Acta Cryst. (2012). E68, m43 [ doi:10.1107/S1600536811050999 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-4-azidobenzoato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2O:O')bis[(N,N-dimethylformamide-O)copper(II)]The binuclear title compound, [Cu2(C7H4N3O2)4(C3H7NO)2], is a discrete metal-organic compound having a paddle-wheel-type structure. The Cu
Cu distance is 2.6366 (5) Å and an inversion center is located at the mid-point of this bond. The CuII cation is coordinated by four carboxylate O atoms from four 4-azidobenzoate ligands, and one O atom from a dimethylformamide molecule, forming an overall distorted octahedral geometry when the CuCu bond is also considered.
4-Azidobenzoic acid was prepared from 4-aminoisophthalic acid by diazotization followed by azidation with sodium azide (Sato et al., 2010). A mixture of Cu(NO3)2 3 H2O (0.130 g, 0.5 mmol) 4-azidobenzoic acid (0.085 g,0.5 mmol) and DMF (5 ml) was sealed in a 20 ml stainless steel reactor with Teflon liner and heated at 393 K for 4 days. Blue crystals of the title complex were obtained.
H atoms bonded to C atoms were positioned geometrically. C—H bonds lengths were fixed at 0.93 Å for aromatic CH groups and 0.96 Å for methyl groups, and H atoms were allowed to ride on their parent atoms. Isotropic displacement parameters were calculated as Uiso(H)=1.2Ueq(carrier C) for aromatic CH and Uiso(H)=1.5Ueq(carrier C) for methyl groups.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./bh2402fig1thm.gif)
| Fig. 1. A molecular drawing of the title complex, showing 30% probability displacement ellipsoids. All H atoms were omitted for clarity. Unlabeled atoms are generated by symmetry -x, 1-y, 1-z. |
| [Cu2(C7H4N3O2)4(C3H7NO)2] | F(000) = 940 |
| Mr = 921.80 | Dx = 1.529 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 4783 reflections |
| a = 11.9209 (8) Å | θ = 3.1–25° |
| b = 17.9387 (10) Å | µ = 1.14 mm−1 |
| c = 9.3680 (5) Å | T = 293 K |
| β = 91.277 (5)° | Block, blue |
| V = 2002.8 (2) Å3 | 0.2 × 0.2 × 0.2 mm |
| Z = 2 |
| Rigaku Mercury70 diffractometer | 3496 independent reflections |
| Radiation source: fine-focus sealed tube | 3141 reflections with I > 2σ(I) |
| graphite | Rint = 0.031 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
| ω scans | h = −14→14 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2002) | k = −19→21 |
| Tmin = 0.805, Tmax = 0.805 | l = −11→11 |
| 12312 measured reflections |
| 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) = 0.091 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.7327P] where P = (Fo2 + 2Fc2)/3 |
| 3496 reflections | (Δ/σ)max = 0.001 |
