The title racemic compound, [Cu(C
12H
11NO
5)(C
4H
6N
2)], adopts a square-pyramidal Cu
II coordination with the tridentate
N-salicylideneglutamate Schiff base dianion and the 2-methylimidazole ligand in the basal plane. The apex of the pyramid is occupied by a carboxylic acid O atom from the neighbouring chelate at a distance of 2.479 (4) Å, leading to infinite one-dimensional chains along the crystallographic
a axis. Strong N—H
O and O—H
O hydrogen bonds form a helix parallel to the
c axis. The electronic structure of the title compound has also been investigated by the
B3
LYP method.
Supporting information
CCDC reference: 231841
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.009 Å
- R factor = 0.046
- wR factor = 0.108
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9
Alert level G
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 25.04
From the CIF: _reflns_number_total 2849
Count of symmetry unique reflns 1448
Completeness (_total/calc) 196.75%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1401
Fraction of Friedel pairs measured 0.968
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL.
(
N-Salicylidene-DL-glutamato)(2-methylimidazole)copper(II)
top
Crystal data top
[Cu(C12H11NO5)(C4H6N2)] | F(000) = 406 |
Mr = 394.87 | Dx = 1.616 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 5004 reflections |
a = 5.2319 (1) Å | θ = 2.5–25.0° |
b = 16.2576 (3) Å | µ = 1.38 mm−1 |
c = 9.6044 (1) Å | T = 183 K |
β = 96.530 (1)° | Needle, blue |
V = 811.63 (2) Å3 | 0.15 × 0.02 × 0.02 mm |
Z = 2 | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2849 independent reflections |
Radiation source: fine-focus sealed tube | 2512 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −6→6 |
Tmin = 0.820, Tmax = 0.980 | k = −19→19 |
7539 measured reflections | l = −11→11 |
Refinement top
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0623P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2849 reflections | Δρmax = 0.41 e Å−3 |
229 parameters | Δρmin = −0.42 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1181 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (2) |
Special details top
Experimental. Data were collected at low temperature using a Siemens SMART CCD
diffractometer equiped with a LT-2 device. A full sphere of reciprocal space
was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 60 s per frame. Preliminary orientation matrix was obtained from the first
