Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030711/xu2281sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030711/xu2281Isup2.hkl |
CCDC reference: 654826
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.029
- wR factor = 0.076
- Data-to-parameter ratio = 18.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cu1 - O1W .. 17.43 su
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N2 .. 5.72 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N3 .. 6.24 su
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.09
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of CuCl2·2H2O (0.171 g, 1 mmol) and NaOH (0.080 g, 2 mmol) in water (10 ml) was stirred for 10 min at room temperature, then the Cu(OH)2 precipitate was collected by filtration and washed with water. 4-Amino-2,5-dichlorobenzenesulfonic acid (0.484 g, 2 mmol) was added to the Cu(OH)2 suspension in water (10 ml) with stirring, and a blue precipitate was obtained. A minimum amount of ammonia solution (14 M) was added to give a blue, clear solution. Suitable crystals of the title compound were obtained after several days.
H atoms bonded to N and O atoms were located in a difference Fourier map and refined as riding in their as-found relative positions, Uiso(H) = 1.5Ueq(N,O). Aromatic H atoms were poisitioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
As metal sulfonates are a class of novel materials showing interesting properties, such as exchange, guest sorption (Côté & Shimizu, 2003; Yang et al., 2006), several studies on the coordination chemistry of transition metal sulfonates and their solid-state properties have been reported. In some cases, sulfonate group can compete with water molecule and coordinate to metal ion (Markku & Reijo, 1993). As part of an investigation of the structure of transition metal sulfonate compounds, we present here the structure of the title compound.
The crystal of the compound is composed of [Cu(NH3)4(H2O)2]2+ cations and 4-amino-2,5-dichlorobenzenesulfonate anions (Fig. 1). The CuII cation lies on an inversion center and is six-coordinated by four NH3 molecules and two water molecules. The Cu—O1W bond in the axial direction is much longer than Cu—N bonds in the equatorial plane (Table 1), showing the typical Jahn-Teller distortion. The anions act as counterions and are hydrogen-bonded to the complex cations, forming a three dimensional supra-molecular structure (Fig. 2).
For general background, see: Côté & Shimizu (2003); Markku & Reijo (1993); Yang et al. (2006).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2 | Z = 1 |
Mr = 649.83 | F(000) = 331 |
Triclinic, P1 | Dx = 1.808 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.367 (6) Å | Cell parameters from 5673 reflections |
b = 7.380 (5) Å | θ = 3.2–27.5° |
c = 12.689 (10) Å | µ = 1.59 mm−1 |
α = 96.22 (4)° | T = 293 K |
β = 94.62 (4)° | Block, blue |
γ = 118.33 (3)° | 0.44 × 0.37 × 0.27 mm |
V = 596.8 (8) Å3 |
Rigaku R-AXIS RAPID IP diffractometer | 2715 independent reflections |
Radiation source: rotor target | 2518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −9→9 |
