Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008972/cf6061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008972/cf6061Isup2.hkl |
CCDC reference: 170730
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.092
- Data-to-parameter ratio = 26.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.471 0.535 Tmin and Tmax expected: 0.396 0.535 RR = 1.189 Please check that your absorption correction is appropriate. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.59 From the CIF: _reflns_number_total 5357 Count of symmetry unique reflns 3125 Completeness (_total/calc) 171.42% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2232 Fraction of Friedel pairs measured 0.714 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
Blue crystals of the title complex were obtained by slow diffusion of a methanolic solution (15 ml) of sodium perchlorate (0.2 g) into a methanolic solution (15 ml) of copper nitrate (0.4 g) and 1,4,7-trimethyl-1,4,7-triazacyclononane (0.28 g).
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Fig. 1. Atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted. |
[Cu(NO3)(C9H21N3)]ClO4 | Dx = 1.727 Mg m−3 |
Mr = 396.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 18683 reflections |
a = 8.5512 (1) Å | θ = 2.2–32.6° |
b = 11.8172 (1) Å | µ = 1.65 mm−1 |
c = 15.0854 (2) Å | T = 173 K |
V = 1524.40 (3) Å3 | Irregular, blue |
Z = 4 | 0.58 × 0.50 × 0.38 mm |
F(000) = 820 |
Nonius KappaCCD diffractometer | 5357 independent reflections |
Radiation source: fine-focus sealed tube | 5008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 9 pixels mm-1 | θmax = 32.6°, θmin = 2.2° |
ϕ and ω scans | h = −11→12 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −17→17 |
Tmin = 0.471, Tmax = 0.535 | l = −22→22 |
18613 measured reflections |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0365P)2 + 1.9698P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
5357 reflections | Δρmax = 1.26 e Å−3 |
199 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2287 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.022 (12) |
[Cu(NO3)(C9H21N3)]ClO4 | V = 1524.40 (3) Å3 |
Mr = 396.29 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.5512 (1) Å | µ = 1.65 mm−1 |
b = 11.8172 (1) Å | T = 173 K |
c = 15.0854 (2) Å | 0.58 × 0.50 × 0.38 mm |
Nonius KappaCCD diffractometer | 5357 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 5008 reflections with I > 2σ(I) |
Tmin = 0.471, Tmax = 0.535 | Rint = 0.030 |
18613 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.092 | Δρmax = 1.26 e Å−3 |
S = 1.04 | Δρmin = −0.52 e Å−3 |
5357 reflections | Absolute structure: Flack (1983), 2287 Friedel pairs |
199 parameters | Absolute structure parameter: 0.022 (12) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.30811 (3) | 0.52508 (2) | 0.68389 (2) | 0.01707 (6) | |
C1 | 0.0622 (4) | 0.4439 (3) | 0.5649 (3) | 0.0423 (8) | |
H1A | 0.1042 | 0.4194 | 0.5068 | 0.051* | |
H1B | −0.0529 | 0.4489 | 0.5594 | 0.051* | |
C2 | 0.1018 (4) | 0.3567 (3) | 0.6328 (3) | 0.0391 (7) | |
H2A | 0.0317 | 0.3667 | 0.6844 | 0.047* | |
H2B | 0.0812 | 0.2808 | 0.6076 | 0.047* | |
