In the title compound, {[Cu(C
10H
14N
4Se)
2(H
2O)]Cl
2·H
2O}
n, the Cu
II ion, lying on a twofold rotation axis, has a square-pyramidal geometry constituted by four N atoms of pyrazolyl groups in the basal plane and an apical O atom of a water molecule. A pair of bis(3,5-dimethyl-1
H-pyrazol-4-yl) selenide ligands bridge the Cu centers into a polymeric double-chain extending along [001]. The chloride anions are involved in intermolecular N—H

Cl and O—H

Cl hydrogen bonds, which link the chains into a three-dimensional network.
Supporting information
CCDC reference: 774110
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.072
- Data-to-parameter ratio = 14.5
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
Alert level C
PLAT057_ALERT_3_C Correction for Absorption Required RT(exp) ... 1.20
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 110
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ?
Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 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
4 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
The ligand L was prepared according to a previously reported method
(Seredyuk et al., 2007). Copper(II) chloride dihydrate (0.034 g, 0.19 mmol) in water (5 ml) was added to 5 ml of hot methanol solution of L
(0.100 g, 0.37 mmol). The solution was left for slow cooling at room
temperature. After several days plate-like blue-violet crystals of the title
compound suitable for X-ray analysis were isolated. Analysis, calculated for
C20H32Cl2CuN8O2Se2: C 33.89, H 4.55, N 15.81%; found: C 33.67, H
4.51, N 15.60%.
C- and N-bound H atoms were placed at calculated positions and treated as riding
on their parent atoms [C—H = 0.98 Å and Uiso(H) =
1.5Ueq(C); N—H = 0.88 Å and Uiso(H) =
1.2Ueq(N)]. The H atoms of water molecules were located from a
difference Fourier map and were refined as riding, with Uiso(H) =
1.5Ueq(O).
Data collection: KM-4 CCD Software (Kuma Diffraction, 1998); cell refinement: KM-4 CCD Software (Kuma Diffraction, 1998); data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
catena-Poly[[[aquacopper(II)]-bis[µ-bis(3,5-dimethyl-1
H-
pyrazol-4-yl) selenide-
κ2N2:
N2']] dichloride monohydrate]
top
Crystal data top
[Cu(C10H14N4Se)2(H2O)]Cl2·H2O | F(000) = 1420 |
Mr = 708.90 | Dx = 1.673 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6625 reflections |
a = 11.332 (1) Å | θ = 3.2–28.4° |
b = 13.229 (2) Å | µ = 3.59 mm−1 |
c = 18.786 (1) Å | T = 100 K |
β = 92.45 (3)° | Plates, blue |
V = 2813.7 (5) Å3 | 0.10 × 0.05 × 0.01 mm |
Z = 4 | |
Data collection top
