In the title compound, [CuCl(C
6H
4N
2)(C
6H
15N
3)]ClO
4, the central copper ion is coordinated by three N atoms from 1,4,7-triazacyclononane, one N atom from the cyanopyridine and one Cl atom, forming a square-pyramidal coordination geometry (τ = 0.31). The crystal packing is stabilized by intermolecular N—H
O and N—H
Cl hydrogen bonds.
Supporting information
CCDC reference: 244890
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.033
- wR factor = 0.086
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C9 - C12 ... 1.45 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 9
N4 -CU1 -N2 -C2 -3.60 0.90 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 13
N4 -CU1 -N2 -C3 -128.50 0.80 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 25
N2 -CU1 -N4 -C7 -30.50 1.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 29
N2 -CU1 -N4 -C11 148.80 0.80 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 58
C10 -C9 -C12 -N5 -48.00 16.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 59
C8 -C9 -C12 -N5 130.00 16.00 1.555 1.555 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
8 ALERT type 4 Improvement, methodology, query or suggestion
checkCIF publication errors
Alert level A
PUBL022_ALERT_1_A There is a mismatched ~ on line 284
_chemical_formula_iupac '[Cu Cl (C6 H4 N2) (C6 H15 N3)] Cl O4~'
If you require a ~ then it should be escaped
with a \, i.e. \~
Otherwise there must be a matching closing ~, e.g. C~2~H~4~
1 ALERT level A = Data missing that is essential or data in wrong format
0 ALERT level G = General alerts. Data that may be required is missing
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Chloro(pyridine-4-carbonitrile-
κN1)(1,4,7-triazacyclononane-
κ3N,
N',
N'')copper(II) perchlorate
top
Crystal data top
[CuCl(C6H4N2)(C6H15N3)]ClO4 | Z = 2 |
Mr = 431.77 | F(000) = 442 |
Triclinic, P1 | Dx = 1.682 Mg m−3 |
a = 7.656 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.707 (5) Å | Cell parameters from 819 reflections |
c = 10.933 (5) Å | θ = 3.3–26.3° |
α = 73.065 (6)° | µ = 1.62 mm−1 |
β = 84.573 (7)° | T = 293 K |
γ = 86.058 (7)° | Block, blue |
V = 852.7 (7) Å3 | 0.24 × 0.20 × 0.16 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3453 independent reflections |
Radiation source: fine-focus sealed tube | 2822 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→9 |
Tmin = 0.621, Tmax = 0.771 | k = −13→11 |
