Poly[[diaqua­bis(μ-3,3′,5,5′-tetra­methyl-4,4′-bipyrazole-κ²N:N′)cobalt(II)] dinitrate]

The Co atom in the title compound, [Co(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂, is six-coordinate in a trans-N₄O₂ octa­hedral geometry as a consequence of bridging by the bipyrazole ligand; the bridging leads to the formation of a polycationic layer. The layers inter­act with the anions through hydrogen bonds, generating a three-dimensional hydrogen-bonded network. The structure is porous as 33.4% of its unit-cell volume is empty space. The Co atom lies on a special position of site symmetry 222, the bipyrazole ligand lies on a special position of site symmetry 2, the water mol­ecule on another special position of site symmetry 2, and the nitrate anion on a special position of site symmetry m.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.051
• wR factor = 0.169
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of .    1228.00 A   3 

Author Response: ... The structure is porous.

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.110
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.02

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2006).

Poly[[diaquabis(µ-3,3',5,5'-tetramethyl-4,4'-bipyrazole-κ²N:N')cobalt(II)] dinitrate]

Crystal data

[Co(C10H14N4)2(H2O)2](NO3)2	Dx = 1.071 Mg m^−3
Mr = 599.49	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6/mcc	Cell parameters from 797 reflections
Hall symbol: -P 6 2c	θ = 2.4–20.5°
a = 19.922 (3) Å	µ = 0.51 mm^−1
c = 16.226 (2) Å	T = 295 K
V = 5577.1 (9) Å^3	Block, purple
Z = 6	0.32 × 0.25 × 0.22 mm
F(000) = 1878

Data collection

Bruker APEX2 area-detector diffractometer	1716 independent reflections
Radiation source: fine-focus sealed tube	996 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.110
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→19
Tmin = 0.855, Tmax = 0.897	k = −23→23
26157 measured reflections	l = −19→19

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.101P)^2] where P = (Fo^2 + 2Fc^2)/3
1716 reflections	(Δ/σ)max = 0.001
96 parameters	Δρmax = 1.01 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.5000	0.2500	0.0374 (3)
O1	0.3592 (2	0.30757 (18)	0.0674 (2)	0.091 (1)
O2	0.3991 (3)	0.4116 (3)	0.0000	0.103 (2)
O3	0.5000	0.5000	0.1206 (2)	0.0553 (9)
N1	0.3782 (1)	0.4616 (2)	0.2446 (2)	0.043 (1)
N2	0.3353 (2)	0.4055 (2)	0.1885 (2)	0.052 (1)
N3	0.3730 (3)	0.3389 (3)	0.0000	0.066 (1)
C1	0.2043 (2)	0.3301 (3)	0.1273 (3)	0.098 (2)
C2	0.3515 (2)	0.5395 (2)	0.3436 (3)	0.068 (1)
C3	0.2617 (2)	0.3904 (2)	0.1839 (2)	0.055 (1)
C4	0.2548 (2)	0.4377 (2)	0.2402 (2)	0.047 (1)
C5	0.3282 (2)	0.4811 (2)	0.2764 (2)	0.048 (1)
H3o	0.4707	0.4560	0.1038	0.083*
H2n	0.3534	0.3823	0.1590	0.062*
H1a	0.1940	0.3548	0.0820	0.147*
H1b	0.1570	0.2980	0.1567	0.147*
H1c	0.2247	0.2988	0.1067	0.147*
H2a	0.3367	0.5135	0.3958	0.102*
H2b	0.3263	0.5693	0.3359	0.102*
H2c	0.4067	0.5733	0.3423	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0316 (4)	0.0316 (4)	0.0532 (6)	0.0188 (4)	0.000	0.000
O1	0.132 (3)	0.083 (2)	0.074 (2)	0.066 (2)	0.018 (2)	0.0245 (2)
O2	0.115 (4)	0.084 (3)	0.063 (3)	0.015 (3)	0.000	0.000
O3	0.052 (2)	0.043 (2)	0.057 (2)	0.013 (2)	0.000	0.000
N1	0.036 (1)	0.039 (1)	0.061 (2)	0.023 (1)	0.000 (1)	−0.004 (1)
N2	0.040 (2)	0.056 (2)	0.064 (2)	0.028 (1)	−0.003 (1)	−0.015 (2)
N3	0.067 (3)	0.049 (3)	0.083 (4)	0.030 (3)	0.000	0.000
C1	0.051 (2)	0.132 (4)	0.108 (4)	0.043 (3)	−0.023 (3)	−0.052 (3)
C2	0.053 (2)	0.067 (3)	0.092 (3)	0.035 (2)	−0.004 (2)	−0.024 (2)
C3	0.036 (2)	0.068 (2)	0.067 (2)	0.030 (2)	−0.004 (2)	−0.011 (2)
C4	0.032 (2)	0.053 (2)	0.063 (2)	0.025 (2)	0.001 (2)	0.003 (2)
C5	0.042 (2)	0.045 (2)	0.066 (2)	0.029 (2)	0.006 (2)	0.003 (2)