N1 | 0.2651 (2) | 0.36088 (17) | 0.66366 (14) | 0.0209 (4) | |
C3 | 0.3819 (4) | 0.3200 (2) | 0.5972 (2) | 0.0347 (6) | |
H3A | 0.3290 | 0.3083 | 0.5396 | 0.042* | |
H3B | 0.4244 | 0.2462 | 0.6169 | 0.042* | |
C4 | 0.5131 (4) | 0.4016 (3) | 0.5854 (2) | 0.0366 (7) | |
H4A | 0.5699 | 0.3837 | 0.5300 | 0.044* | |
H4B | 0.5873 | 0.3939 | 0.6354 | 0.044* | |
N2 | 0.4542 (2) | 0.52076 (18) | 0.58149 (12) | 0.0190 (3) | |
C5 | 0.3702 (4) | 0.5453 (3) | 0.49849 (17) | 0.0350 (6) | |
H5A | 0.3493 | 0.4732 | 0.4672 | 0.042* | |
H5B | 0.4380 | 0.5920 | 0.4599 | 0.042* | |
C6 | 0.2191 (4) | 0.6058 (3) | 0.5127 (2) | 0.0372 (7) | |
H6A | 0.2410 | 0.6862 | 0.5261 | 0.045* | |
H6B | 0.1572 | 0.6030 | 0.4573 | 0.045* | |
N3 | 0.1248 (3) | 0.55671 (18) | 0.58601 (14) | 0.0217 (4) | |
C7 | 0.2790 (5) | 0.2954 (2) | 0.74693 (19) | 0.0397 (8) | |
H7A | 0.2594 | 0.2152 | 0.7348 | 0.060* | |
H7B | 0.2023 | 0.3232 | 0.7900 | 0.060* | |
H7C | 0.3846 | 0.3046 | 0.7712 | 0.060* | |
C8 | 0.5888 (4) | 0.5974 (3) | 0.5937 (2) | 0.0353 (6) | |
H8A | 0.6579 | 0.5923 | 0.5420 | 0.053* | |
H8B | 0.6467 | 0.5754 | 0.6471 | 0.053* | |
H8C | 0.5513 | 0.6753 | 0.6001 | 0.053* | |
C9 | 0.0079 (4) | 0.6380 (3) | 0.6158 (2) | 0.0378 (7) | |
H9A | −0.0705 | 0.6487 | 0.5692 | 0.057* | |
H9B | 0.0587 | 0.7105 | 0.6288 | 0.057* | |
H9C | −0.0431 | 0.6094 | 0.6695 | 0.057* | |
N4 | 0.2650 (2) | 0.64862 (17) | 0.80874 (14) | 0.0217 (4) | |
O1 | 0.2008 (2) | 0.55106 (15) | 0.80114 (11) | 0.0272 (4) | |
O2 | 0.3491 (2) | 0.67710 (15) | 0.74297 (12) | 0.0253 (4) | |
O3 | 0.2453 (3) | 0.70790 (18) | 0.87347 (13) | 0.0342 (5) | |
Cl1 | 0.69620 (8) | 0.46211 (5) | 0.84834 (4) | 0.02538 (11) | |
O4 | 0.5505 (4) | 0.4930 (3) | 0.8089 (2) | 0.0699 (9) | |
O5 | 0.7523 (4) | 0.5551 (2) | 0.90031 (19) | 0.0525 (7) | |
O6 | 0.8029 (4) | 0.4361 (3) | 0.7792 (2) | 0.0717 (10) | |
O7 | 0.6700 (4) | 0.3670 (2) | 0.90447 (17) | 0.0545 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01792 (11) | 0.01877 (10) | 0.01451 (10) | −0.00223 (10) | 0.00225 (10) | −0.00021 (9) |
C1 | 0.0369 (16) | 0.0340 (14) | 0.056 (2) | −0.0064 (12) | −0.0219 (15) | 0.0005 (14) |
C2 | 0.0288 (14) | 0.0318 (14) | 0.057 (2) | −0.0104 (11) | −0.0092 (14) | 0.0054 (14) |
N1 | 0.0225 (9) | 0.0175 (8) | 0.0229 (9) | −0.0028 (7) | 0.0008 (7) | 0.0020 (7) |
C3 | 0.0391 (15) | 0.0216 (11) | 0.0435 (16) | 0.0030 (10) | 0.0157 (13) | −0.0003 (10) |
C4 | 0.0357 (15) | 0.0287 (13) | 0.0455 (17) | 0.0032 (11) | 0.0141 (13) | −0.0011 (12) |
N2 | 0.0195 (8) | 0.0198 (8) | 0.0178 (7) | −0.0046 (8) | 0.0036 (6) | −0.0007 (7) |
C5 | 0.0334 (14) | 0.0528 (19) | 0.0189 (10) | −0.0055 (13) | −0.0018 (10) | 0.0070 (11) |
C6 | 0.0384 (17) | 0.0458 (16) | 0.0273 (13) | 0.0086 (13) | 0.0012 (12) | 0.0147 (12) |
N3 | 0.0200 (9) | 0.0233 (9) | 0.0217 (9) | 0.0011 (7) | −0.0009 (7) | 0.0008 (7) |
C7 | 0.066 (2) | 0.0259 (11) | 0.0277 (12) | −0.0043 (13) | 0.0049 (14) | 0.0081 (10) |
C8 | 0.0261 (13) | 0.0516 (18) | 0.0281 (12) | −0.0163 (12) | 0.0049 (11) | −0.0054 (12) |
C9 | 0.0251 (13) | 0.0471 (17) | 0.0413 (16) | 0.0115 (12) | −0.0033 (12) | −0.0023 (14) |