4946 measured reflections | l = −13→13 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0409P)2 + 0.5194P] where P = (Fo2 + 2Fc2)/3 |
3453 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
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 | Uiso*/Ueq | |
Cu1 | 0.06081 (4) | 0.74897 (3) | 0.12784 (3) | 0.03029 (11) | |
N1 | 0.2074 (3) | 0.6065 (2) | 0.2580 (2) | 0.0353 (5) | |
H1 | 0.1342 | 0.5638 | 0.3255 | 0.042* | |
N2 | 0.1905 (3) | 0.6674 (2) | −0.0011 (2) | 0.0332 (5) | |
H2 | 0.1199 | 0.6751 | −0.0656 | 0.040* | |
N3 | 0.3021 (3) | 0.8568 (2) | 0.0996 (2) | 0.0343 (5) | |
H3 | 0.2779 | 0.9380 | 0.1093 | 0.041* | |
N4 | −0.0708 (3) | 0.8120 (2) | 0.2706 (2) | 0.0337 (5) | |
N5 | −0.3874 (5) | 0.9583 (4) | 0.6672 (3) | 0.0767 (10) | |
Cl1 | −0.15771 (9) | 0.82263 (8) | −0.00475 (7) | 0.04274 (19) | |
C1 | 0.2931 (4) | 0.5111 (3) | 0.1936 (3) | 0.0425 (7) | |
H1A | 0.2776 | 0.4230 | 0.2490 | 0.051* | |
H1B | 0.4180 | 0.5251 | 0.1775 | 0.051* | |
C2 | 0.2141 (4) | 0.5267 (3) | 0.0685 (3) | 0.0437 (7) | |
H2A | 0.2906 | 0.4833 | 0.0161 | 0.052* | |
H2B | 0.1014 | 0.4863 | 0.0851 | 0.052* | |
C3 | 0.3568 (4) | 0.7328 (3) | −0.0578 (3) | 0.0408 (7) | |
H3A | 0.3689 | 0.7431 | −0.1493 | 0.049* | |
H3B | 0.4556 | 0.6783 | −0.0200 | 0.049* | |
C4 | 0.3600 (4) | 0.8652 (3) | −0.0350 (3) | 0.0399 (7) | |
H4A | 0.4781 | 0.8967 | −0.0547 | 0.048* | |
H4B | 0.2831 | 0.9269 | −0.0914 | 0.048* | |
C5 | 0.4242 (4) | 0.7815 (3) | 0.1934 (3) | 0.0414 (7) | |
H5A | 0.4817 | 0.8410 | 0.2271 | 0.050* | |
H5B | 0.5141 | 0.7373 | 0.1505 | 0.050* | |
C6 | 0.3310 (4) | 0.6813 (3) | 0.3035 (3) | 0.0436 (7) | |
H6A | 0.4175 | 0.6210 | 0.3516 | 0.052* | |
H6B | 0.2666 | 0.7254 | 0.3608 | 0.052* | |
C7 | −0.1823 (4) | 0.7341 (3) | 0.3556 (3) | 0.0408 (7) | |
H7 | −0.2016 | 0.6530 | 0.3454 | 0.049* | |
C8 | −0.2698 (4) | 0.7685 (3) | 0.4575 (3) | 0.0419 (7) | |
H8 | −0.3462 | 0.7117 | 0.5152 | 0.050* | |
C9 | −0.2422 (4) | 0.8890 (3) | 0.4723 (3) | 0.0372 (6) | |
C10 | −0.1312 (4) | 0.9715 (3) | 0.3831 (3) | 0.0452 (7) | |
H10 | −0.1127 | 1.0540 | 0.3899 | 0.054* | |
C11 | −0.0485 (4) | 0.9299 (3) | 0.2842 (3) | 0.0423 (7) | |
H11 | 0.0260 | 0.9860 | 0.2241 | 0.051* | |
C12 | −0.3254 (5) | 0.9274 (4) | 0.5812 (3) | 0.0518 (8) | |
Cl2 | 0.17806 (10) | 0.62979 (8) | 0.66298 (7) | 0.04503 (19) | |
O1 | 0.0566 (4) | 0.7081 (3) | 0.7227 (3) | 0.0765 (8) | |
