Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803015861/lh6087sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803015861/lh6087Isup2.hkl |
CCDC reference: 222797
Key indicators
- Single-crystal X-ray study
- T = 223 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.101
- Data-to-parameter ratio = 20.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - N2 = 6.28 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion
A single-crystal of (I) was grown in aqueous solution by slow diffusion using an H-double-tube glass vessel. Methanol solutions of Cu(Me2phen)(NO3)2 (0.01 M) and NaN3 (0.02 M) were placed in separate arms. After two months, brown crystals had separated.
The C—H atoms were included in the riding-model approximation, with C—H distances of 0.94 Å (0.97 Å for methyl), Uiso(phenyl-H) = 1.2Ueq(C) and Uiso(methyl-H) = 1.5Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHEXLTL.
[Cu2(N3)4(C14H12N2)2] | F(000) = 1448 |
Mr = 711.72 | Dx = 1.611 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 3661 reflections |
a = 13.3691 (5) Å | θ = 2.4–30.0° |
b = 11.2648 (5) Å | µ = 1.50 mm−1 |
c = 19.5792 (9) Å | T = 223 K |
β = 95.565 (2)° | Block, brown |
V = 2934.7 (2) Å3 | 0.49 × 0.16 × 0.16 mm |
Z = 4 |
Bruker AXS SMART CCD diffractometer | 4259 independent reflections |
Radiation source: fine-focus sealed tube | 3450 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 30.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000; Blessing, 1995) | h = −18→18 |
Tmin = 0.750, Tmax = 0.787 | k = −14→15 |
11979 measured reflections | l = −27→19 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0584P)2 + 0.0245P] where P = (Fo2 + 2Fc2)/3 |
4259 reflections | (Δ/σ)max = 0.001 |
210 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Cu2(N3)4(C14H12N2)2] | V = 2934.7 (2) Å3 |
Mr = 711.72 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.3691 (5) Å | µ = 1.50 mm−1 |
b = 11.2648 (5) Å | T = 223 K |
c = 19.5792 (9) Å | 0.49 × 0.16 × 0.16 mm |
β = 95.565 (2)° |
Bruker AXS SMART CCD diffractometer | 4259 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000; Blessing, 1995) | 3450 reflections with I > 2σ(I) |
Tmin = 0.750, Tmax = 0.787 | Rint = 0.032 |
11979 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.62 e Å−3 |
4259 reflections | Δρmin = −0.33 e Å−3 |
210 parameters |
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 | ||
Cu | 0.152642 (16) | 0.259903 (18) | 0.039472 (11) | 0.02300 (9) | |
N1 | 0.30477 (13) | 0.26186 (14) | 0.05616 (9) | 0.0285 (3) | |
N2 | 0.35279 (13) | 0.23119 (15) | 0.10891 (9) | 0.0309 (4) | |
N3 | 0.39785 (17) | 0.2044 (2) | 0.15878 (10) | 0.0558 (6) | |
N4 | 0.01649 (13) | 0.29821 (17) | 0.00094 (9) | 0.0348 (4) | |
N5 | −0.05016 (12) | 0.33126 (16) | 0.03205 (8) | 0.0327 (4) | |
N6 | −0.11857 (16) | 0.3630 (2) | 0.05827 (10) | 0.0570 (6) | |
N7 | 0.13577 (11) | 0.31505 (13) | 0.13648 (7) | 0.0233 (3) | |
N8 | 0.13538 (11) | 0.08577 (13) | 0.09397 (8) | 0.0253 (3) | |
C1 | 0.13146 (14) | 0.42862 (16) | 0.15577 (10) | 0.0271 (4) | |
C2 | 0.12784 (15) | 0.45956 (18) | 0.22500 (11) | 0.0331 (4) | |
H2 | 0.1249 | 0.5399 | 0.2376 | 0.040* | |
C3 | 0.12863 (15) | 0.37389 (19) | 0.27385 (10) | 0.0338 (4) | |
H3 | 0.1273 | 0.3949 | 0.3202 | 0.041* | |