N4 | 0.0240 (9) | 0.0244 (8) | 0.0165 (8) | −0.0021 (7) | 0.0020 (7) | −0.0008 (7) |
O1 | 0.0310 (9) | 0.0270 (8) | 0.0235 (8) | −0.0103 (7) | 0.0079 (8) | −0.0034 (6) |
O2 | 0.0306 (10) | 0.0253 (8) | 0.0199 (8) | −0.0046 (7) | 0.0056 (7) | 0.0006 (6) |
O3 | 0.0460 (12) | 0.0340 (10) | 0.0226 (9) | −0.0047 (9) | 0.0074 (8) | −0.0099 (8) |
Cl1 | 0.0271 (3) | 0.0273 (2) | 0.0218 (2) | 0.0020 (2) | −0.0015 (2) | 0.00087 (19) |
O4 | 0.0503 (16) | 0.088 (2) | 0.072 (2) | 0.0142 (16) | −0.0305 (16) | 0.0087 (19) |
O5 | 0.0766 (19) | 0.0335 (11) | 0.0473 (14) | −0.0063 (12) | −0.0132 (13) | −0.0095 (10) |
O6 | 0.0585 (18) | 0.088 (2) | 0.0692 (19) | −0.0136 (18) | 0.0365 (17) | −0.0250 (17) |
O7 | 0.096 (2) | 0.0320 (11) | 0.0355 (12) | −0.0048 (14) | −0.0047 (15) | 0.0093 (9) |
Cu1—N2 | 1.987 (2) | C4—N2 | 1.497 (4) |
Cu1—N1 | 1.998 (2) | N2—C5 | 1.472 (3) |
Cu1—O1 | 2.016 (2) | N2—C8 | 1.476 (3) |
Cu1—O2 | 2.036 (2) | C5—C6 | 1.492 (5) |
Cu1—N3 | 2.186 (2) | C6—N3 | 1.486 (4) |
Cu1—N4 | 2.411 (2) | N3—C9 | 1.457 (4) |
Cu1—O4 | 2.828 (3) | N4—O3 | 1.213 (3) |
C1—N3 | 1.472 (4) | N4—O2 | 1.271 (3) |
C1—C2 | 1.492 (5) | N4—O1 | 1.282 (3) |
C2—N1 | 1.473 (4) | Cl1—O6 | 1.419 (3) |
N1—C7 | 1.480 (3) | Cl1—O7 | 1.425 (2) |
N1—C3 | 1.495 (4) | Cl1—O4 | 1.428 (3) |
C3—C4 | 1.490 (4) | Cl1—O5 | 1.433 (2) |
N2—Cu1—N1 | 88.40 (9) | C8—N2—C4 | 108.1 (2) |
N2—Cu1—O1 | 166.39 (8) | C5—N2—Cu1 | 110.4 (2) |
N1—Cu1—O1 | 101.43 (8) | C8—N2—Cu1 | 112.2 (2) |
N2—Cu1—O2 | 104.75 (8) | C4—N2—Cu1 | 101.8 (2) |
N1—Cu1—O2 | 162.82 (8) | N2—C5—C6 | 113.2 (2) |
O1—Cu1—O2 | 63.89 (7) | N3—C6—C5 | 113.0 (2) |
N2—Cu1—N3 | 85.99 (8) | C9—N3—C1 | 114.5 (3) |
N1—Cu1—N3 | 86.04 (8) | C9—N3—C6 | 110.2 (2) |
O1—Cu1—N3 | 103.91 (9) | C1—N3—C6 | 112.9 (3) |
O2—Cu1—N3 | 105.57 (8) | C9—N3—Cu1 | 113.3 (2) |
N2—Cu1—N4 | 135.96 (8) | C1—N3—Cu1 | 104.6 (2) |
N1—Cu1—N4 | 132.77 (8) | C6—N3—Cu1 | 100.4 (2) |
O1—Cu1—N4 | 32.11 (7) | O3—N4—O2 | 123.6 (2) |
O2—Cu1—N4 | 31.81 (7) | O3—N4—O1 | 122.1 (2) |
N3—Cu1—N4 | 108.32 (8) | O2—N4—O1 | 114.3 (2) |
N3—C1—C2 | 113.2 (3) | O3—N4—Cu1 | 177.7 (2) |
N1—C2—C1 | 114.1 (3) | O2—N4—Cu1 | 57.59 (11) |
C2—N1—C7 | 109.1 (2) | O1—N4—Cu1 | 56.71 (11) |
C2—N1—C3 | 114.2 (3) | N4—O1—Cu1 | 91.19 (13) |
C7—N1—C3 | 110.3 (2) | N4—O2—Cu1 | 90.60 (13) |
C2—N1—Cu1 | 104.8 (2) | O6—Cl1—O7 | 111.5 (2) |
C7—N1—Cu1 | 111.3 (2) | O6—Cl1—O4 | 108.1 (2) |
C3—N1—Cu1 | 107.0 (2) | O7—Cl1—O4 | 108.2 (2) |
N1—C3—C4 | 112.0 (2) | O6—Cl1—O5 | 110.6 (2) |
C3—C4—N2 | 111.1 (2) | O7—Cl1—O5 | 109.4 (2) |
C5—N2—C8 | 111.5 (2) | O4—Cl1—O5 | 108.9 (2) |
C5—N2—C4 | 112.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1i | 0.99 | 2.56 | 3.245 (3) | 126 |
C4—H4B···O3ii | 0.99 | 2.63 | 3.145 (4) | 113 |
C3—H3A···O3i | 0.99 | 2.59 | 3.562 (4) | 166 |
C5—H5A···O3i | 0.99 | 2.69 | 3.672 (4) | 172 |
C4—H4A···O5iii | 0.99 | 2.58 | 3.477 (4) | 150 |
C2—H2A···O6iv | 0.99 | 2.56 | 3.506 (5) | 160 |
C8—H8A···O7iii | 0.98 | 2.59 | 3.547 (4) | 166 |
C9—H9A···O7i | 0.98 | 2.63 | 3.533 (5) | 153 |
C6—H6A···O7v | 0.99 | 2.50 | 3.463 (5) | 165 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+3/2, −y+1, z−1/2; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NO3)(C9H21N3)]ClO4 |
