Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811031175/bt5595sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811031175/bt5595Isup2.hkl |
CCDC reference: 827587
Key indicators
- Single-crystal X-ray study
- T = 223 K
- Mean (C-C) = 0.008 Å
- R factor = 0.039
- wR factor = 0.102
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 94 PerFi
Alert level C PLAT113_ALERT_2_C ADDSYM Suggests Possible Pseudo/New Space-group. C2/c PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 -- O2 .. 5.9 su PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0081 Ang PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 4 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 15 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 21 PLAT915_ALERT_3_C Low Friedel Pair Coverage ...................... 51 Perc.
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 27.47 From the CIF: _reflns_number_total 4089 Count of symmetry unique reflns 2732 Completeness (_total/calc) 149.67% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1357 Fraction of Friedel pairs measured 0.497 Are heavy atom types Z>Si present yes PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT033_ALERT_4_G Flack x Parameter Value Deviates from Zero ..... 0.254 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1 (II) 2.25
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 7 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
0.2 mmol phen, 0.1 mmol CuSO4.5H2O, 2.0 ml e thane-1,2-diol and 1.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 96 h, whereupon Blue block-shaped crystals of (I) were obtained. The presence of pseudo-symmetry in the structure suggests a higher symmetry space group C2/c. But attempts to refine the structure in the space group C2/c resulted in a disorder model with high R and wR values. Hence the requirement to solve in Cc. The reported Flack parameter was refined as s full least-squares and obtained by TWIN/BASF procedure in SHELXL (Sheldrick, 2008).
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) or C—H = 0.97 Å and O—H = 0.82 Å; Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. The molecular structure showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. The dashed lines represent O—H···O interactions. |
[Cu(SO4)(C12H8N2)2]·C2H6O2 | F(000) = 1196 |
Mr = 582.08 | Dx = 1.622 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 5713 reflections |
a = 17.666 (4) Å | θ = 3.2–27.5° |
b = 11.992 (2) Å | µ = 1.06 mm−1 |
c = 13.122 (3) Å | T = 223 K |
β = 120.96 (3)° | Block, green |
V = 2383.8 (11) Å3 | 0.40 × 0.35 × 0.25 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 4089 independent reflections |