C4 | 0.13139 (15) | 0.25342 (16) | 0.25485 (10) | 0.0283 (4) | |
C5 | 0.13421 (14) | 0.22804 (16) | 0.18496 (10) | 0.0236 (4) | |
C6 | 0.13254 (13) | 0.10597 (16) | 0.16216 (9) | 0.0248 (4) | |
C7 | 0.12679 (15) | 0.01531 (18) | 0.21068 (10) | 0.0306 (4) | |
C8 | 0.12536 (15) | 0.0440 (2) | 0.28141 (11) | 0.0372 (5) | |
H8 | 0.1224 | −0.0174 | 0.3137 | 0.045* | |
C9 | 0.12818 (15) | 0.1579 (2) | 0.30287 (10) | 0.0357 (5) | |
H9 | 0.1280 | 0.1748 | 0.3499 | 0.043* | |
C10 | 0.12010 (17) | −0.10215 (18) | 0.18507 (11) | 0.0388 (5) | |
H10 | 0.1148 | −0.1664 | 0.2151 | 0.047* | |
C11 | 0.12147 (17) | −0.12118 (18) | 0.11668 (12) | 0.0391 (5) | |
H11 | 0.1159 | −0.1990 | 0.0994 | 0.047* | |
C12 | 0.13115 (14) | −0.02539 (16) | 0.07126 (10) | 0.0292 (4) | |
C13 | 0.12982 (17) | 0.52244 (17) | 0.10197 (11) | 0.0365 (5) | |
H13A | 0.1420 | 0.4866 | 0.0585 | 0.055* | |
H13B | 0.1817 | 0.5806 | 0.1149 | 0.055* | |
H13C | 0.0647 | 0.5611 | 0.0975 | 0.055* | |
C14 | 0.13416 (17) | −0.04688 (18) | −0.00341 (11) | 0.0372 (5) | |
H14A | 0.1422 | 0.0281 | −0.0266 | 0.056* | |
H14B | 0.0720 | −0.0842 | −0.0219 | 0.056* | |
H14C | 0.1903 | −0.0986 | −0.0105 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02508 (13) | 0.02718 (13) | 0.01676 (13) | 0.00025 (8) | 0.00218 (8) | 0.00196 (8) |
N1 | 0.0278 (8) | 0.0404 (9) | 0.0174 (8) | 0.0011 (6) | 0.0023 (6) | 0.0043 (6) |
N2 | 0.0300 (9) | 0.0406 (9) | 0.0223 (8) | −0.0018 (7) | 0.0037 (7) | −0.0004 (7) |
N3 | 0.0514 (13) | 0.0852 (16) | 0.0289 (11) | 0.0056 (12) | −0.0052 (9) | 0.0127 (11) |
N4 | 0.0298 (9) | 0.0499 (10) | 0.0239 (8) | 0.0066 (8) | −0.0007 (7) | −0.0004 (8) |
N5 | 0.0329 (9) | 0.0443 (9) | 0.0201 (8) | 0.0030 (7) | −0.0012 (6) | 0.0071 (7) |
N6 | 0.0469 (12) | 0.0960 (18) | 0.0296 (10) | 0.0245 (12) | 0.0105 (9) | 0.0077 (11) |
N7 | 0.0240 (7) | 0.0264 (7) | 0.0193 (7) | 0.0014 (6) | 0.0020 (5) | 0.0004 (6) |
N8 | 0.0257 (7) | 0.0255 (7) | 0.0248 (8) | −0.0015 (6) | 0.0025 (6) | 0.0013 (6) |
C1 | 0.0260 (9) | 0.0293 (9) | 0.0257 (9) | 0.0013 (7) | 0.0015 (7) | −0.0020 (7) |
C2 | 0.0340 (10) | 0.0336 (10) | 0.0318 (10) | 0.0008 (8) | 0.0041 (8) | −0.0066 (8) |
C3 | 0.0321 (10) | 0.0473 (11) | 0.0224 (9) | 0.0006 (9) | 0.0041 (7) | −0.0089 (8) |
C4 | 0.0238 (9) | 0.0406 (11) | 0.0206 (9) | 0.0012 (7) | 0.0029 (7) | 0.0025 (7) |
C5 | 0.0208 (8) | 0.0307 (8) | 0.0196 (9) | 0.0012 (7) | 0.0029 (6) | 0.0039 (7) |
C6 | 0.0216 (8) | 0.0292 (9) | 0.0234 (9) | −0.0002 (7) | 0.0012 (6) | 0.0050 (7) |
C7 | 0.0262 (9) | 0.0353 (10) | 0.0299 (10) | −0.0009 (8) | 0.0015 (7) | 0.0111 (8) |
C8 | 0.0353 (11) | 0.0481 (12) | 0.0284 (11) | 0.0012 (9) | 0.0053 (8) | 0.0153 (9) |
C9 | 0.0365 (11) | 0.0519 (12) | 0.0190 (9) | 0.0005 (9) | 0.0045 (8) | 0.0079 (9) |
C10 | 0.0441 (12) | 0.0296 (10) | 0.0417 (12) | −0.0026 (8) | −0.0007 (10) | 0.0134 (9) |
C11 | 0.0458 (12) | 0.0273 (9) | 0.0431 (12) | −0.0031 (8) | −0.0022 (10) | 0.0053 (8) |
C12 | 0.0284 (9) | 0.0275 (9) | 0.0313 (10) | −0.0012 (7) | 0.0006 (8) | 0.0023 (8) |
C13 | 0.0501 (12) | 0.0250 (9) | 0.0338 (11) | 0.0013 (8) | 0.0007 (9) | 0.0014 (8) |
C14 | 0.0467 (12) | 0.0280 (9) | 0.0371 (11) | −0.0032 (9) | 0.0045 (9) | −0.0038 (8) |
Cu—N1 | 2.0285 (17) | C4—C9 | 1.432 (3) |
Cu—N4 | 1.9499 (17) | C5—C6 | 1.445 (3) |