Kuma KM-4 CCD diffractometer | 2217 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 25.0°, θmin = 3.2° |
ω scans | h = −13→7 |
6625 measured reflections | k = −15→15 |
2377 independent reflections | l = −22→22 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0419P)2 + 1.7165P] where P = (Fo2 + 2Fc2)/3 |
2377 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
Crystal data top
[Cu(C10H14N4Se)2(H2O)]Cl2·H2O | V = 2813.7 (5) Å3 |
Mr = 708.90 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.332 (1) Å | µ = 3.59 mm−1 |
b = 13.229 (2) Å | T = 100 K |
c = 18.786 (1) Å | 0.10 × 0.05 × 0.01 mm |
β = 92.45 (3)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 2217 reflections with I > 2σ(I) |
6625 measured reflections | Rint = 0.061 |
2377 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.57 e Å−3 |
2377 reflections | Δρmin = −0.44 e Å−3 |
164 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.0470 (2) | −0.1461 (2) | 0.41623 (14) | 0.0171 (6) | |
H22A | 0.0111 | −0.1105 | 0.4471 | 0.026* | |
H22B | −0.0068 | −0.1790 | 0.3773 | 0.026* | |
H22C | −0.0873 | −0.1974 | 0.4440 | 0.026* | |
C2 | −0.1350 (2) | −0.07273 (19) | 0.38631 (13) | 0.0112 (5) | |
C3 | 0.2414 (2) | 0.04235 (18) | 0.58358 (13) | 0.0106 (5) | |
C4 | −0.2939 (2) | 0.02624 (19) | 0.36872 (14) | 0.0137 (5) | |
C5 | −0.4086 (2) | 0.0822 (2) | 0.36926 (16) | 0.0232 (7) | |
H9A | −0.4637 | 0.0538 | 0.3330 | 0.035* | |
H9B | −0.3950 | 0.1538 | 0.3589 | 0.035* | |
H9C | −0.4421 | 0.0758 | 0.4163 | 0.035* | |
C6 | 0.0587 (2) | 0.14112 (19) | 0.38756 (14) | 0.0124 (5) | |
H5A | 0.0236 | 0.1593 | 0.3407 | 0.019* | |
H5B | 0.1033 | 0.1988 | 0.4074 | 0.019* | |
H5C | −0.0040 | 0.1230 | 0.4196 | 0.019* | |
C7 | 0.1401 (2) | 0.05297 (19) | 0.37995 (13) | 0.0106 (5) | |
C8 | 0.2365 (2) | 0.02232 (19) | 0.42508 (13) | 0.0115 (5) | |
C9 | 0.2796 (2) | −0.0650 (2) | 0.39493 (13) | 0.0129 (5) | |
C10 | 0.3787 (2) | −0.1344 (2) | 0.41780 (15) | 0.0205 (6) | |
H14A | 0.3463 | −0.1955 | 0.4392 | 0.031* | |
H14B | 0.4311 | −0.1001 | 0.4529 | 0.031* | |
H14C | 0.4234 | −0.1532 | 0.3763 | 0.031* | |
N1 | −0.12324 (17) | −0.02426 (15) | 0.32427 (11) | 0.0112 (4) | |
N2 | −0.22165 (18) | 0.03492 (15) | 0.31502 (11) | 0.0128 (4) | |
H2N | −0.2356 | 0.0742 | 0.2778 | 0.015* | |
N3 | 0.12555 (17) | −0.01244 (16) | 0.32624 (11) | 0.0113 (4) | |
N4 | 0.21226 (19) | −0.08360 (16) | 0.33652 (12) | 0.0123 (5) | |
H4N | 0.2223 | −0.1354 | 0.3080 | 0.015* | |
O1 | 0.0000 | −0.19654 (18) | 0.2500 | 0.0154 (5) | |
H1O1 | −0.0625 | −0.2317 | 0.2606 | 0.023* | |
O1W | −0.5000 | −0.1193 (3) | 0.2500 | 0.0387 (8) | |
H1W | −0.4338 | −0.1589 | 0.2619 | 0.058* | |
Cl1 | −0.25642 (5) | −0.26253 (5) | 0.26925 (3) | 0.01824 (17) | |