Radiation source: fine-focus sealed tube | 3835 reflections with I > 2/s(I) |
Graphite Monochromator monochromator | Rint = 0.018 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ω scans | h = −21→22 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −13→15 |
Tmin = 0.776, Tmax = 1.000 | l = −15→17 |
6663 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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.064P)2 + 1.9064P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4089 reflections | Δρmax = 1.07 e Å−3 |
344 parameters | Δρmin = −0.81 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1396 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.254 (14) |
[Cu(SO4)(C12H8N2)2]·C2H6O2 | V = 2383.8 (11) Å3 |
Mr = 582.08 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 17.666 (4) Å | µ = 1.06 mm−1 |
b = 11.992 (2) Å | T = 223 K |
c = 13.122 (3) Å | 0.40 × 0.35 × 0.25 mm |
β = 120.96 (3)° |
Rigaku Mercury CCD diffractometer | 4089 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3835 reflections with I > 2/s(I) |
Tmin = 0.776, Tmax = 1.000 | Rint = 0.018 |
6663 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 1.07 e Å−3 |
S = 1.06 | Δρmin = −0.81 e Å−3 |
4089 reflections | Absolute structure: Flack (1983), 1396 Friedel pairs |
344 parameters | Absolute structure parameter: 0.254 (14) |
2 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 | 0.17114 (3) | 0.28325 (3) | 0.03203 (4) | 0.02354 (12) | |
S1 | 0.16061 (6) | 0.54366 (7) | 0.04366 (9) | 0.0262 (2) | |
N3 | 0.2587 (3) | 0.2724 (3) | −0.0216 (4) | 0.0220 (8) | |
N2 | 0.0827 (3) | 0.2673 (3) | 0.0820 (4) | 0.0253 (8) | |
C24 | 0.3290 (3) | 0.2059 (3) | 0.0478 (4) | 0.0215 (9) | |
N1 | 0.0735 (2) | 0.1831 (3) | −0.1135 (3) | 0.0246 (8) | |
N4 | 0.2650 (2) | 0.1851 (3) | 0.1690 (3) | 0.0223 (7) | |
C11 | 0.0105 (3) | 0.2038 (3) | 0.0078 (4) | 0.0235 (9) | |
C8 | −0.0484 (3) | 0.2248 (4) | 0.1356 (5) | 0.0298 (11) | |
H8A | −0.0915 | 0.2107 | 0.1546 | 0.036* | |
C15 | 0.3855 (4) | 0.2311 (4) | −0.0817 (5) | 0.0335 (11) | |
H15A | 0.4279 | 0.2186 | −0.1023 | 0.040* | |
O4 | 0.0858 (2) | 0.6189 (3) | −0.0263 (3) | 0.0336 (7) | |
C14 | 0.2517 (3) | 0.3163 (4) | −0.1194 (4) | 0.0268 (9) | |
H14A | 0.2038 | 0.3622 | −0.1669 | 0.032* | |
C10 | 0.0876 (3) | 0.3084 (4) | 0.1789 (5) | 0.0313 (10) | |
H10A | 0.1356 | 0.3532 | 0.2291 | 0.038* | |
C12 | 0.0056 (3) | 0.1594 (4) | −0.0968 (4) | 0.0218 (8) | |
C19 | 0.4077 (3) | 0.0962 (3) | 0.2325 (4) | 0.0255 (10) | |
C4 | −0.0682 (3) | 0.0986 (4) | −0.1775 (4) | 0.0264 (10) | |
O3 | 0.2432 (2) | 0.5960 (3) | 0.0654 (3) | 0.0365 (8) | |
