Tetra­aqua­(ethane-1,2-di­amine-κ²N,N′)nickel(II) naphthalene-1,5-di­sulfonate dihydrate

The reaction of ethane-1,2-di­amine (en, C₂H₈N₂), the sodium salt of naphthalene-1,5-di­sulfonic acid (H₂NDS, C₁₀H₈O₆S₂), and nickel sulfate in an aqueous solution resulted in the formation of the title salt, [Ni(C₂H₈N₂)(H₂O)₄](C₁₀H₆O₆S₂)·2H₂O or [Ni(en)(H₂O)₄](NDS)·2H₂O. In the asymmetric unit, one half of an [Ni(en)(H₂O)₄]²⁺ cation and one half of an NDS²⁻ anion, and one water mol­ecule of crystallization are present. The Ni²⁺ cation in the complex is positioned on a twofold rotation axis and exhibits a slight tetra­gonal distortion of the cis-NiO₄N₂ octa­hedron, with an Ni—N bond length of 2.0782 (16) Å, and Ni—O bond lengths of 2.1170 (13) Å and 2.0648 (14) Å. The anion is completed by inversion symmetry. In the extended structure, the cations, anions, and non-coordinating water mol­ecules are connected by inter­molecular N—H...O and O—H...O hydrogen bonding, as well as C—H...π inter­actions, forming a three-dimensional network.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.085
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         12 Note
PLAT013_ALERT_1_G N.O.K.   _shelx_hkl_checksum Found in CIF ......     Please Check
PLAT128_ALERT_4_G Alternate Setting for Input Space Group  I2/a          I2/c Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          6 Note
              H1WA    H1WB    H2WA    H2WB    H3WA    H3WB
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       1.95 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          8 Note
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

Computing details

Tetraaqua(ethane-1,2-diamine-κ²N,N')nickel(II) naphthalene-1,5-disulfonate dihydrate

