C16—H16 | 0.9500 |
C1—C6 | 1.390 (4) | C17—C18 | 1.383 (4) |
C1—C2 | 1.390 (4) | C17—H17 | 0.9500 |
C2—C3 | 1.385 (4) | C18—H18 | 0.9500 |
C2—H2 | 0.9500 | C19—C24 | 1.392 (4) |
C3—C4 | 1.378 (4) | C19—C20 | 1.395 (4) |
C3—H3 | 0.9500 | C20—C21 | 1.386 (4) |
C4—C5 | 1.384 (4) | C20—H20 | 0.9500 |
C4—H4 | 0.9500 | C21—C22 | 1.376 (4) |
C5—C6 | 1.380 (4) | C21—H21 | 0.9500 |
C5—H5 | 0.9500 | C22—C23 | 1.379 (4) |
C6—H6 | 0.9500 | C22—H22 | 0.9500 |
C7—C12 | 1.391 (4) | C23—C24 | 1.389 (4) |
C7—C8 | 1.395 (4) | C23—H23 | 0.9500 |
C8—C9 | 1.387 (4) | C24—H24 | 0.9500 |
C8—H8 | 0.9500 | Cu1—N34 | 1.985 (3) |
C9—C10 | 1.375 (4) | Cu1—N33i | 1.995 (2) |
C9—H9 | 0.9500 | Cu1—N31 | 2.068 (2) |
C10—C11 | 1.383 (4) | Cu1—N36ii | 2.080 (3) |
C10—H10 | 0.9500 | N31—C31 | 1.148 (4) |
C11—C12 | 1.383 (4) | N32—C33 | 1.304 (4) |
C11—H11 | 0.9500 | N32—C31 | 1.320 (4) |
C12—H12 | 0.9500 | N33—C33 | 1.156 (3) |
C13—C18 | 1.384 (4) | N34—C34 | 1.157 (4) |
C13—C14 | 1.396 (4) | N35—C36 | 1.299 (4) |
C14—C15 | 1.376 (4) | N35—C34 | 1.307 (4) |
C14—H14 | 0.9500 | N36—C36 | 1.151 (4) |
C13—P1—C7 | 108.28 (13) | C13—C14—H14 | 120.0 |
C13—P1—C19 | 109.53 (12) | C14—C15—C16 | 119.5 (3) |
C7—P1—C19 | 110.77 (12) | C14—C15—H15 | 120.3 |
C13—P1—C1 | 109.89 (12) | C16—C15—H15 | 120.3 |
C7—P1—C1 | 108.89 (12) | C17—C16—C15 | 120.6 (3) |
C19—P1—C1 | 109.46 (12) | C17—C16—H16 | 119.7 |
C6—C1—C2 | 120.1 (2) | C15—C16—H16 | 119.7 |
C6—C1—P1 | 118.9 (2) | C16—C17—C18 | 120.3 (3) |
C2—C1—P1 | 120.9 (2) | C16—C17—H17 | 119.9 |
C3—C2—C1 | 119.9 (3) | C18—C17—H17 | 119.9 |
C3—C2—H2 | 120.1 | C17—C18—C13 | 119.3 (3) |
C1—C2—H2 | 120.1 | C17—C18—H18 | 120.3 |
C4—C3—C2 | 119.9 (3) | C13—C18—H18 | 120.3 |
C4—C3—H3 | 120.0 | C24—C19—C20 | 120.0 (2) |
C2—C3—H3 | 120.0 | C24—C19—P1 | 120.53 (19) |
C3—C4—C5 | 120.1 (3) | C20—C19—P1 | 119.5 (2) |
C3—C4—H4 | 119.9 | C21—C20—C19 | 120.0 (3) |
C5—C4—H4 | 119.9 | C21—C20—H20 | 120.0 |
C6—C5—C4 | 120.6 (3) | C19—C20—H20 | 120.0 |
C6—C5—H5 | 119.7 | C22—C21—C20 | 119.8 (3) |
C4—C5—H5 | 119.7 | C22—C21—H21 | 120.1 |
C5—C6—C1 | 119.3 (3) | C20—C21—H21 | 120.1 |
C5—C6—H6 | 120.3 | C21—C22—C23 | 120.5 (3) |
C1—C6—H6 | 120.3 | C21—C22—H22 | 119.7 |
C12—C7—C8 | 119.9 (2) | C23—C22—H22 | 119.7 |
C12—C7—P1 | 121.0 (2) | C22—C23—C24 | 120.5 (2) |
C8—C7—P1 | 118.8 (2) | C22—C23—H23 | 119.8 |
C9—C8—C7 | 119.7 (3) | C24—C23—H23 | 119.8 |
C9—C8—H8 | 120.2 | C23—C24—C19 | 119.2 (2) |
C7—C8—H8 | 120.2 | C23—C24—H24 | 120.4 |
C10—C9—C8 | 120.1 (3) | C19—C24—H24 | 120.4 |
C10—C9—H9 | 119.9 | N34—Cu1—N33i | 118.95 (11) |
C8—C9—H9 | 119.9 | N34—Cu1—N31 | 106.27 (11) |
C9—C10—C11 | 120.4 (3) | N33i—Cu1—N31 | 110.54 (10) |
C9—C10—H10 | 119.8 | N34—Cu1—N36ii | 110.96 (12) |
C11—C10—H10 | 119.8 | N33i—Cu1—N36ii | 108.09 (11) |
C12—C11—C10 | 120.3 (3) | N31—Cu1—N36ii | 100.46 (11) |