100 frames using SMART (Siemens, 1995). The collected frames were
integrated using the preliminary orientation matrix which was updated every
100 frames. Final cell parameters were obtained by refinement on the position
of 5004 reflections with I>10σ(I) after integration of all the frames data
using SAINT (Siemens, 1995). |
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 | 0.36104 (8) | 0.20165 (3) | 0.75965 (7) | 0.01363 (17) | |
O1 | 0.5828 (8) | 0.2631 (2) | 0.6472 (4) | 0.0171 (8) | |
O2 | 0.0957 (7) | 0.1468 (2) | 0.8587 (4) | 0.0151 (8) | |
O3 | −0.2754 (7) | 0.1748 (2) | 0.9430 (4) | 0.0201 (9) | |
O4 | 0.2575 (9) | 0.3256 (3) | 1.3647 (4) | 0.0363 (12) | |
O5 | 0.5298 (8) | 0.2184 (2) | 1.3767 (4) | 0.0266 (10) | |
H5 | 0.5760 | 0.2371 | 1.4572 | 0.032* | |
N1 | 0.2319 (9) | 0.3007 (3) | 0.8415 (5) | 0.0144 (10) | |
N2 | 0.4145 (8) | 0.0965 (3) | 0.6633 (5) | 0.0184 (10) | |
N3 | 0.3345 (11) | −0.0142 (3) | 0.5366 (5) | 0.0298 (13) | |
H3 | 0.2625 | −0.0477 | 0.4715 | 0.036* | |
C1 | 0.2842 (13) | 0.3752 (4) | 0.8116 (7) | 0.0209 (16) | |
H1 | 0.1888 | 0.4175 | 0.8503 | 0.025* | |
C2 | 0.4789 (13) | 0.4001 (4) | 0.7227 (7) | 0.0190 (14) | |
C3 | 0.5174 (13) | 0.4855 (4) | 0.7117 (7) | 0.0317 (15) | |
H3A | 0.4216 | 0.5222 | 0.7625 | 0.038* | |
C4 | 0.6907 (14) | 0.5162 (4) | 0.6287 (8) | 0.0373 (17) | |
H4 | 0.7164 | 0.5738 | 0.6213 | 0.045* | |
C5 | 0.8288 (13) | 0.4609 (4) | 0.5552 (7) | 0.0368 (17) | |
H5A | 0.9504 | 0.4815 | 0.4977 | 0.044* | |
C6 | 0.7933 (11) | 0.3765 (4) | 0.5639 (6) | 0.0269 (14) | |
H6 | 0.8922 | 0.3405 | 0.5135 | 0.032* | |
C7 | 0.6143 (11) | 0.3442 (4) | 0.6458 (6) | 0.0209 (13) | |
C8 | 0.0189 (11) | 0.2856 (3) | 0.9271 (6) | 0.0171 (12) | |
H8 | −0.1290 | 0.3219 | 0.8923 | 0.020* | |
C9 | 0.0956 (10) | 0.3036 (3) | 1.0849 (5) | 0.0166 (11) | |
H9A | 0.1582 | 0.3610 | 1.0949 | 0.020* | |
H9B | −0.0599 | 0.2993 | 1.1343 | 0.020* | |
C10 | 0.3008 (12) | 0.2470 (4) | 1.1558 (6) | 0.0201 (14) | |
H10A | 0.2410 | 0.1893 | 1.1464 | 0.024* | |
H10B | 0.4596 | 0.2521 | 1.1094 | 0.024* | |
C11 | 0.3589 (11) | 0.2685 (4) | 1.3095 (6) | 0.0193 (13) | |
C12 | −0.0663 (10) | 0.1957 (3) | 0.9081 (5) | 0.0154 (11) | |
C13 | 0.5907 (12) | 0.0364 (3) | 0.7099 (7) | 0.0252 (14) | |
H13 | 0.7246 | 0.0422 | 0.7848 | 0.030* | |
C14 | 0.5410 (12) | −0.0321 (4) | 0.6311 (7) | 0.0306 (15) | |
H14 | 0.6322 | −0.0827 | 0.6401 | 0.037* | |