C13 | 0.3122 (4) | 0.2966 (4) | −0.1525 (5) | 0.0320 (11) | |
H13A | 0.3042 | 0.3272 | −0.2225 | 0.038* | |
C9 | 0.0224 (4) | 0.2870 (3) | 0.2096 (5) | 0.0298 (11) | |
H9A | 0.0287 | 0.3154 | 0.2795 | 0.036* | |
C18 | 0.4738 (3) | 0.0761 (4) | 0.2050 (5) | 0.0302 (11) | |
H18A | 0.5224 | 0.0334 | 0.2573 | 0.036* | |
C5 | −0.1378 (3) | 0.0776 (4) | −0.1545 (4) | 0.0316 (11) | |
H5A | −0.1872 | 0.0370 | −0.2087 | 0.038* | |
C7 | −0.0582 (3) | 0.1810 (4) | 0.0300 (4) | 0.0251 (9) | |
C16 | 0.3945 (3) | 0.1835 (4) | 0.0227 (4) | 0.0260 (9) | |
C17 | 0.4695 (3) | 0.1164 (4) | 0.1054 (4) | 0.0315 (10) | |
H17A | 0.5145 | 0.1010 | 0.0904 | 0.038* | |
C3 | −0.0707 (3) | 0.0591 (4) | −0.2814 (4) | 0.0310 (10) | |
H3A | −0.1183 | 0.0171 | −0.3374 | 0.037* | |
C23 | 0.3340 (3) | 0.1616 (4) | 0.1529 (4) | 0.0218 (8) | |
C6 | −0.1316 (3) | 0.1171 (4) | −0.0534 (4) | 0.0318 (10) | |
H6A | −0.1766 | 0.1018 | −0.0385 | 0.038* | |
C20 | 0.4089 (3) | 0.0575 (4) | 0.3340 (4) | 0.0318 (10) | |
H20A | 0.4558 | 0.0141 | 0.3892 | 0.038* | |
C2 | −0.0025 (4) | 0.0838 (4) | −0.2974 (5) | 0.0350 (12) | |
H2A | −0.0038 | 0.0601 | −0.3658 | 0.042* | |
C22 | 0.2710 (3) | 0.1466 (4) | 0.2686 (4) | 0.0294 (10) | |
H22A | 0.2257 | 0.1632 | 0.2826 | 0.035* | |
C21 | 0.3416 (4) | 0.0832 (4) | 0.3522 (4) | 0.0348 (12) | |
H21A | 0.3430 | 0.0584 | 0.4203 | 0.042* | |
C1 | 0.0701 (3) | 0.1451 (4) | −0.2109 (4) | 0.0300 (9) | |
H1A | 0.1171 | 0.1593 | −0.2220 | 0.036* | |
O1 | 0.1418 (2) | 0.4369 (2) | −0.0255 (3) | 0.0357 (7) | |
O6 | 0.1139 (3) | 0.8222 (3) | 0.0846 (4) | 0.0541 (11) | |
H6B | 0.1059 | 0.7631 | 0.0492 | 0.081* | |
O5 | 0.2232 (3) | 0.8087 (3) | −0.0330 (4) | 0.0503 (10) | |
H5B | 0.2288 | 0.7496 | 0.0017 | 0.075* | |
C26 | 0.1316 (6) | 0.9055 (4) | 0.0264 (7) | 0.058 (2) | |
H26A | 0.1279 | 0.9770 | 0.0584 | 0.070* | |
H26B | 0.0857 | 0.9042 | −0.0569 | 0.070* | |
C25 | 0.2177 (4) | 0.8984 (5) | 0.0348 (6) | 0.0586 (18) | |
H25A | 0.2289 | 0.9681 | 0.0072 | 0.070* | |
H25B | 0.2635 | 0.8890 | 0.1175 | 0.070* | |
O2 | 0.1672 (2) | 0.5194 (2) | 0.1578 (2) | 0.0332 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0233 (2) | 0.0247 (2) | 0.0272 (2) | 0.0012 (2) | 0.01621 (16) | 0.0011 (3) |
S1 | 0.0221 (5) | 0.0222 (4) | 0.0277 (5) | 0.0012 (4) | 0.0079 (4) | −0.0003 (4) |
N3 | 0.022 (2) | 0.0252 (19) | 0.0229 (19) | 0.0066 (14) | 0.0142 (17) | 0.0048 (15) |
N2 | 0.025 (2) | 0.0251 (19) | 0.027 (2) | 0.0026 (15) | 0.0137 (19) | −0.0009 (16) |
C24 | 0.024 (2) | 0.021 (2) | 0.019 (2) | 0.0000 (16) | 0.0106 (18) | −0.0046 (16) |
N1 | 0.0242 (19) | 0.0254 (19) | 0.0228 (18) | −0.0047 (15) | 0.0110 (16) | −0.0030 (15) |