C12—C11—H11 | 119.9 | C31—N31—Cu1 | 172.4 (2) |
C10—C11—H11 | 119.9 | C33—N32—C31 | 120.2 (2) |
C11—C12—C7 | 119.6 (3) | C33—N33—Cu1iii | 171.0 (3) |
C11—C12—H12 | 120.2 | C34—N34—Cu1 | 164.4 (3) |
C7—C12—H12 | 120.2 | C36—N35—C34 | 123.3 (3) |
C18—C13—C14 | 120.3 (3) | C36—N36—Cu1iv | 148.9 (3) |
C18—C13—P1 | 121.0 (2) | N31—C31—N32 | 174.2 (3) |
C14—C13—P1 | 118.7 (2) | N33—C33—N32 | 173.8 (3) |
C15—C14—C13 | 119.9 (3) | N34—C34—N35 | 173.7 (4) |
C15—C14—H14 | 120.0 | N36—C36—N35 | 172.9 (3) |
C13—P1—C1—C6 | 73.3 (3) | C7—P1—C13—C18 | 128.1 (2) |
C7—P1—C1—C6 | −45.1 (3) | C19—P1—C13—C18 | −111.1 (2) |
C19—P1—C1—C6 | −166.4 (2) | C1—P1—C13—C18 | 9.2 (3) |
C13—P1—C1—C2 | −104.6 (2) | C7—P1—C13—C14 | −54.2 (3) |
C7—P1—C1—C2 | 137.0 (2) | C19—P1—C13—C14 | 66.7 (2) |
C19—P1—C1—C2 | 15.7 (3) | C1—P1—C13—C14 | −173.0 (2) |
C6—C1—C2—C3 | 1.3 (4) | C18—C13—C14—C15 | 1.5 (4) |
P1—C1—C2—C3 | 179.2 (2) | P1—C13—C14—C15 | −176.3 (2) |
C1—C2—C3—C4 | −0.8 (4) | C13—C14—C15—C16 | −1.8 (4) |
C2—C3—C4—C5 | −0.4 (4) | C14—C15—C16—C17 | 0.7 (5) |
C3—C4—C5—C6 | 1.2 (5) | C15—C16—C17—C18 | 0.7 (5) |
C4—C5—C6—C1 | −0.7 (5) | C16—C17—C18—C13 | −1.0 (5) |
C2—C1—C6—C5 | −0.5 (4) | C14—C13—C18—C17 | −0.1 (4) |
P1—C1—C6—C5 | −178.4 (2) | P1—C13—C18—C17 | 177.6 (2) |
C13—P1—C7—C12 | 154.1 (2) | C13—P1—C19—C24 | 172.4 (2) |
C19—P1—C7—C12 | 33.9 (3) | C7—P1—C19—C24 | −68.2 (2) |
C1—P1—C7—C12 | −86.5 (2) | C1—P1—C19—C24 | 51.8 (2) |
C13—P1—C7—C8 | −32.3 (3) | C13—P1—C19—C20 | −8.6 (3) |
C19—P1—C7—C8 | −152.4 (2) | C7—P1—C19—C20 | 110.8 (2) |
C1—P1—C7—C8 | 87.2 (2) | C1—P1—C19—C20 | −129.1 (2) |
C12—C7—C8—C9 | 0.7 (4) | C24—C19—C20—C21 | −0.1 (4) |
P1—C7—C8—C9 | −173.0 (2) | P1—C19—C20—C21 | −179.1 (2) |
C7—C8—C9—C10 | 0.1 (4) | C19—C20—C21—C22 | 1.1 (5) |
C8—C9—C10—C11 | −1.2 (4) | C20—C21—C22—C23 | −1.5 (5) |
C9—C10—C11—C12 | 1.3 (4) | C21—C22—C23—C24 | 0.8 (4) |
C10—C11—C12—C7 | −0.5 (4) | C22—C23—C24—C19 | 0.2 (4) |
C8—C7—C12—C11 | −0.5 (4) | C20—C19—C24—C23 | −0.6 (4) |
P1—C7—C12—C11 | 173.1 (2) | P1—C19—C24—C23 | 178.43 (19) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C24H20P)[Cu(C2N3)2] |
Mr | 535.01 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 12.7929 (12), 13.4006 (12), 14.4847 (14) |
V (Å3) | 2483.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.40 × 0.06 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Integration (SHELXTL; Sheldrick, 2001) |
Tmin, Tmax | 0.787, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21614, 5978, 4855 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.083, 1.03 |
No. of reflections | 5978 |
No. of parameters | 325 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.89, −0.63 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.061 (12) |
Computer programs: SMART (Siemens, 1995), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and PLATON (Spek, 2003).
