Poly[[tris­(μ₂-4,4′-bipyridyl-κ²N:N′)bis­(μ₂-nitrato-κ²O,O′)hexa-μ₂-oxo-dioxo­dimolybdenum­tricopper(II)] tetra­hydrate]: a polymeric hybrid framework containing Cu²⁺, 4,4-bipyridine, [MoO₄]²⁻ and NO₃⁻ building units

The hydro­thermally prepared title compound, {[Cu₃Mo₂(NO₃)₂O₈(C₁₀H₈N₂)₃]·4H₂O}_n, is a hybrid organic/inorganic polymer containing a 16-atom ring built up from molybdate anions, nitrate ions and copper cations. This inorganic network is crosslinked by infinite linear 4,4′-bpy-bridged copper chains (4,4′-bpy is 4,4'-bipyridine) to form channels along the c axis containing the disordered non-coordinated water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 76%
• Disorder in solvent or counterion
• R factor = 0.032
• wR factor = 0.085
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W

Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1W    ..  O2      ..       2.71 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O1W    ..  O2W     ..       2.84 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O2W    ..  O5      ..       2.79 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O5     ..  O2W'    ..       2.76 Ang.

Alert level C
DENSD01_ALERT_1_C  The ratio of the submitted crystal density and that
            calculated from the formula is outside the range 0.99 <> 1.01
            Crystal density given    =      2.064
            Calculated crystal density =      2.033
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT044_ALERT_1_C Calculated and Reported Dx Differ ..............          ?
PLAT046_ALERT_1_C Reported Z, MW and D(calc) are Inconsistent ....       2.03
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.08 Ratio
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       >O2W
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....      <O2W'
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

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:C30 H32 Cu3 Mo2 N8 O18
            Atom count from the _atom_site data:  C30 H24 Cu3 Mo2 N8 O18
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    1
           From the CIF: _chemical_formula_sum  C30 H32 Cu3 Mo2 N8 O18
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         30.00     30.00    0.00
           H         32.00     24.00    8.00
           Cu         3.00      3.00    0.00
           Mo         2.00      2.00    0.00
           N          8.00      8.00    0.00
           O         18.00     18.00    0.00

   1 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  13 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
   9 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Poly[[tris(µ₂-4,4'-bipyridyl-κ²N:N')bis(µ₂-nitrato-κ²O,O') hexa-µ₂oxo-dioxodimolybdenumtricopper(II)] tetrahydrate]

Crystal data

[Cu3Mo2(NO3)2O8(C10H8N2)3]·4H2O	Z = 1
Mr = 1175.14	F(000) = 583
Triclinic, P1	Dx = 2.064 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6189 (18) Å	Cell parameters from 5192 reflections
b = 10.639 (2) Å	θ = 2.4–28.3°
c = 10.986 (2) Å	µ = 2.36 mm^−1
α = 79.523 (3)°	T = 293 K
β = 64.995 (3)°	Block, blue
γ = 70.574 (3)°	0.16 × 0.14 × 0.12 mm
V = 959.8 (3) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	3703 independent reflections
Radiation source: fine-focus sealed tube	3482 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
Tmin = 0.704, Tmax = 0.765	k = −13→13
7441 measured reflections	l = −13→13