Crystal data

[Ni(C2H8N2)(H2O)4](C10H6O6S2)·2H2O	F(000) = 1072
Mr = 513.18	Dx = 1.716 Mg m^−3
Monoclinic, I2/a	Cu Kα radiation, λ = 1.54184 Å
a = 15.4103 (3) Å	Cell parameters from 8478 reflections
b = 10.1338 (2) Å	θ = 3.8–71.3°
c = 13.4284 (2) Å	µ = 3.99 mm^−1
β = 108.692 (2)°	T = 291 K
V = 1986.44 (7) Å^3	Block, light green
Z = 4	0.28 × 0.24 × 0.2 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	1926 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1881 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.037
Detector resolution: 10.0000 pixels mm^-1	θmax = 71.5°, θmin = 3.8°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −11→12
Tmin = 0.419, Tmax = 1.000	l = −15→16
10963 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 1.9301P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.085	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.40 e Å^−3
1926 reflections	Δρmin = −0.33 e Å^−3
165 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
8 restraints	Extinction coefficient: 0.00087 (12)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ni1	0.750000	0.31595 (4)	0.500000	0.02364 (16)
O1W	0.66391 (10)	0.16745 (13)	0.51659 (11)	0.0345 (3)
H1WA	0.6474 (19)	0.106 (2)	0.4714 (17)	0.055 (8)*
H1WB	0.6172 (15)	0.191 (3)	0.532 (3)	0.069 (10)*
O2W	0.69189 (10)	0.31220 (13)	0.33422 (11)	0.0341 (3)
H2WA	0.6830 (19)	0.2367 (15)	0.306 (2)	0.051 (7)*
H2WB	0.6401 (11)	0.350 (3)	0.312 (2)	0.059 (8)*
N1	0.83603 (11)	0.46867 (16)	0.48778 (13)	0.0301 (3)
H1A	0.8373 (19)	0.473 (3)	0.4228 (11)	0.048 (7)*
H1B	0.8942 (9)	0.459 (2)	0.5276 (18)	0.050 (7)*
C6	0.80179 (13)	0.59247 (19)	0.52035 (16)	0.0363 (4)
H6A	0.825144	0.667734	0.492234	0.044*
H6B	0.822909	0.599187	0.596421	0.044*
S1	0.57628 (3)	0.54449 (4)	0.76422 (3)	0.02430 (16)
O1	0.59637 (9)	0.54691 (13)	0.87797 (10)	0.0337 (3)
O2	0.47965 (9)	0.56091 (14)	0.70702 (11)	0.0369 (3)
O3	0.61490 (9)	0.42790 (12)	0.73007 (11)	0.0343 (3)
C1	0.63244 (11)	0.68365 (16)	0.73175 (13)	0.0231 (3)
C2	0.57843 (12)	0.78162 (18)	0.67353 (14)	0.0281 (4)
H2	0.514988	0.774290	0.653357	0.034*
C3	0.61849 (12)	0.89311 (18)	0.64417 (14)	0.0301 (4)
H3	0.581294	0.959325	0.604714	0.036*
C4	0.71119 (12)	0.90538 (17)	0.67283 (14)	0.0274 (4)
H4	0.736531	0.979213	0.651599	0.033*
C5	0.76989 (12)	0.80698 (15)	0.73475 (13)	0.0224 (3)
O3W	0.52056 (11)	0.25077 (18)	0.57325 (13)	0.0495 (4)
H3WA	0.540 (2)	0.304 (2)	0.6243 (16)	0.062 (9)*
H3WB	0.485 (2)	0.196 (3)	0.588 (3)	0.076 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0186 (2)	0.0240 (2)	0.0265 (2)	0.000	0.00471 (17)	0.000
O1W	0.0315 (7)	0.0306 (7)	0.0426 (8)	−0.0085 (5)	0.0135 (6)	−0.0048 (6)
O2W	0.0309 (7)	0.0348 (7)	0.0307 (7)	0.0010 (6)	0.0017 (6)	−0.0023 (5)
N1	0.0231 (7)	0.0330 (8)	0.0338 (8)	−0.0030 (6)	0.0086 (6)	0.0004 (6)
C6	0.0348 (11)	0.0275 (9)	0.0436 (10)	−0.0046 (8)	0.0085 (8)	−0.0027 (8)
S1	0.0179 (2)	0.0253 (2)	0.0283 (2)	−0.00158 (14)	0.00546 (17)	0.00269 (14)
O1	0.0335 (7)	0.0381 (7)	0.0309 (7)	0.0009 (5)	0.0123 (6)	0.0064 (5)
O2	0.0184 (7)	0.0412 (7)	0.0459 (8)	−0.0040 (5)	0.0030 (6)	0.0088 (6)
O3	0.0322 (7)	0.0258 (6)	0.0431 (7)	−0.0022 (5)	0.0097 (6)	−0.0036 (5)
C1	0.0185 (8)	0.0247 (8)	0.0249 (8)	−0.0009 (6)	0.0053 (6)	0.0003 (6)
C2	0.0181 (8)	0.0308 (9)	0.0324 (9)	0.0023 (7)	0.0039 (7)	0.0040 (7)
C3	0.0220 (8)	0.0281 (9)	0.0360 (9)	0.0067 (7)	0.0034 (7)	0.0099 (7)
C4	0.0235 (8)	0.0243 (8)	0.0325 (8)	0.0008 (6)	0.0064 (7)	0.0060 (7)
C5	0.0197 (8)	0.0232 (8)	0.0230 (8)	0.0004 (6)	0.0049 (6)	−0.0002 (6)
O3W	0.0438 (9)	0.0612 (10)	0.0485 (9)	−0.0163 (8)	0.0219 (7)	−0.0165 (8)

Geometric parameters (Å, º)