Mr | 396.29 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 8.5512 (1), 11.8172 (1), 15.0854 (2) |
V (Å3) | 1524.40 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.58 × 0.50 × 0.38 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.471, 0.535 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18613, 5357, 5008 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.758 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.092, 1.04 |
No. of reflections | 5357 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.26, −0.52 |
Absolute structure | Flack (1983), 2287 Friedel pairs |
Absolute structure parameter | 0.022 (12) |
Computer programs: COLLECT (Hooft, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
Cu1—N2 | 1.987 (2) | Cu1—N3 | 2.186 (2) |
Cu1—N1 | 1.998 (2) | Cu1—N4 | 2.411 (2) |
Cu1—O1 | 2.016 (2) | Cu1—O4 | 2.828 (3) |
Cu1—O2 | 2.036 (2) | ||
N2—Cu1—N1 | 88.40 (9) | O1—Cu1—N3 | 103.91 (9) |
N2—Cu1—O1 | 166.39 (8) | O2—Cu1—N3 | 105.57 (8) |
N1—Cu1—O1 | 101.43 (8) | N2—Cu1—N4 | 135.96 (8) |
N2—Cu1—O2 | 104.75 (8) | N1—Cu1—N4 | 132.77 (8) |
N1—Cu1—O2 | 162.82 (8) | O1—Cu1—N4 | 32.11 (7) |
O1—Cu1—O2 | 63.89 (7) | O2—Cu1—N4 | 31.81 (7) |
N2—Cu1—N3 | 85.99 (8) | N3—Cu1—N4 | 108.32 (8) |
N1—Cu1—N3 | 86.04 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1i | 0.99 | 2.56 | 3.245 (3) | 126 |
C4—H4B···O3ii | 0.99 | 2.63 | 3.145 (4) | 113 |
C3—H3A···O3i | 0.99 | 2.59 | 3.562 (4) | 166 |
C5—H5A···O3i | 0.99 | 2.69 | 3.672 (4) | 172 |
C4—H4A···O5iii | 0.99 | 2.58 | 3.477 (4) | 150 |
C2—H2A···O6iv | 0.99 | 2.56 | 3.506 (5) | 160 |
C8—H8A···O7iii | 0.98 | 2.59 | 3.547 (4) | 166 |
C9—H9A···O7i | 0.98 | 2.63 | 3.533 (5) | 153 |
C6—H6A···O7v | 0.99 | 2.50 | 3.463 (5) | 165 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+3/2, −y+1, z−1/2; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+3/2. |
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Recent work has reported the synthesis of M8(CN)12 cubes in which the formation of the cubes is directed by the occupation of three facial coordination sites of the octahedral metal ions by `capping' ligands, such as cyclopentadiene or triazacyclononane derivatives (Heinrich et al., 1998; Klausmeyer et al., 1998, 1999). In such work, precursor complexes which contain one such tridentate `capping' ligand and three further accessible coordination sites are important components in the reaction design. We report here the structure of one such complex.
The structure of the title complex, (I), is shown in Fig. 1. It consists of a Cu atom coordinated facially by the tridentate 1,4,7-trimethyl-1,4,7-triazacyclononane ligand, and also by a chelating nitrate anion (Table 1). Although the Cu atom is nominally five-coordinate, it also makes a weak interaction [2.828 (3) Å] with an O atom of the perchlorate anion. An unusual feature of this simple complex is the presence of two different types of counter-anion. This is likely due to crystal packing effects; both the nitrate and the perchlorate participate in a number of weak intermolecular C—H···O contacts with the organic ligands (Table 2).