Poly[[tris(di-2-pyridylamine)tris(μ-5-sulfonatosalicylato)tricopper(II)] trihydrate]

In the title compound, [Cu₃(C₁₀H₉N₃)₃(C₇H₃O₆S)₂]·3H₂O, [Cu₃(ssal)₂(dpa)₃] units (dpa is 2,2′-dipyridylamine and ssal is 5-sulfonatosalicylate) are found, which consist of one crystallographically independent ssal anion, and two each of crystallographically independent dpa ligands and Cu atoms, the unit lying on a twofold rotation axis. One Cu atom is four-coordinated by one dpa ligand and one ssal anion within a square-planar geometry, whereas the second Cu atom is coordinated by one dpa ligand and two ssal anions which are related by symmetry. The first Cu atom has one longer contact to one O atom of a symmetry-related sulfonate group and is, therefore, five-coordinated within a distorted square-pyramidal coordination. The [Cu₃(ssal)₂(dpa)₃] units are connected via the sulfonate groups into layers which are parallel to the ab plane. These layers are further connected by O—H...O and N—H...O hydrogen bonding via the water molecules.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• H-atom completeness 90%
• R factor = 0.042
• wR factor = 0.102
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......         O8

Author Response: see _publ_section_exptl_refinement.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.03
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........          ?
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........          ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C44 H39 Cu3 N9 O15 S2
            Atom count from the _atom_site data:  C44 H35 Cu3 N9 O15 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C44 H39 Cu3 N9 O15 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        176.00    176.00    0.00
           H        156.00    140.00   16.00
           Cu        12.00     12.00    0.00
           N         36.00     36.00    0.00
           O         60.00     60.00    0.00
           S          8.00      8.00    0.00

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   9 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

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

Poly[[tris(di-2-pyridylamine)bis(µ-5-sulfonatosalicylato)tricopper(II)] trihydrate]

Crystal data

[Cu3(C10H9N3)3(C7H3O6S)2]·3H2O	F(000) = 2420
Mr = 1188.58	Dx = 1.748 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3596 reflections
a = 11.3447 (10) Å	θ = 4.8–53.8°
b = 13.4618 (11) Å	µ = 1.58 mm^−1
c = 29.910 (3) Å	T = 293 K
β = 98.650 (2)°	Plate, green
V = 4516.0 (7) Å^3	0.51 × 0.32 × 0.13 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4979 independent reflections
Radiation source: fine-focus sealed tube	3744 reflections with I > 2s˘I)
Graphite monochromator	Rint = 0.087
φ and ω scans	θmax = 27.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.550, Tmax = 0.816	k = −9→17
13200 measured reflections	l = −37→38