Tmin = 0.521, Tmax = 0.650 | l = −16→16 |
5849 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0461P)2 + 0.1532P] where P = (Fo2 + 2Fc2)/3 |
2715 reflections | (Δ/σ)max = 0.001 |
151 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2 | γ = 118.33 (3)° |
Mr = 649.83 | V = 596.8 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.367 (6) Å | Mo Kα radiation |
b = 7.380 (5) Å | µ = 1.59 mm−1 |
c = 12.689 (10) Å | T = 293 K |
α = 96.22 (4)° | 0.44 × 0.37 × 0.27 mm |
β = 94.62 (4)° |
Rigaku R-AXIS RAPID IP diffractometer | 2715 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2518 reflections with I > 2σ(I) |
Tmin = 0.521, Tmax = 0.650 | Rint = 0.020 |
5849 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.43 e Å−3 |
2715 reflections | Δρmin = −0.42 e Å−3 |
151 parameters |
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 | 1.0000 | 0.0000 | 1.0000 | 0.02605 (10) | |
Cl1 | 0.12744 (6) | 0.22744 (8) | 0.68358 (3) | 0.03803 (12) | |
Cl2 | 0.80402 (7) | 0.27818 (7) | 0.40904 (3) | 0.03640 (12) | |
S1 | 0.57643 (6) | 0.30274 (6) | 0.80181 (3) | 0.02445 (11) | |
C1 | 0.5153 (2) | 0.2819 (2) | 0.66165 (12) | 0.0231 (3) | |
C2 | 0.3236 (2) | 0.2471 (2) | 0.61119 (13) | 0.0248 (3) | |
C3 | 0.2789 (2) | 0.2209 (3) | 0.50137 (13) | 0.0279 (3) | |
H3 | 0.1496 | 0.1983 | 0.4704 | 0.033* | |
C4 | 0.4238 (3) | 0.2275 (3) | 0.43586 (12) | 0.0270 (3) | |
C5 | 0.6171 (2) | 0.2647 (2) | 0.48716 (13) | 0.0256 (3) | |
C6 | 0.6623 (2) | 0.2912 (2) | 0.59713 (12) | 0.0246 (3) | |
H6 | 0.7921 | 0.3155 | 0.6284 | 0.030* | |
N1 | 0.3790 (3) | 0.1971 (3) | 0.32678 (12) | 0.0384 (4) | |
H1N | 0.2620 | 0.1798 | 0.2962 | 0.058* | |
H2N | 0.4689 | 0.2039 | 0.2910 | 0.058* | |
O1 | 0.4554 (2) | 0.0939 (2) | 0.82788 (10) | 0.0357 (3) | |
O2 | 0.79984 (18) | 0.3761 (2) | 0.82209 (10) | 0.0357 (3) | |
O1W | 1.0063 (2) | −0.1798 (2) | 0.81528 (12) | 0.0445 (3) | |
H1A | 0.9705 | −0.3136 | 0.8054 | 0.067* | |
H1B | 1.1262 | −0.1150 | 0.8014 | 0.067* | |
N2 | 0.6962 (2) | −0.0932 (2) | 0.95054 (12) | 0.0317 (3) | |
H2A | 0.6650 | −0.0215 | 0.9104 | 0.048* | |
H2B | 0.6300 | −0.1033 | 1.0089 | 0.048* | |
H2C | 0.6394 | −0.2209 | 0.9211 | 0.048* | |
O3 | 0.5222 (2) | 0.4502 (2) | 0.85509 (10) | 0.0362 (3) | |
N3 | 1.0992 (2) | 0.2790 (2) | 0.95026 (11) | 0.0314 (3) | |
H3A | 1.0038 | 0.2791 | 0.9115 | 0.047* | |
H3B | 1.1447 | 0.3759 | 1.0025 | 0.047* | |
H3C | 1.1979 | 0.3035 | 0.9140 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02468 (15) | 0.02976 (17) | 0.02568 (15) | 0.01440 (12) | 0.00308 (11) | 0.00729 (11) |
Cl1 | 0.0261 (2) | 0.0597 (3) | 0.0322 (2) | 0.0231 (2) | 0.00693 (16) | 0.01044 (19) |
Cl2 | 0.0330 (2) | 0.0446 (3) | 0.0305 (2) | 0.01790 (19) | 0.01035 (16) | 0.00277 (17) |
S1 | 0.02302 (18) | 0.0277 (2) | 0.02057 (18) | 0.01111 (15) | 0.00088 (14) | 0.00409 (14) |
C1 | 0.0238 (7) | 0.0231 (7) | 0.0216 (7) | 0.0110 (6) | 0.0017 (6) | 0.0046 (5) |
C2 | 0.0227 (7) | 0.0256 (8) | 0.0270 (7) | 0.0116 (6) | 0.0045 (6) | 0.0074 (6) |
