Polymeric tetra­aqua(1,2,4,5-benzene­tetra­carboxyl­ato)(pyrazine)­dinickel(II) dihydrate

The Ni atom in the title compound, {[Ni₂(C₁₀H₂O₈)(C₄H₄N₂)(H₂O)₄]·2H₂O}_n, exists in an octahedral NO₅Ni coordination environment that is defined by the two O atoms of a chelating carboxyl group, the O atom of a monodentate carboxyl group belonging to another carboxy­lato tetraanion, two water mol­ecules and the N atom of the N-heterocycle. The tetra­carboxyl­ato anion and the pyrazine mol­ecule are each located on a center of inversion. The bonding pattern leads to the formation of a layer structure; the layers are linked into a three-dimensional network by extensive hydrogen bonds involving the water mol­ecules and the O atoms of the anionic unit.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.065
• wR factor = 0.142
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .....       0.93

Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.84(5), Rep   0.840(10) ....       5.00 su-Ratio
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.84(6), Rep   0.850(10) ....       6.00 su-Ratio
              O2W  -H2W1    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ....       5.00 su-Ratio
              O2W  -H2W2    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(6), Rep   0.850(10) ....       6.00 su-Ratio
              O3W  -H3W1    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.84(5), Rep   0.840(10) ....       5.00 su-Ratio
              O1W  -H1W1    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ....       5.00 su-Ratio
              O2W  -H2W2    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.84(6), Rep   0.850(10) ....       6.00 su-Ratio
              O2W  -H2W1    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(6), Rep   0.850(10) ....       6.00 su-Ratio
              O3W  -H3W1    1.555   1.555
PLAT736_ALERT_1_B H...A   Calc     1.96(5), Rep   1.960(10) ....       5.00 su-Ratio
              H2W2 -O1W     1.555   2.676
PLAT736_ALERT_1_B H...A   Calc     1.90(6), Rep   1.900(10) ....       6.00 su-Ratio
              H2W1 -O3W     1.555   1.455

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.616     0.919
            Tmin' and Tmax expected:      0.738     0.919
            RR' =      0.835
            Please check that your absorption correction is appropriate.
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           28.30
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               2152
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2304
           Completeness (_total/calc)             93.40%
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 ..........       2.00 Ratio
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ...........       0.82
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .....          ?
PLAT213_ALERT_2_C Atom C3      has ADP max/min Ratio ...........       3.10 oblate
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang..          7
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #       11
            O3  -NI1 -N1  -C6    -64.00  2.00   2.667   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #       16
            O3  -NI1 -N1  -C7    107.00  1.00   2.667   1.555   1.555   1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ......          6
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
              O1W  -H1W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
              O3W  -H3W2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
              O1W  -H1W2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
              O3W  -H3W2    1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.82(5), Rep     1.82(2) ....       2.50 su-Ratio
              H1W1 -O4      1.555   2.667
PLAT736_ALERT_1_C H...A   Calc     2.02(3), Rep   2.020(10) ....       3.00 su-Ratio
              H3W2 -O3      1.555   1.665
PLAT764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd)       1.11 Ratio

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

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

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S1. Comment

A number of the adducts of nickel benzenepolycarboxylates with N-heterocycles have been reported (Li et al., 2003; Yuan et al., 2001). To this number has been added the 4,4'-bipyridine adduct of nickel terephthalate (Yang et al., 2003a) and of nickel phthalate (Yang et al., 2003b). The present pyrazine adduct, (I), of dinickel 1,2,4,5-benzenetetracarboxylate exists as a dihydrate (Fig. 1).

The Ni atom in (I) exists in an octahedral NO₅Ni environment that is defined by the two O atoms of a chelating –CO₂ group, the O atom of a monodentate CO₂ group of another tetraanion, two water molecules and the N atom of pyrazine (Table 1). The tetracarboxylate anion and the pyrazine molecule are located on a center of inversion. The bonding pattern leads to the formation of layers (Fig. 2); the layers are linked into a three-dimensional network by hydrogen bonds involving the water molecules (Table 2).

