The title compound, [Cu
2(OH)
2(C
12H
8N
2)
2(H
2O)
2](NO
3)
2·6H
2O, consists of a hydroxo-bridged dinuclear complex dication, two nitrate anions and six water molecules arranged around an inversion center. The Cu
Cu distance is 2.902 (1) Å. The packing is governed by an intricate O—H
O hydrogen-bond network and also by π–π interactions.
Supporting information
CCDC reference: 191166
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.005 Å
- R factor = 0.045
- wR factor = 0.115
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact O3 .. O4 .. 2.59 Ang.
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
N O3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4
H2 O
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 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
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: SHELXTL/PC.
Di-µ-hydroxo-bis[aqua(1,10-phenanthroline-
κ2N,
N')copper(II)]
dinitrate hexahydrate
top
Crystal data top
[Cu2(OH)2(C12H8N2)2(H2O)2](NO3)2·6H2O | Z = 1 |
Mr = 789.65 | F(000) = 406 |
Triclinic, P1 | Dx = 1.684 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.078 (2) Å | Cell parameters from 1793 reflections |
b = 9.604 (2) Å | θ = 2.6–26.8° |
c = 10.480 (3) Å | µ = 1.45 mm−1 |
α = 81.145 (3)° | T = 173 K |
β = 88.341 (4)° | Block, blue |
γ = 75.731 (3)° | 0.25 × 0.20 × 0.20 mm |
V = 778.4 (3) Å3 | |
Data collection top
Bruker SMART 1K CCD area-detector diffractometer | 2687 independent reflections |
Radiation source: fine-focus sealed tube | 2359 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −9→8 |
Tmin = 0.699, Tmax = 0.745 | k = −11→11 |
3804 measured reflections | l = −11→12 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0703P)2] where P = (Fo2 + 2Fc2)/3 |
2687 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.80 e Å−3 |
13 restraints | Δρmin = −0.61 e Å−3 |
Special details top
Experimental. CHN were analysed in a Perkin-Elmer 240 C Elemental Analyzer.? |
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 | 0.58181 (5) | 0.86055 (4) | 0.96171 (4) | 0.01861 (17) | |
N1 | 0.7245 (4) | 0.6677 (3) | 1.0486 (3) | 0.0199 (7) | |
N2 | 0.5391 (4) | 0.7353 (3) | 0.8334 (3) | 0.0189 (7) | |
O1 | 0.4013 (3) | 1.0311 (3) | 0.9001 (2) | 0.0200 (6) | |
H1A | 0.423 (5) | 1.076 (4) | 0.834 (3) | 0.024* | |
O2 | 0.7832 (4) | 0.9338 (3) | 0.8371 (3) | 0.0329 (7) | |
H2C | 0.768 (5) | 0.957 (5) | 0.7609 (19) | 0.040* | |
H2B | 0.870 (4) | 0.944 (5) | 0.865 (4) | 0.040* | |