N4 | 0.0291 (19) | 0.0201 (17) | 0.0215 (17) | −0.0015 (15) | 0.0158 (16) | −0.0010 (15) |
C11 | 0.020 (2) | 0.022 (2) | 0.028 (2) | 0.0029 (16) | 0.012 (2) | 0.0011 (18) |
C8 | 0.027 (3) | 0.033 (3) | 0.038 (3) | −0.0001 (19) | 0.023 (2) | 0.005 (2) |
C15 | 0.040 (3) | 0.037 (3) | 0.034 (3) | −0.003 (2) | 0.026 (2) | −0.001 (2) |
O4 | 0.0286 (16) | 0.0358 (16) | 0.0351 (16) | 0.0043 (13) | 0.0155 (14) | 0.0010 (14) |
C14 | 0.025 (2) | 0.035 (2) | 0.023 (2) | 0.0033 (19) | 0.015 (2) | 0.005 (2) |
C10 | 0.035 (3) | 0.028 (2) | 0.034 (3) | −0.002 (2) | 0.019 (2) | −0.003 (2) |
C12 | 0.024 (2) | 0.0184 (18) | 0.0227 (19) | 0.0034 (17) | 0.0119 (18) | 0.0053 (17) |
C19 | 0.025 (2) | 0.018 (2) | 0.023 (2) | −0.0011 (17) | 0.0053 (19) | −0.0057 (18) |
C4 | 0.024 (2) | 0.028 (2) | 0.025 (2) | 0.0002 (18) | 0.010 (2) | 0.0010 (19) |
O3 | 0.0219 (16) | 0.0410 (19) | 0.049 (2) | 0.0042 (13) | 0.0197 (15) | 0.0121 (15) |
C13 | 0.034 (3) | 0.038 (3) | 0.029 (3) | 0.004 (2) | 0.019 (2) | 0.005 (2) |
C9 | 0.037 (3) | 0.031 (3) | 0.033 (3) | 0.0004 (19) | 0.026 (2) | 0.0018 (19) |
C18 | 0.022 (2) | 0.032 (3) | 0.032 (2) | 0.0006 (18) | 0.010 (2) | −0.002 (2) |
C5 | 0.025 (3) | 0.028 (2) | 0.030 (2) | −0.0058 (18) | 0.005 (2) | −0.0016 (19) |
C7 | 0.027 (2) | 0.024 (2) | 0.028 (2) | 0.0057 (18) | 0.016 (2) | 0.0078 (19) |
C16 | 0.020 (2) | 0.027 (2) | 0.031 (2) | −0.0002 (18) | 0.013 (2) | −0.001 (2) |
C17 | 0.023 (2) | 0.032 (2) | 0.035 (2) | −0.0005 (19) | 0.012 (2) | −0.006 (2) |
C3 | 0.033 (3) | 0.029 (2) | 0.025 (2) | −0.001 (2) | 0.010 (2) | −0.004 (2) |
C23 | 0.021 (2) | 0.022 (2) | 0.0214 (19) | 0.0024 (17) | 0.0105 (18) | 0.0008 (17) |
C6 | 0.025 (2) | 0.037 (3) | 0.038 (3) | −0.006 (2) | 0.019 (2) | 0.001 (2) |
C20 | 0.031 (3) | 0.030 (3) | 0.025 (2) | 0.006 (2) | 0.007 (2) | 0.002 (2) |
C2 | 0.046 (3) | 0.032 (3) | 0.028 (2) | −0.007 (2) | 0.020 (2) | −0.006 (2) |
C22 | 0.033 (3) | 0.035 (2) | 0.027 (2) | 0.008 (2) | 0.021 (2) | 0.006 (2) |
C21 | 0.040 (3) | 0.035 (3) | 0.025 (2) | 0.004 (2) | 0.014 (2) | 0.009 (2) |
C1 | 0.035 (3) | 0.030 (2) | 0.026 (2) | −0.001 (2) | 0.017 (2) | −0.002 (2) |
O1 | 0.0474 (18) | 0.0267 (13) | 0.0325 (15) | 0.0058 (13) | 0.0201 (14) | −0.0012 (12) |
O6 | 0.084 (3) | 0.037 (2) | 0.069 (3) | −0.003 (2) | 0.059 (3) | −0.008 (2) |
O5 | 0.068 (3) | 0.047 (2) | 0.057 (2) | −0.006 (2) | 0.048 (2) | 0.0026 (19) |
C26 | 0.111 (6) | 0.020 (2) | 0.068 (4) | −0.002 (3) | 0.065 (5) | −0.006 (3) |
C25 | 0.053 (4) | 0.059 (4) | 0.058 (4) | −0.029 (3) | 0.025 (3) | −0.014 (3) |
O2 | 0.0381 (17) | 0.0364 (15) | 0.0265 (13) | −0.0035 (13) | 0.0176 (13) | 0.0002 (13) |