| 271 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.31 e Å−3 |
| 0 constraints |
| [Cu2(C7H4N3O2)4(C3H7NO)2] | V = 2002.8 (2) Å3 |
| Mr = 921.80 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.9209 (8) Å | µ = 1.14 mm−1 |
| b = 17.9387 (10) Å | T = 293 K |
| c = 9.3680 (5) Å | 0.2 × 0.2 × 0.2 mm |
| β = 91.277 (5)° |
| Rigaku Mercury70 diffractometer | 3496 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2002) | 3141 reflections with I > 2σ(I) |
| Tmin = 0.805, Tmax = 0.805 | Rint = 0.031 |
| 12312 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.091 | Δρmax = 0.33 e Å−3 |
| S = 1.02 | Δρmin = −0.31 e Å−3 |
| 3496 reflections | Absolute structure: ? |
| 271 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.05068 (2) | 0.451211 (14) | 0.58459 (3) | 0.03461 (12) | |
| O1 | 0.16267 (14) | 0.44589 (9) | 0.43570 (18) | 0.0472 (4) | |
| O5 | 0.12483 (14) | 0.36844 (9) | 0.72800 (17) | 0.0470 (4) | |
| O3 | 0.04281 (13) | 0.62087 (9) | 0.52445 (18) | 0.0461 (4) | |
| O2 | 0.07599 (14) | 0.52740 (10) | 0.28944 (17) | 0.0467 (4) | |
| O4 | 0.12931 (15) | 0.53807 (9) | 0.66805 (19) | 0.0497 (4) | |
| N7 | 0.1214 (2) | 0.31119 (12) | 0.9451 (2) | 0.0567 (6) | |
| N1 | 0.4690 (2) | 0.4056 (2) | −0.1016 (3) | 0.0854 (9) | |
| N2 | 0.4467 (3) | 0.4246 (2) | −0.2269 (4) | 0.1045 (11) | |
| N6 | 0.4782 (4) | 0.8193 (3) | 1.0817 (4) | 0.1397 (18) | |
| N3 | 0.4367 (4) | 0.4395 (3) | −0.3436 (4) | 0.155 (2) | |
| N4 | 0.3389 (3) | 0.84292 (18) | 0.9011 (3) | 0.0855 (9) | |
| N5 | 0.4106 (3) | 0.8267 (2) | 0.9946 (3) | 0.0987 (12) | |
| C4 | 0.3881 (2) | 0.42884 (18) | −0.0005 (3) | 0.0584 (7) | |
| C7 | 0.15287 (19) | 0.48163 (13) | 0.3208 (2) | 0.0398 (5) | |
| C15 | 0.0863 (2) | 0.35912 (14) | 0.8475 (3) | 0.0484 (6) | |
| H15A | 0.0259 | 0.3892 | 0.8714 | 0.058* | |
| C1 | 0.2378 (2) | 0.46654 (13) | 0.2094 (3) | 0.0414 (5) | |
| C8 | 0.17273 (19) | 0.66528 (13) | 0.6976 (2) | 0.0409 (5) | |
| C2 | 0.2172 (2) | 0.48554 (14) | 0.0677 (2) | 0.0460 (6) | |
| H2A | 0.1524 | 0.5118 | 0.0430 | 0.055* | |
| C6 | 0.3359 (2) | 0.42912 (18) | 0.2440 (3) | 0.0595 (7) | |
| H6A | 0.3512 | 0.4159 | 0.3384 | 0.071* | |
| C13 | 0.1512 (2) | 0.73877 (15) | 0.6624 (3) | 0.0539 (6) | |
| H13A | 0.0985 | 0.7498 | 0.5907 | 0.065* | |
| C3 | 0.2911 (2) | 0.46609 (15) | −0.0371 (3) | 0.0512 (6) | |
| H3A | 0.2753 | 0.4781 | −0.1320 | 0.061* | |
| C9 | 0.2511 (2) | 0.65078 (16) | 0.8053 (3) | 0.0556 (7) | |
| H9A | 0.2661 | 0.6016 | 0.8308 | 0.067* | |
| C14 | 0.11051 (19) | 0.60338 (13) | 0.6237 (2) | 0.0397 (5) | |
| C10 | 0.3073 (2) | 0.70738 (18) | 0.8752 (3) | 0.0603 (7) | |
| H10A | 0.3596 | 0.6966 | 0.9475 | 0.072* | |
