The Cu atom in the title compound, [Cu(C
16H
10BrN
4O
3)
2(C
3H
7NO)
2], lies on a special position of
site symmetry in a grossly elongated CuN
2O
4 octahedral geometry [Cu
O
DMF = 3.014 (4) Å]. The Cu atom is also
N,
O-chelated by the hydrazonate ligand. An N—H
O hydrogen bond helps to consolidate the crystal packing.
Supporting information
CCDC reference: 605071
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.006 Å
- R factor = 0.055
- wR factor = 0.180
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level B
ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
Tmin and Tmax reported: 0.114 0.686
Tmin(prime) and Tmax expected: 0.201 0.686
RR(prime) = 0.568
Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.52
PLAT731_ALERT_1_B Bond Calc 0.85(5), Rep 0.850(10) ...... 5.00 su-Rat
N4 -H4N 1.555 1.555
PLAT735_ALERT_1_B D-H Calc 0.85(5), Rep 0.850(10) ...... 5.00 su-Rat
N4 -H4N 1.555 1.555
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.62 mm
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N5
PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O3 .. 3.36 Ang.
PLAT736_ALERT_1_C H...A Calc 1.95(5), Rep 1.95(2) ...... 2.50 su-Rat
H4N -O4 1.555 1.565
0 ALERT level A = In general: serious problem
4 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
4 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
3 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: CrystalStructure (Rigaku/MSC, 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Bis(5-bromo-1
H-indole-3-carbaldehyde 2-nitrobenzoylhydrazonato-
κ2N,
O)bis(
N,
N-dimethylformamide-
κO)copper(II)
top
Crystal data top
[Cu(C16H10BrN4O3)2(C3H7NO)2] | Z = 1 |
Mr = 982.11 | F(000) = 495 |
Triclinic, P1 | Dx = 1.573 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.643 (5) Å | Cell parameters from 3209 reflections |
b = 9.102 (5) Å | θ = 2.4–28.0° |
c = 14.302 (9) Å | µ = 2.52 mm−1 |
α = 99.84 (2)° | T = 295 K |
β = 99.27 (1)° | Block, green |
γ = 106.43 (1)° | 0.62 × 0.44 × 0.15 mm |
V = 1037 (1) Å3 | |
Data collection top
Rigaku Mercury CCD diffractometer | 3797 independent reflections |
Radiation source: medium-focus sealed tube | 2915 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 13.65 pixels mm-1 | θmax = 25.5°, θmin = 2.4° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −10→11 |
Tmin = 0.114, Tmax = 0.686 | l = −17→15 |
17658 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: Cu atom placed at 1/2, 1/2, 1/2 |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: difmap and geom |
wR(F2) = 0.180 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.1064P)2 + 0.1574P] where P = (Fo2 + 2Fc2)/3 |