C1 | 0.8201 (5) | 0.6376 (4) | 1.1541 (3) | 0.0229 (8) | |
H1 | 0.8268 | 0.7132 | 1.1979 | 0.027* | |
C2 | 0.9111 (5) | 0.4975 (4) | 1.2023 (4) | 0.0256 (9) | |
H2A | 0.9776 | 0.4807 | 1.2767 | 0.031* | |
C3 | 0.9025 (5) | 0.3846 (4) | 1.1400 (4) | 0.0261 (9) | |
H3 | 0.9625 | 0.2905 | 1.1720 | 0.031* | |
C4 | 0.8022 (5) | 0.4117 (4) | 1.0271 (4) | 0.0226 (8) | |
C5 | 0.7170 (4) | 0.5555 (4) | 0.9849 (3) | 0.0197 (8) | |
C6 | 0.6167 (5) | 0.5927 (4) | 0.8690 (3) | 0.0210 (8) | |
C7 | 0.7871 (5) | 0.3019 (4) | 0.9529 (4) | 0.0281 (9) | |
H7 | 0.8437 | 0.2055 | 0.9804 | 0.034* | |
C8 | 0.6912 (5) | 0.3368 (4) | 0.8430 (4) | 0.0271 (9) | |
H8 | 0.6828 | 0.2638 | 0.7966 | 0.033* | |
C9 | 0.6029 (5) | 0.4837 (4) | 0.7973 (4) | 0.0235 (8) | |
C10 | 0.5036 (5) | 0.5284 (4) | 0.6842 (4) | 0.0266 (9) | |
H10 | 0.4902 | 0.4602 | 0.6337 | 0.032* | |
C11 | 0.4267 (5) | 0.6713 (4) | 0.6481 (4) | 0.0278 (9) | |
H11 | 0.3608 | 0.7014 | 0.5730 | 0.033* | |
C12 | 0.4474 (5) | 0.7731 (4) | 0.7250 (4) | 0.0238 (8) | |
H12 | 0.3949 | 0.8708 | 0.6992 | 0.029* | |
N3 | 0.0219 (5) | 1.2914 (4) | 0.5455 (3) | 0.0443 (10) | |
O3 | 0.1462 (3) | 1.3469 (3) | 0.5175 (3) | 0.0329 (7) | |
O4 | −0.1362 (3) | 1.3799 (3) | 0.5443 (3) | 0.0290 (6) | |
O5 | 0.0327 (4) | 1.1573 (3) | 0.5776 (3) | 0.0304 (7) | |
O6 | 0.7643 (4) | 1.0316 (3) | 0.5700 (3) | 0.0316 (7) | |
H6A | 0.801 (5) | 0.971 (4) | 0.524 (4) | 0.038* | |
H6B | 0.835 (4) | 1.080 (4) | 0.577 (4) | 0.038* | |
O7 | 0.4406 (4) | 1.1663 (4) | 0.6498 (3) | 0.0417 (8) | |
H7B | 0.363 (4) | 1.205 (5) | 0.599 (3) | 0.050* | |
H7A | 0.528 (3) | 1.121 (5) | 0.621 (4) | 0.050* | |
O8 | 0.0816 (4) | 1.0159 (4) | 0.8339 (3) | 0.0406 (8) | |
H8A | 0.072 (5) | 1.058 (5) | 0.760 (2) | 0.049* | |
H8B | 0.173 (4) | 1.010 (5) | 0.867 (4) | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0208 (3) | 0.0131 (3) | 0.0213 (3) | −0.00258 (18) | −0.00257 (18) | −0.00258 (18) |
N1 | 0.0209 (16) | 0.0182 (16) | 0.0209 (16) | −0.0054 (13) | 0.0010 (13) | −0.0029 (13) |
N2 | 0.0203 (16) | 0.0129 (16) | 0.0226 (16) | −0.0033 (12) | 0.0001 (13) | −0.0011 (13) |
O1 | 0.0234 (14) | 0.0153 (13) | 0.0199 (14) | −0.0029 (11) | −0.0020 (11) | −0.0012 (11) |
O2 | 0.0277 (16) | 0.0438 (18) | 0.0290 (16) | −0.0172 (14) | −0.0019 (13) | 0.0034 (14) |
C1 | 0.022 (2) | 0.022 (2) | 0.024 (2) | −0.0038 (16) | 0.0018 (16) | −0.0042 (16) |
C2 | 0.023 (2) | 0.028 (2) | 0.022 (2) | −0.0018 (17) | −0.0004 (16) | −0.0002 (17) |
C3 | 0.029 (2) | 0.018 (2) | 0.026 (2) | 0.0009 (16) | 0.0027 (17) | 0.0033 (16) |