C3 | 0.0238 (7) | 0.0302 (8) | 0.0286 (8) | 0.0127 (6) | −0.0011 (6) | 0.0062 (6) |
C4 | 0.0301 (8) | 0.0242 (8) | 0.0236 (7) | 0.0110 (6) | 0.0015 (6) | 0.0047 (6) |
C5 | 0.0264 (7) | 0.0242 (8) | 0.0256 (7) | 0.0115 (6) | 0.0065 (6) | 0.0045 (6) |
C6 | 0.0220 (6) | 0.0251 (7) | 0.0264 (7) | 0.0115 (6) | 0.0015 (6) | 0.0046 (6) |
N1 | 0.0371 (8) | 0.0530 (10) | 0.0225 (7) | 0.0205 (7) | 0.0008 (6) | 0.0062 (6) |
O1 | 0.0392 (7) | 0.0336 (7) | 0.0297 (6) | 0.0128 (5) | 0.0042 (5) | 0.0122 (5) |
O2 | 0.0250 (6) | 0.0494 (8) | 0.0300 (6) | 0.0167 (5) | −0.0017 (5) | 0.0074 (5) |
O1W | 0.0394 (7) | 0.0418 (8) | 0.0477 (8) | 0.0143 (6) | 0.0165 (6) | 0.0087 (6) |
N2 | 0.0298 (7) | 0.0364 (8) | 0.0317 (7) | 0.0185 (6) | 0.0024 (6) | 0.0062 (6) |
O3 | 0.0378 (6) | 0.0382 (7) | 0.0310 (6) | 0.0198 (6) | 0.0014 (5) | −0.0042 (5) |
N3 | 0.0328 (7) | 0.0339 (8) | 0.0286 (7) | 0.0169 (6) | 0.0028 (6) | 0.0073 (6) |
Cu1—N2 | 2.024 (2) | C3—H3 | 0.9300 |
Cu1—N2i | 2.024 (2) | C4—N1 | 1.365 (2) |
Cu1—N3 | 2.025 (2) | C4—C5 | 1.403 (3) |
Cu1—N3i | 2.025 (2) | C5—C6 | 1.379 (2) |
Cu1—O1W | 2.580 (2) | C6—H6 | 0.9300 |
Cl1—C2 | 1.731 (2) | N1—H1N | 0.8605 |
Cl2—C5 | 1.732 (2) | N1—H2N | 0.8179 |
S1—O3 | 1.4482 (15) | O1W—H1A | 0.8836 |
S1—O2 | 1.4574 (17) | O1W—H1B | 0.8260 |
S1—O1 | 1.4608 (17) | N2—H2A | 0.8642 |
S1—C1 | 1.771 (2) | N2—H2B | 0.9089 |
C1—C6 | 1.390 (2) | N2—H2C | 0.8531 |
C1—C2 | 1.395 (2) | N3—H3A | 0.8251 |
C2—C3 | 1.377 (2) | N3—H3B | 0.8346 |
C3—C4 | 1.391 (3) | N3—H3C | 0.8488 |
N2—Cu1—N2i | 180.000 (1) | C3—C4—C5 | 116.84 (15) |
N2—Cu1—N3 | 92.99 (7) | C6—C5—C4 | 122.08 (15) |
N2i—Cu1—N3 | 87.01 (7) | C6—C5—Cl2 | 119.39 (13) |
N2—Cu1—N3i | 87.01 (7) | C4—C5—Cl2 | 118.53 (14) |
N2i—Cu1—N3i | 92.99 (7) | C5—C6—C1 | 120.52 (15) |
N3—Cu1—N3i | 180.000 (1) | C5—C6—H6 | 119.7 |
O3—S1—O2 | 112.05 (9) | C1—C6—H6 | 119.7 |
O3—S1—O1 | 112.11 (10) | C4—N1—H1N | 120.9 |
O2—S1—O1 | 111.67 (9) | C4—N1—H2N | 118.6 |
O3—S1—C1 | 108.15 (8) | H1N—N1—H2N | 120.3 |
O2—S1—C1 | 105.56 (8) | H1A—O1W—H1B | 107.3 |
O1—S1—C1 | 106.89 (9) | Cu1—N2—H2A | 119.1 |
C6—C1—C2 | 117.67 (15) | Cu1—N2—H2B | 109.0 |
C6—C1—S1 | 118.57 (12) | H2A—N2—H2B | 108.1 |
C2—C1—S1 | 123.70 (12) | Cu1—N2—H2C | 106.8 |
C3—C2—C1 | 121.70 (15) | H2A—N2—H2C | 111.0 |
C3—C2—Cl1 | 116.75 (13) | H2B—N2—H2C | 101.4 |
C1—C2—Cl1 | 121.53 (13) | Cu1—N3—H3A | 110.6 |
C2—C3—C4 | 121.18 (15) | Cu1—N3—H3B | 110.9 |
C2—C3—H3 | 119.4 | H3A—N3—H3B | 109.9 |
C4—C3—H3 | 119.4 | Cu1—N3—H3C | 110.4 |
N1—C4—C3 | 121.51 (16) | H3A—N3—H3C | 107.6 |
N1—C4—C5 | 121.65 (16) | H3B—N3—H3C | 107.4 |
O3—S1—C1—C6 | 133.25 (13) | Cl1—C2—C3—C4 | −178.05 (13) |
O2—S1—C1—C6 | 13.16 (15) | C2—C3—C4—N1 | 178.56 (16) |
O1—S1—C1—C6 | −105.86 (14) | C2—C3—C4—C5 | −0.8 (2) |
O3—S1—C1—C2 | −49.74 (16) | N1—C4—C5—C6 | −178.61 (16) |
O2—S1—C1—C2 | −169.83 (14) | C3—C4—C5—C6 | 0.7 (2) |
O1—S1—C1—C2 | 71.15 (16) | N1—C4—C5—Cl2 | 1.6 (2) |
C6—C1—C2—C3 | 0.6 (2) | C3—C4—C5—Cl2 | −179.06 (12) |
S1—C1—C2—C3 | −176.48 (13) | C4—C5—C6—C1 | 0.0 (3) |
C6—C1—C2—Cl1 | 178.68 (12) | Cl2—C5—C6—C1 | 179.77 (12) |
S1—C1—C2—Cl1 | 1.6 (2) | C2—C1—C6—C5 | −0.6 (2) |