C15 | 0.2585 (11) | 0.0637 (3) | 0.5596 (6) | 0.0232 (13) | |
C16 | 0.0393 (13) | 0.1046 (4) | 0.4758 (7) | 0.0358 (16) | |
H16A | 0.0341 | 0.1627 | 0.5025 | 0.043* | |
H16B | −0.1216 | 0.0778 | 0.4935 | 0.043* | |
H16C | 0.0604 | 0.1003 | 0.3760 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0159 (3) | 0.0111 (3) | 0.0144 (3) | −0.0002 (4) | 0.0040 (2) | −0.0013 (4) |
O1 | 0.021 (2) | 0.012 (2) | 0.018 (2) | −0.0041 (17) | 0.0000 (17) | 0.0017 (17) |
O2 | 0.013 (2) | 0.014 (2) | 0.020 (2) | 0.0031 (15) | 0.0060 (16) | 0.0007 (15) |
O3 | 0.019 (2) | 0.023 (2) | 0.019 (2) | −0.0043 (16) | 0.0055 (17) | 0.0004 (16) |
O4 | 0.036 (3) | 0.048 (3) | 0.023 (2) | 0.021 (2) | −0.002 (2) | −0.013 (2) |
O5 | 0.033 (3) | 0.031 (3) | 0.014 (2) | 0.010 (2) | −0.0040 (19) | −0.0033 (18) |
N1 | 0.020 (3) | 0.012 (2) | 0.011 (2) | −0.002 (2) | −0.0003 (19) | 0.004 (2) |
N2 | 0.020 (3) | 0.014 (2) | 0.022 (2) | 0.002 (2) | 0.005 (2) | −0.003 (2) |
N3 | 0.037 (3) | 0.024 (3) | 0.029 (4) | −0.012 (3) | 0.009 (3) | −0.015 (2) |
C1 | 0.029 (4) | 0.013 (3) | 0.020 (3) | 0.001 (3) | 0.002 (3) | −0.002 (3) |
C2 | 0.022 (3) | 0.014 (3) | 0.020 (3) | −0.002 (3) | 0.000 (3) | 0.003 (3) |
C3 | 0.033 (4) | 0.020 (3) | 0.041 (4) | −0.004 (3) | 0.001 (3) | 0.008 (3) |
C4 | 0.046 (4) | 0.016 (3) | 0.050 (4) | −0.014 (3) | 0.004 (4) | 0.009 (3) |
C5 | 0.031 (4) | 0.039 (4) | 0.041 (4) | −0.017 (3) | 0.005 (3) | 0.017 (3) |
C6 | 0.024 (3) | 0.030 (4) | 0.027 (3) | −0.007 (3) | 0.001 (3) | 0.001 (3) |
C7 | 0.023 (3) | 0.025 (4) | 0.013 (3) | −0.006 (3) | −0.001 (2) | 0.006 (2) |
C8 | 0.018 (3) | 0.012 (3) | 0.021 (3) | 0.003 (2) | 0.006 (2) | −0.001 (2) |
C9 | 0.019 (3) | 0.017 (3) | 0.013 (3) | 0.001 (2) | 0.000 (2) | −0.002 (2) |
C10 | 0.022 (4) | 0.023 (3) | 0.015 (3) | 0.007 (3) | 0.004 (3) | 0.003 (3) |
C11 | 0.018 (3) | 0.021 (3) | 0.019 (3) | −0.003 (2) | 0.005 (3) | 0.000 (2) |
C12 | 0.018 (3) | 0.019 (3) | 0.008 (2) | −0.001 (2) | −0.001 (2) | 0.000 (2) |
C13 | 0.028 (3) | 0.016 (3) | 0.032 (3) | 0.000 (2) | 0.005 (3) | −0.004 (3) |
C14 | 0.032 (4) | 0.015 (3) | 0.047 (4) | 0.003 (3) | 0.015 (3) | −0.009 (3) |
C15 | 0.030 (3) | 0.019 (3) | 0.022 (3) | −0.008 (2) | 0.007 (3) | −0.003 (2) |
C16 | 0.040 (4) | 0.030 (4) | 0.034 (4) | −0.012 (3) | −0.009 (3) | 0.000 (3) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.946 (5) | C3—H3A | 0.950 |
Cu1—O1 | 1.948 (4) | C4—C5 | 1.394 (10) |
Cu1—N2 | 1.979 (5) | C4—H4 | 0.950 |