C4 | 0.0226 (19) | 0.020 (2) | 0.025 (2) | −0.0061 (16) | 0.0076 (16) | −0.0015 (16) |
C5 | 0.0167 (18) | 0.0168 (19) | 0.025 (2) | −0.0046 (15) | 0.0045 (15) | −0.0022 (15) |
C6 | 0.024 (2) | 0.018 (2) | 0.0216 (19) | −0.0053 (15) | 0.0054 (15) | −0.0041 (15) |
C7 | 0.034 (2) | 0.015 (2) | 0.032 (2) | −0.0038 (17) | 0.0064 (18) | −0.0005 (17) |
C8 | 0.036 (2) | 0.018 (2) | 0.029 (2) | −0.0082 (17) | 0.0047 (18) | −0.0068 (17) |
C9 | 0.025 (2) | 0.020 (2) | 0.027 (2) | −0.0075 (16) | 0.0073 (16) | −0.0062 (16) |
C10 | 0.033 (2) | 0.027 (2) | 0.025 (2) | −0.0126 (18) | 0.0032 (17) | −0.0110 (17) |
C11 | 0.030 (2) | 0.032 (2) | 0.023 (2) | −0.0099 (18) | −0.0004 (16) | −0.0029 (17) |
C12 | 0.023 (2) | 0.019 (2) | 0.028 (2) | −0.0038 (16) | −0.0001 (16) | −0.0020 (16) |
N3 | 0.053 (3) | 0.052 (3) | 0.029 (2) | −0.013 (2) | −0.0040 (18) | −0.0087 (19) |
O3 | 0.0214 (15) | 0.0235 (15) | 0.0528 (19) | −0.0082 (12) | 0.0015 (13) | 0.0013 (13) |
O4 | 0.0216 (14) | 0.0260 (15) | 0.0378 (16) | −0.0036 (12) | 0.0009 (12) | −0.0040 (13) |
O5 | 0.0398 (17) | 0.0128 (14) | 0.0388 (17) | −0.0087 (12) | 0.0024 (13) | −0.0010 (12) |
O6 | 0.0289 (16) | 0.0300 (17) | 0.0362 (17) | −0.0074 (13) | 0.0021 (13) | −0.0059 (13) |
O7 | 0.0296 (17) | 0.054 (2) | 0.0305 (17) | 0.0047 (15) | 0.0011 (13) | 0.0037 (15) |
O8 | 0.0285 (16) | 0.052 (2) | 0.0407 (19) | −0.0211 (15) | −0.0117 (14) | 0.0135 (16) |
Geometric parameters (Å, º) top
Cu1—O1i | 1.935 (2) | C5—C6 | 1.428 (5) |
Cu1—O1 | 1.944 (2) | C6—C9 | 1.406 (5) |
Cu1—N1 | 2.019 (3) | C7—C8 | 1.358 (5) |
Cu1—N2 | 2.025 (3) | C7—H7 | 0.9300 |
Cu1—O2 | 2.237 (3) | C8—C9 | 1.430 (5) |
Cu1—Cu1i | 2.9018 (9) | C8—H8 | 0.9300 |
N1—C1 | 1.320 (5) | C9—C10 | 1.400 (5) |
N1—C5 | 1.366 (5) | C10—C11 | 1.359 (5) |
N2—C12 | 1.327 (5) | C10—H10 | 0.9300 |
N2—C6 | 1.357 (4) | C11—C12 | 1.402 (5) |
O1—Cu1i | 1.935 (2) | C11—H11 | 0.9300 |
O1—H1A | 0.80 (4) | C12—H12 | 0.9300 |
O2—H2C | 0.80 (4) | N3—O3 | 1.256 (5) |
O2—H2B | 0.80 (4) | N3—O5 | 1.261 (5) |
C1—C2 | 1.390 (5) | N3—O4 | 1.348 (4) |
C1—H1 | 0.9300 | O6—H6A | 0.80 (4) |
C2—C3 | 1.365 (5) | O6—H6B | 0.83 (3) |
C2—H2A | 0.9300 | O7—H7B | 0.81 (4) |
C3—C4 | 1.408 (5) | O7—H7A | 0.81 (4) |
C3—H3 | 0.9300 | O8—H8A | 0.81 (4) |
C4—C5 | 1.391 (5) | O8—H8B | 0.81 (3) |
C4—C7 | 1.432 (5) | | |
| | | |
O1i—Cu1—O1 | 83.14 (10) | C4—C3—H3 | 120.2 |
O1i—Cu1—N1 | 96.36 (11) | C5—C4—C3 | 116.8 (3) |
O1—Cu1—N1 | 166.59 (11) | C5—C4—C7 | 119.1 (3) |