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 2.0607P] where P = (Fo^2 + 2Fc^2)/3
3703 reflections	(Δ/σ)max = 0.004
301 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.80 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	Occ. (<1)
Mo1	0.64671 (3)	0.79159 (3)	0.59385 (3)	0.01807 (10)
Cu1	0.34826 (5)	0.84292 (4)	0.45421 (4)	0.01889 (12)
Cu2	1.0000	0.5000	0.5000	0.02089 (14)
O1	0.0584 (6)	0.8051 (5)	0.2709 (5)	0.0777 (13)
O2	0.1836 (4)	0.6484 (3)	0.4045 (3)	0.0417 (7)
O3	0.2125 (3)	0.8518 (3)	0.3638 (2)	0.0253 (5)
O4	0.5021 (3)	0.7915 (3)	0.5352 (2)	0.0328 (6)
O5	0.5631 (3)	0.7882 (3)	0.7668 (3)	0.0359 (6)
O6	0.7066 (3)	0.9342 (3)	0.5342 (3)	0.0363 (6)
O7	0.8114 (3)	0.6508 (2)	0.5398 (2)	0.0280 (6)
N1	0.1575 (4)	0.7628 (4)	0.3517 (3)	0.0375 (8)
N2	−0.4731 (3)	0.8507 (3)	1.2681 (3)	0.0234 (6)
N3	0.1654 (3)	0.8370 (3)	0.6381 (3)	0.0205 (6)
N4	0.9993 (3)	0.4935 (3)	0.3210 (3)	0.0206 (6)
C1	−0.4745 (4)	0.8167 (4)	1.1579 (4)	0.0321 (9)
H1A	−0.5611	0.7902	1.1662	0.038*
C2	−0.3555 (4)	0.8188 (4)	1.0334 (4)	0.0307 (8)
H2A	−0.3637	0.7968	0.9590	0.037*
C3	−0.2239 (4)	0.8534 (3)	1.0187 (3)	0.0224 (7)
C4	−0.0883 (4)	0.8482 (3)	0.8874 (3)	0.0219 (7)
C5	−0.1118 (4)	0.8687 (4)	0.7697 (3)	0.0244 (7)
H5A	−0.2141	0.8865	0.7717	0.029*
C6	0.0158 (4)	0.8630 (4)	0.6499 (3)	0.0249 (7)
H6A	−0.0034	0.8783	0.5715	0.030*
C7	0.1880 (4)	0.8170 (4)	0.7530 (4)	0.0260 (8)
H7A	0.2917	0.7989	0.7481	0.031*
C8	0.0676 (4)	0.8218 (4)	0.8762 (4)	0.0271 (8)
H8A	0.0896	0.8075	0.9531	0.033*
C9	−0.2245 (4)	0.8923 (4)	1.1317 (4)	0.0266 (8)
H9A	−0.1393	0.9192	1.1261	0.032*
C10	−0.3499 (4)	0.8913 (4)	1.2520 (3)	0.0255 (7)
H10A	−0.3491	0.9207	1.3264	0.031*
C11	0.8610 (5)	0.5110 (4)	0.1817 (4)	0.0302 (8)
H11A	0.7649	0.5202	0.1750	0.036*
C12	0.8654 (4)	0.5090 (4)	0.3051 (4)	0.0290 (8)
H12A	0.7703	0.5190	0.3809	0.035*
C13	0.9996 (4)	0.4995 (3)	0.0674 (3)	0.0224 (7)
C14	1.1367 (4)	0.4855 (4)	0.0859 (4)	0.0268 (8)
H14A	1.2330	0.4785	0.0118	0.032*
C15	1.1330 (4)	0.4818 (4)	0.2118 (4)	0.0255 (7)
H15A	1.2280	0.4707	0.2214	0.031*
O1W	0.4928 (7)	0.5097 (7)	0.3595 (11)	0.168 (4)
O2W	1.4547 (19)	0.567 (2)	−0.1054 (18)	0.193 (14)	0.70
O2W'	1.374 (2)	0.679 (2)	0.0007 (16)	0.080 (6)	0.30