Cu1—O2 | 1.982 (4) | C5—C6 | 1.387 (9) |
Cu1—O3i | 2.479 (4) | C5—H5A | 0.950 |
O1—C7 | 1.328 (7) | C6—C7 | 1.393 (8) |
O2—C12 | 1.291 (6) | C6—H6 | 0.950 |
O3—C12 | 1.228 (6) | C8—C12 | 1.532 (7) |
O4—C11 | 1.221 (7) | C8—C9 | 1.551 (7) |
O5—C11 | 1.322 (7) | C8—H8 | 1.000 |
O5—H5 | 0.840 | C9—C10 | 1.516 (8) |
N1—C1 | 1.282 (8) | C9—H9A | 0.990 |
N1—C8 | 1.478 (7) | C9—H9B | 0.990 |
N2—C15 | 1.325 (7) | C10—C11 | 1.513 (9) |
N2—C13 | 1.382 (7) | C10—H10A | 0.990 |
N3—C15 | 1.354 (8) | C10—H10B | 0.990 |
N3—C14 | 1.361 (8) | C13—C14 | 1.355 (8) |
N3—H3 | 0.880 | C13—H13 | 0.950 |
C1—C2 | 1.459 (8) | C14—H14 | 0.950 |
C1—H1 | 0.950 | C15—C16 | 1.482 (9) |
C2—C3 | 1.409 (8) | C16—H16A | 0.980 |
C2—C7 | 1.411 (9) | C16—H16B | 0.980 |
C3—C4 | 1.368 (10) | C16—H16C | 0.980 |
| | | |
N1—Cu1—O1 | 93.2 (2) | N1—C8—C12 | 108.6 (4) |
N1—Cu1—N2 | 167.84 (19) | N1—C8—C9 | 112.6 (4) |
O1—Cu1—N2 | 93.41 (18) | C12—C8—C9 | 109.6 (4) |
N1—Cu1—O2 | 83.31 (17) | N1—C8—H8 | 108.6 |
O1—Cu1—O2 | 172.15 (17) | C12—C8—H8 | 108.6 |
N2—Cu1—O2 | 88.86 (17) | C9—C8—H8 | 108.6 |
C7—O1—Cu1 | 126.7 (4) | C10—C9—C8 | 114.6 (5) |
C12—O2—Cu1 | 115.1 (3) | C10—C9—H9A | 108.6 |
C11—O5—H5 | 109.5 | C8—C9—H9A | 108.6 |
C1—N1—C8 | 118.3 (5) | C10—C9—H9B | 108.6 |
C1—N1—Cu1 | 126.8 (5) | C8—C9—H9B | 108.6 |
C8—N1—Cu1 | 114.0 (3) | H9A—C9—H9B | 107.6 |
C15—N2—C13 | 106.9 (5) | C11—C10—C9 | 110.6 (5) |
C15—N2—Cu1 | 126.2 (4) | C11—C10—H10A | 109.5 |
C13—N2—Cu1 | 125.7 (4) | C9—C10—H10A | 109.5 |
C15—N3—C14 | 108.5 (5) | C11—C10—H10B | 109.5 |
C15—N3—H3 | 125.8 | C9—C10—H10B | 109.5 |
C14—N3—H3 | 125.8 | H10A—C10—H10B | 108.1 |
N1—C1—C2 | 125.1 (6) | O4—C11—O5 | 124.0 (5) |
N1—C1—H1 | 117.5 | O4—C11—C10 | 123.4 (5) |
C2—C1—H1 | 117.5 | O5—C11—C10 | 112.6 (5) |
C3—C2—C7 | 120.7 (6) | O3—C12—O2 | 124.9 (5) |
C3—C2—C1 | 115.6 (6) | O3—C12—C8 | 119.2 (5) |
C7—C2—C1 | 123.6 (5) | O2—C12—C8 | 115.9 (5) |
C4—C3—C2 | 120.9 (7) | C14—C13—N2 | 108.8 (6) |
C4—C3—H3A | 119.6 | C14—C13—H13 | 125.6 |
C2—C3—H3A | 119.6 | N2—C13—H13 | 125.6 |
C3—C4—C5 | 118.4 (6) | N3—C14—C13 | 106.5 (5) |
C3—C4—H4 | 120.8 | N3—C14—H14 | 126.8 |
C5—C4—H4 | 120.8 | C13—C14—H14 | 126.8 |
C6—C5—C4 | 121.7 (6) | N2—C15—N3 | 109.4 (5) |
C6—C5—H5A | 119.1 | N2—C15—C16 | 126.9 (5) |
C4—C5—H5A | 119.1 | N3—C15—C16 | 123.7 (5) |
C5—C6—C7 | 120.7 (6) | C15—C16—H16A | 109.5 |
C5—C6—H6 | 119.7 | C15—C16—H16B | 109.5 |
C7—C6—H6 | 119.7 | H16A—C16—H16B | 109.5 |
