μ-Oxalato-bis­[(1,4,8,11-tetra­azacyclo­tetra­decane)nickel(II)] bis­(perchlorate) hemihydrate

The title compound, [Ni₂(C₂O₄)(C₂₀H₄₈N₈](ClO₄)₂·0.5H₂O, contains dinuclear [Ni₂(C₂O₄)(cyclam)₂]²⁺ cations (cyclam is 1,4,8,11-tetra­azacyclo­tetra­decane) lying on centres of inversion. The geometry of the complex is comparable to that in a previously reported nitrate salt.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 98%
• Disorder in solvent or counterion
• R factor = 0.047
• wR factor = 0.128
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.627     0.878
            Tmin(prime) and Tmax expected:      0.728     0.878
            RR(prime) =      0.862
            Please check that your absorption correction is appropriate.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.86
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................       4.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....        <O7
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C11    -   C11_a  ...       1.55 Ang.
PLAT411_ALERT_2_C Short Inter H...H Contact  H6B    ..  H8A     ..       2.14 Ang.

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:C22 H49 Cl2 N8 Ni2 O12.5
            Atom count from the _atom_site data:  C22 H48 Cl2 N8 Ni2 O12.5
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    2
           From the CIF: _chemical_formula_sum  C22 H49 Cl2 N8 Ni2 O12.5
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         44.00     44.00    0.00
           H         98.00     96.00    2.00
           Cl         4.00      4.00    0.00
           N         16.00     16.00    0.00
           Ni         4.00      4.00    0.00
           O         25.00     25.00    0.00
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

µ-Oxalato-bis[(1,4,8,11-tetraazacyclotetradecane)nickel(II)] bis(perchlorate) hemihydrate

Crystal data

[Ni2(C2O4)(C20H48N8](ClO4)2·0.5H2O	F(000) = 854
Mr = 814.01	Dx = 1.550 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2035 reflections
a = 8.854 (2) Å	θ = 2.4–24.4°
b = 13.350 (3) Å	µ = 1.30 mm^−1
c = 15.245 (4) Å	T = 293 K
β = 104.513 (4)°	Block, purple
