Aqua­bis(3,5-di­carboxy­benzoato-κO)­bis­(hexa­methyl­enetetr­amine-κN)­nickel(II)

The Ni atom in the title compound, [Ni(C₉H₅O₆)₂(C₆H₁₂N₄)₂(H₂O)], is bonded to two monobasic 3,5-di­carboxy­benzoate ions and datively bonded to two hexa­methyl­enetetr­amine mol­ecules; the apical position of the square-pyramidal geometry is occupied by a water mol­ecule. The complex lies on a crystallographic twofold axis that passes through the Ni atom and the water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.122
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT702_ALERT_1_B Angle   Calc    93.43(3), Rep   93.50(10), Dev..       2.33 Sigma
              O1W  -NI1  -N1      1.555   1.555   2.565
PLAT702_ALERT_1_B Angle   Calc    93.43(3), Rep   93.50(10), Dev..       2.33 Sigma
              O1W  -NI1  -N1      1.555   1.555   1.555

Alert level C
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...    3257.00 Ang-3
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O1  -NI1 -O1  -C13     5.20  0.20   2.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            N1  -NI1 -N1  -C1     21.50  0.10   2.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            N1  -NI1 -N1  -C6    141.90  0.10   2.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            N1  -NI1 -N1  -C5    -97.50  0.10   2.565   1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc    93.39(4), Rep   93.40(10) ......       2.50 su-Rat
              O1   -NI1  -O1W     1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc    93.43(3), Rep   93.50(10) ......       3.33 su-Rat
              O1W  -NI1  -N1      1.555   1.555   1.555
PLAT745_ALERT_1_C D-H     Calc     0.85(2), Rep     0.85000 ......    Missing su
              O6   -H6O     1.555   1.555

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

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   4 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); 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.

Aquabis(3,5-dicarboxybenzoato-κO)bis(hexamethylenetetramine-κN)nickel(II)

Crystal data

[Ni(C9H5O6)2(C6H12N4)2(H2O)]	F(000) = 1616
Mr = 775.38	Dx = 1.581 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 28656 reflections
a = 20.610 (4) Å	θ = 3.0–27.5°
b = 12.246 (2) Å	µ = 0.68 mm^−1
c = 12.907 (3) Å	T = 295 K
V = 3257 (1) Å^3	Prism, green
Z = 4	0.35 × 0.24 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3732 independent reflections
Radiation source: fine-focus sealed tube	3221 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −26→26
Tmin = 0.730, Tmax = 0.888	k = −15→15
28890 measured reflections	l = −16→16