3797 reflections | (Δ/σ)max = 0.001 |
274 parameters | Δρmax = 0.78 e Å−3 |
1 restraint | Δρmin = −0.64 e Å−3 |
Special details top
Experimental. A large crystal was used as the smaller ones did not diffract well; a 0.8 mm
collimator was used on the diffractometer. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.29765 (9) | 1.06647 (7) | 0.95543 (3) | 0.0955 (3) | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0468 (2) | |
O1 | 0.4860 (3) | 0.5059 (3) | 0.3647 (2) | 0.054 (1) | |
O2 | 0.5973 (5) | 0.3978 (5) | 0.1791 (3) | 0.096 (1) | |
O3 | 0.3561 (5) | 0.2577 (4) | 0.1874 (3) | 0.087 (1) | |
O4 | 0.1452 (4) | 0.2901 (4) | 0.4329 (3) | 0.083 (1) | |
N1 | 0.4541 (5) | 0.3808 (5) | 0.1808 (2) | 0.065 (1) | |
N2 | 0.3812 (4) | 0.7082 (3) | 0.4090 (2) | 0.046 (1) | |
N3 | 0.4216 (4) | 0.6795 (3) | 0.5011 (2) | 0.044 (1) | |
N4 | 0.2160 (4) | 1.0726 (4) | 0.5329 (2) | 0.053 (1) | |
N5 | 0.0272 (4) | 0.3587 (5) | 0.3019 (3) | 0.074 (1) | |
C1 | 0.3896 (5) | 0.5105 (5) | 0.1646 (3) | 0.053 (1) | |
C2 | 0.3428 (6) | 0.5127 (7) | 0.0685 (3) | 0.072 (1) | |
C3 | 0.2820 (7) | 0.6296 (7) | 0.0465 (3) | 0.084 (2) | |
C4 | 0.2684 (7) | 0.7407 (6) | 0.1209 (3) | 0.078 (1) | |
C5 | 0.3137 (6) | 0.7362 (5) | 0.2170 (3) | 0.062 (1) | |
C6 | 0.3764 (5) | 0.6184 (4) | 0.2419 (3) | 0.046 (1) | |
C7 | 0.4193 (4) | 0.6104 (4) | 0.3454 (3) | 0.045 (1) | |
C8 | 0.3941 (4) | 0.7669 (4) | 0.5735 (2) | 0.043 (1) | |
C9 | 0.2773 (4) | 0.9596 (4) | 0.5002 (3) | 0.048 (1) | |
C10 | 0.3261 (4) | 0.8926 (4) | 0.5750 (3) | 0.044 (1) | |
C11 | 0.2921 (4) | 0.9755 (4) | 0.6603 (3) | 0.044 (1) | |
C12 | 0.3158 (5) | 0.9696 (4) | 0.7588 (3) | 0.053 (1) | |
C13 | 0.2653 (6) | 1.0696 (5) | 0.8204 (3) | 0.063 (1) | |
C14 | 0.1935 (7) | 1.1778 (6) | 0.7900 (4) | 0.079 (1) | |
C15 | 0.1717 (6) | 1.1878 (5) | 0.6955 (4) | 0.070 (1) | |
C16 | 0.2227 (5) | 1.0870 (4) | 0.6306 (3) | 0.051 (1) | |
C17 | 0.1028 (6) | 0.2731 (6) | 0.3438 (4) | 0.073 (1) | |
C18 | −0.0207 (8) | 0.4752 (8) | 0.3585 (6) | 0.117 (2) | |
C19 | −0.0172 (7) | 0.334 (1) | 0.1964 (5) | 0.118 (3) | |
H4n | 0.178 (6) | 1.123 (6) | 0.495 (3) | 0.10 (2)* | |
H2 | 0.3521 | 0.4366 | 0.0194 | 0.086* | |
H3 | 0.2502 | 0.6340 | −0.0180 | 0.101* | |
H4 | 0.2279 | 0.8202 | 0.1058 | 0.094* | |
H5 | 0.3025 | 0.8119 | 0.2657 | 0.075* | |
H8 | 0.4230 | 0.7445 | 0.6337 | 0.052* | |
H9 | 0.2860 | 0.9300 | 0.4363 | 0.058* | |
H12 | 0.3645 | 0.8998 | 0.7815 | 0.064* | |
H14 | 0.1605 | 1.2430 | 0.8345 | 0.094* | |
H15 | 0.1244 | 1.2596 | 0.6744 | 0.084* | |
H17 | 0.1262 | 0.1940 | 0.3038 | 0.087* | |