S2. Experimental

1,2,4,5-Benzenetetracarboxylic acid anhydride (pyromellitic anhydride, 0.22 g, 1 mmol) dissolved in water (15 ml) containing sodium hydroxide (0.16 g, 4 mmol). Nickel dinitrate hexahydrate (0.58 g, 2 mmol) and pyrazine (0.16 g, 2 mmol) dissolved in water (3 ml) were added. The mixture was placed in a 20 ml Teflon-lined stainless-steel bomb. The bomb was heated at 453 K for 100 h. Crystals separated from the solution when the bomb was cooled down at a rate of 5 K h⁻¹.

S3. Refinement

The use of too small a value for the ω-dependent absorption correction in SADABS (Sheldrick, 1996) lead to non-positive definites for several atoms, and a compromise value of 0.5 was used for which only one atom (C3) was non-positive definite. The displacement parameter of this atom was made nearly isotropic by an ISOR 0.01 command in SHELXL97 (Sheldrick, 1997). The aromatic H atoms were generated geometrically and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2U_eq(C). The water H atoms were located and refined with restraints of O—H = 0.85±0.01 Å and H···H = 1.39±0.01 Å, and U_iso(H) = 1.2U_eq(O).

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.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of a segment of the title structure at the 75% probability level. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.] Fig. 2. ORTEPII (Johnson, 1976) plot of the layer structure.

tetraaqua(1,2,4,5-benzenetetracarboxylato)(pyrazine)dinickel(II) dihydrate

Crystal data

[Ni2(C10H2O8)(C4H4N2)(H2O)4]·2H2O	Z = 1
Mr = 555.72	F(000) = 284
Triclinic, P1	Dx = 1.991 Mg m^−3
a = 7.2005 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0322 (5) Å	Cell parameters from 2804 reflections
c = 9.3735 (6) Å	θ = 2.3–28.3°
α = 96.175 (1)°	µ = 2.12 mm^−1
β = 101.872 (1)°	T = 298 K
γ = 116.245 (1)°	Irregular block, green
V = 463.50 (5) Å^3	0.14 × 0.13 × 0.04 mm

Data collection

Bruker APEX area-detector diffractometer	2152 independent reflections
Radiation source: fine-focus sealed tube	2055 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.616, Tmax = 0.919	k = −10→10
5415 measured reflections	l = −12→12

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0629P)^2 + 0.259P] where P = (Fo^2 + 2Fc^2)/3