V = 1744.5 (7) Å^3	0.24 × 0.16 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEXII CCD diffractometer	3067 independent reflections
Radiation source: fine-focus sealed tube	1951 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→7
Tmin = 0.627, Tmax = 0.878	k = −15→11
8405 measured reflections	l = −16→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0603P)^2 + 0.2902P] where P = (Fo^2 + 2Fc^2)/3
3067 reflections	(Δ/σ)max = 0.005
217 parameters	Δρmax = 0.52 e Å^−3
34 restraints	Δρmin = −0.36 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)
Ni1	0.81975 (5)	0.65563 (3)	0.91792 (3)	0.03078 (12)
O1	1.0446 (3)	0.62708 (16)	0.99655 (17)	0.0409 (7)
O2	1.1938 (3)	0.49976 (17)	1.06355 (16)	0.0411 (7)
N1	0.8815 (4)	0.6372 (2)	0.7940 (2)	0.0460 (9)
H1	0.9159	0.5730	0.7942	0.055*
N2	0.8650 (3)	0.8102 (2)	0.9170 (2)	0.0395 (9)
H2	0.7801	0.8399	0.8801	0.047*
N3	0.7399 (4)	0.6923 (2)	1.0320 (2)	0.0455 (9)
H3	0.8144	0.6699	1.0806	0.055*
N4	0.5931 (3)	0.6514 (2)	0.8347 (2)	0.0417 (9)
H4	0.5621	0.7152	0.8185	0.050*
C1	1.0085 (5)	0.7005 (3)	0.7763 (3)	0.0650 (14)
H1A	1.0158	0.6887	0.7147	0.078*
H1B	1.1065	0.6798	0.8167	0.078*
C2	0.9870 (5)	0.8097 (3)	0.7884 (3)	0.0627 (13)
H2A	0.8848	0.8292	0.7523	0.075*
H2B	1.0642	0.8461	0.7657	0.075*
C3	1.0015 (5)	0.8402 (3)	0.8860 (3)	0.0612 (14)
H3A	1.0939	0.8095	0.9244	0.073*
H3B	1.0139	0.9123	0.8914	0.073*
C4	0.8747 (5)	0.8442 (3)	1.0108 (3)	0.0593 (13)
H4A	0.8723	0.9168	1.0128	0.071*
H4B	0.9717	0.8215	1.0509	0.071*
C5	0.7393 (5)	0.8020 (3)	1.0408 (3)	0.0623 (14)
H5A	0.7471	0.8204	1.1033	0.075*
H5B	0.6426	0.8290	1.0037	0.075*
C6	0.5918 (5)	0.6460 (3)	1.0399 (3)	0.0679 (14)
H6A	0.5627	0.6750	1.0917	0.081*
H6B	0.6091	0.5750	1.0516	0.081*
C7	0.4576 (5)	0.6590 (4)	0.9571 (3)	0.0736 (15)
H7A	0.3629	0.6350	0.9711	0.088*
H7B	0.4441	0.7299	0.9434	0.088*
C8	0.4784 (5)	0.6051 (3)	0.8746 (3)	0.0652 (15)
H8A	0.5097	0.5366	0.8908	0.078*
H8B	0.3790	0.6031	0.8297	0.078*
C9	0.6072 (5)	0.5968 (3)	0.7534 (3)	0.0594 (14)
H9A	0.5104	0.6016	0.7066	0.071*
H9B	0.6284	0.5266	0.7677	0.071*
C10	0.7389 (5)	0.6424 (3)	0.7202 (3)	0.0627 (14)
H10A	0.7531	0.6058	0.6679	0.075*
H10B	0.7150	0.7115	0.7026	0.075*