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01497 (15)	0.02091 (16)	0.01656 (16)	−0.00256 (11)	−0.00605 (11)	−0.00199 (11)
Cu1	0.0145 (2)	0.0285 (2)	0.0138 (2)	−0.00809 (16)	−0.00441 (16)	−0.00057 (16)
Cu2	0.0205 (3)	0.0249 (3)	0.0151 (3)	0.0037 (2)	−0.0107 (2)	−0.0061 (2)
O1	0.086 (3)	0.084 (3)	0.084 (3)	−0.027 (3)	−0.054 (3)	0.006 (2)
O2	0.0505 (19)	0.0309 (15)	0.0513 (19)	−0.0091 (13)	−0.0313 (16)	0.0038 (13)
O3	0.0221 (12)	0.0374 (14)	0.0207 (12)	−0.0139 (11)	−0.0096 (10)	0.0019 (10)
O4	0.0185 (13)	0.0565 (18)	0.0226 (13)	−0.0093 (12)	−0.0103 (11)	0.0025 (12)
O5	0.0347 (15)	0.0486 (17)	0.0192 (13)	−0.0071 (13)	−0.0081 (11)	−0.0052 (12)
O6	0.0399 (16)	0.0268 (14)	0.0372 (16)	−0.0137 (12)	−0.0067 (13)	−0.0030 (12)
O7	0.0252 (13)	0.0271 (13)	0.0288 (14)	0.0041 (11)	−0.0142 (11)	−0.0075 (11)
N1	0.0332 (18)	0.041 (2)	0.0306 (18)	−0.0104 (15)	−0.0047 (15)	−0.0040 (15)
N2	0.0196 (14)	0.0328 (16)	0.0171 (14)	−0.0104 (12)	−0.0047 (11)	−0.0010 (12)
N3	0.0176 (14)	0.0263 (15)	0.0162 (13)	−0.0078 (11)	−0.0039 (11)	−0.0019 (11)
N4	0.0234 (15)	0.0225 (14)	0.0163 (14)	−0.0025 (11)	−0.0100 (11)	−0.0042 (11)
C1	0.0226 (19)	0.055 (3)	0.0215 (18)	−0.0175 (18)	−0.0034 (15)	−0.0090 (17)
C2	0.0255 (19)	0.051 (2)	0.0191 (17)	−0.0177 (17)	−0.0047 (15)	−0.0078 (16)
C3	0.0190 (16)	0.0265 (18)	0.0186 (16)	−0.0063 (14)	−0.0046 (13)	−0.0011 (13)
C4	0.0208 (17)	0.0222 (17)	0.0195 (17)	−0.0077 (13)	−0.0029 (14)	−0.0030 (13)
C5	0.0173 (16)	0.0345 (19)	0.0213 (17)	−0.0073 (14)	−0.0068 (14)	−0.0031 (14)
C6	0.0204 (17)	0.035 (2)	0.0188 (17)	−0.0070 (15)	−0.0082 (14)	−0.0013 (14)
C7	0.0192 (17)	0.037 (2)	0.0220 (18)	−0.0090 (15)	−0.0081 (14)	0.0006 (15)
C8	0.0243 (18)	0.041 (2)	0.0182 (17)	−0.0123 (16)	−0.0095 (14)	0.0020 (15)
C9	0.0237 (18)	0.036 (2)	0.0227 (18)	−0.0146 (15)	−0.0070 (14)	−0.0019 (15)
C10	0.0262 (18)	0.035 (2)	0.0179 (17)	−0.0107 (15)	−0.0089 (14)	−0.0028 (14)
C11	0.0241 (18)	0.050 (2)	0.0201 (17)	−0.0090 (17)	−0.0113 (15)	−0.0046 (16)
C12	0.0234 (18)	0.044 (2)	0.0192 (17)	−0.0082 (16)	−0.0085 (14)	−0.0037 (16)
C13	0.0279 (18)	0.0246 (17)	0.0184 (17)	−0.0076 (14)	−0.0125 (14)	−0.0012 (13)
C14	0.0242 (18)	0.038 (2)	0.0188 (17)	−0.0100 (16)	−0.0069 (14)	−0.0033 (15)
C15	0.0218 (17)	0.0331 (19)	0.0237 (18)	−0.0051 (15)	−0.0117 (14)	−0.0046 (15)
O1W	0.051 (3)	0.104 (5)	0.319 (12)	−0.031 (3)	−0.061 (5)	0.052 (6)
O2W	0.110 (9)	0.26 (2)	0.24 (2)	−0.136 (14)	−0.107 (13)	0.18 (2)
O2W'	0.072 (11)	0.116 (15)	0.051 (9)	−0.060 (11)	−0.002 (7)	0.004 (9)

Geometric parameters (Å, º)