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0385P)^2] where P = (Fo^2 + 2Fc^2)/3
4979 reflections	(Δ/σ)max < 0.001
338 parameters	Δρmax = 0.58 e Å^−3
3 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.35206 (3)	0.2500	0.02643 (15)
Cu2	0.16085 (3)	0.40996 (2)	0.118533 (12)	0.02849 (12)
S1	−0.01886 (7)	−0.10251 (5)	0.12587 (3)	0.02966 (19)
N1	0.2139 (2)	0.52019 (17)	0.16044 (9)	0.0282 (6)
N2	0.1294 (3)	0.64202 (18)	0.10944 (10)	0.0395 (7)
N3	0.1572 (2)	0.50165 (18)	0.06608 (9)	0.0333 (6)
N4	0.0774 (2)	0.45240 (17)	0.29276 (8)	0.0267 (6)
N5	0.0000	0.5910 (3)	0.2500	0.0339 (9)
O1	0.1190 (2)	0.34033 (14)	0.17079 (7)	0.0326 (5)
O2	0.00318 (19)	0.24699 (14)	0.20558 (7)	0.0303 (5)
O3	0.0995 (2)	0.30461 (15)	0.07958 (7)	0.0388 (6)
O4	−0.1421 (2)	−0.13190 (16)	0.11576 (9)	0.0494 (7)
O5	0.0535 (2)	−0.15779 (14)	0.09863 (8)	0.0403 (6)
O6	0.0260 (3)	−0.10788 (16)	0.17344 (8)	0.0519 (7)
O7	0.0000	−0.2040 (3)	0.2500	0.0934 (18)
O8	−0.1678 (4)	−0.2745 (3)	0.04190 (13)	0.1071 (13)
C1	0.0554 (3)	0.2637 (2)	0.17188 (10)	0.0248 (6)
C2	0.0398 (3)	0.19217 (19)	0.13439 (10)	0.0239 (6)
C3	0.0620 (3)	0.2180 (2)	0.09111 (10)	0.0288 (7)
C4	0.0437 (3)	0.1432 (2)	0.05734 (10)	0.0376 (8)
H4	0.0525	0.1589	0.0277	0.045*
C5	0.0137 (3)	0.0488 (2)	0.06750 (11)	0.0353 (8)
H5	0.0041	0.0008	0.0449	0.042*
C6	−0.0026 (3)	0.0231 (2)	0.11085 (10)	0.0277 (7)
C7	0.0067 (3)	0.0955 (2)	0.14363 (10)	0.0258 (6)
H7	−0.0093	0.0797	0.1724	0.031*
C8	0.2730 (3)	0.4974 (2)	0.20185 (11)	0.0330 (7)
H8	0.2982	0.4323	0.2075	0.040*
C9	0.2971 (3)	0.5651 (3)	0.23552 (12)	0.0383 (8)
H9	0.3400	0.5471	0.2633	0.046*
C10	0.2567 (3)	0.6615 (3)	0.22775 (12)	0.0420 (9)
H10	0.2685	0.7084	0.2508	0.050*
C11	0.1995 (3)	0.6866 (2)	0.18612 (11)	0.0352 (8)
H11	0.1720	0.7511	0.1803	0.042*
C12	0.1826 (3)	0.6146 (2)	0.15219 (10)	0.0272 (7)
C13	0.1395 (3)	0.5992 (2)	0.06846 (11)	0.0324 (7)
C14	0.1298 (3)	0.6605 (2)	0.03053 (12)	0.0457 (9)
H14	0.1167	0.7284	0.0330	0.055*
C15	0.1396 (4)	0.6193 (3)	−0.00977 (13)	0.0580 (11)
H15	0.1321	0.6587	−0.0356	0.070*
C16	0.1610 (4)	0.5187 (3)	−0.01274 (12)	0.0558 (11)
H16	0.1702	0.4895	−0.0402	0.067*
C17	0.1682 (4)	0.4634 (3)	0.02588 (12)	0.0496 (10)
H17	0.1815	0.3954	0.0240	0.059*
C18	0.1459 (3)	0.4196 (2)	0.33111 (11)	0.0350 (8)
H18	0.1591	0.3516	0.3343	0.042*
C19	0.1956 (3)	0.4793 (3)	0.36465 (12)	0.0427 (9)
H19	0.2434	0.4531	0.3899	0.051*
C20	0.1746 (3)	0.5797 (3)	0.36108 (12)	0.0437 (9)
H20	0.2055	0.6222	0.3844	0.052*
C21	0.1083 (3)	0.6160 (2)	0.32310 (12)	0.0370 (8)
H21	0.0942	0.6838	0.3200	0.044*
C22	0.0609 (3)	0.5503 (2)	0.28834 (10)	0.0271 (7)
H2A	0.124 (3)	0.7017 (8)	0.1109 (12)	0.050*
H5A	0.0000	0.6503 (8)	0.2500	0.050*
H7A	−0.001 (4)	−0.176 (3)	0.2738 (8)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0433 (3)	0.0169 (3)	0.0196 (3)	0.000	0.0064 (2)	0.000