Cu1—N34 | 1.985 (3) | Cu1—N31 | 2.068 (2) |
Cu1—N33i | 1.995 (2) | Cu1—N36ii | 2.080 (3) |
N34—Cu1—N33i | 118.95 (11) | N31—Cu1—N36ii | 100.46 (11) |
N34—Cu1—N31 | 106.27 (11) | C31—N31—Cu1 | 172.4 (2) |
N33i—Cu1—N31 | 110.54 (10) | C33—N33—Cu1iii | 171.0 (3) |
N34—Cu1—N36ii | 110.96 (12) | C34—N34—Cu1 | 164.4 (3) |
N33i—Cu1—N36ii | 108.09 (11) | C36—N36—Cu1iv | 148.9 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The dicyanamide pseudohalide anion [N(CN)2-, hereinafter abbreviated dca] has become a component of a growing number of coordination polymers because its large variety of bonding modes enables the formation of a wide range of structural types (Miller & Manson, 2001; Batten & Murray, 2003; Manson, 2005). With divalent first row transition elements, neutral binary M(dca)2 complexes with rutile-like structures form, in which the dca anion is coordinated in a µ1,3,5 fashion. Long-range magnetic order is observed in the cobalt and nickel compounds, which order ferromagnetically (Manson et al., 1998; Kurmoo & Kepert, 1998), while the vanadium, chromium, manganese and iron analogs possess antiferromagnetic ground states (Kurmoo & Kepert, 1998; Manson et al., 1999, 2001; Kmety et al., 2000; Batten et al., 1999). The isostructural Cu(dca)2 complex is paramagnetic to temperatures as low as 2 K (Kurmoo & Kepert, 1998, 1999).
There has recently been a rapid increase in the study of anionic dca complexes in which the use of diverse cationic templates has led to an increasing variety of structural types with various dimensionalities. Various trans and cis µ1,5-dibridged chains have been reported (Raebiger et al., 2001; Jager et al., 2001; Wang et al., 2002). Ladder-type structures represent an intermediate motif between one- and two-dimensional systems (van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Wang et al., 2003). Three two-dimensional anionic structural types are known, namely square (Raebiger et al., 2001; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Biswas et al., 2006), hexagonal honeycombs (Batten et al., 2000) and triangular (Schlueter, Geiser & Manson, 2004) Three-dimensional topologies with cubelike (Tong et al., 2003; Schlueter, Manson et al., 2004; Schlueter et al., 2005; van der Werff et al., 2005), triple rutile (Schlueter et al., 2005; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff et al., 2004) and lithium antimonate (Schlueter et al., 2005) packing motifs have also been identified. These various structural types differ in the ratio and arrangement of single and double dca bridges. The vast majority of these complexes contain divalent first row transition elements.