| C12 | 0.2067 (3) | 0.79604 (16) | 0.7321 (3) | 0.0635 (8) | |
| H12B | 0.1908 | 0.8453 | 0.7081 | 0.076* | |
| C11 | 0.2856 (2) | 0.78027 (17) | 0.8373 (3) | 0.0576 (7) | |
| C17 | 0.0706 (3) | 0.3082 (2) | 1.0850 (3) | 0.0822 (11) | |
| H17A | 0.0097 | 0.3432 | 1.0881 | 0.123* | |
| H17B | 0.1258 | 0.3207 | 1.1572 | 0.123* | |
| H17C | 0.0428 | 0.2588 | 1.1018 | 0.123* | |
| C16 | 0.2150 (3) | 0.26297 (19) | 0.9201 (4) | 0.0807 (10) | |
| H16A | 0.2407 | 0.2704 | 0.8248 | 0.121* | |
| H16B | 0.1923 | 0.2120 | 0.9315 | 0.121* | |
| H16C | 0.2746 | 0.2742 | 0.9873 | 0.121* | |
| C5 | 0.4114 (2) | 0.4111 (2) | 0.1403 (3) | 0.0717 (9) | |
| H5A | 0.4781 | 0.3871 | 0.1652 | 0.086* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.04444 (19) | 0.02783 (19) | 0.03131 (18) | 0.00240 (10) | −0.00460 (12) | 0.00345 (10) |
| O1 | 0.0503 (10) | 0.0503 (11) | 0.0409 (9) | 0.0099 (7) | 0.0020 (7) | 0.0104 (8) |
| O5 | 0.0606 (10) | 0.0393 (10) | 0.0408 (9) | 0.0062 (8) | −0.0076 (7) | 0.0085 (8) |
| O3 | 0.0538 (10) | 0.0364 (10) | 0.0474 (9) | −0.0021 (7) | −0.0126 (8) | 0.0021 (8) |
| O2 | 0.0541 (10) | 0.0447 (10) | 0.0416 (9) | 0.0133 (8) | 0.0052 (7) | 0.0058 (8) |
| O4 | 0.0648 (11) | 0.0328 (10) | 0.0507 (10) | −0.0040 (8) | −0.0167 (8) | 0.0013 (8) |
| N7 | 0.0779 (15) | 0.0430 (13) | 0.0485 (12) | −0.0044 (11) | −0.0166 (11) | 0.0141 (10) |
| N1 | 0.0804 (18) | 0.112 (3) | 0.0643 (18) | 0.0276 (17) | 0.0221 (14) | −0.0009 (17) |
| N2 | 0.088 (2) | 0.157 (3) | 0.069 (2) | 0.035 (2) | 0.0240 (17) | −0.016 (2) |
| N6 | 0.135 (3) | 0.192 (5) | 0.091 (3) | −0.087 (3) | −0.021 (2) | −0.024 (3) |
| N3 | 0.131 (3) | 0.272 (7) | 0.061 (2) | 0.059 (3) | 0.026 (2) | −0.009 (3) |
| N4 | 0.094 (2) | 0.088 (2) | 0.0738 (18) | −0.0434 (17) | 0.0006 (16) | −0.0252 (16) |
| N5 | 0.105 (2) | 0.124 (3) | 0.0677 (19) | −0.068 (2) | 0.0097 (18) | −0.0299 (19) |
| C4 | 0.0564 (16) | 0.0638 (19) | 0.0553 (16) | 0.0072 (14) | 0.0110 (13) | −0.0019 (14) |
| C7 | 0.0454 (13) | 0.0319 (13) | 0.0421 (13) | 0.0001 (10) | −0.0022 (10) | −0.0011 (10) |
| C15 | 0.0594 (15) | 0.0403 (15) | 0.0450 (14) | −0.0014 (11) | −0.0108 (11) | 0.0081 (11) |
| C1 | 0.0471 (13) | 0.0353 (13) | 0.0418 (13) | 0.0009 (10) | 0.0004 (10) | 0.0003 (10) |
| C8 | 0.0455 (12) | 0.0370 (13) | 0.0403 (12) | −0.0018 (10) | 0.0023 (10) | −0.0048 (10) |
| C2 | 0.0527 (14) | 0.0416 (14) | 0.0437 (13) | 0.0080 (11) | −0.0016 (10) | 0.0015 (11) |
| C6 | 0.0550 (16) | 0.076 (2) | 0.0476 (15) | 0.0150 (14) | −0.0009 (12) | 0.0108 (14) |
| C13 | 0.0583 (15) | 0.0437 (16) | 0.0593 (16) | 0.0019 (12) | −0.0070 (12) | −0.0032 (13) |