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) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0693P)^2 + 1.6993P] where P = (Fo^2 + 2Fc^2)/3
3732 reflections	(Δ/σ)max = 0.001
248 parameters	Δρmax = 0.43 e Å^−3
4 restraints	Δρmin = −0.72 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ni1	0.2500	0.7500	0.07870 (3)	0.0191 (1)
O1	0.3424 (1)	0.7958 (2)	0.0696 (1)	0.0309 (4)
O2	0.3217 (1)	0.8131 (2)	−0.0974 (1)	0.0454 (5)
O3	0.5101 (1)	0.8911 (2)	−0.3376 (1)	0.0408 (5)
O4	0.6087 (1)	0.9020 (2)	−0.2671 (1)	0.0424 (5)
O5	0.6401 (1)	0.8956 (2)	0.1095 (1)	0.0426 (5)
O6	0.5524 (1)	0.8861 (2)	0.2101 (1)	0.0286 (4)
O1w	0.2500	0.7500	0.2392 (2)	0.0431 (7)
N1	0.2890 (1)	0.5756 (1)	0.0681 (1)	0.0168 (4)
N2	0.3449 (1)	0.4433 (2)	−0.0435 (1)	0.0198 (4)
N3	0.2593 (1)	0.3814 (2)	0.0731 (1)	0.0216 (4)
N4	0.3635 (1)	0.4400 (2)	0.1425 (1)	0.0206 (4)
C1	0.3199 (1)	0.5556 (2)	−0.0343 (2)	0.0200 (4)
C2	0.3932 (1)	0.4251 (2)	0.0394 (2)	0.0219 (5)
C3	0.2904 (1)	0.3658 (2)	−0.0281 (2)	0.0231 (5)
C4	0.3081 (1)	0.3630 (2)	0.1531 (2)	0.0239 (5)
C5	0.2355 (1)	0.4933 (2)	0.0796 (2)	0.0202 (4)
C6	0.3384 (1)	0.5523 (2)	0.1494 (2)	0.0201 (4)
C7	0.4310 (1)	0.8352 (2)	−0.0401 (2)	0.0193 (4)
C8	0.4556 (1)	0.8471 (2)	−0.1396 (2)	0.0222 (4)
C9	0.5211 (1)	0.8697 (2)	−0.1547 (2)	0.0211 (5)
C10	0.5621 (1)	0.8793 (2)	−0.0698 (2)	0.0203 (4)
C11	0.5375 (1)	0.8677 (2)	0.0303 (2)	0.0183 (4)
C12	0.4721 (1)	0.8460 (2)	0.0450 (2)	0.0191 (4)
C13	0.3600 (1)	0.8137 (2)	−0.0233 (2)	0.0252 (5)
C14	0.5451 (1)	0.8882 (2)	−0.2629 (2)	0.0255 (5)
C15	0.5821 (1)	0.8839 (2)	0.1202 (2)	0.0204 (4)
H4o	0.618 (2)	0.920 (3)	−0.329 (1)	0.05 (1)*
H6o	0.581 (1)	0.904 (2)	0.254 (2)	0.04 (1)*
H1w	0.217 (1)	0.763 (3)	0.276 (1)	0.05 (1)*
H1a	0.2883	0.5685	−0.0886	0.024*
H1b	0.3553	0.6068	−0.0439	0.024*
H2a	0.4289	0.4760	0.0311	0.026*
H2b	0.4105	0.3516	0.0338	0.026*
H3a	0.2585	0.3764	−0.0825	0.028*
H3b	0.3065	0.2916	−0.0332	0.028*
H4a	0.3240	0.2886	0.1481	0.029*
H4b	0.2884	0.3722	0.2208	0.029*
H5a	0.2143	0.5040	0.1460	0.024*