Anionic copper dicyanamide complexes are relatively unknown, but we have recently reported the first three structures that contain anionic copper(II) dicyanamide coordination polymers. The (PPh4)3[Cu4(dca)11] salt possesses a novel triple ladder structure, in which the rungs are comprised of single µ1,5-dca bridges while the sides are constructed of double µ1,5-dca bridges (Schlueter, Manson & Geiser, 2006). We have also found that the (PPh4)Cu(dca)3H2O salt contains singly bridged µ1,5-dca chains that are linked into a two-dimensional network through coordinated water molecules (Schlueter, Manson et al., 2006). Replacement of one of the cation phenyl groups with a butyl group results in the formation of the (PPh3Bu)2Cu(dca)4 salt, which contains doubly-bridged µ1,5-dca chains (Schlueter, Manson et al., 2006). Only two examples of anionic copper(I) dca salts have been reported to date, namely the [Rb(18-crown-6)]3Cu2(dca)5 salt, which contains both tetrahedrally and triangularly coordinated Cu, forming complex one-dimensional chains (Reference?), while [Tl(18-crown-6)]Cu(dca)2 contains only tetrahedrally coordinated Cu linked through single µ1,5-dca bridges into two-dimensional polymeric sheets (Manskaya et al., 1999). Here, we report the first example of a three-dimensional copper(I) dicyanamide network, PPh4Cu(dca)2, (I). This salt has been used as a precursor (Wang et al., 1990, 1992) for the electrochemical synthesis of the superconducting charge-transfer salts (BEDT-TTF)2Cu(dca)X (X is Br or Cl; BEDT-TTF is ? [Please define]) (Williams et al., 1990; Kini et al., 1990). In order to control the electrocrystallization process better, it is necessary to understand more fully the structure of the anionic network in electrolyte precursors.
The atom-numbering scheme of the tetraphenylphosphonium cation and the copper(I) dicyanamide anion of (I) are illustrated in Fig. 1. The geometry of the dca anions in the PPh4Cu(dca)2 structure is typical. The nitrile C≡ N bond lengths range from 1.148 (4) to 1.157 (4) Å, the amide N—C bond lengths range from 1.299 (4) to 1.320 (4) Å, the C—N—C bond angles are 120.1 (2) and 123.3 (3)° and the N≡C—N bond angles range from 172.9 (3) to 174.3 (3)°. The displacement ellipsoids of the amide N atoms are elongated, indicating a rocking thermal motion of the dca anion. The coordination about the CuI center is distorted tetrahedral, with the N—Cu—N bond angles ranging from 100.5 (1) to 119.0 (1)°. Two of the Cu—N bond lengths are slightly shorter (0.07 Å) than the other two. A polymeric network is formed by two sets of copper dicyanamide chains; one runs along the a axis, while the other runs along the b axis. These zigzag chains wind around 21 screw axes. The chain along the a axis has N—Cu—N bond angles of 111.0 (1)°, while for the b axis chain this angle is 110.6 (1)°. As illustrated in Fig. 2, each Cu atom is joined to four equivalent ones through dca linkages, resulting in Cu···Cu separations of 7.9641 (7) and 8.1075 (7) Å, thus forming a highly distorted single diamondoid net.
As seen in Fig. 1, the molecular structure of the tetraphenylphosphonium cation that templates the anionic pores is typical of that commonly described in the literature. The P—C bond lengths range from 1.795 (3) to 1.804 (3) Å with C—P—C bond angles slightly distorted from tetrahedral, ranging from 108.3 (1) to 110.8 (1)°. The C—C distances within the aromatic rings range from 1.375 (4) to 1.396 (4) Å and the C—C—C bond angles range from 119.2 (2) to 120.6 (3)°.
As illustrated in Fig. 3, zigzag chains of PPh4+ cations form along the b axis, with P···P separations of 7.2621 (7) Å. These chains are stabilized through multiple phenyl embraces of both the offset-face-to-face (off) and edge-to-face (ef) types. The most prominent off interaction is between phenyl rings defined by atoms C1–C6 and C13–C18, respectively. The centroid-to-centroid distance between these rings is 4.4080 Å, with a dihedral angle of 15.51° between their respective planes, confirming the presence of π–π interactions (Spek, 2003). The most significant ef interaction is between atom H10 and the phenyl ring defined by atoms C1–C6. The associated H-to-centroid distance is 3.28 Å. This type of concerted supramolecular motif is not one of the modes commonly observed for tetraphenylphosphonium salts (Dance & Scudder, 1996; Scudder & Dance, 1998a,b).
We conclude that, although the three-dimensional Cu(dca)2- lattice of the PPh4+ salt breaks down in solution prior to electrocrystallization of (BEDT-TTF)2Cu(dca)X (X is Br and Cl), the one-dimensional zigzag anionic chain structure is retained in these BEDT-TTF salts. The presence of coordinating Br- or Cl- anions and the two-dimensional templating effect of the (BEDT-TTF)2+ cations likely cause the anionic structural transformation.