O1i—Cu1—N2 | 171.68 (12) | C3—C4—C7 | 124.1 (3) |
O1—Cu1—N2 | 96.75 (11) | N1—C5—C4 | 123.3 (3) |
N1—Cu1—N2 | 81.81 (11) | N1—C5—C6 | 116.4 (3) |
O1i—Cu1—O2 | 96.44 (11) | C4—C5—C6 | 120.3 (3) |
O1—Cu1—O2 | 94.59 (11) | N2—C6—C9 | 123.2 (3) |
N1—Cu1—O2 | 98.77 (12) | N2—C6—C5 | 116.8 (3) |
N2—Cu1—O2 | 91.86 (12) | C9—C6—C5 | 120.0 (3) |
O1i—Cu1—Cu1i | 41.69 (7) | C8—C7—C4 | 120.7 (3) |
O1—Cu1—Cu1i | 41.45 (7) | C8—C7—H7 | 119.6 |
N1—Cu1—Cu1i | 136.51 (9) | C4—C7—H7 | 119.6 |
N2—Cu1—Cu1i | 137.60 (8) | C7—C8—C9 | 121.3 (4) |
O2—Cu1—Cu1i | 97.38 (9) | C7—C8—H8 | 119.3 |
C1—N1—C5 | 117.9 (3) | C9—C8—H8 | 119.3 |
C1—N1—Cu1 | 129.6 (3) | C10—C9—C6 | 116.8 (3) |
C5—N1—Cu1 | 112.5 (2) | C10—C9—C8 | 124.6 (3) |
C12—N2—C6 | 118.0 (3) | C6—C9—C8 | 118.5 (3) |
C12—N2—Cu1 | 129.5 (2) | C11—C10—C9 | 120.1 (3) |
C6—N2—Cu1 | 112.4 (2) | C11—C10—H10 | 120.0 |
Cu1i—O1—Cu1 | 96.86 (10) | C9—C10—H10 | 120.0 |
Cu1i—O1—H1A | 108 (3) | C10—C11—C12 | 119.5 (4) |
Cu1—O1—H1A | 114 (3) | C10—C11—H11 | 120.3 |
Cu1—O2—H2C | 120 (3) | C12—C11—H11 | 120.3 |
Cu1—O2—H2B | 124 (3) | N2—C12—C11 | 122.4 (3) |
H2C—O2—H2B | 116 (3) | N2—C12—H12 | 118.8 |
N1—C1—C2 | 122.7 (4) | C11—C12—H12 | 118.8 |
N1—C1—H1 | 118.7 | O3—N3—O5 | 125.1 (4) |
C2—C1—H1 | 118.7 | O3—N3—O4 | 118.7 (4) |
C3—C2—C1 | 119.7 (4) | O5—N3—O4 | 116.3 (4) |
C3—C2—H2A | 120.2 | H6A—O6—H6B | 110 (3) |
C1—C2—H2A | 120.2 | H7B—O7—H7A | 117 (3) |
C2—C3—C4 | 119.6 (3) | H8A—O8—H8B | 114 (3) |
C2—C3—H3 | 120.2 | | |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O7 | 0.80 (4) | 2.01 (2) | 2.789 (4) | 166 (4) |
O2—H2C···O6 | 0.80 (4) | 2.02 (2) | 2.809 (4) | 170 (4) |
O2—H2B···O8ii | 0.80 (4) | 2.00 (3) | 2.713 (4) | 149 (4) |
O6—H6A···O5iii | 0.80 (4) | 1.99 (2) | 2.761 (4) | 160 (4) |
O6—H6B···O5ii | 0.83 (3) | 1.92 (2) | 2.738 (4) | 168 (4) |
O7—H7B···O3 | 0.81 (4) | 2.05 (2) | 2.829 (4) | 160 (4) |
O7—H7A···O6 | 0.81 (4) | 1.99 (2) | 2.784 (4) | 169 (5) |
O8—H8A···O5 | 0.81 (4) | 2.00 (2) | 2.809 (4) | 176 (4) |
O8—H8B···O1 | 0.81 (4) | 1.95 (2) | 2.737 (4) | 164 (4) |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1. |
Comparison of Cu—Cu and Cu—O distances (Å) within the cations
for the different structures topAnion | Cu-Cu | Cu-O(OH) | Cu-O(OH) | Cu-O(H2O) | ref. |
NO3- | 2.902 (1) | 1.935 (2) | 1.944 (2) | 2.235 (3) | a |
HCO3- | 2.905 (1) | 1.941 (1) | 1.949 (1) | 2.254 (2) | b |
Cl- | 2.933 (1) | 1.925 (1) | 1.949 (1) | 2.347 (2) | c |
References: a. this work; b. Zheng et al., 2000; c. Lu et al., 2003 |