H18a | −0.0239 | 0.4543 | 0.4218 | 0.175* | |
H18b | −0.1283 | 0.4732 | 0.3270 | 0.175* | |
H18c | 0.0578 | 0.5770 | 0.3649 | 0.175* | |
H19a | 0.0277 | 0.2574 | 0.1668 | 0.177* | |
H19b | 0.0269 | 0.4315 | 0.1780 | 0.177* | |
H19c | −0.1355 | 0.2970 | 0.1748 | 0.177* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.1613 (7) | 0.0884 (4) | 0.0477 (4) | 0.0516 (4) | 0.0358 (3) | 0.0125 (3) |
Cu1 | 0.0722 (5) | 0.0496 (4) | 0.0300 (4) | 0.0346 (3) | 0.0124 (3) | 0.0119 (3) |
O1 | 0.081 (2) | 0.061 (2) | 0.033 (2) | 0.043 (1) | 0.013 (1) | 0.013 (1) |
O2 | 0.094 (3) | 0.136 (3) | 0.083 (3) | 0.072 (3) | 0.025 (2) | 0.023 (2) |
O3 | 0.125 (3) | 0.070 (2) | 0.070 (2) | 0.040 (2) | 0.017 (2) | 0.014 (2) |
O4 | 0.099 (2) | 0.090 (2) | 0.070 (2) | 0.045 (2) | 0.003 (2) | 0.038 (2) |
N1 | 0.088 (3) | 0.080 (3) | 0.033 (2) | 0.044 (2) | 0.011 (2) | 0.004 (2) |
N2 | 0.060 (2) | 0.051 (2) | 0.035 (2) | 0.026 (1) | 0.012 (1) | 0.016 (1) |
N3 | 0.061 (2) | 0.044 (2) | 0.036 (2) | 0.027 (1) | 0.013 (1) | 0.013 (1) |
N4 | 0.068 (2) | 0.051 (2) | 0.051 (2) | 0.032 (2) | 0.011 (2) | 0.019 (2) |
N5 | 0.060 (2) | 0.076 (2) | 0.085 (3) | 0.017 (2) | −0.003 (2) | 0.044 (2) |
C1 | 0.060 (2) | 0.067 (2) | 0.038 (2) | 0.028 (2) | 0.012 (2) | 0.016 (2) |
C2 | 0.091 (3) | 0.096 (3) | 0.038 (2) | 0.043 (3) | 0.016 (2) | 0.016 (2) |
C3 | 0.111 (4) | 0.118 (4) | 0.040 (3) | 0.057 (3) | 0.015 (2) | 0.032 (3) |
C4 | 0.105 (4) | 0.094 (3) | 0.053 (3) | 0.050 (3) | 0.013 (2) | 0.036 (3) |
C5 | 0.081 (3) | 0.070 (2) | 0.049 (2) | 0.036 (2) | 0.015 (2) | 0.026 (2) |
C6 | 0.052 (2) | 0.055 (2) | 0.036 (2) | 0.021 (2) | 0.008 (2) | 0.016 (2) |
C7 | 0.052 (2) | 0.046 (2) | 0.039 (2) | 0.017 (2) | 0.008 (2) | 0.014 (2) |
C8 | 0.050 (2) | 0.047 (2) | 0.034 (2) | 0.018 (2) | 0.007 (1) | 0.011 (2) |
C9 | 0.056 (2) | 0.051 (2) | 0.042 (2) | 0.024 (2) | 0.009 (2) | 0.015 (2) |
C10 | 0.051 (2) | 0.046 (2) | 0.043 (2) | 0.021 (2) | 0.013 (2) | 0.016 (2) |
C11 | 0.052 (2) | 0.041 (2) | 0.043 (2) | 0.020 (2) | 0.011 (2) | 0.010 (2) |
C12 | 0.073 (3) | 0.044 (2) | 0.047 (2) | 0.023 (2) | 0.018 (2) | 0.012 (2) |
C13 | 0.087 (3) | 0.060 (2) | 0.047 (2) | 0.030 (2) | 0.021 (2) | 0.011 (2) |
C14 | 0.114 (4) | 0.070 (3) | 0.070 (3) | 0.052 (3) | 0.037 (3) | 0.009 (2) |
C15 | 0.098 (3) | 0.062 (3) | 0.072 (3) | 0.052 (3) | 0.027 (3) | 0.018 (2) |
C16 | 0.061 (2) | 0.046 (2) | 0.051 (2) | 0.025 (2) | 0.013 (2) | 0.012 (2) |
C17 | 0.072 (3) | 0.068 (3) | 0.078 (3) | 0.025 (2) | 0.008 (2) | 0.024 (2) |
C18 | 0.093 (4) | 0.088 (4) | 0.178 (7) | 0.046 (4) | 0.011 (4) | 0.045 (4) |
C19 | 0.078 (4) | 0.170 (6) | 0.092 (4) | 0.004 (4) | −0.011 (3) | 0.080 (5) |