C1—C2—C3—C4 | 0.2 (3) | S1—C1—C6—C5 | 176.58 (13) |
Symmetry code: (i) −x+2, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2ii | 0.88 | 2.07 | 2.900 (3) | 156 |
O1W—H1B···O1iii | 0.83 | 2.14 | 2.925 (3) | 159 |
N1—H1N···O1Wiv | 0.86 | 2.34 | 3.179 (4) | 166 |
N1—H2N···Cl2 | 0.82 | 2.56 | 2.967 (3) | 112 |
N2—H2A···O1 | 0.86 | 2.32 | 3.134 (3) | 157 |
N2—H2B···O1v | 0.91 | 2.22 | 3.108 (3) | 166 |
N2—H2C···O3ii | 0.85 | 2.19 | 3.038 (3) | 174 |
N3—H3A···O2 | 0.82 | 2.23 | 3.033 (3) | 164 |
N3—H3B···O2vi | 0.84 | 2.59 | 3.412 (3) | 166 |
N3—H3B···O3vi | 0.84 | 2.59 | 3.226 (3) | 133 |
N3—H3C···O3iii | 0.85 | 2.33 | 3.157 (3) | 164 |
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (v) −x+1, −y, −z+2; (vi) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2 |
Mr | 649.83 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.367 (6), 7.380 (5), 12.689 (10) |
α, β, γ (°) | 96.22 (4), 94.62 (4), 118.33 (3) |
V (Å3) | 596.8 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.44 × 0.37 × 0.27 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.521, 0.650 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5849, 2715, 2518 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.076, 1.10 |
No. of reflections | 2715 |
No. of parameters | 151 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.42 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2i | 0.88 | 2.07 | 2.900 (3) | 156 |
O1W—H1B···O1ii | 0.83 | 2.14 | 2.925 (3) | 159 |
N1—H1N···O1Wiii | 0.86 | 2.34 | 3.179 (4) | 166 |
N1—H2N···Cl2 | 0.82 | 2.56 | 2.967 (3) | 112 |
N2—H2A···O1 | 0.86 | 2.32 | 3.134 (3) | 157 |
N2—H2B···O1iv | 0.91 | 2.22 | 3.108 (3) | 166 |
N2—H2C···O3i | 0.85 | 2.19 | 3.038 (3) | 174 |
N3—H3A···O2 | 0.82 | 2.23 | 3.033 (3) | 164 |
N3—H3B···O2v | 0.84 | 2.59 | 3.412 (3) | 166 |
N3—H3B···O3v | 0.84 | 2.59 | 3.226 (3) | 133 |
N3—H3C···O3ii | 0.85 | 2.33 | 3.157 (3) | 164 |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z+2; (v) −x+2, −y+1, −z+2. |
As metal sulfonates are a class of novel materials showing interesting properties, such as exchange, guest sorption (Côté & Shimizu, 2003; Yang et al., 2006), several studies on the coordination chemistry of transition metal sulfonates and their solid-state properties have been reported. In some cases, sulfonate group can compete with water molecule and coordinate to metal ion (Markku & Reijo, 1993). As part of an investigation of the structure of transition metal sulfonate compounds, we present here the structure of the title compound.
The crystal of the compound is composed of [Cu(NH3)4(H2O)2]2+ cations and 4-amino-2,5-dichlorobenzenesulfonate anions (Fig. 1). The CuII cation lies on an inversion center and is six-coordinated by four NH3 molecules and two water molecules. The Cu—O1W bond in the axial direction is much longer than Cu—N bonds in the equatorial plane (Table 1), showing the typical Jahn-Teller distortion. The anions act as counterions and are hydrogen-bonded to the complex cations, forming a three dimensional supra-molecular structure (Fig. 2).