O2 | 0.0889 (3) | 0.5869 (2) | 0.5737 (2) | 0.0579 (6) | |
O3 | 0.2285 (5) | 0.5188 (3) | 0.7651 (3) | 0.0846 (9) | |
O4 | 0.3192 (5) | 0.7065 (4) | 0.6023 (3) | 0.1115 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.02201 (17) | 0.0419 (2) | 0.02978 (18) | 0.00410 (13) | 0.00026 (12) | −0.01666 (14) |
N1 | 0.0305 (12) | 0.0454 (14) | 0.0274 (11) | −0.0001 (10) | 0.0020 (9) | −0.0081 (10) |
N2 | 0.0267 (11) | 0.0462 (14) | 0.0308 (12) | 0.0022 (10) | −0.0021 (9) | −0.0183 (10) |
N3 | 0.0299 (12) | 0.0394 (13) | 0.0361 (12) | −0.0039 (10) | 0.0037 (9) | −0.0159 (10) |
N4 | 0.0262 (11) | 0.0453 (14) | 0.0325 (12) | 0.0035 (10) | 0.0003 (9) | −0.0176 (10) |
N5 | 0.086 (2) | 0.097 (3) | 0.0525 (19) | 0.012 (2) | 0.0143 (17) | −0.0402 (19) |
Cl1 | 0.0297 (3) | 0.0569 (5) | 0.0382 (4) | 0.0098 (3) | −0.0050 (3) | −0.0102 (3) |
C1 | 0.0395 (16) | 0.0390 (16) | 0.0461 (17) | 0.0063 (13) | −0.0034 (13) | −0.0096 (13) |
C2 | 0.0421 (17) | 0.0441 (17) | 0.0496 (18) | 0.0034 (13) | 0.0000 (13) | −0.0233 (14) |
C3 | 0.0347 (15) | 0.0578 (19) | 0.0302 (14) | 0.0011 (13) | 0.0068 (11) | −0.0170 (13) |
C4 | 0.0349 (15) | 0.0483 (17) | 0.0328 (15) | −0.0037 (13) | 0.0051 (12) | −0.0080 (13) |
C5 | 0.0288 (14) | 0.062 (2) | 0.0407 (16) | −0.0065 (13) | −0.0031 (12) | −0.0247 (15) |
C6 | 0.0397 (16) | 0.061 (2) | 0.0306 (15) | 0.0031 (14) | −0.0064 (12) | −0.0136 (14) |
C7 | 0.0338 (15) | 0.0427 (17) | 0.0506 (18) | −0.0021 (12) | 0.0030 (13) | −0.0228 (14) |
C8 | 0.0333 (15) | 0.0496 (18) | 0.0402 (16) | −0.0023 (13) | 0.0089 (12) | −0.0126 (14) |
C9 | 0.0347 (15) | 0.0484 (17) | 0.0298 (14) | 0.0083 (12) | −0.0005 (11) | −0.0163 (13) |
C10 | 0.0554 (19) | 0.0386 (17) | 0.0446 (17) | 0.0000 (14) | 0.0061 (14) | −0.0202 (14) |
C11 | 0.0444 (17) | 0.0409 (17) | 0.0383 (16) | −0.0021 (13) | 0.0095 (13) | −0.0102 (13) |
C12 | 0.0510 (19) | 0.065 (2) | 0.0435 (18) | 0.0055 (16) | 0.0030 (15) | −0.0254 (17) |
Cl2 | 0.0499 (4) | 0.0505 (5) | 0.0384 (4) | −0.0126 (3) | −0.0011 (3) | −0.0170 (3) |
O1 | 0.090 (2) | 0.0704 (18) | 0.0738 (18) | 0.0082 (15) | 0.0061 (15) | −0.0345 (15) |
O2 | 0.0679 (16) | 0.0674 (16) | 0.0430 (12) | −0.0195 (13) | −0.0116 (11) | −0.0170 (12) |
O3 | 0.122 (3) | 0.0716 (19) | 0.0650 (17) | 0.0219 (17) | −0.0403 (17) | −0.0228 (15) |
O4 | 0.103 (3) | 0.171 (4) | 0.083 (2) | −0.089 (3) | 0.0417 (19) | −0.068 (2) |