Geometric parameters (Å, º) top
C13—Br1 | 1.912 (5) | C8—C10 | 1.426 (5) |
Cu1—O1 | 1.930 (3) | C9—C10 | 1.384 (5) |
Cu1—O1i | 1.930 (3) | C10—C11 | 1.438 (5) |
Cu1—O4 | 3.014 (4) | C11—C12 | 1.403 (5) |
Cu1—O4i | 3.014 (4) | C11—C16 | 1.407 (5) |
Cu1—N3 | 1.937 (3) | C12—C13 | 1.368 (6) |
Cu1—N3i | 1.937 (3) | C13—C14 | 1.396 (6) |
O1—C7 | 1.289 (4) | C14—C15 | 1.356 (7) |
O2—N1 | 1.208 (5) | C15—C16 | 1.403 (6) |
O3—N1 | 1.227 (5) | N4—H4n | 0.85 (1) |
O4—C17 | 1.239 (6) | C2—H2 | 0.93 |
N1—C1 | 1.478 (5) | C3—H3 | 0.93 |
N2—C7 | 1.308 (5) | C4—H4 | 0.93 |
N2—N3 | 1.395 (4) | C5—H5 | 0.93 |
N3—C8 | 1.291 (5) | C8—H8 | 0.93 |
N4—C9 | 1.334 (5) | C9—H9 | 0.93 |
N4—C16 | 1.371 (5) | C12—H12 | 0.93 |
N5—C17 | 1.309 (5) | C14—H14 | 0.93 |
N5—C18 | 1.419 (8) | C15—H15 | 0.93 |
N5—C19 | 1.458 (7) | C17—H17 | 0.93 |
C1—C2 | 1.373 (6) | C18—H18a | 0.96 |
C1—C6 | 1.390 (6) | C18—H18b | 0.96 |
C2—C3 | 1.373 (7) | C18—H18c | 0.96 |
C3—C4 | 1.381 (7) | C19—H19a | 0.96 |
C4—C5 | 1.378 (6) | C19—H19b | 0.96 |
C5—C6 | 1.403 (5) | C19—H19c | 0.96 |
C6—C7 | 1.486 (5) | | |
| | | |
O1i—Cu1—O1 | 180 | C12—C11—C10 | 134.9 (3) |
O1—Cu1—O4 | 85.0 (1) | C16—C11—C10 | 106.6 (3) |
O1—Cu1—N3 | 81.8 (1) | C13—C12—C11 | 118.1 (4) |
O1—Cu1—N3i | 98.2 (1) | C12—C13—C14 | 123.0 (4) |
O1i—Cu1—N3 | 98.2 (1) | C12—C13—Br1 | 119.3 (3) |
O1i—Cu1—N3i | 81.8 (1) | C14—C13—Br1 | 117.7 (3) |
O1i—Cu1—O4 | 95.0 (1) | C15—C14—C13 | 120.1 (4) |
N3—Cu1—N3i | 180 | C14—C15—C16 | 118.2 (4) |
N3—Cu1—O4 | 88.4 (1) | N4—C16—C15 | 130.3 (4) |
N3i—Cu1—O4 | 91.7 (1) | N4—C16—C11 | 107.6 (3) |
O1—Cu1—O4i | 95.0 (1) | C15—C16—C11 | 122.1 (4) |
O1i—Cu1—O4i | 85.0 (1) | O4—C17—N5 | 124.5 (5) |
N3—Cu1—O4i | 91.7 (1) | C9—N4—H4n | 122 (4) |
N3i—Cu1—O4i | 88.4 (1) | C16—N4—H4n | 129 (4) |
O4—Cu1—O4i | 180 | C3—C2—H2 | 120.7 |
C7—O1—Cu1 | 109.4 (2) | C1—C2—H2 | 120.7 |
C17—O4—Cu1 | 108.5 (3) | C2—C3—H3 | 120.2 |
O2—N1—O3 | 123.7 (4) | C4—C3—H3 | 120.2 |
O2—N1—C1 | 117.9 (4) | C5—C4—H4 | 119.3 |
O3—N1—C1 | 118.1 (4) | C3—C4—H4 | 119.3 |
C7—N2—N3 | 109.1 (3) | C4—C5—H5 | 119.7 |
C8—N3—N2 | 117.7 (3) | C6—C5—H5 | 119.7 |
C8—N3—Cu1 | 128.6 (2) | N3—C8—H8 | 115.2 |
N2—N3—Cu1 | 113.5 (2) | C10—C8—H8 | 115.2 |
C9—N4—C16 | 109.8 (3) | N4—C9—H9 | 124.8 |
C17—N5—C18 | 120.6 (5) | C10—C9—H9 | 124.8 |
C17—N5—C19 | 121.7 (5) | C13—C12—H12 | 121.0 |
C18—N5—C19 | 117.6 (5) | C11—C12—H12 | 121.0 |
C2—C1—C6 | 124.0 (4) | C15—C14—H14 | 120.0 |
C2—C1—N1 | 114.6 (4) | C13—C14—H14 | 120.0 |
C6—C1—N1 | 121.4 (3) | C14—C15—H15 | 120.9 |
C3—C2—C1 | 118.7 (5) | C16—C15—H15 | 120.9 |
C2—C3—C4 | 119.5 (4) | O4—C17—H17 | 117.8 |