H5b	0.2034	0.5052	0.0257	0.024*
H6a	0.3741	0.6033	0.1423	0.024*
H6b	0.3191	0.5633	0.2172	0.024*
H8	0.4281	0.8398	−0.1964	0.027*
H10	0.6060	0.8934	−0.0797	0.024*
H12	0.4556	0.8386	0.1118	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0141 (2)	0.0244 (2)	0.0189 (2)	−0.0023 (2)	0.000	0.000
O1	0.015 (1)	0.030 (1)	0.048 (1)	−0.004 (1)	0.011 (1)	0.001 (1)
O2	0.022 (1)	0.052 (1)	0.063 (1)	0.000 (1)	−0.019 (1)	−0.020 (1)
O3	0.039 (1)	0.064 (1)	0.019 (1)	−0.005 (1)	−0.004 (1)	0.004 (1)
O4	0.029 (1)	0.080 (2)	0.018 (1)	−0.010 (1)	0.004 (1)	0.009 (1)
O5	0.015 (1)	0.088 (2)	0.024 (1)	−0.008 (1)	−0.003 (1)	0.001 (1)
O6	0.021 (1)	0.050 (1)	0.016 (1)	−0.008 (1)	−0.001 (1)	−0.004 (1)
O1w	0.037 (2)	0.078 (2)	0.014 (1)	0.030 (2)	0.000	0.000
N1	0.014 (1)	0.021 (1)	0.016 (1)	−0.001 (1)	0.000 (1)	−0.002 (1)
N2	0.020 (1)	0.023 (1)	0.016 (1)	0.002 (1)	0.001 (1)	−0.002 (1)
N3	0.020 (1)	0.021 (1)	0.024 (1)	−0.002 (1)	0.001 (1)	0.000 (1)
N4	0.020 (1)	0.025 (1)	0.017 (1)	0.003 (1)	−0.003 (1)	0.000 (1)
C1	0.022 (1)	0.021 (1)	0.017 (1)	0.000 (1)	0.001 (1)	0.002 (1)
C2	0.016 (1)	0.029 (1)	0.021 (1)	0.004 (1)	0.000 (1)	−0.001 (1)
C3	0.024 (1)	0.022 (1)	0.023 (1)	−0.001 (1)	−0.003 (1)	−0.005 (1)
C4	0.027 (1)	0.023 (1)	0.022 (1)	0.000 (1)	0.000 (1)	0.006 (1)
C5	0.012 (1)	0.024 (1)	0.024 (1)	−0.002 (1)	0.001 (1)	−0.001 (1)
C6	0.019 (1)	0.024 (1)	0.018 (1)	0.001 (1)	−0.003 (1)	−0.003 (1)
C7	0.013 (1)	0.020 (1)	0.025 (1)	−0.002 (1)	−0.002 (1)	−0.001 (1)
C8	0.020 (1)	0.027 (1)	0.020 (1)	−0.002 (1)	−0.006 (1)	0.000 (1)
C9	0.021 (1)	0.026 (1)	0.016 (1)	−0.001 (1)	0.001 (1)	0.000 (1)
C10	0.016 (1)	0.026 (1)	0.020 (1)	−0.001 (1)	0.002 (1)	0.000 (1)
C11	0.015 (1)	0.023 (1)	0.017 (1)	−0.000 (1)	−0.001 (1)	0.000 (1)
C12	0.016 (1)	0.023 (1)	0.018 (1)	0.002 (1)	0.003 (1)	0.001 (1)
C13	0.015 (1)	0.019 (1)	0.042 (1)	−0.002 (1)	−0.001 (1)	−0.007 (1)
C14	0.027 (1)	0.032 (1)	0.017 (1)	−0.001 (1)	0.003 (1)	0.000 (1)
C15	0.015 (1)	0.027 (1)	0.019 (1)	−0.002 (1)	−0.001 (1)	0.002 (1)