Mo1—O5	1.720 (3)	C1—C2	1.365 (5)
Mo1—O6	1.722 (3)	C1—H1A	0.9300
Mo1—O7	1.748 (2)	C2—C3	1.372 (5)
Mo1—O4	1.764 (2)	C2—H2A	0.9300
Cu1—O4	1.917 (2)	C3—C9	1.375 (5)
Cu1—O3	1.918 (2)	C3—C4	1.475 (5)
Cu1—N3	2.050 (3)	C4—C5	1.372 (5)
Cu1—N2^i	2.050 (3)	C4—C8	1.385 (5)
Cu1—O6^ii	2.267 (3)	C5—C6	1.363 (5)
Cu2—O2^iii	2.529 (3)	C5—H5A	0.9300
Cu2—O2^iv	2.529 (3)	C6—H6A	0.9300
Cu2—O7	1.925 (2)	C7—C8	1.355 (5)
Cu2—O7^v	1.925 (2)	C7—H7A	0.9300
Cu2—N4^v	1.984 (3)	C8—H8A	0.9300
Cu2—N4	1.984 (3)	C9—C10	1.362 (5)
N1—O1	1.477 (5)	C9—H9A	0.9300
N1—O2	1.242 (5)	C10—H10A	0.9300
N1—O3	1.278 (4)	C11—C12	1.370 (5)
O6—Cu1^ii	2.267 (3)	C11—C13	1.379 (5)
N2—C10	1.326 (5)	C11—H11A	0.9300
N2—C1	1.331 (5)	C12—H12A	0.9300
N2—Cu1^vi	2.050 (3)	C13—C14	1.374 (5)
N3—C6	1.325 (4)	C13—C13^vii	1.477 (6)
N3—C7	1.338 (4)	C14—C15	1.361 (5)
N4—C12	1.325 (5)	C14—H14A	0.9300
N4—C15	1.324 (5)	C15—H15A	0.9300
O5—Mo1—O6	108.97 (14)	C15—N4—Cu2	120.3 (2)
O5—Mo1—O7	109.55 (13)	N2—C1—C2	123.5 (3)
O6—Mo1—O7	109.96 (13)	N2—C1—H1A	118.2
O5—Mo1—O4	108.89 (13)	C2—C1—H1A	118.2
O6—Mo1—O4	109.86 (14)	C1—C2—C3	119.5 (3)
O7—Mo1—O4	109.60 (13)	C1—C2—H2A	120.2
O4—Cu1—O3	166.78 (12)	C3—C2—H2A	120.2
O4—Cu1—N3	91.33 (11)	C2—C3—C9	116.9 (3)
O3—Cu1—N3	91.07 (11)	C2—C3—C4	121.1 (3)
O4—Cu1—N2^i	90.14 (11)	C9—C3—C4	122.0 (3)
O3—Cu1—N2^i	87.52 (11)	C5—C4—C8	116.8 (3)
N3—Cu1—N2^i	178.53 (11)	C5—C4—C3	120.9 (3)
O4—Cu1—O6^ii	95.93 (12)	C8—C4—C3	122.3 (3)
O3—Cu1—O6^ii	97.07 (11)	C6—C5—C4	119.6 (3)
N3—Cu1—O6^ii	90.20 (11)	C6—C5—H5A	120.2
N2^i—Cu1—O6^ii	89.54 (11)	C4—C5—H5A	120.2
O7—Cu2—O7^v	180.0	N3—C6—C5	124.0 (3)
O7—Cu2—N4^v	90.12 (11)	N3—C6—H6A	118.0
O7^v—Cu2—N4^v	89.88 (11)	C5—C6—H6A	118.0
O7—Cu2—N4	89.88 (11)	N3—C7—C8	123.4 (3)
O7^v—Cu2—N4	90.12 (11)	N3—C7—H7A	118.3
N4^v—Cu2—N4	180.0	C8—C7—H7A	118.3
O7—Cu2—O2^iii	87.75 (11)	C7—C8—C4	119.9 (3)
O7^v—Cu2—O2^iii	92.25 (11)	C7—C8—H8A	120.0
N4^v—Cu2—O2^iii	91.36 (12)	C4—C8—H8A	120.0
N4—Cu2—O2^iii	88.64 (12)	C10—C9—C3	120.1 (3)
O7—Cu2—O2^iv	92.25 (11)	C10—C9—H9A	120.0
O7^v—Cu2—O2^iv	87.75 (11)	C3—C9—H9A	120.0
N4^v—Cu2—O2^iv	88.64 (12)	N2—C10—C9	123.2 (3)
N4—Cu2—O2^iv	91.36 (12)	N2—C10—H10A	118.4
O2^iii—Cu2—O2^iv	180.0	C9—C10—H10A	118.4
N1—O3—Cu1	130.5 (2)	C12—C11—C13	119.8 (3)
Mo1—O4—Cu1	163.42 (18)	C12—C11—H11A	120.1
Mo1—O6—Cu1^ii	148.52 (16)	C13—C11—H11A	120.1
Mo1—O7—Cu2	171.98 (15)	N4—C12—C11	122.8 (3)
O2—N1—O3	122.9 (4)	N4—C12—H12A	118.6
O2—N1—O1	121.6 (4)	C11—C12—H12A	118.6
O3—N1—O1	115.5 (3)	C14—C13—C11	116.5 (3)
C10—N2—C1	116.6 (3)	C14—C13—C13^vii	121.9 (4)
C10—N2—Cu1^vi	120.9 (2)	C11—C13—C13^vii	121.5 (4)
C1—N2—Cu1^vi	122.5 (2)	C15—C14—C13	120.6 (3)
C6—N3—C7	116.3 (3)	C15—C14—H14A	119.7
C6—N3—Cu1	121.5 (2)	C13—C14—H14A	119.7
C7—N3—Cu1	122.0 (2)	N4—C15—C14	122.5 (3)
C12—N4—C15	117.8 (3)	N4—C15—H15A	118.7
C12—N4—Cu2	121.8 (2)	C14—C15—H15A	118.7

Symmetry codes: (i) x+1, y, z−1; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z; (v) −x+2, −y+1, −z+1; (vi) x−1, y, z+1; (vii) −x+2, −y+1, −z.