The crystal structure of the title compound, [Cu(C12H8N2){N(CN)2}](ClO4), consists of zigzag chain [Cu(phen)(dca)]nn+ cations and [ClO4]− anions (phen = 1,10-phenanthroline and dca = [N(CN)2]−). The CuII atom has a near square planar coordination environment with two N atoms of phen ligands and two N-terminal atoms of dca ligands. The complex forms a one-dimensional chain structure along the c axis, using dca as an end-to-end bridging ligand. The hydrogen-bonding interactions produce a three-dimensional network.
Supporting information
CCDC reference: 214568
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.115
- Data-to-parameter ratio = 13.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
Absorption corrections should be applied.
Tmin and Tmax expected: 0.748 0.848
RT(exp) = 1.133
General Notes
ABSTY_01 Extra text has been found in the _exptl_absorpt_correction_type
field, which should be only a single keyword. A literature
citation should be included in the _exptl_absorpt_process_details
field.
REFLT_03
From the CIF: _diffrn_reflns_theta_max 27.48
From the CIF: _reflns_number_total 2952
Count of symmetry unique reflns 1736
Completeness (_total/calc) 170.05%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1216
Fraction of Friedel pairs measured 0.700
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Aqueous solution of Cu(ClO4)2 (1 M, 0.5 ml) and 4 ml aqueous solution of Nadca (1 mmol, 91 mg) was thoroughly mixed, then 10 ml of an ethanol solution of 1,10-phen (0.5 mmol, 99 mg) was added dropwise with stirring. The resulting mixture was filtered and the filtrate was left undisturbed at room temperature. The transparent green needle-like crystals were obtained after a few days.
H atoms were added according to theoretical models, assigned isotropic displacement parameters and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
catena-poly[[[(1,10-phenanthroline)copper(II)]-µ-dicyanamido] perchlorate]
top
Crystal data top
[Cu(C2N3)(C12H8N2)](ClO4) | Dx = 1.798 Mg m−3 |
Mr = 409.24 | Melting point: not measured K |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.260 (5) Å | Cell parameters from 2248 reflections |
b = 9.660 (2) Å | θ = 3.3–27.5° |
c = 12.789 (5) Å | µ = 1.65 mm−1 |
β = 120.878 (12)° | T = 293 K |
V = 1512.0 (9) Å3 | Needle-like, green |
Z = 4 | 0.50 × 0.15 × 0.10 mm |
F(000) = 820 | |
Data collection top
Rigaku Mercury CCD diffractometer | 2571 reflections with I > 2σ(I) |
Radiation source: rotating-anode generator | Rint = 0.042 |
Graphite Monochromator monochromator | θmax = 27.5°, θmin = 3.3° |
ω scans | h = −18→18 |
5925 measured reflections | k = −12→12 |
2952 independent reflections | l = −16→16 |
Refinement top
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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0654P)2 + 0.0356P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
2952 reflections | Δρmax = 0.45 e Å−3 |
226 parameters | Δρmin = −0.27 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 0000 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (2) |