Cu—N7 | 2.0316 (15) | C6—C7 | 1.402 (2) |
Cu—N8 | 2.2554 (15) | C7—C10 | 1.415 (3) |
Cu—N1i | 2.0240 (17) | C7—C8 | 1.424 (3) |
N1—N2 | 1.212 (2) | C8—C9 | 1.350 (3) |
N2—N3 | 1.137 (2) | C8—H8 | 0.9400 |
N4—N5 | 1.187 (2) | C9—H9 | 0.9400 |
N5—N6 | 1.149 (2) | C10—C11 | 1.358 (3) |
N7—C1 | 1.337 (2) | C10—H10 | 0.9400 |
N7—C5 | 1.366 (2) | C11—C12 | 1.412 (3) |
N8—C12 | 1.328 (2) | C11—H11 | 0.9400 |
N8—C6 | 1.359 (2) | C12—C14 | 1.486 (3) |
C1—C2 | 1.405 (3) | C13—H13A | 0.9700 |
C1—C13 | 1.491 (3) | C13—H13B | 0.9700 |
C2—C3 | 1.358 (3) | C13—H13C | 0.9700 |
C2—H2 | 0.9400 | C14—H14A | 0.9700 |
C3—C4 | 1.409 (3) | C14—H14B | 0.9700 |
C3—H3 | 0.9400 | C14—H14C | 0.9700 |
C4—C5 | 1.402 (3) | ||
N1—Cu—N4 | 160.67 (7) | N7—C5—C6 | 117.96 (16) |
N1—Cu—N7 | 92.67 (6) | C4—C5—C6 | 119.64 (16) |
N1—Cu—N8 | 94.60 (6) | N8—C6—C7 | 123.54 (17) |
N1—Cu—N1i | 77.45 (7) | N8—C6—C5 | 117.51 (15) |
N4—Cu—N7 | 96.31 (7) | C7—C6—C5 | 118.94 (17) |
N4—Cu—N8 | 103.95 (7) | C6—C7—C10 | 116.54 (18) |
N4—Cu—N1i | 90.27 (7) | C6—C7—C8 | 120.03 (18) |
N7—Cu—N8 | 78.34 (6) | C10—C7—C8 | 123.41 (18) |
N7—Cu—N1i | 165.60 (6) | C9—C8—C7 | 121.06 (19) |
N8—Cu—N1i | 112.53 (6) | C9—C8—H8 | 119.5 |
Cu—N1—N2 | 125.03 (14) | C7—C8—H8 | 119.5 |
Cui—N1—N2 | 125.47 (14) | C8—C9—C4 | 120.76 (18) |
Cu—N1—Cui | 102.55 (7) | C8—C9—H9 | 119.6 |
N1—N2—N3 | 178.8 (2) | C4—C9—H9 | 119.6 |
Cu—N4—N5 | 126.15 (14) | C11—C10—C7 | 119.39 (18) |
N4—N5—N6 | 175.6 (2) | C11—C10—H10 | 120.3 |
C1—N7—C5 | 119.11 (16) | C7—C10—H10 | 120.3 |
C1—N7—Cu | 124.64 (12) | C10—C11—C12 | 120.74 (19) |
C5—N7—Cu | 116.16 (12) | C10—C11—H11 | 119.6 |
C12—N8—C6 | 118.85 (16) | C12—C11—H11 | 119.6 |
C12—N8—Cu | 131.65 (13) | N8—C12—C11 | 120.88 (18) |
C6—N8—Cu | 109.46 (11) | N8—C12—C14 | 118.58 (17) |
N7—C1—C2 | 121.09 (17) | C11—C12—C14 | 120.52 (17) |
N7—C1—C13 | 118.49 (17) | C1—C13—H13A | 109.5 |
C2—C1—C13 | 120.42 (17) | C1—C13—H13B | 109.5 |
C3—C2—C1 | 120.31 (18) | H13A—C13—H13B | 109.5 |
C3—C2—H2 | 119.8 | C1—C13—H13C | 109.5 |
C1—C2—H2 | 119.8 | H13A—C13—H13C | 109.5 |
C2—C3—C4 | 119.81 (18) | H13B—C13—H13C | 109.5 |
C2—C3—H3 | 120.1 | C12—C14—H14A | 109.5 |
C4—C3—H3 | 120.1 | C12—C14—H14B | 109.5 |
C5—C4—C3 | 117.27 (17) | H14A—C14—H14B | 109.5 |
C5—C4—C9 | 119.53 (17) | C12—C14—H14C | 109.5 |
C3—C4—C9 | 123.16 (18) | H14A—C14—H14C | 109.5 |
N7—C5—C4 | 122.38 (16) | H14B—C14—H14C | 109.5 |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(N3)4(C14H12N2)2] |
Mr | 711.72 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 223 |
a, b, c (Å) | 13.3691 (5), 11.2648 (5), 19.5792 (9) |
β (°) | 95.565 (2) |
V (Å3) | 2934.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.50 |
Crystal size (mm) | 0.49 × 0.16 × 0.16 |
Data collection | |
Diffractometer | Bruker AXS SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000; Blessing, 1995) |
Tmin, Tmax | 0.750, 0.787 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11979, 4259, 3450 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.101, 1.04 |
No. of reflections | 4259 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.33 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), PATTY in DIRDIF92 (Beurskens et al., 1992), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHEXLTL.