Cu1—O1 | 1.957 (3) | C19—C18 | 1.409 (7) |
Cu1—N2 | 1.990 (4) | C19—C23 | 1.415 (6) |
Cu1—N3 | 2.006 (4) | C4—C3 | 1.422 (7) |
Cu1—N4 | 2.073 (4) | C4—C5 | 1.432 (7) |
Cu1—N1 | 2.162 (4) | C13—H13A | 0.9300 |
S1—O4 | 1.469 (3) | C9—H9A | 0.9300 |
S1—O2 | 1.470 (3) | C18—C17 | 1.358 (7) |
S1—O3 | 1.475 (3) | C18—H18A | 0.9300 |
S1—O1 | 1.504 (3) | C5—C6 | 1.359 (7) |
N3—C14 | 1.333 (6) | C5—H5A | 0.9300 |
N3—C24 | 1.358 (6) | C7—C6 | 1.416 (7) |
N2—C10 | 1.324 (7) | C16—C17 | 1.451 (7) |
N2—C11 | 1.371 (6) | C17—H17A | 0.9300 |
C24—C16 | 1.382 (6) | C3—C2 | 1.358 (7) |
C24—C23 | 1.437 (6) | C3—H3A | 0.9300 |
N1—C1 | 1.330 (6) | C6—H6A | 0.9300 |
N1—C12 | 1.354 (5) | C20—C21 | 1.363 (7) |
N4—C22 | 1.338 (6) | C20—H20A | 0.9300 |
N4—C23 | 1.369 (5) | C2—C1 | 1.406 (7) |
C11—C7 | 1.412 (6) | C2—H2A | 0.9300 |
C11—C12 | 1.433 (6) | C22—C21 | 1.389 (7) |
C8—C9 | 1.347 (8) | C22—H22A | 0.9300 |
C8—C7 | 1.408 (7) | C21—H21A | 0.9300 |
C8—H8A | 0.9300 | C1—H1A | 0.9300 |
C15—C13 | 1.386 (8) | O6—C26 | 1.386 (7) |
C15—C16 | 1.415 (7) | O6—H6B | 0.8200 |
C15—H15A | 0.9300 | O5—C25 | 1.430 (7) |
C14—C13 | 1.365 (7) | O5—H5B | 0.8200 |
C14—H14A | 0.9300 | C26—C25 | 1.472 (8) |
C10—C9 | 1.426 (7) | C26—H26A | 0.9700 |
C10—H10A | 0.9300 | C26—H26B | 0.9700 |
C12—C4 | 1.390 (6) | C25—H25A | 0.9700 |
C19—C20 | 1.401 (7) | C25—H25B | 0.9700 |
O1—Cu1—N2 | 96.90 (14) | C8—C9—C10 | 118.8 (5) |
O1—Cu1—N3 | 91.43 (13) | C8—C9—H9A | 120.6 |
N2—Cu1—N3 | 170.72 (10) | C10—C9—H9A | 120.6 |
O1—Cu1—N4 | 143.49 (13) | C17—C18—C19 | 122.8 (5) |
N2—Cu1—N4 | 94.19 (15) | C17—C18—H18A | 118.6 |
N3—Cu1—N4 | 81.39 (15) | C19—C18—H18A | 118.6 |
O1—Cu1—N1 | 104.46 (13) | C6—C5—C4 | 119.8 (4) |
N2—Cu1—N1 | 80.37 (15) | C6—C5—H5A | 120.1 |
N3—Cu1—N1 | 93.63 (15) | C4—C5—H5A | 120.1 |
N4—Cu1—N1 | 111.67 (10) | C8—C7—C11 | 116.6 (4) |
O4—S1—O2 | 109.46 (18) | C8—C7—C6 | 124.2 (4) |
O4—S1—O3 | 110.01 (16) | C11—C7—C6 | 119.2 (4) |
O2—S1—O3 | 109.6 (2) | C24—C16—C15 | 117.5 (4) |
O4—S1—O1 | 107.30 (19) | C24—C16—C17 | 119.0 (4) |
O2—S1—O1 | 108.83 (17) | C15—C16—C17 | 123.5 (4) |
O3—S1—O1 | 111.61 (19) | C18—C17—C16 | 119.6 (5) |
C14—N3—C24 | 118.5 (4) | C18—C17—H17A | 120.2 |
C14—N3—Cu1 | 127.3 (3) | C16—C17—H17A | 120.2 |
C24—N3—Cu1 | 114.0 (3) | C2—C3—C4 | 118.9 (4) |
C10—N2—C11 | 117.8 (4) | C2—C3—H3A | 120.6 |
C10—N2—Cu1 | 127.3 (4) | C4—C3—H3A | 120.6 |
C11—N2—Cu1 | 114.9 (3) | N4—C23—C19 | 123.7 (4) |
N3—C24—C16 | 122.9 (4) | N4—C23—C24 | 116.9 (4) |
N3—C24—C23 | 116.3 (4) | C19—C23—C24 | 119.4 (4) |
C16—C24—C23 | 120.7 (4) | C5—C6—C7 | 121.7 (4) |
C1—N1—C12 | 118.5 (4) | C5—C6—H6A | 119.2 |
C1—N1—Cu1 | 131.3 (3) | C7—C6—H6A | 119.2 |