Crystal data top
[Cu(C2N3)(C12H8N2)](ClO4) | V = 1512.0 (9) Å3 |
Mr = 409.24 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 14.260 (5) Å | µ = 1.65 mm−1 |
b = 9.660 (2) Å | T = 293 K |
c = 12.789 (5) Å | 0.50 × 0.15 × 0.10 mm |
β = 120.878 (12)° | |
Data collection top
Rigaku Mercury CCD diffractometer | 2571 reflections with I > 2σ(I) |
5925 measured reflections | Rint = 0.042 |
2952 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.115 | Δρmax = 0.45 e Å−3 |
S = 1.05 | Δρmin = −0.27 e Å−3 |
2952 reflections | Absolute structure: Flack (1983), 0000 Friedel pairs |
226 parameters | Absolute structure parameter: 0.03 (2) |
2 restraints | |
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. The electrostatic interactions exist between the [Cu(phen)(dca)]+ cations and the [ClO4]− anions. All atoms are not connected by chemical binding, so atoms given in a CIF don't form a 'connected set'. |
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 | Uiso*/Ueq | |
Cu1 | 0.37752 (3) | 0.24939 (2) | 0.43022 (3) | 0.03491 (5) | |
Cl1 | 1.13815 (4) | 0.05316 (4) | 0.18648 (4) | 0.04123 (11) | |
O1 | 1.06513 (14) | −0.0556 (2) | 0.17678 (16) | 0.0896 (7) | |
O2 | 1.20426 (13) | 0.0083 (2) | 0.13894 (16) | 0.0930 (6) | |
O3 | 1.07396 (14) | 0.1713 (2) | 0.12134 (15) | 0.0839 (7) | |
O4 | 1.20552 (16) | 0.0885 (2) | 0.30898 (16) | 0.0838 (7) | |
N5 | 0.44323 (11) | −0.16794 (19) | 0.84346 (12) | 0.0453 (5) | |
N4 | 0.50825 (14) | −0.0578 (2) | 0.72143 (17) | 0.0873 (7) | |
N3 | 0.41739 (12) | 0.09309 (16) | 0.54535 (13) | 0.0409 (5) | |
N1 | 0.38428 (10) | 0.44487 (16) | 0.37902 (11) | 0.0378 (4) | |
N2 | 0.28288 (10) | 0.33669 (14) | 0.48467 (11) | 0.0343 (4) | |
C14 | 0.46648 (13) | −0.1129 (2) | 0.78186 (15) | 0.0413 (6) | |
C13 | 0.45370 (12) | 0.0244 (2) | 0.62794 (15) | 0.0401 (5) | |
C1 | 0.43935 (14) | 0.4951 (2) | 0.32990 (16) | 0.0453 (6) | |
H1A | 0.4738 | 0.4342 | 0.3041 | 0.054* | |
C2 | 0.44692 (15) | 0.6367 (2) | 0.31596 (17) | 0.0568 (7) | |
H2A | 0.4865 | 0.6690 | 0.2815 | 0.068* | |
C3 | 0.39659 (19) | 0.7287 (2) | 0.3525 (2) | 0.0574 (8) | |
H3A | 0.4021 | 0.8233 | 0.3435 | 0.069* | |
C4 | 0.33732 (14) | 0.67952 (19) | 0.40307 (16) | 0.0422 (6) | |
C5 | 0.28131 (19) | 0.7655 (2) | 0.4459 (2) | 0.0530 (8) | |
H5A | 0.2820 | 0.8611 | 0.4376 | 0.064* | |
C6 | 0.22737 (16) | 0.7103 (2) | 0.49823 (18) | 0.0523 (7) | |
H6A | 0.1916 | 0.7682 | 0.5246 | 0.063* | |
C7 | 0.22530 (13) | 0.5632 (2) | 0.51294 (15) | 0.0411 (6) | |
C8 | 0.17059 (12) | 0.4964 (2) | 0.56608 (16) | 0.0482 (6) | |
H8A | 0.1346 | 0.5487 | 0.5958 | 0.058* | |
C9 | 0.17122 (13) | 0.3565 (2) | 0.57308 (15) | 0.0473 (6) | |
H9A | 0.1338 | 0.3123 | 0.6054 | 0.057* | |
C10 | 0.22851 (15) | 0.2789 (2) | 0.53150 (17) | 0.0433 (6) | |
H10A | 0.2283 | 0.1829 | 0.5370 | 0.052* | |
C11 | 0.27837 (11) | 0.47773 (17) | 0.47230 (13) | 0.0298 (5) | |
C12 | 0.33392 (12) | 0.53514 (18) | 0.41469 (13) | 0.0327 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.04528 (6) | 0.03228 (8) | 0.03751 (6) | 0.00895 (7) | 0.02867 (5) | 0.00588 (6) |