| C3 | 0.0627 (16) | 0.0511 (16) | 0.0398 (14) | −0.0009 (13) | −0.0006 (11) | −0.0011 (12) |
| C9 | 0.0623 (16) | 0.0483 (16) | 0.0557 (16) | −0.0008 (13) | −0.0105 (12) | −0.0027 (13) |
| C14 | 0.0473 (13) | 0.0348 (13) | 0.0370 (12) | −0.0003 (10) | 0.0025 (10) | −0.0008 (10) |
| C10 | 0.0559 (16) | 0.073 (2) | 0.0517 (16) | −0.0075 (14) | −0.0087 (12) | −0.0109 (15) |
| C12 | 0.0780 (19) | 0.0398 (16) | 0.0725 (19) | −0.0082 (14) | −0.0040 (15) | −0.0064 (14) |
| C11 | 0.0612 (16) | 0.0577 (18) | 0.0543 (16) | −0.0193 (14) | 0.0113 (13) | −0.0180 (14) |
| C17 | 0.124 (3) | 0.076 (2) | 0.0466 (17) | −0.021 (2) | −0.0081 (17) | 0.0223 (15) |
| C16 | 0.098 (2) | 0.059 (2) | 0.084 (2) | 0.0146 (18) | −0.0344 (19) | 0.0090 (18) |
| C5 | 0.0555 (17) | 0.097 (3) | 0.0628 (18) | 0.0284 (16) | 0.0050 (14) | 0.0108 (18) |
| Cu1—O1 | 1.9545 (17) | C1—C2 | 1.387 (3) |
| Cu1—O4 | 1.9711 (17) | C1—C6 | 1.382 (4) |
| Cu1—O2i | 1.9747 (16) | C8—C13 | 1.382 (4) |
| Cu1—O3i | 1.9765 (16) | C8—C9 | 1.384 (3) |
| Cu1—O5 | 2.1767 (16) | C8—C14 | 1.496 (3) |
| Cu1—Cu1i | 2.6363 (5) | C2—C3 | 1.379 (3) |
| O1—C7 | 1.256 (3) | C2—H2A | 0.9300 |
| O5—C15 | 1.231 (3) | C6—C5 | 1.377 (4) |
| O3—C14 | 1.258 (3) | C6—H6A | 0.9300 |
| O3—Cu1i | 1.9765 (16) | C13—C12 | 1.379 (4) |
| O2—C7 | 1.260 (3) | C13—H13A | 0.9300 |
| O2—Cu1i | 1.9747 (16) | C3—H3A | 0.9300 |
| O4—C14 | 1.261 (3) | C9—C10 | 1.375 (4) |
| N7—C15 | 1.316 (3) | C9—H9A | 0.9300 |
| N7—C16 | 1.436 (4) | C10—C11 | 1.378 (4) |
| N7—C17 | 1.456 (4) | C10—H10A | 0.9300 |
| N1—N2 | 1.245 (4) | C12—C11 | 1.376 (4) |
| N1—C4 | 1.429 (3) | C12—H12B | 0.9300 |
| N2—N3 | 1.130 (5) | C17—H17A | 0.9600 |
| N6—N5 | 1.142 (5) | C17—H17B | 0.9600 |
| N4—N5 | 1.245 (5) | C17—H17C | 0.9600 |
| N4—C11 | 1.417 (4) | C16—H16A | 0.9600 |
| C4—C3 | 1.373 (4) | C16—H16B | 0.9600 |
| C4—C5 | 1.379 (4) | C16—H16C | 0.9600 |
| C7—C1 | 1.495 (3) | C5—H5A | 0.9300 |
| C15—H15A | 0.9300 | ||
| O1—Cu1—O4 | 89.73 (8) | C3—C2—C1 | 121.1 (2) |
| O1—Cu1—O2i | 168.40 (7) | C3—C2—H2A | 119.4 |
| O4—Cu1—O2i | 88.43 (8) | C1—C2—H2A | 119.4 |
| O1—Cu1—O3i | 89.17 (7) | C5—C6—C1 | 120.8 (3) |
| O4—Cu1—O3i | 168.48 (7) | C5—C6—H6A | 119.6 |
| O2i—Cu1—O3i | 90.35 (7) | C1—C6—H6A | 119.6 |
| O1—Cu1—O5 | 97.62 (6) | C12—C13—C8 | 120.9 (3) |
| O4—Cu1—O5 | 96.40 (7) | C12—C13—H13A | 119.6 |
| O2i—Cu1—O5 | 93.97 (7) | C8—C13—H13A | 119.6 |
| O3i—Cu1—O5 | 95.12 (7) | C4—C3—C2 | 119.6 (2) |
| O1—Cu1—Cu1i | 85.10 (5) | C4—C3—H3A | 120.2 |
| O4—Cu1—Cu1i | 85.48 (5) | C2—C3—H3A | 120.2 |
| O2i—Cu1—Cu1i | 83.34 (5) | C10—C9—C8 | 121.5 (3) |
| O3i—Cu1—Cu1i | 83.00 (5) | C10—C9—H9A | 119.2 |