Cu2	0.0455 (3)	0.01585 (19)	0.0253 (2)	−0.00287 (16)	0.00905 (17)	−0.00065 (14)
S1	0.0413 (5)	0.0144 (4)	0.0348 (5)	0.0011 (3)	0.0107 (4)	−0.0002 (3)
N1	0.0352 (15)	0.0190 (13)	0.0312 (15)	−0.0027 (11)	0.0081 (12)	0.0003 (10)
N2	0.061 (2)	0.0188 (14)	0.0396 (17)	0.0081 (14)	0.0112 (14)	−0.0012 (12)
N3	0.0524 (18)	0.0207 (13)	0.0284 (15)	0.0000 (12)	0.0115 (13)	0.0023 (11)
N4	0.0341 (15)	0.0210 (13)	0.0257 (14)	0.0014 (11)	0.0065 (11)	−0.0022 (10)
N5	0.047 (2)	0.0189 (19)	0.036 (2)	0.000	0.0059 (18)	0.000
O1	0.0477 (14)	0.0247 (11)	0.0271 (12)	−0.0146 (10)	0.0117 (10)	−0.0050 (9)
O2	0.0517 (14)	0.0197 (10)	0.0222 (11)	−0.0054 (9)	0.0137 (10)	−0.0035 (8)
O3	0.0718 (17)	0.0196 (11)	0.0250 (12)	−0.0121 (11)	0.0074 (11)	0.0008 (9)
O4	0.0413 (14)	0.0278 (13)	0.081 (2)	−0.0033 (11)	0.0156 (13)	−0.0060 (12)
O5	0.0547 (15)	0.0201 (11)	0.0501 (15)	0.0083 (10)	0.0212 (12)	−0.0009 (10)
O6	0.095 (2)	0.0260 (12)	0.0345 (14)	−0.0022 (12)	0.0078 (14)	0.0052 (10)
O7	0.222 (6)	0.024 (2)	0.047 (3)	0.000	0.061 (3)	0.000
O8	0.136 (4)	0.105 (3)	0.081 (3)	0.003 (2)	0.018 (2)	−0.021 (2)
C1	0.0347 (17)	0.0167 (14)	0.0224 (16)	0.0026 (12)	0.0026 (13)	0.0021 (11)
C2	0.0332 (17)	0.0153 (14)	0.0234 (15)	−0.0002 (12)	0.0053 (13)	−0.0026 (11)
C3	0.048 (2)	0.0167 (15)	0.0224 (16)	0.0015 (13)	0.0055 (14)	0.0012 (11)
C4	0.070 (3)	0.0238 (17)	0.0190 (16)	−0.0045 (16)	0.0079 (16)	−0.0005 (12)
C5	0.059 (2)	0.0212 (16)	0.0259 (17)	−0.0045 (15)	0.0057 (15)	−0.0071 (13)
C6	0.0377 (18)	0.0160 (14)	0.0288 (17)	0.0015 (12)	0.0031 (14)	−0.0007 (12)
C7	0.0353 (17)	0.0186 (15)	0.0245 (16)	0.0034 (12)	0.0080 (13)	0.0015 (12)
C8	0.0327 (18)	0.0272 (17)	0.039 (2)	−0.0034 (13)	0.0063 (15)	0.0003 (14)
C9	0.0351 (19)	0.046 (2)	0.0331 (19)	−0.0099 (16)	0.0024 (15)	−0.0034 (15)
C10	0.046 (2)	0.038 (2)	0.043 (2)	−0.0136 (16)	0.0093 (17)	−0.0192 (16)
C11	0.041 (2)	0.0224 (16)	0.044 (2)	−0.0058 (14)	0.0116 (16)	−0.0073 (14)
C12	0.0325 (17)	0.0186 (15)	0.0317 (18)	−0.0031 (12)	0.0090 (14)	0.0002 (12)
C13	0.0416 (19)	0.0227 (16)	0.0336 (19)	0.0031 (14)	0.0079 (15)	0.0032 (13)
C14	0.073 (3)	0.0255 (18)	0.040 (2)	0.0064 (17)	0.0111 (19)	0.0090 (15)
C15	0.091 (3)	0.045 (2)	0.037 (2)	0.003 (2)	0.009 (2)	0.0204 (18)
C16	0.102 (4)	0.041 (2)	0.028 (2)	0.000 (2)	0.021 (2)	−0.0013 (16)
C17	0.089 (3)	0.0265 (19)	0.037 (2)	−0.0011 (18)	0.024 (2)	−0.0020 (15)
C18	0.042 (2)	0.0307 (18)	0.0318 (19)	0.0057 (14)	0.0036 (15)	−0.0013 (14)
C19	0.037 (2)	0.059 (2)	0.0303 (19)	0.0022 (17)	−0.0020 (15)	−0.0013 (16)
C20	0.046 (2)	0.052 (2)	0.033 (2)	−0.0100 (17)	0.0059 (16)	−0.0150 (16)
C21	0.048 (2)	0.0246 (17)	0.039 (2)	−0.0053 (15)	0.0096 (16)	−0.0073 (14)
C22	0.0320 (17)	0.0210 (15)	0.0296 (17)	−0.0026 (13)	0.0095 (13)	−0.0024 (12)