Geometric parameters (Å, º)

Co1—O3	2.099 (4)	C2—C5	1.488 (5)
Co1—O3^i	2.099 (4)	C3—C4	1.368 (4)
Co1—N1	2.151 (2)	C4—C5	1.402 (4)
Co1—N1^ii	2.151 (2)	C4—C4^v	1.468 (6)
Co1—N1^i	2.151 (2)	O3—H3o	0.82
Co1—N1^iii	2.151 (2)	N2—H2n	0.86
O1—N3	1.221 (3)	C1—H1a	0.96
O2—N3	1.271 (6)	C1—H1b	0.96
N1—C5	1.341 (4)	C1—H1c	0.96
N1—N2	1.362 (3)	C2—H2a	0.96
N2—C3	1.343 (4)	C2—H2b	0.96
N3—O1^iv	1.221 (3)	C2—H2c	0.96
C1—C3	1.490 (5)
O3—Co1—O3^i	180	C5—C4—C4^v	128.7 (3)
O3—Co1—N1	87.7 (1)	N1—C5—C4	110.9 (3)
O3—Co1—N1^ii	87.7 (1)	N1—C5—C2	121.4 (3)
O3—Co1—N1^i	92.3 (1)	C4—C5—C2	127.7 (3)
O3—Co1—N1^iii	92.3 (1)	Co1—O3—H3o	109.5
N1—Co1—N1^ii	175.4 (1)	C3—N2—H2n	123.6
N1—Co1—N1^i	96.0 (1)	N1—N2—H2n	123.6
N1—Co1—N1^iii	84.2 (1)	C3—C1—H1a	109.5
C5—N1—N2	104.1 (2)	C3—C1—H1b	109.5
C5—N1—Co1	138.7 (2)	H1a—C1—H1b	109.5
N2—N1—Co1	116.7 (2)	C3—C1—H1c	109.5
C3—N2—N1	112.8 (3)	H1a—C1—H1c	109.5
O1^iv—N3—O1	127.4 (5)	H1b—C1—H1c	109.5
O1^iv—N3—O2	116.2 (3)	C5—C2—H2a	109.5
O1—N3—O2	116.2 (3)	C5—C2—H2b	109.5
N2—C3—C4	106.5 (3)	H2a—C2—H2b	109.5
N2—C3—C1	121.8 (3)	C5—C2—H2c	109.5
C4—C3—C1	131.7 (3)	H2a—C2—H2c	109.5
C3—C4—C5	105.8 (3)	H2b—C2—H2c	109.5
C3—C4—C4^v	125.4 (3)
O3^i—Co1—N1—C5	51.0 (3)	C1—C3—C4—C5	178.7 (4)
N1^i—Co1—N1—C5	−37.0 (3)	N2—C3—C4—C4^v	−176.3 (3)
N1^iii—Co1—N1—C5	138.4 (4)	C1—C3—C4—C4^v	1.8 (7)
O3^i—Co1—N1—N2	−136.9 (2)	N2—N1—C5—C4	−0.2 (4)
N1^i—Co1—N1—N2	135.2 (2)	Co1—N1—C5—C4	172.6 (2)
N1^iii—Co1—N1—N2	−49.5 (2)	N2—N1—C5—C2	177.6 (3)
C5—N1—N2—C3	0.6 (4)	Co1—N1—C5—C2	−9.7 (6)
Co1—N1—N2—C3	−174.1 (2)	C3—C4—C5—N1	−0.3 (4)
N1—N2—C3—C4	−0.8 (4)	C4^v—C4—C5—N1	176.4 (3)
N1—N2—C3—C1	−179.1 (3)	C3—C4—C5—C2	−177.8 (4)
N2—C3—C4—C5	0.6 (4)	C4^v—C4—C5—C2	−1.1 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···O2	0.82	2.10	2.727 (4)	134
N2—H2n···O1	0.86	2.15	2.970 (4)	160