Cu1 | 0.0000 | −0.02962 (3) | 0.2500 | 0.00888 (13) | |
Se1 | 0.30884 (2) | 0.097275 (18) | 0.501388 (12) | 0.01122 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0139 (12) | 0.0217 (15) | 0.0161 (14) | 0.0071 (11) | 0.0043 (11) | 0.0059 (10) |
C2 | 0.0097 (11) | 0.0122 (12) | 0.0116 (13) | −0.0016 (10) | −0.0015 (10) | −0.0020 (10) |
C3 | 0.0099 (11) | 0.0106 (12) | 0.0114 (13) | −0.0014 (9) | 0.0035 (10) | −0.0007 (9) |
C4 | 0.0112 (12) | 0.0169 (14) | 0.0134 (14) | 0.0001 (10) | 0.0038 (11) | −0.0019 (10) |
C5 | 0.0174 (14) | 0.0321 (17) | 0.0204 (15) | 0.0133 (12) | 0.0048 (12) | 0.0067 (12) |
C6 | 0.0120 (12) | 0.0111 (13) | 0.0139 (13) | 0.0018 (10) | 0.0005 (10) | −0.0001 (9) |
C7 | 0.0087 (11) | 0.0117 (12) | 0.0113 (13) | −0.0023 (10) | 0.0020 (10) | 0.0011 (9) |
C8 | 0.0077 (11) | 0.0162 (13) | 0.0105 (13) | −0.0012 (10) | 0.0007 (10) | −0.0004 (9) |
C9 | 0.0091 (12) | 0.0158 (13) | 0.0138 (14) | 0.0009 (10) | 0.0004 (11) | −0.0009 (10) |
C10 | 0.0153 (13) | 0.0217 (15) | 0.0242 (15) | 0.0091 (11) | −0.0030 (12) | −0.0013 (11) |
N1 | 0.0090 (10) | 0.0106 (11) | 0.0139 (11) | 0.0019 (8) | −0.0005 (9) | −0.0001 (8) |
N2 | 0.0118 (10) | 0.0162 (11) | 0.0103 (11) | 0.0042 (9) | −0.0009 (9) | 0.0022 (8) |
N3 | 0.0069 (10) | 0.0116 (11) | 0.0154 (11) | 0.0024 (8) | 0.0013 (9) | 0.0009 (8) |
N4 | 0.0108 (10) | 0.0126 (11) | 0.0134 (11) | 0.0041 (8) | 0.0004 (9) | −0.0020 (8) |
O1 | 0.0122 (12) | 0.0104 (13) | 0.0241 (14) | 0.000 | 0.0053 (11) | 0.000 |
O1W | 0.0318 (17) | 0.0365 (19) | 0.048 (2) | 0.000 | 0.0058 (16) | 0.000 |
Cl1 | 0.0215 (3) | 0.0131 (3) | 0.0206 (4) | −0.0055 (2) | 0.0061 (3) | −0.0008 (2) |
Cu1 | 0.0069 (2) | 0.0108 (2) | 0.0089 (2) | 0.000 | 0.00069 (17) | 0.000 |
Se1 | 0.00924 (16) | 0.01421 (17) | 0.01027 (17) | −0.00342 (9) | 0.00104 (11) | −0.00041 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.485 (3) | C7—N3 | 1.334 (3) |
C1—H22A | 0.9800 | C7—C8 | 1.413 (4) |
C1—H22B | 0.9800 | C8—C9 | 1.385 (4) |
C1—H22C | 0.9800 | C8—Se1 | 1.900 (2) |
C2—N1 | 1.342 (3) | C9—N4 | 1.332 (3) |
C2—C3i | 1.412 (3) | C9—C10 | 1.499 (3) |
C3—C4i | 1.391 (4) | C10—H14A | 0.9800 |
C3—C2i | 1.412 (3) | C10—H14B | 0.9800 |
C3—Se1 | 1.896 (2) | C10—H14C | 0.9800 |
C4—N2 | 1.331 (3) | N1—N2 | 1.368 (3) |
C4—C3i | 1.391 (4) | N2—H2N | 0.8800 |
C4—C5 | 1.496 (4) | N3—N4 | 1.368 (3) |
C5—H9A | 0.9800 | N4—H4N | 0.8800 |
C5—H9B | 0.9800 | O1—H1O1 | 0.8771 |
C5—H9C | 0.9800 | O1W—H1W | 0.9337 |
C6—C7 | 1.497 (3) | Cu1—N1ii | 2.017 (2) |
C6—H5A | 0.9800 | Cu1—N3ii | 1.988 (2) |
C6—H5B | 0.9800 | Cu1—O1 | 2.208 (3) |
C6—H5C | 0.9800 | | |
| | | |