C12—N1—Cu1 | 110.2 (3) | C21—C20—C19 | 120.3 (4) |
C22—N4—C23 | 116.7 (4) | C21—C20—H20A | 119.9 |
C22—N4—Cu1 | 132.0 (3) | C19—C20—H20A | 119.9 |
C23—N4—Cu1 | 111.2 (3) | C3—C2—C1 | 120.1 (5) |
N2—C11—C7 | 123.1 (4) | C3—C2—H2A | 119.9 |
N2—C11—C12 | 117.5 (4) | C1—C2—H2A | 119.9 |
C7—C11—C12 | 119.4 (4) | N4—C22—C21 | 123.3 (4) |
C9—C8—C7 | 121.0 (5) | N4—C22—H22A | 118.4 |
C9—C8—H8A | 119.5 | C21—C22—H22A | 118.4 |
C7—C8—H8A | 119.5 | C20—C21—C22 | 119.6 (4) |
C13—C15—C16 | 118.6 (5) | C20—C21—H21A | 120.2 |
C13—C15—H15A | 120.7 | C22—C21—H21A | 120.2 |
C16—C15—H15A | 120.7 | N1—C1—C2 | 121.8 (4) |
N3—C14—C13 | 122.6 (4) | N1—C1—H1A | 119.1 |
N3—C14—H14A | 118.7 | C2—C1—H1A | 119.1 |
C13—C14—H14A | 118.7 | S1—O1—Cu1 | 129.51 (18) |
N2—C10—C9 | 122.7 (5) | C26—O6—H6B | 109.5 |
N2—C10—H10A | 118.6 | C25—O5—H5B | 109.5 |
C9—C10—H10A | 118.6 | O6—C26—C25 | 115.7 (6) |
N1—C12—C4 | 123.3 (4) | O6—C26—H26A | 108.3 |
N1—C12—C11 | 117.1 (4) | C25—C26—H26A | 108.3 |
C4—C12—C11 | 119.7 (4) | O6—C26—H26B | 108.3 |
C20—C19—C18 | 125.2 (4) | C25—C26—H26B | 108.3 |
C20—C19—C23 | 116.4 (4) | H26A—C26—H26B | 107.4 |
C18—C19—C23 | 118.4 (4) | O5—C25—C26 | 113.3 (5) |
C12—C4—C3 | 117.4 (4) | O5—C25—H25A | 108.9 |
C12—C4—C5 | 120.2 (4) | C26—C25—H25A | 108.9 |
C3—C4—C5 | 122.4 (4) | O5—C25—H25B | 108.9 |
C14—C13—C15 | 119.9 (5) | C26—C25—H25B | 108.9 |
C14—C13—H13A | 120.0 | H25A—C25—H25B | 107.7 |
C15—C13—H13A | 120.0 | ||
O1—Cu1—N3—C14 | −37.2 (4) | N2—C10—C9—C8 | −1.8 (7) |
N4—Cu1—N3—C14 | 178.8 (4) | C20—C19—C18—C17 | −179.6 (5) |
N1—Cu1—N3—C14 | 67.4 (4) | C23—C19—C18—C17 | −0.2 (7) |
O1—Cu1—N3—C24 | 147.5 (3) | C12—C4—C5—C6 | −0.1 (7) |
N4—Cu1—N3—C24 | 3.5 (3) | C3—C4—C5—C6 | 179.7 (5) |
N1—Cu1—N3—C24 | −107.9 (3) | C9—C8—C7—C11 | 1.2 (7) |
O1—Cu1—N2—C10 | −76.9 (4) | C9—C8—C7—C6 | −178.6 (4) |
N4—Cu1—N2—C10 | 68.3 (4) | N2—C11—C7—C8 | −1.6 (6) |
N1—Cu1—N2—C10 | 179.6 (4) | C12—C11—C7—C8 | 178.5 (4) |
O1—Cu1—N2—C11 | 105.0 (3) | N2—C11—C7—C6 | 178.2 (4) |
N4—Cu1—N2—C11 | −109.8 (3) | C12—C11—C7—C6 | −1.6 (6) |
N1—Cu1—N2—C11 | 1.5 (3) | N3—C24—C16—C15 | −1.2 (7) |
C14—N3—C24—C16 | 1.2 (7) | C23—C24—C16—C15 | −179.3 (4) |
Cu1—N3—C24—C16 | 176.9 (3) | N3—C24—C16—C17 | 176.7 (4) |
C14—N3—C24—C23 | 179.4 (4) | C23—C24—C16—C17 | −1.4 (7) |
Cu1—N3—C24—C23 | −4.9 (5) | C13—C15—C16—C24 | −0.2 (7) |
O1—Cu1—N1—C1 | 83.4 (4) | C13—C15—C16—C17 | −178.1 (5) |
N2—Cu1—N1—C1 | 178.1 (4) | C19—C18—C17—C16 | 0.2 (7) |
N3—Cu1—N1—C1 | −9.1 (4) | C24—C16—C17—C18 | 0.6 (7) |
N4—Cu1—N1—C1 | −91.2 (4) | C15—C16—C17—C18 | 178.4 (5) |
O1—Cu1—N1—C12 | −95.9 (3) | C12—C4—C3—C2 | −1.0 (7) |
N2—Cu1—N1—C12 | −1.1 (3) | C5—C4—C3—C2 | 179.2 (5) |