C11	1.0685 (4)	0.5372 (3)	1.0171 (2)	0.0347 (10)
Cl1	0.41880 (12)	0.91520 (8)	0.77010 (7)	0.0568 (3)
O3	0.3629 (4)	0.8145 (2)	0.7554 (3)	0.0950 (13)
O4	0.3801 (4)	0.9668 (2)	0.6862 (2)	0.0936 (13)
O5	0.5790 (4)	0.9202 (3)	0.8085 (3)	0.1360 (18)
O6	0.3357 (5)	0.9657 (4)	0.8246 (3)	0.170 (2)
O7	0.634 (2)	0.0580 (16)	0.9809 (12)	0.138 (8)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0271 (2)	0.0255 (2)	0.0365 (2)	−0.0008 (2)	0.00189 (17)	0.0060 (2)
O1	0.0362 (14)	0.0252 (13)	0.0535 (15)	−0.0013 (10)	−0.0036 (12)	0.0112 (11)
O2	0.0292 (13)	0.0334 (13)	0.0538 (16)	−0.0024 (11)	−0.0025 (12)	0.0102 (12)
N1	0.0536 (19)	0.0412 (18)	0.0444 (18)	0.0129 (15)	0.0147 (15)	0.0054 (15)
N2	0.0355 (17)	0.0318 (15)	0.0468 (18)	−0.0012 (13)	0.0019 (15)	0.0042 (14)
N3	0.0520 (19)	0.0452 (18)	0.0397 (18)	0.0050 (15)	0.0118 (15)	0.0073 (15)
N4	0.0319 (15)	0.0300 (15)	0.0580 (19)	0.0000 (14)	0.0016 (14)	0.0103 (15)
C1	0.061 (3)	0.070 (3)	0.073 (3)	0.009 (2)	0.035 (2)	0.018 (2)
C2	0.060 (3)	0.054 (3)	0.080 (3)	0.000 (2)	0.029 (2)	0.025 (2)
C3	0.045 (2)	0.043 (2)	0.094 (3)	−0.010 (2)	0.012 (2)	0.013 (2)
C4	0.079 (3)	0.040 (2)	0.051 (2)	−0.009 (2)	0.002 (2)	−0.008 (2)
C5	0.083 (3)	0.055 (3)	0.051 (3)	0.006 (2)	0.021 (2)	−0.011 (2)
C6	0.069 (3)	0.072 (3)	0.075 (3)	−0.001 (3)	0.043 (2)	0.015 (2)
C7	0.042 (2)	0.080 (3)	0.107 (3)	0.001 (2)	0.033 (2)	0.036 (3)
C8	0.037 (2)	0.059 (3)	0.096 (4)	−0.005 (2)	0.008 (2)	0.022 (3)
C9	0.062 (3)	0.052 (3)	0.048 (3)	0.001 (2)	−0.017 (2)	−0.002 (2)
C10	0.073 (3)	0.064 (3)	0.046 (2)	0.006 (2)	0.004 (2)	−0.002 (2)
C11	0.0249 (17)	0.038 (2)	0.038 (2)	−0.0026 (16)	0.0002 (16)	0.0051 (17)
Cl1	0.0562 (6)	0.0495 (6)	0.0615 (7)	0.0009 (5)	0.0085 (5)	0.0139 (5)
O3	0.098 (3)	0.0468 (18)	0.127 (3)	−0.0008 (18)	0.004 (2)	0.0274 (19)
O4	0.099 (3)	0.075 (2)	0.088 (2)	−0.0221 (19)	−0.011 (2)	0.0279 (19)
O5	0.069 (2)	0.126 (3)	0.178 (4)	0.005 (2)	−0.035 (2)	0.055 (3)
O6	0.191 (4)	0.174 (4)	0.174 (4)	−0.016 (3)	0.097 (3)	−0.065 (3)
O7	0.138 (15)	0.180 (18)	0.096 (12)	0.006 (14)	0.026 (11)	−0.011 (12)

Geometric parameters (Å, º)

Ni1—O1	2.086 (2)	C2—H2B	0.970
Ni1—N4	2.089 (3)	C3—H3A	0.970