C2—C1—H22A | 109.5 | N4—C9—C8 | 106.9 (2) |
C2—C1—H22B | 109.5 | N4—C9—C10 | 121.2 (2) |
H22A—C1—H22B | 109.5 | C8—C9—C10 | 131.8 (2) |
C2—C1—H22C | 109.5 | C9—C10—H14A | 109.5 |
H22A—C1—H22C | 109.5 | C9—C10—H14B | 109.5 |
H22B—C1—H22C | 109.5 | H14A—C10—H14B | 109.5 |
N1—C2—C3i | 109.3 (2) | C9—C10—H14C | 109.5 |
N1—C2—C1 | 123.4 (2) | H14A—C10—H14C | 109.5 |
C3i—C2—C1 | 127.3 (2) | H14B—C10—H14C | 109.5 |
C4i—C3—C2i | 106.1 (2) | C2—N1—N2 | 105.85 (19) |
C4i—C3—Se1 | 126.76 (19) | C2—N1—Cu1 | 132.97 (17) |
C2i—C3—Se1 | 126.70 (19) | N2—N1—Cu1 | 121.14 (15) |
N2—C4—C3i | 106.5 (2) | C4—N2—N1 | 112.3 (2) |
N2—C4—C5 | 121.7 (2) | C4—N2—H2N | 123.9 |
C3i—C4—C5 | 131.8 (2) | N1—N2—H2N | 123.9 |
C4—C5—H9A | 109.5 | C7—N3—N4 | 105.95 (19) |
C4—C5—H9B | 109.5 | C7—N3—Cu1 | 132.87 (17) |
H9A—C5—H9B | 109.5 | N4—N3—Cu1 | 120.69 (16) |
C4—C5—H9C | 109.5 | C9—N4—N3 | 111.8 (2) |
H9A—C5—H9C | 109.5 | C9—N4—H4N | 124.1 |
H9B—C5—H9C | 109.5 | N3—N4—H4N | 124.1 |
C7—C6—H5A | 109.5 | Cu1—O1—H1O1 | 122.0 |
C7—C6—H5B | 109.5 | N3ii—Cu1—N3 | 166.88 (12) |
H5A—C6—H5B | 109.5 | N3ii—Cu1—N1ii | 89.60 (8) |
C7—C6—H5C | 109.5 | N3—Cu1—N1ii | 89.94 (8) |
H5A—C6—H5C | 109.5 | N3ii—Cu1—N1 | 89.94 (8) |
H5B—C6—H5C | 109.5 | N3—Cu1—N1 | 89.60 (8) |
N3—C7—C8 | 109.6 (2) | N1ii—Cu1—N1 | 175.97 (11) |
N3—C7—C6 | 121.4 (2) | N3ii—Cu1—O1 | 96.56 (6) |
C8—C7—C6 | 129.0 (2) | N3—Cu1—O1 | 96.56 (6) |
C9—C8—C7 | 105.7 (2) | N1ii—Cu1—O1 | 92.01 (6) |
C9—C8—Se1 | 126.54 (19) | N1—Cu1—O1 | 92.01 (6) |
C7—C8—Se1 | 126.90 (19) | C3—Se1—C8 | 103.80 (10) |
| | | |
N3—C7—C8—C9 | 0.5 (3) | C10—C9—N4—N3 | 178.6 (2) |
C6—C7—C8—C9 | 178.4 (2) | C7—N3—N4—C9 | 0.4 (3) |
N3—C7—C8—Se1 | 170.61 (17) | Cu1—N3—N4—C9 | −172.60 (17) |
C6—C7—C8—Se1 | −11.5 (4) | C7—N3—Cu1—N3ii | 38.4 (2) |
C7—C8—C9—N4 | −0.2 (3) | N4—N3—Cu1—N3ii | −150.87 (17) |
Se1—C8—C9—N4 | −170.41 (18) | C7—N3—Cu1—N1ii | 126.3 (2) |
C7—C8—C9—C10 | −178.7 (3) | N4—N3—Cu1—N1ii | −62.89 (17) |
Se1—C8—C9—C10 | 11.1 (4) | C7—N3—Cu1—N1 | −49.7 (2) |
C3i—C2—N1—N2 | −0.7 (3) | N4—N3—Cu1—N1 | 121.11 (17) |
C1—C2—N1—N2 | 179.3 (2) | C7—N3—Cu1—O1 | −141.6 (2) |
C3i—C2—N1—Cu1 | −178.10 (17) | N4—N3—Cu1—O1 | 29.13 (17) |
C1—C2—N1—Cu1 | 2.0 (4) | C2—N1—Cu1—N3ii | 143.2 (2) |
C3i—C4—N2—N1 | −0.1 (3) | N2—N1—Cu1—N3ii | −33.83 (17) |
C5—C4—N2—N1 | −178.6 (2) | C2—N1—Cu1—N3 | −49.9 (2) |
C2—N1—N2—C4 | 0.5 (3) | N2—N1—Cu1—N3 | 133.06 (17) |
Cu1—N1—N2—C4 | 178.26 (17) | C2—N1—Cu1—O1 | 46.7 (2) |
C8—C7—N3—N4 | −0.5 (3) | N2—N1—Cu1—O1 | −130.39 (16) |
C6—C7—N3—N4 | −178.6 (2) | C4i—C3—Se1—C8 | 102.0 (2) |
C8—C7—N3—Cu1 | 171.23 (17) | C2i—C3—Se1—C8 | −87.0 (2) |
C6—C7—N3—Cu1 | −6.9 (4) | C9—C8—Se1—C3 | −92.4 (2) |