2152 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.95 e Å^−3
12 restraints	Δρmin = −0.65 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ni1	0.60108 (8)	0.81218 (8)	0.67559 (6)	0.0110 (2)
O1	0.6582 (5)	0.5750 (5)	0.6851 (4)	0.017 (1)
O2	0.8599 (5)	0.8424 (4)	0.8517 (4)	0.018 (1)
O3	0.5956 (5)	0.2995 (5)	1.1964 (4)	0.021 (1)
O4	0.9037 (5)	0.3347 (6)	1.3403 (4)	0.028 (1)
N1	0.8301 (6)	0.9266 (6)	0.5624 (4)	0.018 (1)
O1w	0.3494 (5)	0.7163 (5)	0.4853 (4)	0.018 (1)
O2w	0.6017 (6)	1.0632 (5)	0.7309 (4)	0.023 (1)
O3w	1.3406 (7)	1.0949 (7)	0.8959 (5)	0.040 (1)
C1	0.8069 (7)	0.6716 (6)	0.8048 (5)	0.015 (1)
C2	0.9098 (7)	0.5810 (6)	0.9020 (5)	0.015 (1)
C3	0.8153 (7)	0.5061 (6)	1.0095 (5)	0.015 (1)
C4	0.9005 (7)	0.4241 (7)	1.1087 (5)	0.017 (1)
C5	0.7944 (7)	0.3455 (7)	1.2247 (5)	0.017 (1)
C6	1.0016 (8)	1.0989 (7)	0.6229 (6)	0.022 (1)
C7	0.8302 (8)	0.8267 (7)	0.4382 (5)	0.021 (1)
H1w1	0.242 (6)	0.689 (7)	0.519 (6)	0.021*
H1w2	0.309 (8)	0.607 (4)	0.433 (5)	0.021*
H2w1	0.520 (8)	1.076 (8)	0.779 (6)	0.028*
H2w2	0.620 (9)	1.135 (7)	0.669 (5)	0.028*
H3w1	1.222 (6)	1.021 (8)	0.911 (8)	0.047*
H3w2	1.418 (9)	1.163 (8)	0.983 (3)	0.047*
H3	0.6903	0.5105	1.0160	0.018*
H6	1.0065	1.1707	0.7097	0.026*
H7	0.7149	0.7059	0.3932	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0108 (3)	0.0142 (3)	0.0113 (3)	0.0073 (2)	0.0052 (2)	0.0062 (2)
O1	0.015 (2)	0.022 (2)	0.016 (2)	0.010 (1)	0.001 (1)	0.004 (1)
O2	0.020 (2)	0.018 (2)	0.018 (2)	0.011 (1)	0.004 (1)	0.005 (1)
O3	0.016 (2)	0.035 (2)	0.021 (2)	0.014 (2)	0.011 (1)	0.016 (2)
O4	0.020 (2)	0.053 (2)	0.021 (2)	0.021 (2)	0.010 (2)	0.021 (2)
N1	0.015 (2)	0.022 (2)	0.019 (2)	0.008 (2)	0.007 (2)	0.008 (2)
O1w	0.017 (2)	0.022 (2)	0.016 (2)	0.010 (1)	0.005 (1)	0.004 (1)
O2w	0.032 (2)	0.023 (2)	0.025 (2)	0.018 (2)	0.015 (2)	0.011 (2)
O3w	0.030 (2)	0.057 (3)	0.023 (2)	0.017 (2)	0.007 (2)	−0.005 (2)
C1	0.011 (2)	0.021 (2)	0.014 (2)	0.008 (2)	0.006 (2)	0.009 (2)
C2	0.013 (2)	0.019 (2)	0.017 (2)	0.011 (2)	0.004 (2)	0.005 (2)
C3	0.019 (2)	0.013 (2)	0.023 (2)	0.011 (2)	0.009 (2)	0.014 (2)
C4	0.014 (2)	0.021 (2)	0.018 (2)	0.008 (2)	0.009 (2)	0.008 (2)
C5	0.018 (2)	0.022 (2)	0.017 (2)	0.012 (2)	0.009 (2)	0.008 (2)
C6	0.022 (2)	0.024 (2)	0.018 (2)	0.010 (2)	0.008 (2)	0.004 (2)
C7	0.017 (2)	0.022 (2)	0.019 (2)	0.006 (2)	0.006 (2)	0.002 (2)