Geometric parameters (Å, º)

Cu1—O2	1.9447 (19)	C2—C3	1.400 (4)
Cu1—O2^i	1.9447 (19)	C3—C4	1.420 (4)
Cu1—N4	1.973 (2)	C4—C5	1.362 (4)
Cu1—N4^i	1.973 (2)	C4—H4	0.9300
Cu2—O3	1.900 (2)	C5—C6	1.381 (4)
Cu2—O1	1.942 (2)	C5—H5	0.9300
Cu2—N1	1.977 (2)	C6—C7	1.375 (4)
Cu2—N3	1.992 (2)	C7—H7	0.9300
Cu2—O4^ii	2.318 (2)	C8—C9	1.355 (4)
S1—O6	1.439 (3)	C8—H8	0.9300
S1—O4	1.441 (2)	C9—C10	1.384 (5)
S1—O5	1.447 (2)	C9—H9	0.9300
S1—C6	1.767 (3)	C10—C11	1.358 (5)
N1—C12	1.333 (4)	C10—H10	0.9300
N1—C8	1.352 (4)	C11—C12	1.396 (4)
N2—C13	1.375 (4)	C11—H11	0.9300
N2—C12	1.380 (4)	C13—C14	1.393 (4)
N2—H2A	0.808 (10)	C14—C15	1.347 (5)
N3—C17	1.331 (4)	C14—H14	0.9300
N3—C13	1.332 (4)	C15—C16	1.382 (5)
N4—C22	1.335 (3)	C15—H15	0.9300
N4—C18	1.359 (4)	C16—C17	1.367 (5)
N5—C22	1.362 (3)	C16—H16	0.9300
N5—C22^i	1.362 (3)	C17—H17	0.9300
N5—H5A	0.798 (10)	C18—C19	1.341 (4)
O1—C1	1.262 (3)	C18—H18	0.9300
O2—C1	1.264 (3)	C19—C20	1.374 (5)
O3—C3	1.305 (3)	C19—H19	0.9300
O4—Cu2^iii	2.318 (2)	C20—C21	1.356 (5)
O7—H7A	0.81 (3)	C20—H20	0.9300
C1—C2	1.468 (4)	C21—C22	1.408 (4)
C2—C7	1.394 (4)	C21—H21	0.9300
O2—Cu1—O2^i	86.67 (12)	C4—C5—H5	119.5
O2—Cu1—N4	152.71 (9)	C6—C5—H5	119.5
O2^i—Cu1—N4	96.15 (9)	C7—C6—C5	119.1 (3)
O2—Cu1—N4^i	96.15 (9)	C7—C6—S1	119.8 (2)
O2^i—Cu1—N4^i	152.71 (9)	C5—C6—S1	120.8 (2)
N4—Cu1—N4^i	93.59 (14)	C6—C7—C2	121.0 (3)
O3—Cu2—O1	91.27 (8)	C6—C7—H7	119.5
O3—Cu2—N1	176.10 (10)	C2—C7—H7	119.5
O1—Cu2—N1	86.56 (9)	N1—C8—C9	123.1 (3)
O3—Cu2—N3	90.99 (10)	N1—C8—H8	118.5
O1—Cu2—N3	162.68 (10)	C9—C8—H8	118.5
N1—Cu2—N3	90.14 (10)	C8—C9—C10	118.7 (3)
O3—Cu2—O4^ii	93.59 (9)	C8—C9—H9	120.6
O1—Cu2—O4^ii	105.37 (9)	C10—C9—H9	120.6
N1—Cu2—O4^ii	90.10 (9)	C11—C10—C9	119.3 (3)
N3—Cu2—O4^ii	91.62 (10)	C11—C10—H10	120.4
O6—S1—O4	112.41 (16)	C9—C10—H10	120.4
O6—S1—O5	112.62 (15)	C10—C11—C12	119.2 (3)