| O5—Cu1—Cu1i | 176.69 (5) | C8—C9—H9A | 119.2 |
| C7—O1—Cu1 | 122.33 (15) | O3—C14—O4 | 125.6 (2) |
| C15—O5—Cu1 | 119.94 (16) | O3—C14—C8 | 117.4 (2) |
| C14—O3—Cu1i | 124.34 (15) | O4—C14—C8 | 117.0 (2) |
| C7—O2—Cu1i | 123.31 (15) | C9—C10—C11 | 119.4 (3) |
| C14—O4—Cu1 | 121.62 (15) | C9—C10—H10A | 120.3 |
| C15—N7—C16 | 121.1 (3) | C11—C10—H10A | 120.3 |
| C15—N7—C17 | 121.1 (3) | C11—C12—C13 | 120.0 (3) |
| C16—N7—C17 | 117.7 (3) | C11—C12—H12B | 120.0 |
| N2—N1—C4 | 114.4 (3) | C13—C12—H12B | 120.0 |
| N3—N2—N1 | 173.3 (4) | C12—C11—C10 | 120.1 (3) |
| N5—N4—C11 | 114.0 (3) | C12—C11—N4 | 115.6 (3) |
| N6—N5—N4 | 173.3 (4) | C10—C11—N4 | 124.3 (3) |
| C3—C4—C5 | 120.1 (2) | N7—C17—H17A | 109.5 |
| C3—C4—N1 | 123.6 (3) | N7—C17—H17B | 109.5 |
| C5—C4—N1 | 116.2 (3) | H17A—C17—H17B | 109.5 |
| O1—C7—O2 | 125.8 (2) | N7—C17—H17C | 109.5 |
| O1—C7—C1 | 117.0 (2) | H17A—C17—H17C | 109.5 |
| O2—C7—C1 | 117.1 (2) | H17B—C17—H17C | 109.5 |
| O5—C15—N7 | 126.9 (3) | N7—C16—H16A | 109.5 |
| O5—C15—H15A | 116.5 | N7—C16—H16B | 109.5 |
| N7—C15—H15A | 116.5 | H16A—C16—H16B | 109.5 |
| C2—C1—C6 | 118.4 (2) | N7—C16—H16C | 109.5 |
| C2—C1—C7 | 121.0 (2) | H16A—C16—H16C | 109.5 |
| C6—C1—C7 | 120.5 (2) | H16B—C16—H16C | 109.5 |
| C13—C8—C9 | 118.2 (2) | C4—C5—C6 | 120.0 (3) |
| C13—C8—C14 | 120.7 (2) | C4—C5—H5A | 120.0 |
| C9—C8—C14 | 121.1 (2) | C6—C5—H5A | 120.0 |
| Symmetry codes: (i) −x, −y+1, −z+1. |
Del Sesto, R. E., Arif, A. M. & Miller, J. S. (2000). Inorg. Chem. 39, 4894–4902.
Li, Y.-W., Zhao, J.-P., Wang, L.-F. & Bu, X.-H. (2011). CrystEngComm, 13, 6002–6006.
Rigaku (2002). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sato, H., Matsuda, R., Sugimoto, K., Takata, M. & Kitagawa, S. (2010). Nat. Mater. 9, 661–666.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The title compound, tetrakis(4-azidobenzoato)bis[(N,N-dimethylformamide)copper(II)], crystallizes in the monoclinic form with centrosymmetric space group P21/c. The asymmetric unit contains one copper atom, two 4-azidobenzoate ligands, and one DMF molecule. The Cu atom has a coordination number of six and is coordinated by four carboxylate O atoms from four 4-azidobenzoate ligands and one O atom from DMF molecule. The Cu—Cu bond length is 2.6366 (5) Å. The main structural feature of the title compound is the presence of the well known paddle-wheel unit (Del Sesto et al., 2000; Li et al., 2011) constructed by the asymmetric unit via the inversion symmetry. The azido groups of the ligands are not coordinated and the axial positions of the octahedral coordination polyhedra are occupied by two DMF molecules, to generate the 0D compound.