Ni1—O1W^i	2.0648 (14)	S1—O1	1.4583 (14)
Ni1—O1W	2.0648 (14)	S1—O2	1.4498 (13)
Ni1—O2W	2.1170 (13)	S1—O3	1.4612 (14)
Ni1—O2W^i	2.1170 (13)	S1—C1	1.7803 (17)
Ni1—N1	2.0782 (16)	C1—C2	1.368 (2)
Ni1—N1^i	2.0783 (15)	C1—C5^ii	1.429 (2)
O1W—H1WA	0.847 (10)	C2—H2	0.9300
O1W—H1WB	0.846 (10)	C2—C3	1.403 (3)
O2W—H2WA	0.844 (10)	C3—H3	0.9300
O2W—H2WB	0.849 (10)	C3—C4	1.361 (2)
N1—H1A	0.880 (10)	C4—H4	0.9300
N1—H1B	0.889 (10)	C4—C5	1.422 (2)
N1—C6	1.480 (2)	C5—C5^ii	1.428 (3)
C6—C6^i	1.512 (4)	O3W—H3WA	0.846 (10)
C6—H6A	0.9700	O3W—H3WB	0.844 (10)
C6—H6B	0.9700
O1W^i—Ni1—O1W	86.43 (8)	N1—C6—H6A	109.9
O1W^i—Ni1—O2W	86.76 (6)	N1—C6—H6B	109.9
O1W—Ni1—O2W	91.75 (6)	C6^i—C6—H6A	109.9
O1W^i—Ni1—O2W^i	91.74 (6)	C6^i—C6—H6B	109.9
O1W—Ni1—O2W^i	86.76 (6)	H6A—C6—H6B	108.3
O1W^i—Ni1—N1	94.94 (6)	O1—S1—O3	111.79 (8)
O1W^i—Ni1—N1^i	178.02 (6)	O1—S1—C1	106.65 (8)
O1W—Ni1—N1	178.02 (6)	O2—S1—O1	112.96 (8)
O1W—Ni1—N1^i	94.94 (6)	O2—S1—O3	112.27 (8)
O2W^i—Ni1—O2W	177.95 (8)	O2—S1—C1	106.06 (8)
N1—Ni1—O2W	89.77 (6)	O3—S1—C1	106.55 (8)
N1—Ni1—O2W^i	91.76 (6)	C2—C1—S1	117.40 (13)
N1^i—Ni1—O2W^i	89.77 (6)	C2—C1—C5^ii	121.20 (15)
N1^i—Ni1—O2W	91.77 (6)	C5^ii—C1—S1	121.41 (12)
N1—Ni1—N1^i	83.73 (9)	C1—C2—H2	119.9
Ni1—O1W—H1WA	120.8 (19)	C1—C2—C3	120.19 (16)
Ni1—O1W—H1WB	117 (2)	C3—C2—H2	119.9
H1WA—O1W—H1WB	107 (3)	C2—C3—H3	119.6
Ni1—O2W—H2WA	116.0 (19)	C4—C3—C2	120.71 (16)
Ni1—O2W—H2WB	113 (2)	C4—C3—H3	119.6
H2WA—O2W—H2WB	105 (3)	C3—C4—H4	119.5
Ni1—N1—H1A	109.5 (17)	C3—C4—C5	120.97 (16)
Ni1—N1—H1B	114.7 (17)	C5—C4—H4	119.5
H1A—N1—H1B	105 (2)	C4—C5—C1^ii	123.08 (15)
C6—N1—Ni1	108.12 (12)	C4—C5—C5^ii	118.94 (19)
C6—N1—H1A	112.0 (17)	C5^ii—C5—C1^ii	117.98 (18)
C6—N1—H1B	107.4 (17)	H3WA—O3W—H3WB	108 (3)
N1—C6—C6^i	109.15 (12)
Ni1—N1—C6—C6^i	−38.8 (2)	O3—S1—C1—C5^ii	−53.25 (16)
S1—C1—C2—C3	−179.17 (14)	C1—C2—C3—C4	0.1 (3)
O1—S1—C1—C2	−113.59 (15)	C2—C3—C4—C5	−1.1 (3)
O1—S1—C1—C5^ii	66.29 (15)	C3—C4—C5—C1^ii	−178.96 (17)
O2—S1—C1—C2	7.07 (16)	C3—C4—C5—C5^ii	1.1 (3)
O2—S1—C1—C5^ii	−173.05 (14)	C5^ii—C1—C2—C3	1.0 (3)
O3—S1—C1—C2	126.87 (14)

Symmetry codes: (i) −x+3/2, y, −z+1; (ii) −x+3/2, −y+3/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the C1–C5/C5' and C1'–C5'/C5 rings, respectively, where primed atoms are related by the symmetry operation 3/2 - x, 3/2 - y, 3/2 - z.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1^iii	0.85 (1)	1.99 (1)	2.8329 (19)	171 (3)
O1W—H1WB···O3W	0.85 (1)	1.85 (1)	2.692 (2)	176 (3)
O2W—H2WA···O3^iii	0.84 (1)	2.06 (1)	2.8670 (19)	160 (3)
O2W—H2WB···O2^iv	0.85 (1)	1.99 (1)	2.830 (2)	168 (3)
N1—H1A···O3^i	0.88 (1)	2.44 (1)	3.274 (2)	159 (2)
N1—H1B···O2^v	0.89 (1)	2.36 (2)	3.079 (2)	139 (2)
O3W—H3WA···O3	0.85 (1)	1.97 (1)	2.794 (2)	164 (3)
O3W—H3WB···O1^vi	0.84 (1)	2.11 (1)	2.950 (2)	175 (3)
C6—H6A···Cg1^i	0.97	2.93	3.755 (2)	143
C6—H6A···Cg2^vii	0.97	2.93	3.755 (2)	143
C6—H6B···Cg1^ii	0.97	2.88	3.781 (2)	155
C6—H6B···Cg2	0.97	2.88	3.781 (2)	155

Symmetry codes: (i) −x+3/2, y, −z+1; (ii) −x+3/2, −y+3/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1; (v) x+1/2, −y+1, z; (vi) −x+1, y−1/2, −z+3/2; (vii) x, −y+3/2, z−1/2.