O4—S1—O5	110.84 (14)	C10—C11—H11	120.4
O6—S1—C6	105.34 (14)	C12—C11—H11	120.4
O4—S1—C6	110.17 (14)	N1—C12—N2	119.6 (3)
O5—S1—C6	105.03 (13)	N1—C12—C11	121.6 (3)
C12—N1—C8	117.9 (3)	N2—C12—C11	118.7 (3)
C12—N1—Cu2	123.4 (2)	N3—C13—N2	119.6 (3)
C8—N1—Cu2	118.2 (2)	N3—C13—C14	122.3 (3)
C13—N2—C12	129.1 (3)	N2—C13—C14	118.1 (3)
C13—N2—H2A	119 (3)	C15—C14—C13	118.6 (3)
C12—N2—H2A	104 (3)	C15—C14—H14	120.7
C17—N3—C13	117.7 (3)	C13—C14—H14	120.7
C17—N3—Cu2	118.5 (2)	C14—C15—C16	120.0 (3)
C13—N3—Cu2	123.7 (2)	C14—C15—H15	120.0
C22—N4—C18	117.3 (3)	C16—C15—H15	120.0
C22—N4—Cu1	124.7 (2)	C17—C16—C15	118.0 (3)
C18—N4—Cu1	117.8 (2)	C17—C16—H16	121.0
C22—N5—C22^i	132.5 (4)	C15—C16—H16	121.0
C22—N5—H5A	113.75 (18)	N3—C17—C16	123.4 (3)
C22^i—N5—H5A	113.75 (18)	N3—C17—H17	118.3
C1—O1—Cu2	128.70 (19)	C16—C17—H17	118.3
C1—O2—Cu1	118.33 (17)	C19—C18—N4	124.0 (3)
C3—O3—Cu2	127.49 (19)	C19—C18—H18	118.0
S1—O4—Cu2^iii	146.74 (14)	N4—C18—H18	118.0
O2—C1—O1	120.3 (3)	C18—C19—C20	118.8 (3)
O2—C1—C2	118.4 (2)	C18—C19—H19	120.6
O1—C1—C2	121.3 (3)	C20—C19—H19	120.6
C7—C2—C3	120.5 (3)	C21—C20—C19	119.2 (3)
C7—C2—C1	117.8 (3)	C21—C20—H20	120.4
C3—C2—C1	121.7 (3)	C19—C20—H20	120.4
O3—C3—C2	125.3 (3)	C20—C21—C22	119.6 (3)
O3—C3—C4	117.7 (3)	C20—C21—H21	120.2
C2—C3—C4	117.0 (3)	C22—C21—H21	120.2
C5—C4—C3	121.2 (3)	N4—C22—N5	121.8 (3)
C5—C4—H4	119.4	N4—C22—C21	121.0 (3)
C3—C4—H4	119.4	N5—C22—C21	117.2 (3)
C4—C5—C6	121.1 (3)

Symmetry codes: (i) −x, y, −z+1/2; (ii) x+1/2, y+1/2, z; (iii) x−1/2, y−1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5^iv	0.81 (1)	2.06 (2)	2.833 (3)	159 (4)
N5—H5A···O7^iv	0.80 (1)	1.96 (1)	2.759 (5)	180 (1)
O7—H7A···O6^i	0.81 (3)	1.88 (3)	2.685 (3)	172 (5)
O8···O8^v	?	?	2.965 (8)	?
O8···O4	?	?	2.908 (4)	?

Symmetry codes: (i) −x, y, −z+1/2; (iv) x, y+1, z; (v) −x−1/2, −y−1/2, −z.