Geometric parameters (Å, º)

Ni1—O1	1.988 (2)	C7—C13	1.502 (3)
Ni1—O1^i	1.988 (2)	C8—C9	1.393 (3)
Ni1—O1w	2.072 (2)	C9—C10	1.390 (3)
Ni1—N1	2.286 (2)	C9—C14	1.498 (3)
Ni1—N1^i	2.286 (2)	C10—C11	1.395 (3)
O1—C13	1.271 (3)	C11—C12	1.388 (3)
O2—C13	1.241 (3)	C11—C15	1.493 (3)
O3—C14	1.204 (3)	O4—H4o	0.85 (1)
O4—C14	1.322 (3)	O6—H6o	0.85 (1)
O5—C15	1.212 (3)	O1w—H1w	0.84 (1)
O6—C15	1.311 (3)	C1—H1a	0.97
N1—C1	1.486 (3)	C1—H1b	0.97
N1—C6	1.490 (3)	C2—H2a	0.97
N1—C5	1.502 (3)	C2—H2b	0.97
N2—C1	1.474 (3)	C3—H3a	0.97
N2—C2	1.478 (3)	C3—H3b	0.97
N2—C3	1.484 (3)	C4—H4a	0.97
N3—C5	1.458 (3)	C4—H4b	0.97
N3—C4	1.458 (3)	C5—H5a	0.97
N3—C3	1.468 (3)	C5—H5b	0.97
N4—C6	1.471 (3)	C6—H6a	0.97
N4—C2	1.476 (3)	C6—H6b	0.97
N4—C4	1.487 (3)	C8—H8	0.93
C7—C8	1.388 (3)	C10—H10	0.93
C7—C12	1.393 (3)	C12—H12	0.93
O1—Ni1—O1^i	173.2 (1)	O1—C13—C7	116.4 (2)
O1—Ni1—O1w	93.4 (1)	O3—C14—O4	123.9 (2)
O1^i—Ni1—O1w	93.4 (1)	O3—C14—C9	123.5 (2)
O1—Ni1—N1^i	94.0 (1)	O4—C14—C9	112.7 (2)
O1^i—Ni1—N1^i	85.6 (1)	O5—C15—O6	123.9 (2)
O1w—Ni1—N1^i	93.5 (1)	O5—C15—C11	122.3 (2)
O1—Ni1—N1	85.6 (1)	O6—C15—C11	113.8 (2)
O1^i—Ni1—N1	94.0 (1)	C14—O4—H4o	107 (2)
O1w—Ni1—N1	93.5 (1)	C15—O6—H6o	106 (2)
N1^i—Ni1—N1	173.1 (1)	Ni1—O1w—H1w	125 (2)
C13—O1—Ni1	112.3 (2)	N2—C1—H1a	109.2
C1—N1—C6	107.6 (2)	N1—C1—H1a	109.2
C1—N1—C5	107.0 (2)	N2—C1—H1b	109.2
C6—N1—C5	107.7 (2)	N1—C1—H1b	109.2
C1—N1—Ni1	111.0 (1)	H1a—C1—H1b	107.9
C6—N1—Ni1	112.1 (1)	N2—C2—H2a	109.5
C5—N1—Ni1	111.2 (1)	N4—C2—H2a	109.5
C1—N2—C2	108.6 (2)	N2—C2—H2b	109.5
C1—N2—C3	108.7 (2)	N4—C2—H2b	109.5
C2—N2—C3	108.5 (2)	H2a—C2—H2b	108.1
C5—N3—C4	109.7 (2)	N3—C3—H3a	109.3
C5—N3—C3	108.7 (2)	N2—C3—H3a	109.3
C4—N3—C3	108.0 (2)	N3—C3—H3b	109.3
C6—N4—C2	108.5 (2)	N2—C3—H3b	109.3
C6—N4—C4	108.5 (2)	H3a—C3—H3b	108.0
C2—N4—C4	108.8 (2)	N3—C4—H4a	109.3
N2—C1—N1	112.0 (2)	N4—C4—H4a	109.3
N2—C2—N4	110.7 (2)	N3—C4—H4b	109.3
N3—C3—N2	111.5 (2)	N4—C4—H4b	109.3
N3—C4—N4	111.5 (2)	H4a—C4—H4b	108.0
N3—C5—N1	112.2 (2)	N3—C5—H5a	109.2
N4—C6—N1	112.1 (2)	N1—C5—H5a	109.2
C8—C7—C12	119.9 (2)	N3—C5—H5b	109.2
C8—C7—C13	120.5 (2)	N1—C5—H5b	109.2
C12—C7—C13	119.6 (2)	H5a—C5—H5b	107.9
C7—C8—C9	120.3 (2)	N4—C6—H6a	109.2
C10—C9—C8	119.7 (2)	N1—C6—H6a	109.2