Cl1 | 0.04269 (15) | 0.04197 (19) | 0.04005 (14) | 0.0031 (2) | 0.02195 (11) | 0.0047 (2) |
O1 | 0.0904 (9) | 0.0779 (11) | 0.0935 (11) | −0.0363 (8) | 0.0422 (8) | 0.0019 (9) |
O2 | 0.1296 (8) | 0.0630 (10) | 0.1410 (8) | −0.0018 (9) | 0.1086 (6) | −0.0207 (9) |
O3 | 0.0661 (8) | 0.0808 (11) | 0.0845 (10) | 0.0218 (9) | 0.0241 (8) | 0.0305 (10) |
O4 | 0.0782 (10) | 0.0938 (14) | 0.0579 (8) | −0.0100 (10) | 0.0196 (7) | −0.0122 (9) |
N5 | 0.0498 (6) | 0.0517 (10) | 0.0466 (6) | −0.0019 (7) | 0.0334 (4) | 0.0054 (7) |
N4 | 0.0483 (7) | 0.1297 (15) | 0.0945 (8) | 0.0262 (9) | 0.0443 (6) | 0.0772 (9) |
N3 | 0.0459 (6) | 0.0360 (8) | 0.0449 (6) | 0.0062 (6) | 0.0262 (5) | 0.0086 (6) |
N1 | 0.0387 (5) | 0.0432 (8) | 0.0379 (6) | 0.0067 (6) | 0.0242 (4) | 0.0093 (6) |
N2 | 0.0355 (5) | 0.0326 (7) | 0.0365 (5) | 0.0012 (6) | 0.0197 (4) | −0.0008 (6) |
C14 | 0.0368 (7) | 0.0473 (10) | 0.0385 (7) | 0.0035 (7) | 0.0184 (6) | 0.0100 (7) |
C13 | 0.0329 (6) | 0.0432 (10) | 0.0492 (8) | 0.0003 (7) | 0.0246 (5) | 0.0094 (7) |
C1 | 0.0435 (7) | 0.0530 (11) | 0.0421 (7) | 0.0041 (8) | 0.0240 (6) | 0.0133 (8) |
C2 | 0.0517 (8) | 0.0648 (13) | 0.0578 (9) | −0.0089 (9) | 0.0308 (7) | 0.0184 (9) |
C3 | 0.0547 (10) | 0.0405 (11) | 0.0620 (12) | −0.0114 (8) | 0.0191 (9) | 0.0107 (8) |
C4 | 0.0422 (8) | 0.0306 (9) | 0.0394 (8) | −0.0028 (7) | 0.0107 (7) | 0.0012 (7) |
C5 | 0.0534 (10) | 0.0337 (10) | 0.0573 (11) | 0.0062 (8) | 0.0178 (9) | −0.0054 (8) |
C6 | 0.0447 (8) | 0.0431 (10) | 0.0580 (10) | 0.0141 (8) | 0.0182 (8) | −0.0125 (8) |
C7 | 0.0338 (7) | 0.0481 (10) | 0.0350 (7) | 0.0098 (7) | 0.0130 (6) | −0.0026 (7) |
C8 | 0.0351 (6) | 0.0688 (13) | 0.0509 (8) | 0.0085 (8) | 0.0294 (5) | −0.0024 (9) |
C9 | 0.0395 (7) | 0.0683 (14) | 0.0465 (7) | 0.0046 (8) | 0.0310 (5) | 0.0057 (8) |
C10 | 0.0423 (7) | 0.0450 (11) | 0.0505 (8) | 0.0011 (7) | 0.0296 (6) | 0.0082 (7) |
C11 | 0.0265 (6) | 0.0287 (8) | 0.0280 (6) | −0.0018 (6) | 0.0097 (5) | 0.0000 (6) |
C12 | 0.0317 (6) | 0.0324 (8) | 0.0292 (6) | 0.0031 (6) | 0.0121 (5) | 0.0052 (6) |
Geometric parameters (Å, º) top
Cu1—N5i | 1.9482 (19) | C2—C3 | 1.366 (4) |
Cu1—N3 | 1.9778 (16) | C2—H2A | 0.9300 |
Cu1—N2 | 1.9956 (17) | C3—C4 | 1.386 (4) |
Cu1—N1 | 2.0170 (16) | C3—H3A | 0.9300 |
Cl1—O4 | 1.3960 (18) | C4—C12 | 1.406 (3) |
Cl1—O2 | 1.426 (2) | C4—C5 | 1.441 (4) |
Cl1—O3 | 1.4323 (18) | C5—C6 | 1.361 (4) |
Cl1—O1 | 1.439 (2) | C5—H5A | 0.9300 |
N5—C14 | 1.132 (3) | C6—C7 | 1.435 (3) |
N5—Cu1ii | 1.9482 (19) | C6—H6A | 0.9300 |
N4—C14 | 1.307 (3) | C7—C11 | 1.389 (3) |
N4—C13 | 1.308 (3) | C7—C8 | 1.425 (3) |
N3—C13 | 1.124 (2) | C8—C9 | 1.354 (3) |
N1—C1 | 1.324 (3) | C8—H8A | 0.9300 |
N1—C12 | 1.349 (2) | C9—C10 | 1.399 (3) |
N2—C10 | 1.322 (3) | C9—H9A | 0.9300 |
N2—C11 | 1.369 (2) | C10—H10A | 0.9300 |
C1—C2 | 1.391 (3) | C11—C12 | 1.441 (3) |
C1—H1A | 0.9300 | | |
| | | |
N5i—Cu1—N3 | 94.43 (8) | C2—C3—H3A | 120.3 |
N5i—Cu1—N2 | 168.11 (5) | C4—C3—H3A | 120.3 |
N3—Cu1—N2 | 92.88 (7) | C3—C4—C12 | 116.8 (2) |
N5i—Cu1—N1 | 94.37 (7) | C3—C4—C5 | 124.74 (19) |
N3—Cu1—N1 | 155.92 (5) | C12—C4—C5 | 118.4 (2) |