O1—C7—C2 | 124.3 (5) | C15—C16—H16C | 109.5 |
O1—C7—C6 | 118.2 (5) | H16A—C16—H16C | 109.5 |
C2—C7—C6 | 117.5 (6) | H16B—C16—H16C | 109.5 |
| | | |
N1—Cu1—O1—C7 | 2.0 (4) | C3—C2—C7—C6 | 2.6 (9) |
N2—Cu1—O1—C7 | 171.8 (4) | C1—C2—C7—C6 | 179.4 (5) |
N1—Cu1—O2—C12 | 11.6 (4) | C5—C6—C7—O1 | 178.1 (5) |
N2—Cu1—O2—C12 | −159.1 (4) | C5—C6—C7—C2 | −2.3 (9) |
O1—Cu1—N1—C1 | 3.8 (5) | C1—N1—C8—C12 | 161.2 (5) |
N2—Cu1—N1—C1 | −118.9 (10) | Cu1—N1—C8—C12 | −8.4 (5) |
O2—Cu1—N1—C1 | −169.1 (5) | C1—N1—C8—C9 | −77.2 (6) |
O1—Cu1—N1—C8 | 172.4 (3) | Cu1—N1—C8—C9 | 113.2 (4) |
N2—Cu1—N1—C8 | 49.7 (11) | N1—C8—C9—C10 | −65.4 (6) |
O2—Cu1—N1—C8 | −0.5 (3) | C12—C8—C9—C10 | 55.6 (6) |
N1—Cu1—N2—C15 | 24.9 (12) | C8—C9—C10—C11 | −179.0 (5) |
O1—Cu1—N2—C15 | −97.8 (5) | C9—C10—C11—O4 | −2.2 (8) |
O2—Cu1—N2—C15 | 74.7 (5) | C9—C10—C11—O5 | 177.5 (5) |
N1—Cu1—N2—C13 | −140.9 (8) | Cu1—O2—C12—O3 | 162.2 (4) |
O1—Cu1—N2—C13 | 96.4 (5) | Cu1—O2—C12—C8 | −19.6 (6) |
O2—Cu1—N2—C13 | −91.2 (5) | N1—C8—C12—O3 | −163.4 (5) |
C8—N1—C1—C2 | −176.7 (5) | C9—C8—C12—O3 | 73.1 (6) |
Cu1—N1—C1—C2 | −8.6 (8) | N1—C8—C12—O2 | 18.3 (6) |
N1—C1—C2—C3 | −175.7 (6) | C9—C8—C12—O2 | −105.1 (5) |
N1—C1—C2—C7 | 7.4 (9) | C15—N2—C13—C14 | 1.1 (7) |
C7—C2—C3—C4 | −1.5 (10) | Cu1—N2—C13—C14 | 169.2 (4) |
C1—C2—C3—C4 | −178.5 (6) | C15—N3—C14—C13 | −0.9 (7) |
C2—C3—C4—C5 | 0.0 (10) | N2—C13—C14—N3 | −0.1 (7) |
C3—C4—C5—C6 | 0.4 (10) | C13—N2—C15—N3 | −1.7 (7) |
C4—C5—C6—C7 | 0.8 (10) | Cu1—N2—C15—N3 | −169.7 (4) |
Cu1—O1—C7—C2 | −3.2 (8) | C13—N2—C15—C16 | −179.6 (6) |
Cu1—O1—C7—C6 | 176.4 (4) | Cu1—N2—C15—C16 | 12.4 (9) |
C3—C2—C7—O1 | −177.8 (5) | C14—N3—C15—N2 | 1.6 (7) |
C1—C2—C7—O1 | −1.1 (9) | C14—N3—C15—C16 | 179.6 (6) |
Symmetry code: (i) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O2ii | 0.88 | 2.08 | 2.940 (6) | 166 |
O5—H5···O1iii | 0.84 | 1.87 | 2.682 (6) | 162 |
C6—H6···O4iv | 0.95 | 2.52 | 3.362 (8) | 147 |
C10—H10B···O3i | 0.99 | 2.56 | 3.391 (7) | 142 |
C14—H14···O3v | 0.95 | 2.50 | 3.157 (7) | 126 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y, z−1/2; (iii) x, y, z+1; (iv) x+1, y, z−1; (v) x+1, −y, z−1/2. |
Bond distances d(Cu—X) (Å) and Mulliken population analysis (|e|)
for Cu and neighbouring atoms (X) topAtom X | d(Cu—X) | Mulliken charges | Overlap population |
Cu1 | | 0.821 | |
N1 | 1.946 (5) | -0.323 | 0.164 |
N2 | 1.947 (4) | -0.333 | 0.178 |
O1 | 1.950 (4) | -0.378 | 0.204 |
O2 | 1.984 (4) | -0.394 | 0.205 |