C10—C9—C14	121.4 (2)	N4—C6—H6b	109.2
C8—C9—C14	118.8 (2)	N1—C6—H6b	109.2
C9—C10—C11	120.1 (2)	H6a—C6—H6b	107.9
C12—C11—C10	119.9 (2)	C7—C8—H8	119.8
C12—C11—C15	121.1 (2)	C9—C8—H8	119.8
C10—C11—C15	118.9 (2)	C9—C10—H10	120.0
C11—C12—C7	120.1 (2)	C11—C10—H10	120.0
O2—C13—O1	122.9 (2)	C11—C12—H12	120.0
O2—C13—C7	120.6 (2)	C7—C12—H12	120.0
O1^i—Ni1—O1—C13	5.2 (2)	C1—N1—C5—N3	58.7 (2)
O1w—Ni1—O1—C13	−174.8 (2)	C6—N1—C5—N3	−56.7 (2)
N1^i—Ni1—O1—C13	−81.1 (2)	Ni1—N1—C5—N3	−180.0 (1)
N1—Ni1—O1—C13	92.0 (2)	C2—N4—C6—N1	59.4 (2)
O1—Ni1—N1—C1	−65.4 (1)	C4—N4—C6—N1	−58.6 (2)
O1^i—Ni1—N1—C1	107.8 (1)	C1—N1—C6—N4	−57.7 (2)
O1w—Ni1—N1—C1	−158.5 (1)	C5—N1—C6—N4	57.3 (2)
N1^i—Ni1—N1—C1	21.5 (1)	Ni1—N1—C6—N4	−180.0 (1)
O1—Ni1—N1—C6	55.0 (1)	C12—C7—C8—C9	0.0 (3)
O1^i—Ni1—N1—C6	−131.8 (1)	C13—C7—C8—C9	178.4 (2)
O1w—Ni1—N1—C6	−38.1 (1)	C7—C8—C9—C10	0.7 (3)
N1^i—Ni1—N1—C6	141.9 (1)	C7—C8—C9—C14	−176.6 (2)
O1—Ni1—N1—C5	175.7 (1)	C8—C9—C10—C11	−0.9 (3)
O1^i—Ni1—N1—C5	−11.1 (1)	C14—C9—C10—C11	176.3 (2)
O1w—Ni1—N1—C5	82.5 (1)	C9—C10—C11—C12	0.4 (3)
N1^i—Ni1—N1—C5	−97.5 (1)	C9—C10—C11—C15	−177.0 (2)
C2—N2—C1—N1	−59.2 (2)	C10—C11—C12—C7	0.3 (3)
C3—N2—C1—N1	58.6 (2)	C15—C11—C12—C7	177.6 (2)
C6—N1—C1—N2	57.5 (2)	C8—C7—C12—C11	−0.5 (3)
C5—N1—C1—N2	−58.0 (2)	C13—C7—C12—C11	−178.9 (2)
Ni1—N1—C1—N2	−179.5 (1)	Ni1—O1—C13—O2	6.9 (3)
C1—N2—C2—N4	59.8 (2)	Ni1—O1—C13—C7	−172.7 (1)
C3—N2—C2—N4	−58.2 (2)	C8—C7—C13—O2	−4.6 (3)
C6—N4—C2—N2	−59.8 (2)	C12—C7—C13—O2	173.8 (2)
C4—N4—C2—N2	58.0 (2)	C8—C7—C13—O1	174.9 (2)
C5—N3—C3—N2	58.9 (2)	C12—C7—C13—O1	−6.6 (3)
C4—N3—C3—N2	−60.0 (2)	C10—C9—C14—O3	−172.6 (2)
C1—N2—C3—N3	−58.3 (2)	C8—C9—C14—O3	4.6 (4)
C2—N2—C3—N3	59.6 (2)	C10—C9—C14—O4	6.8 (3)
C5—N3—C4—N4	−58.7 (2)	C8—C9—C14—O4	−176.0 (2)
C3—N3—C4—N4	59.6 (2)	C12—C11—C15—O5	174.9 (2)
C6—N4—C4—N3	58.6 (2)	C10—C11—C15—O5	−7.7 (3)
C2—N4—C4—N3	−59.2 (2)	C12—C11—C15—O6	−6.2 (3)
C4—N3—C5—N1	58.2 (2)	C10—C11—C15—O6	171.1 (2)
C3—N3—C5—N1	−59.7 (2)

Symmetry code: (i) −x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···N2^ii	0.85 (1)	1.83 (1)	2.674 (2)	167 (3)
O6—H6o···N4^iii	0.85 (1)	1.82 (1)	2.657 (2)	174 (3)
O1w—H1w···O2^iv	0.84 (1)	1.92 (2)	2.688 (3)	152 (2)

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