N2—Cu1—N1 | 82.60 (7) | C6—C5—C4 | 121.61 (19) |
O4—Cl1—O2 | 109.14 (12) | C6—C5—H5A | 119.2 |
O4—Cl1—O3 | 108.92 (11) | C4—C5—H5A | 119.2 |
O2—Cl1—O3 | 111.04 (13) | C5—C6—C7 | 120.5 (2) |
O4—Cl1—O1 | 109.02 (13) | C5—C6—H6A | 119.8 |
O2—Cl1—O1 | 110.40 (13) | C7—C6—H6A | 119.8 |
O3—Cl1—O1 | 108.27 (11) | C11—C7—C8 | 116.47 (18) |
C14—N5—Cu1ii | 169.85 (14) | C11—C7—C6 | 119.2 (2) |
C14—N4—C13 | 123.37 (19) | C8—C7—C6 | 124.3 (2) |
C13—N3—Cu1 | 165.54 (14) | C9—C8—C7 | 119.8 (2) |
C1—N1—C12 | 118.13 (17) | C9—C8—H8A | 120.1 |
C1—N1—Cu1 | 129.50 (14) | C7—C8—H8A | 120.1 |
C12—N1—Cu1 | 111.90 (13) | C8—C9—C10 | 119.7 (2) |
C10—N2—C11 | 117.95 (17) | C8—C9—H9A | 120.2 |
C10—N2—Cu1 | 129.69 (13) | C10—C9—H9A | 120.2 |
C11—N2—Cu1 | 112.34 (13) | N2—C10—C9 | 122.58 (19) |
N5—C14—N4 | 171.13 (19) | N2—C10—H10A | 118.7 |
N3—C13—N4 | 171.4 (2) | C9—C10—H10A | 118.7 |
N1—C1—C2 | 121.7 (2) | N2—C11—C7 | 123.42 (18) |
N1—C1—H1A | 119.1 | N2—C11—C12 | 115.88 (16) |
C2—C1—H1A | 119.1 | C7—C11—C12 | 120.70 (16) |
C3—C2—C1 | 120.4 (2) | N1—C12—C4 | 123.52 (19) |
C3—C2—H2A | 119.8 | N1—C12—C11 | 116.85 (15) |
C1—C2—H2A | 119.8 | C4—C12—C11 | 119.57 (18) |
C2—C3—C4 | 119.4 (2) | | |
Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O1iii | 0.93 | 2.56 | 3.301 (4) | 138 |
C6—H6A···O2iv | 0.93 | 2.56 | 3.368 (3) | 146 |
C10—H10A···O2v | 0.93 | 2.39 | 3.193 (3) | 145 |
C10—H10A···O4vi | 0.93 | 2.91 | 3.261 (3) | 104 |
Symmetry codes: (iii) x−1/2, y+1/2, z; (iv) x−1, −y+1, z+1/2; (v) x−1, −y, z+1/2; (vi) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Cu(C2N3)(C12H8N2)](ClO4) |
Mr | 409.24 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 14.260 (5), 9.660 (2), 12.789 (5) |
β (°) | 120.878 (12) |
V (Å3) | 1512.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.50 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5925, 2952, 2571 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 1.05 |
No. of reflections | 2952 |
No. of parameters | 226 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.27 |
Absolute structure | Flack (1983), 0000 Friedel pairs |
Absolute structure parameter | 0.03 (2) |
Selected geometric parameters (Å, º) topCu1—N5i | 1.9482 (19) | N5—Cu1ii | 1.9482 (19) |
Cu1—N3 | 1.9778 (16) | N4—C14 | 1.307 (3) |
Cu1—N2 | 1.9956 (17) | N4—C13 | 1.308 (3) |
Cu1—N1 | 2.0170 (16) | N3—C13 | 1.124 (2) |
N5—C14 | 1.132 (3) | | |
| | | |
N5i—Cu1—N3 | 94.43 (8) | O2—Cl1—O1 | 110.40 (13) |
N5i—Cu1—N2 | 168.11 (5) | O3—Cl1—O1 | 108.27 (11) |
N3—Cu1—N2 | 92.88 (7) | C14—N5—Cu1ii | 169.85 (14) |
N5i—Cu1—N1 | 94.37 (7) | C14—N4—C13 | 123.37 (19) |
N3—Cu1—N1 | 155.92 (5) | C13—N3—Cu1 | 165.54 (14) |
N2—Cu1—N1 | 82.60 (7) | C1—N1—Cu1 | 129.50 (14) |
O4—Cl1—O2 | 109.14 (12) | C12—N1—Cu1 | 111.90 (13) |
O4—Cl1—O3 | 108.92 (11) | C10—N2—Cu1 | 129.69 (13) |
O2—Cl1—O3 | 111.04 (13) | C11—N2—Cu1 | 112.34 (13) |
O4—Cl1—O1 | 109.02 (13) | N5—C14—N4 | 171.13 (19) |
Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O1iii | 0.93 | 2.56 | 3.301 (4) | 138 |
C6—H6A···O2iv | 0.93 | 2.56 | 3.368 (3) | 146 |