N3—Cu1—N1—C12 | 171.7 (3) | C22—N4—C23—C19 | 2.7 (6) |
N4—Cu1—N1—C12 | 89.6 (3) | Cu1—N4—C23—C19 | 180.0 (3) |
O1—Cu1—N4—C22 | 94.6 (4) | C22—N4—C23—C24 | −178.0 (4) |
N2—Cu1—N4—C22 | −12.9 (4) | Cu1—N4—C23—C24 | −0.7 (5) |
N3—Cu1—N4—C22 | 175.3 (4) | C20—C19—C23—N4 | −1.8 (6) |
N1—Cu1—N4—C22 | −94.2 (4) | C18—C19—C23—N4 | 178.8 (4) |
O1—Cu1—N4—C23 | −82.1 (3) | C20—C19—C23—C24 | 178.9 (4) |
N2—Cu1—N4—C23 | 170.3 (3) | C18—C19—C23—C24 | −0.5 (6) |
N3—Cu1—N4—C23 | −1.5 (3) | N3—C24—C23—N4 | 3.7 (6) |
N1—Cu1—N4—C23 | 89.0 (3) | C16—C24—C23—N4 | −178.0 (4) |
C10—N2—C11—C7 | 0.2 (7) | N3—C24—C23—C19 | −176.9 (4) |
Cu1—N2—C11—C7 | 178.5 (3) | C16—C24—C23—C19 | 1.3 (6) |
C10—N2—C11—C12 | −179.9 (4) | C4—C5—C6—C7 | 1.2 (8) |
Cu1—N2—C11—C12 | −1.6 (5) | C8—C7—C6—C5 | 179.5 (5) |
C24—N3—C14—C13 | 0.4 (7) | C11—C7—C6—C5 | −0.3 (7) |
Cu1—N3—C14—C13 | −174.7 (4) | C18—C19—C20—C21 | 179.3 (4) |
C11—N2—C10—C9 | 1.5 (7) | C23—C19—C20—C21 | −0.1 (7) |
Cu1—N2—C10—C9 | −176.5 (3) | C4—C3—C2—C1 | 1.5 (7) |
C1—N1—C12—C4 | −1.0 (6) | C23—N4—C22—C21 | −1.7 (7) |
Cu1—N1—C12—C4 | 178.3 (3) | Cu1—N4—C22—C21 | −178.3 (4) |
C1—N1—C12—C11 | −178.7 (4) | C19—C20—C21—C22 | 1.0 (7) |
Cu1—N1—C12—C11 | 0.7 (5) | N4—C22—C21—C20 | −0.1 (8) |
N2—C11—C12—N1 | 0.6 (6) | C12—N1—C1—C2 | 1.6 (6) |
C7—C11—C12—N1 | −179.6 (4) | Cu1—N1—C1—C2 | −177.6 (3) |
N2—C11—C12—C4 | −177.2 (4) | C3—C2—C1—N1 | −1.9 (7) |
C7—C11—C12—C4 | 2.7 (6) | O4—S1—O1—Cu1 | −145.3 (2) |
N1—C12—C4—C3 | 0.7 (7) | O2—S1—O1—Cu1 | −26.9 (3) |
C11—C12—C4—C3 | 178.3 (4) | O3—S1—O1—Cu1 | 94.2 (3) |
N1—C12—C4—C5 | −179.4 (4) | N2—Cu1—O1—S1 | 72.8 (3) |
C11—C12—C4—C5 | −1.8 (6) | N3—Cu1—O1—S1 | −111.3 (3) |
N3—C14—C13—C15 | −1.8 (8) | N4—Cu1—O1—S1 | −33.9 (4) |
C16—C15—C13—C14 | 1.6 (8) | N1—Cu1—O1—S1 | 154.6 (2) |
C7—C8—C9—C10 | 0.3 (7) | O6—C26—C25—O5 | 71.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O4 | 0.82 | 1.93 | 2.751 (5) | 176 |
O5—H5B···O3 | 0.82 | 1.98 | 2.798 (5) | 171 |
Experimental details
Crystal data | |
Chemical formula | [Cu(SO4)(C12H8N2)2]·C2H6O2 |
Mr | 582.08 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 223 |
a, b, c (Å) | 17.666 (4), 11.992 (2), 13.122 (3) |
β (°) | 120.96 (3) |
V (Å3) | 2383.8 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.40 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.776, 1.000 |
No. of measured, independent and observed [I > 2/s(I)] reflections | 6663, 4089, 3835 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.102, 1.06 |
No. of reflections | 4089 |
No. of parameters | 344 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −0.81 |
Absolute structure | Flack (1983), 1396 Friedel pairs |