Geometric parameters (Å, º) top
Cu1—N2 | 2.017 (2) | C3—H3A | 0.9700 |
Cu1—N4 | 2.032 (2) | C3—H3B | 0.9700 |
Cu1—N1 | 2.101 (2) | C4—H4A | 0.9700 |
Cu1—N3 | 2.195 (2) | C4—H4B | 0.9700 |
Cu1—Cl1 | 2.2658 (10) | C5—C6 | 1.517 (4) |
N1—C6 | 1.486 (4) | C5—H5A | 0.9700 |
N1—C1 | 1.486 (4) | C5—H5B | 0.9700 |
N1—H1 | 0.9100 | C6—H6A | 0.9700 |
N2—C2 | 1.484 (4) | C6—H6B | 0.9700 |
N2—C3 | 1.489 (4) | C7—C8 | 1.374 (4) |
N2—H2 | 0.9100 | C7—H7 | 0.9300 |
N3—C5 | 1.474 (4) | C8—C9 | 1.378 (4) |
N3—C4 | 1.475 (3) | C8—H8 | 0.9300 |
N3—H3 | 0.9100 | C9—C10 | 1.377 (4) |
N4—C7 | 1.336 (4) | C9—C12 | 1.449 (4) |
N4—C11 | 1.338 (4) | C10—C11 | 1.372 (4) |
N5—C12 | 1.137 (4) | C10—H10 | 0.9300 |
C1—C2 | 1.508 (4) | C11—H11 | 0.9300 |
C1—H1A | 0.9700 | Cl2—O4 | 1.397 (3) |
C1—H1B | 0.9700 | Cl2—O3 | 1.433 (3) |
C2—H2A | 0.9700 | Cl2—O2 | 1.435 (2) |
C2—H2B | 0.9700 | Cl2—O1 | 1.446 (3) |
C3—C4 | 1.512 (4) | | |
| | | |
N2—Cu1—N4 | 174.01 (9) | C4—C3—H3A | 109.4 |
N2—Cu1—N1 | 82.99 (9) | N2—C3—H3B | 109.4 |
N4—Cu1—N1 | 92.22 (9) | C4—C3—H3B | 109.4 |
N2—Cu1—N3 | 82.77 (9) | H3A—C3—H3B | 108.0 |
N4—Cu1—N3 | 100.23 (9) | N3—C4—C3 | 110.5 (2) |
N1—Cu1—N3 | 82.53 (9) | N3—C4—H4A | 109.6 |
N2—Cu1—Cl1 | 90.25 (7) | C3—C4—H4A | 109.6 |
N4—Cu1—Cl1 | 92.63 (7) | N3—C4—H4B | 109.6 |
N1—Cu1—Cl1 | 155.03 (7) | C3—C4—H4B | 109.6 |
N3—Cu1—Cl1 | 120.56 (7) | H4A—C4—H4B | 108.1 |
C6—N1—C1 | 114.6 (2) | N3—C5—C6 | 112.0 (2) |
C6—N1—Cu1 | 104.89 (18) | N3—C5—H5A | 109.2 |
C1—N1—Cu1 | 109.61 (17) | C6—C5—H5A | 109.2 |
C6—N1—H1 | 109.2 | N3—C5—H5B | 109.2 |
C1—N1—H1 | 109.2 | C6—C5—H5B | 109.2 |
Cu1—N1—H1 | 109.2 | H5A—C5—H5B | 107.9 |
C2—N2—C3 | 114.3 (2) | N1—C6—C5 | 112.0 (2) |
C2—N2—Cu1 | 105.13 (16) | N1—C6—H6A | 109.2 |
C3—N2—Cu1 | 112.33 (17) | C5—C6—H6A | 109.2 |
C2—N2—H2 | 108.3 | N1—C6—H6B | 109.2 |
C3—N2—H2 | 108.3 | C5—C6—H6B | 109.2 |
Cu1—N2—H2 | 108.3 | H6A—C6—H6B | 107.9 |
C5—N3—C4 | 114.5 (2) | N4—C7—C8 | 122.9 (3) |
C5—N3—Cu1 | 108.40 (17) | N4—C7—H7 | 118.5 |
C4—N3—Cu1 | 101.57 (17) | C8—C7—H7 | 118.5 |
C5—N3—H3 | 110.7 | C7—C8—C9 | 118.6 (3) |
C4—N3—H3 | 110.7 | C7—C8—H8 | 120.7 |
Cu1—N3—H3 | 110.7 | C9—C8—H8 | 120.7 |
C7—N4—C11 | 117.8 (2) | C10—C9—C8 | 118.9 (3) |
C7—N4—Cu1 | 120.00 (19) | C10—C9—C12 | 120.4 (3) |
C11—N4—Cu1 | 122.15 (19) | C8—C9—C12 | 120.7 (3) |
N1—C1—C2 | 110.2 (2) | C11—C10—C9 | 119.0 (3) |
N1—C1—H1A | 109.6 | C11—C10—H10 | 120.5 |