C10—H10A···O2v | 0.93 | 2.39 | 3.193 (3) | 145 |
C10—H10A···O4vi | 0.93 | 2.91 | 3.261 (3) | 104 |
Symmetry codes: (iii) x−1/2, y+1/2, z; (iv) x−1, −y+1, z+1/2; (v) x−1, −y, z+1/2; (vi) x−1, y, z. |
In recent years, metal–dicyanamide (dca, [N(CN)2]−) coordination chemistry has become a fast growing research field because of its interesting coordination and physical properties (Marshall et al., 2002; Shi et al., 2002; Brown & Manson, 2002). Since dicyanamide has three N-donor atoms, it can exhibit several possible coordination modes (Marshall et al., 2002; Shi et al., 2002). The complexes formulated as [M(dca)2]n (M = Mn, Fe, Co, Ni, Cu, Zn, Ag, etc.) containing only dca have been synthesized, which are of a quite limited structural type (Batten et al., 1998, 1999; Jensen, Batten, Fallon, Moubaraki et al., 1999; Jensen et al., 2000; Kurmoo & Kepert, 1998; Manson, Lee et al., 1998; Britton, 1990). By introducing co-ligands that may be monodentate or bidentate ligands, such as pyridine, bipyridine, 1,10-phenanthroline, 2,2'-biimidazole etc., many complexes have been synthesized with various interesting structures (Manson, Incarvito et al., 1998; Manson et al., 1999; Jensen, Batten, Fallon, Hockless et al., 1999; Batten et al., 1999; Wang, Luo, Sun, Yan, Gao & Liao, 2000; Wang, Luo, Sun, Yan, Liao & Gao, 2000; Sun et al., 2000; Werff et al., 2001). As an extension of this research area, we synthesized a new one-dimensional complex [Cu(1,10-phen)(dca)](ClO4), (I). Herein we report the preparation and crystal structure of (I). [Note that the scheme is incorrect; please provide revision with unsaturation in the phen ligand]
The coordination mode of Cu atom in (I) is similar to the complex [Cu(dca)(MeCN)] reported by Batten et al. (2000). The CuII atom is four-coordinated with two terminal N atoms of two different [N(CN)2]− ligands [Cu1—N3 1.978 (2) Å and Cu1—N5i 1.948 (2) Å; symmetry code: (i) x, −y, z − 0.5] and two N atoms of phen ligands [Cu1—N1 2.017 (2) Å and Cu1—N1 1.996 (2) Å]. The Cu and four coordinated N atoms (N1, N2, N3 and N5) constitute a near square coplanar geometry defined by the equation −7.7931 x + 3.1106 y − 4.8987 z = −3.4625, and deviate from the plane by 0.087, −0.323, 0.286, −0.302 and 0.253 Å, respectively. The Cu—N distances are in good agreement with those found in the complexes reported by Wang, Luo, Sun, Yan, Gao & Liao (2000) and Potocnak et al. (1996). Each [N(CN)2]− is coordinated to two metal atoms via the two nitrile N atoms. The [N(CN)2]− ligands end-to-end bridge the CuII atoms into one-dimensional zigzag chain extended along the c axis, as shown in Fig. 1, and between which the [ClO4]− anions are located, as shown in Fig. 2. The parallel chains are further connected by the C—H···O hydrogen bonds, consisting of three O atoms of [ClO4]− anion and the C atoms of phen [C1—H···O1 = 3.301 (4), C6—H···O2 = 3.368 (3), C10—H···O2 3.193 (3) and C10—H···O4 3.261 (3) Å], to form a three-dimensional framework. It is worthy of note that the [ClO4]− anion is ordered due to the hydrogen-bonding interactions.