Absolute structure parameter | 0.254 (14) |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cu1—O1 | 1.957 (3) | S1—O4 | 1.469 (3) |
Cu1—N2 | 1.990 (4) | S1—O2 | 1.470 (3) |
Cu1—N3 | 2.006 (4) | S1—O3 | 1.475 (3) |
Cu1—N4 | 2.073 (4) | S1—O1 | 1.504 (3) |
Cu1—N1 | 2.162 (4) | C26—C25 | 1.472 (8) |
O1—Cu1—N2 | 96.90 (14) | O4—S1—O2 | 109.46 (18) |
O1—Cu1—N3 | 91.43 (13) | O4—S1—O3 | 110.01 (16) |
O1—Cu1—N4 | 143.49 (13) | O2—S1—O3 | 109.6 (2) |
N3—Cu1—N4 | 81.39 (15) | O4—S1—O1 | 107.30 (19) |
O1—Cu1—N1 | 104.46 (13) | O2—S1—O1 | 108.83 (17) |
N2—Cu1—N1 | 80.37 (15) | O3—S1—O1 | 111.61 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O4 | 0.82 | 1.93 | 2.751 (5) | 176.1 |
O5—H5B···O3 | 0.82 | 1.98 | 2.798 (5) | 171.3 |
In the past few years, we have reported many metal-Phen complexes with bidentate-chelating sulfate auxiliary ligand via a alcohlol-solvothermal reaction, such as [CoSO4(C12H8N2)2].C2H6O2 (Zhong et al., 2006), [NiSO4(C12H8N2)2].C2H6O2 (Zhong et al., 2009), [CoSO4(C12H8N2)2].C3H8O2 (Zhong, 2010), [ZnSO4(C12H8N2)2].C3H8O2 (Cui et al., 2010), [NiSO4(C12H8N2)2].C3H8O2 (Ni et al., 2010 and [CdSO4(C12H8N2)2].C3H8O2 (Zhong & Cui, 2010). The title compound was obtained during an attempt to synthesize a complex of Cu-complex with bidentate-chelating sulfate ligand by the similar route. The crystal structure of the title complex [CuSO4(C12H8N2)2].C2H6O2, (I) has not hitherto been reported.
Single crystal X-ray diffraction experiment indicated that the title compound is isostructual to the recently reported Cu(C12H8N2)2(SO4).C3H8O2, (II) (Zhong, 2011), the CuII metal ion is five-coordinated in a distorted square-pyramidal coordination environment formed by four N atoms(N1, N2, N3 and N4) from two chelating phen ligands and an O atoms(O1) from a monodentate sulfate ligand, the N1, N2, N3 and N4 atoms comprise a square, and the O3 atom the apex of a square pyramid surrounding each metal atom. The geometry of the phen and sulfate ligands is in good agreement with those reported in the isomorphs complex(II). The dihedral angle between the two chelating N2C2 groups is 71.1 (2)°, this is smaller than that found in (II) [84.9 (4)°]. The Cu—O bond distance [1.957 (3) Å], the Cu—N bond distance [1.990 (4) - 2.162 (4) Å], and the N—Cu—N bite angle [80.4 (2) - 81.4 (2)°] are in good agreement with observed in (II), [1.901 (1) Å, 1.991 (7) - 2.154 (8)Å and 80.4 (3) - 80.7 (3)°, respectively](see Table 1). The metal complex and solvent entities of (I) are held together by a pair of intermolecular O—H···O hydrogen bonds with the uncoordinated O atoms of the sulfate group(see Table 2 & Fig. 1).