Ni1—N3	2.093 (3)	C3—H3B	0.970
Ni1—O2^i	2.101 (2)	C4—C5	1.496 (6)
Ni1—N2	2.103 (3)	C4—H4A	0.970
Ni1—N1	2.109 (3)	C4—H4B	0.970
O1—C11	1.244 (4)	C5—H5A	0.970
O2—C11	1.261 (4)	C5—H5B	0.970
O2—Ni1^i	2.101 (2)	C6—C7	1.510 (6)
N1—C10	1.467 (5)	C6—H6A	0.970
N1—C1	1.484 (5)	C6—H6B	0.970
N1—H1	0.910	C7—C8	1.500 (7)
N2—C3	1.460 (5)	C7—H7A	0.970
N2—C4	1.481 (5)	C7—H7B	0.970
N2—H2	0.910	C8—H8A	0.970
N3—C5	1.471 (5)	C8—H8B	0.970
N3—C6	1.482 (5)	C9—C10	1.510 (6)
N3—H3	0.910	C9—H9A	0.970
N4—C8	1.446 (5)	C9—H9B	0.970
N4—C9	1.471 (5)	C10—H10A	0.970
N4—H4	0.910	C10—H10B	0.970
C1—C2	1.488 (6)	C11—C11^i	1.553 (6)
C1—H1A	0.970	Cl1—O5	1.394 (3)
C1—H1B	0.970	Cl1—O6	1.411 (4)
C2—C3	1.516 (6)	Cl1—O4	1.417 (3)
C2—H2A	0.970	Cl1—O3	1.430 (3)
O1—Ni1—N4	167.83 (10)	C2—C3—H3A	109.3
O1—Ni1—N3	92.15 (11)	N2—C3—H3B	109.3
N4—Ni1—N3	92.16 (12)	C2—C3—H3B	109.3
O1—Ni1—O2^i	79.68 (8)	H3A—C3—H3B	107.9
N4—Ni1—O2^i	88.65 (10)	N2—C4—C5	108.8 (3)
N3—Ni1—O2^i	94.39 (11)	N2—C4—H4A	109.9
O1—Ni1—N2	91.55 (10)	C5—C4—H4A	109.9
N4—Ni1—N2	100.26 (11)	N2—C4—H4B	109.9
N3—Ni1—N2	83.13 (12)	C5—C4—H4B	109.9
O2^i—Ni1—N2	170.81 (10)	H4A—C4—H4B	108.3
O1—Ni1—N1	93.96 (11)	N3—C5—C4	109.0 (4)
N4—Ni1—N1	83.02 (12)	N3—C5—H5A	109.9
N3—Ni1—N1	171.58 (12)	C4—C5—H5A	109.9
O2^i—Ni1—N1	92.40 (11)	N3—C5—H5B	109.9
N2—Ni1—N1	90.91 (12)	C4—C5—H5B	109.9
C11—O1—Ni1	113.5 (2)	H5A—C5—H5B	108.3
C11—O2—Ni1^i	113.3 (2)	N3—C6—C7	114.3 (4)
C10—N1—C1	112.3 (3)	N3—C6—H6A	108.7
C10—N1—Ni1	108.3 (3)	C7—C6—H6A	108.7
C1—N1—Ni1	118.4 (3)	N3—C6—H6B	108.7
C10—N1—H1	105.6	C7—C6—H6B	108.7
C1—N1—H1	105.6	H6A—C6—H6B	107.6
Ni1—N1—H1	105.6	C8—C7—C6	114.2 (4)
C3—N2—C4	112.1 (3)	C8—C7—H7A	108.7
C3—N2—Ni1	116.5 (2)	C6—C7—H7A	108.7
C4—N2—Ni1	105.0 (2)	C8—C7—H7B	108.7
C3—N2—H2	107.6	C6—C7—H7B	108.7
C4—N2—H2	107.6	H7A—C7—H7B	107.6
Ni1—N2—H2	107.6	N4—C8—C7	113.2 (4)
C5—N3—C6	112.6 (3)	N4—C8—H8A	108.9
C5—N3—Ni1	108.5 (2)	C7—C8—H8A	108.9
C6—N3—Ni1	117.4 (2)	N4—C8—H8B	108.9
C5—N3—H3	105.8	C7—C8—H8B	108.9
C6—N3—H3	105.8	H8A—C8—H8B	107.7
Ni1—N3—H3	105.8	N4—C9—C10	108.6 (3)
C8—N4—C9	111.1 (3)	N4—C9—H9A	110.0
C8—N4—Ni1	115.2 (2)	C10—C9—H9A	110.0
C9—N4—Ni1	104.7 (2)	N4—C9—H9B	110.0
C8—N4—H4	108.6	C10—C9—H9B	110.0