C5—C4—C3 | 121.3 (4) | N5—C17—H17 | 117.8 |
C4—C5—C6 | 120.6 (4) | N5—C18—H18a | 109.5 |
C1—C6—C5 | 115.9 (3) | N5—C18—H18b | 109.5 |
C1—C6—C7 | 123.7 (3) | H18a—C18—H18b | 109.5 |
C5—C6—C7 | 120.4 (4) | N5—C18—H18c | 109.5 |
O1—C7—N2 | 125.7 (3) | H18a—C18—H18c | 109.5 |
O1—C7—C6 | 117.8 (3) | H18b—C18—H18c | 109.5 |
N2—C7—C6 | 116.6 (3) | N5—C19—H19a | 109.5 |
N3—C8—C10 | 129.6 (3) | N5—C19—H19b | 109.5 |
N4—C9—C10 | 110.4 (3) | H19a—C19—H19b | 109.5 |
C9—C10—C8 | 130.0 (3) | N5—C19—H19c | 109.5 |
C9—C10—C11 | 105.6 (3) | H19a—C19—H19c | 109.5 |
C8—C10—C11 | 124.4 (3) | H19b—C19—H19c | 109.5 |
C12—C11—C16 | 118.5 (3) | | |
| | | |
N3—Cu1—O1—C7 | −6.2 (2) | C1—C6—C7—O1 | 6.3 (6) |
N3i—Cu1—O1—C7 | 173.8 (2) | C5—C6—C7—O1 | −175.8 (4) |
O4—Cu1—O1—C7 | 82.8 (2) | C1—C6—C7—N2 | −171.8 (4) |
O1i—Cu1—O4—C17 | −179.7 (3) | C5—C6—C7—N2 | 6.1 (5) |
O1—Cu1—O4—C17 | 0.3 (3) | N2—N3—C8—C10 | 0.2 (6) |
N3—Cu1—O4—C17 | 82.1 (3) | Cu1—N3—C8—C10 | −175.3 (3) |
N3i—Cu1—O4—C17 | −97.9 (3) | C16—N4—C9—C10 | 0.6 (4) |
C7—N2—N3—C8 | 179.2 (3) | N4—C9—C10—C8 | 178.4 (4) |
C7—N2—N3—Cu1 | −4.6 (3) | N4—C9—C10—C11 | −0.7 (4) |
O1i—Cu1—N3—C8 | 1.8 (3) | N3—C8—C10—C9 | −3.0 (7) |
O1—Cu1—N3—C8 | −178.2 (3) | N3—C8—C10—C11 | 176.0 (4) |
O4—Cu1—N3—C8 | 96.6 (3) | C9—C10—C11—C12 | −177.8 (4) |
O1i—Cu1—N3—N2 | −173.9 (2) | C8—C10—C11—C12 | 3.0 (7) |
O1—Cu1—N3—N2 | 6.1 (2) | C9—C10—C11—C16 | 0.6 (4) |
O4—Cu1—N3—N2 | −79.0 (2) | C8—C10—C11—C16 | −178.6 (3) |
O2—N1—C1—C2 | 82.3 (5) | C16—C11—C12—C13 | 2.0 (6) |
O3—N1—C1—C2 | −92.0 (5) | C10—C11—C12—C13 | −179.7 (4) |
O2—N1—C1—C6 | −98.7 (5) | C11—C12—C13—C14 | −0.8 (7) |
O3—N1—C1—C6 | 87.0 (5) | C11—C12—C13—Br1 | −179.4 (3) |
C6—C1—C2—C3 | 1.3 (8) | C12—C13—C14—C15 | −0.4 (8) |
N1—C1—C2—C3 | −179.7 (5) | Br1—C13—C14—C15 | 178.2 (4) |
C1—C2—C3—C4 | −0.4 (8) | C13—C14—C15—C16 | 0.2 (8) |
C2—C3—C4—C5 | −0.4 (9) | C9—N4—C16—C15 | −179.4 (5) |
C3—C4—C5—C6 | 0.5 (8) | C9—N4—C16—C11 | −0.2 (4) |
C2—C1—C6—C5 | −1.2 (6) | C14—C15—C16—N4 | −179.8 (5) |
N1—C1—C6—C5 | 179.9 (4) | C14—C15—C16—C11 | 1.1 (7) |
C2—C1—C6—C7 | 176.8 (4) | C12—C11—C16—N4 | 178.5 (3) |
N1—C1—C6—C7 | −2.1 (6) | C10—C11—C16—N4 | −0.2 (4) |
C4—C5—C6—C1 | 0.3 (6) | C12—C11—C16—C15 | −2.3 (6) |
C4—C5—C6—C7 | −177.8 (4) | C10—C11—C16—C15 | 179.0 (4) |
Cu1—O1—C7—N2 | 6.0 (5) | Cu1—O4—C17—N5 | −94.4 (5) |
Cu1—O1—C7—C6 | −171.9 (3) | C18—N5—C17—O4 | −3.7 (8) |
N3—N2—C7—O1 | −1.0 (5) | C19—N5—C17—O4 | 179.1 (5) |
N3—N2—C7—C6 | 176.9 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4n···O4ii | 0.85 (1) | 1.95 (2) | 2.777 (4) | 163 (5) |
Symmetry code: (ii) x, y+1, z. |