C2—C1—H1A | 109.6 | C9—C10—H10 | 120.5 |
N1—C1—H1B | 109.6 | N4—C11—C10 | 122.7 (3) |
C2—C1—H1B | 109.6 | N4—C11—H11 | 118.7 |
H1A—C1—H1B | 108.1 | C10—C11—H11 | 118.7 |
N2—C2—C1 | 110.0 (2) | N5—C12—C9 | 178.5 (4) |
N2—C2—H2A | 109.7 | O4—Cl2—O3 | 112.9 (2) |
C1—C2—H2A | 109.7 | O4—Cl2—O2 | 111.72 (17) |
N2—C2—H2B | 109.7 | O3—Cl2—O2 | 109.39 (17) |
C1—C2—H2B | 109.7 | O4—Cl2—O1 | 107.9 (2) |
H2A—C2—H2B | 108.2 | O3—Cl2—O1 | 105.57 (18) |
N2—C3—C4 | 111.3 (2) | O2—Cl2—O1 | 109.10 (17) |
N2—C3—H3A | 109.4 | | |
| | | |
N2—Cu1—N1—C6 | 112.30 (17) | N3—Cu1—N4—C11 | 29.2 (2) |
N4—Cu1—N1—C6 | −71.31 (17) | Cl1—Cu1—N4—C11 | −92.5 (2) |
N3—Cu1—N1—C6 | 28.72 (16) | C6—N1—C1—C2 | −131.4 (3) |
Cl1—Cu1—N1—C6 | −172.38 (13) | Cu1—N1—C1—C2 | −13.8 (3) |
N2—Cu1—N1—C1 | −11.26 (18) | C3—N2—C2—C1 | 72.6 (3) |
N4—Cu1—N1—C1 | 165.13 (19) | Cu1—N2—C2—C1 | −51.1 (3) |
N3—Cu1—N1—C1 | −94.84 (19) | N1—C1—C2—N2 | 43.1 (3) |
Cl1—Cu1—N1—C1 | 64.1 (2) | C2—N2—C3—C4 | −136.5 (3) |
N4—Cu1—N2—C2 | −3.6 (9) | Cu1—N2—C3—C4 | −16.8 (3) |
N1—Cu1—N2—C2 | 33.47 (18) | C5—N3—C4—C3 | 68.1 (3) |
N3—Cu1—N2—C2 | 116.79 (18) | Cu1—N3—C4—C3 | −48.5 (2) |
Cl1—Cu1—N2—C2 | −122.42 (17) | N2—C3—C4—N3 | 46.2 (3) |
N4—Cu1—N2—C3 | −128.5 (8) | C4—N3—C5—C6 | −130.8 (3) |
N1—Cu1—N2—C3 | −91.47 (19) | Cu1—N3—C5—C6 | −18.2 (3) |
N3—Cu1—N2—C3 | −8.15 (18) | C1—N1—C6—C5 | 72.0 (3) |
Cl1—Cu1—N2—C3 | 112.64 (18) | Cu1—N1—C6—C5 | −48.3 (3) |
N2—Cu1—N3—C5 | −89.98 (18) | N3—C5—C6—N1 | 45.8 (3) |
N4—Cu1—N3—C5 | 84.77 (18) | C11—N4—C7—C8 | −2.0 (4) |
N1—Cu1—N3—C5 | −6.14 (17) | Cu1—N4—C7—C8 | 177.2 (2) |
Cl1—Cu1—N3—C5 | −175.98 (14) | N4—C7—C8—C9 | 0.3 (5) |
N2—Cu1—N3—C4 | 30.91 (17) | C7—C8—C9—C10 | 1.5 (4) |
N4—Cu1—N3—C4 | −154.34 (17) | C7—C8—C9—C12 | −177.3 (3) |
N1—Cu1—N3—C4 | 114.75 (18) | C8—C9—C10—C11 | −1.6 (5) |
Cl1—Cu1—N3—C4 | −55.09 (18) | C12—C9—C10—C11 | 177.2 (3) |
N2—Cu1—N4—C7 | −30.5 (10) | C7—N4—C11—C10 | 1.9 (4) |
N1—Cu1—N4—C7 | −67.2 (2) | Cu1—N4—C11—C10 | −177.3 (2) |
N3—Cu1—N4—C7 | −150.0 (2) | C9—C10—C11—N4 | −0.2 (5) |
Cl1—Cu1—N4—C7 | 88.3 (2) | C10—C9—C12—N5 | −48 (16) |
N2—Cu1—N4—C11 | 148.8 (8) | C8—C9—C12—N5 | 130 (16) |
N1—Cu1—N4—C11 | 112.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.91 | 2.39 | 3.234 (3) | 154 |
N2—H2···O1ii | 0.91 | 2.33 | 3.181 (4) | 156 |
N3—H3···Cl1iii | 0.91 | 2.63 | 3.420 (3) | 146 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −x, −y+2, −z. |