C9—N4—H4	108.6	H9A—C9—H9B	108.4
Ni1—N4—H4	108.6	N1—C10—C9	108.3 (3)
N1—C1—C2	114.1 (4)	N1—C10—H10A	110.0
N1—C1—H1A	108.7	C9—C10—H10A	110.0
C2—C1—H1A	108.7	N1—C10—H10B	110.0
N1—C1—H1B	108.7	C9—C10—H10B	110.0
C2—C1—H1B	108.7	H10A—C10—H10B	108.4
H1A—C1—H1B	107.6	O1—C11—O2	126.4 (3)
C1—C2—C3	113.8 (4)	O1—C11—C11^i	117.6 (4)
C1—C2—H2A	108.8	O2—C11—C11^i	115.9 (4)
C3—C2—H2A	108.8	O5—Cl1—O6	110.8 (3)
C1—C2—H2B	108.8	O5—Cl1—O4	110.3 (3)
C3—C2—H2B	108.8	O6—Cl1—O4	104.8 (3)
H2A—C2—H2B	107.7	O5—Cl1—O3	112.7 (2)
N2—C3—C2	111.8 (3)	O6—Cl1—O3	109.3 (3)
N2—C3—H3A	109.3	O4—Cl1—O3	108.6 (2)
N4—Ni1—O1—C11	−16.1 (7)	N1—Ni1—N4—C8	146.1 (3)
N3—Ni1—O1—C11	94.5 (3)	O1—Ni1—N4—C9	−52.4 (6)
O2^i—Ni1—O1—C11	0.5 (3)	N3—Ni1—N4—C9	−163.1 (2)
N2—Ni1—O1—C11	177.7 (3)	O2^i—Ni1—N4—C9	−68.8 (2)
N1—Ni1—O1—C11	−91.3 (3)	N2—Ni1—N4—C9	113.5 (2)
O1—Ni1—N1—C10	174.0 (2)	N1—Ni1—N4—C9	23.8 (2)
N4—Ni1—N1—C10	5.8 (2)	C10—N1—C1—C2	75.1 (5)
O2^i—Ni1—N1—C10	94.1 (2)	Ni1—N1—C1—C2	−52.4 (4)
N2—Ni1—N1—C10	−94.4 (3)	N1—C1—C2—C3	68.3 (5)
O1—Ni1—N1—C1	−56.7 (3)	C4—N2—C3—C2	−177.1 (3)
N4—Ni1—N1—C1	135.1 (3)	Ni1—N2—C3—C2	61.9 (4)
O2^i—Ni1—N1—C1	−136.5 (3)	C1—C2—C3—N2	−73.9 (5)
N2—Ni1—N1—C1	34.9 (3)	C3—N2—C4—C5	−174.4 (3)
O1—Ni1—N2—C3	54.1 (3)	Ni1—N2—C4—C5	−47.0 (4)
N4—Ni1—N2—C3	−122.9 (3)	C6—N3—C5—C4	−166.8 (3)
N3—Ni1—N2—C3	146.1 (3)	Ni1—N3—C5—C4	−35.2 (4)
N1—Ni1—N2—C3	−39.8 (3)	N2—C4—C5—N3	56.3 (4)
O1—Ni1—N2—C4	−70.5 (2)	C5—N3—C6—C7	75.1 (5)
N4—Ni1—N2—C4	112.4 (2)	Ni1—N3—C6—C7	−52.0 (4)
N3—Ni1—N2—C4	21.4 (2)	N3—C6—C7—C8	66.3 (5)
N1—Ni1—N2—C4	−164.5 (2)	C9—N4—C8—C7	−179.1 (3)
O1—Ni1—N3—C5	98.7 (2)	Ni1—N4—C8—C7	62.1 (4)
N4—Ni1—N3—C5	−92.7 (3)	C6—C7—C8—N4	−72.6 (5)
O2^i—Ni1—N3—C5	178.5 (2)	C8—N4—C9—C10	−174.6 (3)
N2—Ni1—N3—C5	7.4 (2)	Ni1—N4—C9—C10	−49.6 (3)
O1—Ni1—N3—C6	−132.3 (3)	C1—N1—C10—C9	−166.7 (3)
N4—Ni1—N3—C6	36.3 (3)	Ni1—N1—C10—C9	−34.0 (4)
O2^i—Ni1—N3—C6	−52.5 (3)	N4—C9—C10—N1	57.4 (4)
N2—Ni1—N3—C6	136.4 (3)	Ni1—O1—C11—O2	179.7 (3)
O1—Ni1—N4—C8	69.8 (7)	Ni1—O1—C11—C11^i	−0.5 (5)
N3—Ni1—N4—C8	−40.9 (3)	Ni1^i—O2—C11—O1	179.6 (3)
O2^i—Ni1—N4—C8	53.5 (3)	Ni1^i—O2—C11—C11^i	−0.3 (5)
N2—Ni1—N4—C8	−124.3 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.