Geometric parameters (Å, º)

Ni1—O1	2.126 (3)	C3—C4	1.389 (6)
Ni1—O2	2.123 (3)	C4—C2^ii	1.408 (6)
Ni1—O3^i	2.014 (3)	C4—C5	1.493 (6)
Ni1—O1w	2.049 (3)	C6—C7^iii	1.367 (7)
Ni1—O2w	2.025 (4)	C7—C6^iii	1.367 (7)
Ni1—N1	2.068 (4)	O1w—H1w1	0.84 (1)
O1—C1	1.262 (6)	O1w—H1w2	0.85 (1)
O2—C1	1.248 (6)	O2w—H2w1	0.85 (1)
O3—C5	1.269 (5)	O2w—H2w2	0.85 (1)
O4—C5	1.237 (6)	O3w—H3w1	0.85 (1)
N1—C6	1.339 (6)	O3w—H3w2	0.85 (1)
N1—C7	1.341 (6)	C3—H3	0.93
C1—C2	1.500 (6)	C6—H6	0.93
C2—C3	1.375 (6)	C7—H7	0.93
C2—C4^ii	1.408 (6)
O1—Ni1—O2	61.7 (1)	C3—C2—C1	117.2 (4)
O1—Ni1—O3^i	84.9 (1)	C4^ii—C2—C1	123.3 (4)
O1—Ni1—O1w	103.2 (1)	C2—C3—C4	122.1 (4)
O1—Ni1—O2w	162.8 (1)	C3—C4—C2^ii	118.4 (4)
O1—Ni1—N1	91.5 (1)	C3—C4—C5	120.6 (4)
O2—Ni1—O3^i	87.8 (1)	C2^ii—C4—C5	121.0 (4)
O2—Ni1—O1w	164.8 (1)	O4—C5—O3	125.2 (4)
O2—Ni1—O2w	101.8 (1)	O4—C5—C4	119.2 (4)
O2—Ni1—N1	85.8 (1)	O3—C5—C4	115.6 (4)
O3^i—Ni1—O1w	93.2 (1)	N1—C6—C7^iii	122.5 (5)
O3^i—Ni1—O2w	89.8 (1)	N1—C7—C6^iii	120.6 (4)
O3^i—Ni1—N1	173.6 (1)	Ni1—O1w—H1w1	103 (4)
O1w—Ni1—O2w	93.4 (1)	Ni1—O1w—H1w2	117 (4)
O1w—Ni1—N1	92.8 (1)	H1w1—O1w—H1w2	98 (5)
O2w—Ni1—N1	92.2 (2)	Ni1—O2w—H2w1	123 (4)
C1—O1—Ni1	88.5 (3)	Ni1—O2w—H2w2	119 (4)
C1—O2—Ni1	89.0 (3)	H2w1—O2w—H2w2	109 (5)
C5—O3—Ni1^i	127.0 (3)	H3w1—O3w—H3w2	103 (7)
C6—N1—C7	116.9 (4)	C2—C3—H3	119.0
C6—N1—Ni1	119.8 (3)	C4—C3—H3	119.0
C7—N1—Ni1	122.8 (3)	N1—C6—H6	118.7
O2—C1—O1	120.5 (4)	C7^iii—C6—H6	118.7
O2—C1—C2	118.0 (4)	N1—C7—H7	119.7
O1—C1—C2	121.2 (4)	C6^iii—C7—H7	119.7
C3—C2—C4^ii	119.5 (4)
O3^i—Ni1—O1—C1	−87.2 (3)	Ni1—O2—C1—C2	−169.0 (3)
O2w—Ni1—O1—C1	−14.7 (6)	Ni1—O1—C1—O2	−5.2 (4)
O1w—Ni1—O1—C1	−179.3 (2)	Ni1—O1—C1—C2	168.8 (4)
N1—Ni1—O1—C1	87.5 (3)	O2—C1—C2—C3	85.6 (5)
O2—Ni1—O1—C1	3.0 (2)	O1—C1—C2—C3	−88.5 (5)
O3^i—Ni1—O2—C1	82.3 (3)	O2—C1—C2—C4^ii	−92.0 (6)
O2w—Ni1—O2—C1	171.7 (3)	O1—C1—C2—C4^ii	93.8 (6)
O1w—Ni1—O2—C1	−11.8 (6)	C4^ii—C2—C3—C4	−0.2 (8)
N1—Ni1—O2—C1	−97.0 (3)	C1—C2—C3—C4	−178.0 (4)
O1—Ni1—O2—C1	−3.0 (2)	C2—C3—C4—C2^ii	0.2 (8)
O3^i—Ni1—N1—C6	−64 (2)	C2—C3—C4—C5	179.5 (4)
O2w—Ni1—N1—C6	43.6 (4)	Ni1^i—O3—C5—O4	−2.5 (7)
O1w—Ni1—N1—C6	137.1 (4)	Ni1^i—O3—C5—C4	179.5 (3)
O2—Ni1—N1—C6	−58.1 (4)	C3—C4—C5—O4	−155.1 (5)
O1—Ni1—N1—C6	−119.6 (4)	C2^ii—C4—C5—O4	24.2 (7)
O3^i—Ni1—N1—C7	107 (1)	C3—C4—C5—O3	22.9 (7)
O2w—Ni1—N1—C7	−144.9 (4)	C2^ii—C4—C5—O3	−157.8 (4)
O1w—Ni1—N1—C7	−51.4 (4)	C7—N1—C6—C7^iii	0.7 (8)
O2—Ni1—N1—C7	113.4 (4)	Ni1—N1—C6—C7^iii	172.7 (4)
O1—Ni1—N1—C7	51.9 (4)	C6—N1—C7—C6^iii	−0.7 (8)
Ni1—O2—C1—O1	5.3 (4)	Ni1—N1—C7—C6^iii	−172.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w2···O1^iv	0.85 (1)	1.87 (3)	2.660 (5)	155 (5)
O1w—H1w1···O4^i	0.84 (1)	1.82 (2)	2.621 (5)	157 (5)
O2w—H2w2···O1w^v	0.85 (1)	1.96 (1)	2.807 (5)	176 (6)
O2w—H2w1···O3w^vi	0.85 (1)	1.90 (1)	2.744 (5)	176 (6)
O3w—H3w1···O2	0.85 (1)	2.26 (3)	3.047 (5)	155 (6)
O3w—H3w2···O3^vii	0.85 (1)	2.02 (1)	2.866 (5)	174 (7)

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