Cu—N1 | 2.0285 (17) | N1—N2 | 1.212 (2) |
Cu—N4 | 1.9499 (17) | N2—N3 | 1.137 (2) |
Cu—N7 | 2.0316 (15) | N4—N5 | 1.187 (2) |
Cu—N8 | 2.2554 (15) | N5—N6 | 1.149 (2) |
Cu—N1i | 2.0240 (17) | ||
N1—Cu—N4 | 160.67 (7) | N7—Cu—N1i | 165.60 (6) |
N1—Cu—N7 | 92.67 (6) | N8—Cu—N1i | 112.53 (6) |
N1—Cu—N8 | 94.60 (6) | Cu—N1—N2 | 125.03 (14) |
N1—Cu—N1i | 77.45 (7) | Cui—N1—N2 | 125.47 (14) |
N4—Cu—N7 | 96.31 (7) | Cu—N1—Cui | 102.55 (7) |
N4—Cu—N8 | 103.95 (7) | N1—N2—N3 | 178.8 (2) |
N4—Cu—N1i | 90.27 (7) | Cu—N4—N5 | 126.15 (14) |
N7—Cu—N8 | 78.34 (6) | N4—N5—N6 | 175.6 (2) |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
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Azide-bridged copper(II) complexes involving combinations of chelating 1,10-phenanthroline (phen) ligands with end-on (µ1,1) and/or end-to-end (µ1,3) azides have been structurally determined. For example, [Cu(phen)(N3)2]n adopts a chain motif (Li et al., 2000) and [Cu(phen)(N3)3]2·2N3·4H2O is dimeric and features lattice azide (Cheng et al., 2002). In order to determine the affect of steric hindrance in the phen ligand by introducing methyl groups at the 4- and 7-positions, so as to generate Me2phen, we synthesized the complex [Cu(Me2phen)(N3)2]2, (I).
The dinuclear structure of [Cu(Me2phen)(N3)2]2 (Fig. 1) is situated about a twofold axis of symmetry and features µ2-bridging and terminal azides as well as chelating Me2phen ligands. The bridges are effectively symmetric (Table 1) and, as expected, the bridging Cu—Nazide distances are longer than the terminal Cu—Nazide distance. The Cu···Cui separation within the dimer is 3.1616 (3) Å [symmetry code: (i) −x + 1/2, −y + 1/2, −z]. The coordination geometry for Cu is based on a square pyramid. Thus, azide atoms N1, N4 and N1i and the Me2phen N7 atom define the basal plane and have deviations of 0.040 (2), 0.022 (3), −0.015 (3) and −0.060 (2) Å, respectively, from their least-squares plane. The Cu atom lies 0.2449 (3) Å out of this plane in the direction of atom N8. This arrangement introduces some of the disparity in the Cu—Nchelate bond distances with the axial Cu—N8 distance being significantly longer than the basal Cu—N distance. Within the molecule, the disposition of the Me2phen methyl groups are such so as to place one of the methyl-H atoms directly above the N1 atom with C14—H···N1i = 2.55 Å, C14···N1i = 3.494 (3) Å and the angle subtended at H = 164°. The most significant contact in the lattice is also of the type C—H···N so that C3—H···N6ii = 2.42 Å, C3···N6ii = 3.305 (3) Å and the angle at H = 157° [symmetry code: (ii) −x, y, 1/2 − z]. Such associations, as described, lead to the formation of weakly associated chains comprising complex molecules.
There is one closely related structure available in the literature available for comparison, namely that of di-µ2-azido-bis[azido(N,N-diethylethylenediamine)copper(II)] (Casagrande et al., 1989). This is centrosymmetric in contrast to the title complex but features essentially the same pattern of bond distances.