C8—C9—N4—N3 | −0.1 (3) | C7—C8—Se1—C3 | 99.4 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···Cl1 | 0.93 | 2.43 | 3.354 (2) | 169 |
O1—H1O1···Cl1 | 0.88 | 2.25 | 3.0702 (10) | 156 |
N2—H2N···Cl1iii | 0.88 | 2.33 | 3.117 (2) | 148 |
N4—H4N···Cl1ii | 0.88 | 2.27 | 3.144 (2) | 176 |
Symmetry codes: (ii) −x, y, −z+1/2; (iii) −x−1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H14N4Se)2(H2O)]Cl2·H2O |
Mr | 708.90 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 11.332 (1), 13.229 (2), 18.786 (1) |
β (°) | 92.45 (3) |
V (Å3) | 2813.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.59 |
Crystal size (mm) | 0.10 × 0.05 × 0.01 |
|
Data collection |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6625, 2377, 2217 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.072, 1.10 |
No. of reflections | 2377 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.44 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···Cl1 | 0.93 | 2.43 | 3.354 (2) | 169 |
O1—H1O1···Cl1 | 0.88 | 2.25 | 3.0702 (10) | 156 |
N2—H2N···Cl1i | 0.88 | 2.33 | 3.117 (2) | 148 |
N4—H4N···Cl1ii | 0.88 | 2.27 | 3.144 (2) | 176 |
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x, y, −z+1/2. |
Study of metal-organic polymers is a well elaborated research area in coordination chemistry. Infinite molecular polymeric arrays are potentially applicable as specifically ordered crystalline substances with reversible selective sorption (Farha et al., 2009; Zhang et al., 2009), electrical conductivity (Zhang et al., 2009) and molecular magnetism functionality (Shibahara et al., 2007).
The title compound was prepared in a water–methanolic medium by mixing solutions of CuCl2.2H2O and the bis(3,5-dimethyl-1H-pyrazolyl)selenide (L) ligand. It is similar to the copper compounds reported recently (Seredyuk et al., 2007, 2009). A square pyramidal environment of the CuII ion is constituted by four non-coplanar N atoms of pyrazolyl rings [the Cu—N distances are 1.988 (2) and 2.017 (2) Å, the Cu—O distance is 2.208 (3) Å]. Adjacent CuII ions are linked by symmetrically equivalent ligands in a double-stranded bridge fashion (Fig. 1). Formed one-dimensional linear chain is running along the c axis, where the Cu atom deviates from the average basal plane by a value of 0.392 (1) Å (Fig. 2). The NH group of a pyrazole ring is involved in hydrogen bonding with chloride anion (Table 1), which further forms hydrogen bonds with both free and coordinated water molecules and additionally with a pyrazole ring of a neighbouring polymeric chain (Table 1). As a result, a dense network of hydrogen bonds is formed.